Advanced cathode materials for polymer electrolyte fuel cells based on pt/ metal oxides: from model electrodes to catalyst systems.

PubMed

Fabbri, Emiliana; Pătru, Alexandra; Rabis, Annett; Kötz, Rüdiger; Schmidt, Thomas J

2014-01-01

The development of stable catalyst systems for application at the cathode side of polymer electrolyte fuel cells (PEFCs) requires the substitution of the state-of-the-art carbon supports with materials showing high corrosion resistance in a strongly oxidizing environment. Metal oxides in their highest oxidation state can represent viable support materials for the next generation PEFC cathodes. In the present work a multilevel approach has been adopted to investigate the kinetics and the activity of Pt nanoparticles supported on SnO2-based metal oxides. Particularly, model electrodes made of SnO2 thin films supporting Pt nanoparticles, and porous catalyst systems made of Pt nanoparticles supported on Sb-doped SnO2 high surface area powders have been investigated. The present results indicate that SnO2-based supports do not modify the oxygen reduction reaction mechanism on the Pt nanoparticle surface, but rather lead to catalysts with enhanced specific activity compared to Pt/carbon systems. Different reasons for the enhancement in the specific activity are considered and discussed.

Oxidation driven ZnS Core-ZnO shell photocatalysts under controlled oxygen atmosphere for improved photocatalytic solar water splitting

NASA Astrophysics Data System (ADS)

Bak, Daegil; Kim, Jung Hyeun

2018-06-01

Zinc type photocatalysts attract great attentions in solar hydrogen production due to their easy availability and benign environmental characteristics. Spherical ZnS particles are synthesized with a facile hydrothermal method, and they are further used as core materials to introduce ZnO shell layer surrounding the core part by partial oxidation under controlled oxygen contents. The resulting ZnS core-ZnO shell photocatalysts represent the heterostructural type II band alignment. The existence of oxide layer also influences on proton adsorption power with an aid of strong base cites derived from highly electronegative oxygen atoms in ZnO shell layer. Photocatalytic water splitting reaction is performed to evaluate catalyst efficiency under standard one sun condition, and the highest hydrogen evolution rate (1665 μmolg-1h-1) is achieved from the sample oxidized at 16.2 kPa oxygen pressure. This highest hydrogen production rate is achieved in cooperation with increased light absorption and promoted charge separations. Photoluminescence analysis reveals that the improved visible light response is obtained after thermal oxidation process due to the oxygen vacancy states in the ZnO shell layer. Therefore, overall photocatalytic efficiency in solar hydrogen production is enhanced by improved charge separations, crystallinity, and visible light responses from the ZnS core-ZnO shell structures induced by thermal oxidation.

Differential correlations between changes to glutathione redox state, protein ubiquitination, and stress-inducible HSPA chaperone expression after different types of oxidative stress.

PubMed

Girard, Pierre-Marie; Peynot, Nathalie; Lelièvre, Jean-Marc

2018-05-12

In primary bovine fibroblasts with an hspa1b/luciferase transgene, we examined the intensity of heat-shock response (HSR) following four types of oxidative stress or heat stress (HS), and its putative relationship with changes to different cell parameters, including reactive oxygen species (ROS), the redox status of the key molecules glutathione (GSH), NADP(H) NAD(H), and the post-translational protein modifications carbonylation, S-glutathionylation, and ubiquitination. We determined the sub-lethal condition generating the maximal luciferase activity and inducible HSPA protein level for treatments with hydrogen peroxide (H 2 O 2 ), UVA-induced oxygen photo-activation, the superoxide-generating agent menadione (MN), and diamide (DA), an electrophilic and sulfhydryl reagent. The level of HSR induced by oxidative stress was the highest after DA and MN, followed by UVA and H 2 O 2 treatments, and was not correlated to the level of ROS production nor to the extent of protein S-glutathionylation or carbonylation observed immediately after stress. We found a correlation following oxidative treatments between HSR and the level of GSH/GSSG immediately after stress, and the increase in protein ubiquitination during the recovery period. Conversely, HS treatment, which led to the highest HSR level, did not generate ROS nor modified or depended on GSH redox state. Furthermore, the level of protein ubiquitination was maximum immediately after HS and lower than after MN and DA treatments thereafter. In these cells, heat-induced HSR was therefore clearly different from oxidative stress-induced HSR, in which conversely early redox changes of the major cellular thiol predicted the level of HSR and polyubiquinated proteins.

Lichen communities on conifers in Southern California mountains: an ecological survey relative to oxidant air pollution

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

Sigal, L.L.; Nash, T.H. III

1983-01-01

In comparison with collections from the early 1900's when oxidant air pollution was essentially absent, 50% fewer lichen species were found on conifers during 3 yr (1976-1979) of collecting and sampling in the mountains of Southern California. Among the five mountain ranges studied, the San Bernardino Mountains, the region with the highest oxidant levels, had lower lichen frequency and cover values. Within the San Bernardino study sites, lichen cover was inversely related to estimated oxidant doses. Furthermore, at sites with high oxidant levels, marked morphological deterioration of the common species Hypogymnia enteromorpha was documented. Transplants of this species from themore » relatively unpolluted Cuyamaca Rancho State Park into the San Bernardino Mountains exhibited similar deterioration after a year's exposure. 4 figures, 9 tables.« less

Observation of Caroli-de Gennes-Matricon Vortex States in YBa2Cu3O7 -δ

NASA Astrophysics Data System (ADS)

Berthod, Christophe; Maggio-Aprile, Ivan; Bruér, Jens; Erb, Andreas; Renner, Christoph

2017-12-01

The copper oxides present the highest superconducting temperature and properties at odds with other compounds, suggestive of a fundamentally different superconductivity. In particular, the Abrikosov vortices fail to exhibit localized states expected and observed in all clean superconductors. We have explored the possibility that the elusive vortex-core signatures are actually present but weak. Combining local tunneling measurements with large-scale theoretical modeling, we positively identify the vortex states in YBa2Cu3O7 -δ . We explain their spectrum and the observed variations thereof from one vortex to the next by considering the effects of nearby vortices and disorder in the vortex lattice. We argue that the superconductivity of copper oxides is conventional, but the spectroscopic signature does not look so because the superconducting carriers are a minority.

The reduction of graphene oxide by zinc powder to produce a zinc oxide-reduced graphene oxide hybrid and its superior photocatalytic activity

NASA Astrophysics Data System (ADS)

Sarkar, Sanjit; Basak, Durga

2013-03-01

We have synthesized for the first time ZnO/rGO hybrids from metal zinc and GO using hydrothermal technique without adding further reducing agent. The photocatalytic property of ZnO-rGO reveals that the hybrid for 50 mg of GO has the highest activity, causing a 94% degradation of methyl orange compared to 70% by only ZnO. The consistent quenching and a gradual decrease in the decay life time of the emission at ˜500 nm as the rGO content increases indicates the interfacial charge transfer process between ZnO and rGO by the defect states responsible for green emission.

Effects of positive ion implantation into antireflection coating of silicon solar cells

NASA Technical Reports Server (NTRS)

Middleton, A. E.; Harpster, J. W.; Collis, W. J.; Kim, C. K.

1971-01-01

The state of technological development of Si solar cells for highest obtained efficiency and radiation resistance is summarized. The various theoretical analyses of Si solar cells are reviewed. It is shown that factors controlling blue response are carrier diffusion length, surface recombination, impurity concentration profile in surface region, high level of surface impurity concentration (degeneracy), reflection coefficient of oxide, and absorption coefficient of Si. The theory of ion implantation of charge into the oxide antireflection coating is developed and side effects are discussed. The experimental investigations were directed at determining whether the blue response of Si solar cells could be improved by phosphorus ion charges introduced into the oxide antireflection coating.

Electrosynthesis of Biomimetic Manganese-Calcium Oxides for Water Oxidation Catalysis--Atomic Structure and Functionality.

PubMed

González-Flores, Diego; Zaharieva, Ivelina; Heidkamp, Jonathan; Chernev, Petko; Martínez-Moreno, Elías; Pasquini, Chiara; Mohammadi, Mohammad Reza; Klingan, Katharina; Gernet, Ulrich; Fischer, Anna; Dau, Holger

2016-02-19

Water-oxidizing calcium-manganese oxides, which mimic the inorganic core of the biological catalyst, were synthesized and structurally characterized by X-ray absorption spectroscopy at the manganese and calcium K edges. The amorphous, birnesite-type oxides are obtained through a simple protocol that involves electrodeposition followed by active-site creation through annealing at moderate temperatures. Calcium ions are inessential, but tune the electrocatalytic properties. For increasing calcium/manganese molar ratios, both Tafel slopes and exchange current densities decrease gradually, resulting in optimal catalytic performance at calcium/manganese molar ratios of close to 10 %. Tracking UV/Vis absorption changes during electrochemical operation suggests that inactive oxides reach their highest, all-Mn(IV) oxidation state at comparably low electrode potentials. The ability to undergo redox transitions and the presence of a minor fraction of Mn(III) ions at catalytic potentials is identified as a prerequisite for catalytic activity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photosynthesis. Electronic structure of the oxygen-evolving complex in photosystem II prior to O-O bond formation.

PubMed

Cox, Nicholas; Retegan, Marius; Neese, Frank; Pantazis, Dimitrios A; Boussac, Alain; Lubitz, Wolfgang

2014-08-15

The photosynthetic protein complex photosystem II oxidizes water to molecular oxygen at an embedded tetramanganese-calcium cluster. Resolving the geometric and electronic structure of this cluster in its highest metastable catalytic state (designated S3) is a prerequisite for understanding the mechanism of O-O bond formation. Here, multifrequency, multidimensional magnetic resonance spectroscopy reveals that all four manganese ions of the catalyst are structurally and electronically similar immediately before the final oxygen evolution step; they all exhibit a 4+ formal oxidation state and octahedral local geometry. Only one structural model derived from quantum chemical modeling is consistent with all magnetic resonance data; its formation requires the binding of an additional water molecule. O-O bond formation would then proceed by the coupling of two proximal manganese-bound oxygens in the transition state of the cofactor. Copyright © 2014, American Association for the Advancement of Science.

Heptavalent Actinide Tetroxides NpO 4 – and PuO 4 –: Oxidation of Pu(V) to Pu(VII) by Adding an Electron to PuO 4

DOE PAGES

Gibson, John K.; de Jong, Wibe A.; Dau, Phuong D.; ...

2017-11-14

The highest known actinide oxidation states are Np(VII) and Pu(VII), both of which have been identified in solution and solid compounds. Recently a molecular Np(VII) complex, NpO 3(NO 3) 2-, was prepared and characterized in the gas phase. In accord with the lower stability of heptavalent Pu, no Pu(VII) molecular species has been identified. Reported here are the gas-phase syntheses and characterizations of NpO 4 - and PuO 4 -. Reactivity studies and density functional theory computations indicate the heptavalent metal oxidation state in both. This is the first instance of Pu(VII) in the absence of stabilizing effects due tomore » condensed phase solvation or crystal fields. Here, the results indicate that addition of an electron to neutral PuO 4, which has a computed electron affinity of 2.56 eV, counterintuitively results in oxidation of Pu(V) to Pu(VII), concomitant with superoxide reduction.« less

Heptavalent Actinide Tetroxides NpO 4 – and PuO 4 –: Oxidation of Pu(V) to Pu(VII) by Adding an Electron to PuO 4

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

Gibson, John K.; de Jong, Wibe A.; Dau, Phuong D.

The highest known actinide oxidation states are Np(VII) and Pu(VII), both of which have been identified in solution and solid compounds. Recently a molecular Np(VII) complex, NpO 3(NO 3) 2-, was prepared and characterized in the gas phase. In accord with the lower stability of heptavalent Pu, no Pu(VII) molecular species has been identified. Reported here are the gas-phase syntheses and characterizations of NpO 4 - and PuO 4 -. Reactivity studies and density functional theory computations indicate the heptavalent metal oxidation state in both. This is the first instance of Pu(VII) in the absence of stabilizing effects due tomore » condensed phase solvation or crystal fields. Here, the results indicate that addition of an electron to neutral PuO 4, which has a computed electron affinity of 2.56 eV, counterintuitively results in oxidation of Pu(V) to Pu(VII), concomitant with superoxide reduction.« less

Fabrication of highly selective tungsten oxide ammonia sensors

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

Llobet, E.; Molas, G.; Molinas, P.

Tungsten oxide is shown to be a very promising material for the fabrication of highly selective ammonia sensors. Films of WO{sub 3} were deposited onto a silicon substrate by means of the drop-coating method. Then, the films were annealed in dry air at two different temperatures (300 and 400 C). X-ray photoelectron spectroscopy was used to investigate the composition of the films. Tungsten appeared both in WO{sub 2} and WO{sub 3} oxidation states, but the second state was clearly dominant. Scanning electron microscopy results showed that the oxide was amorphous or nanocrystalline. The WO{sub 3}-based devices were sensitive to ammoniamore » vapors when operated between 250 and 350 C. The optimal operating temperature for the highest sensitivity to ammonia was 300 C. Furthermore, when the devices were operated at 300 C, their sensitivity to other reducing species such as ethanol, methane, toluene, and water vapor was significantly lower, and this resulted in a high selectivity to ammonia. A model for the sensing mechanisms of the fabricated sensors is proposed.« less

Highly efficient binuclear ruthenium catalyst for water oxidation.

PubMed

Sander, Anett C; Maji, Somnath; Francàs, Laia; Böhnisch, Torben; Dechert, Sebastian; Llobet, Antoni; Meyer, Franc

2015-05-22

Water splitting is one of the key steps in the conversion of sunlight into a usable renewable energy carrier such as dihydrogen or more complex chemical fuels. Developing rugged and highly efficient catalysts for the oxidative part of water splitting, the water oxidation reaction generating dioxygen, is a major challenge in the field. Herein, we introduce a new, and rationally designed, pyrazolate-based diruthenium complex with the highest activity in water oxidation catalysis for binuclear systems reported to date. Single-crystal X-ray diffraction showed favorable preorganization of the metal ions, well suited for binding two water molecules at a distance adequate for OO bond formation; redox titrations as well as spectroelectrochemistry allowed characterization of the system in several oxidation states. Low oxidation potentials reflect the trianionic character of the elaborate compartmental pyrazolate ligand furnished with peripheral carboxylate groups. Water oxidation has been mediated both by a chemical oxidant (Ce(IV) )-by means of manometry and a Clark electrode for monitoring the dioxygen production-and electrochemically with impressive activities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Demonstration of a day-night rhythm in human skeletal muscle oxidative capacity.

PubMed

van Moorsel, Dirk; Hansen, Jan; Havekes, Bas; Scheer, Frank A J L; Jörgensen, Johanna A; Hoeks, Joris; Schrauwen-Hinderling, Vera B; Duez, Helene; Lefebvre, Philippe; Schaper, Nicolaas C; Hesselink, Matthijs K C; Staels, Bart; Schrauwen, Patrick

2016-08-01

A disturbed day-night rhythm is associated with metabolic perturbations that can lead to obesity and type 2 diabetes mellitus (T2DM). In skeletal muscle, a reduced oxidative capacity is also associated with the development of T2DM. However, whether oxidative capacity in skeletal muscle displays a day-night rhythm in humans has so far not been investigated. Lean, healthy subjects were enrolled in a standardized living protocol with regular meals, physical activity and sleep to reflect our everyday lifestyle. Mitochondrial oxidative capacity was examined in skeletal muscle biopsies taken at five time points within a 24-hour period. Core-body temperature was lower during the early night, confirming a normal day-night rhythm. Skeletal muscle oxidative capacity demonstrated a robust day-night rhythm, with a significant time effect in ADP-stimulated respiration (state 3 MO, state 3 MOG and state 3 MOGS, p < 0.05). Respiration was lowest at 1 PM and highest at 11 PM (state 3 MOGS: 80.6 ± 4.0 vs. 95.8 ± 4.7 pmol/mg/s). Interestingly, the fluctuation in mitochondrial function was also observed in whole-body energy expenditure, with peak energy expenditure at 11 PM and lowest energy expenditure at 4 AM (p < 0.001). In addition, we demonstrate rhythmicity in mRNA expression of molecular clock genes in human skeletal muscle. Our results suggest that the biological clock drives robust rhythms in human skeletal muscle oxidative metabolism. It is tempting to speculate that disruption of these rhythms contribute to the deterioration of metabolic health associated with circadian misalignment.

Intrinsic charge trapping in amorphous oxide films: status and challenges

NASA Astrophysics Data System (ADS)

Strand, Jack; Kaviani, Moloud; Gao, David; El-Sayed, Al-Moatasem; Afanas’ev, Valeri V.; Shluger, Alexander L.

2018-06-01

We review the current understanding of intrinsic electron and hole trapping in insulating amorphous oxide films on semiconductor and metal substrates. The experimental and theoretical evidences are provided for the existence of intrinsic deep electron and hole trap states stemming from the disorder of amorphous metal oxide networks. We start from presenting the results for amorphous (a) HfO2, chosen due to the availability of highest purity amorphous films, which is vital for studying their intrinsic electronic properties. Exhaustive photo-depopulation spectroscopy measurements and theoretical calculations using density functional theory shed light on the atomic nature of electronic gap states responsible for deep electron trapping observed in a-HfO2. We review theoretical methods used for creating models of amorphous structures and electronic structure calculations of amorphous oxides and outline some of the challenges in modeling defects in amorphous materials. We then discuss theoretical models of electron polarons and bi-polarons in a-HfO2 and demonstrate that these intrinsic states originate from low-coordinated ions and elongated metal-oxygen bonds in the amorphous oxide network. Similarly, holes can be captured at under-coordinated O sites. We then discuss electron and hole trapping in other amorphous oxides, such as a-SiO2, a-Al2O3, a-TiO2. We propose that the presence of low-coordinated ions in amorphous oxides with electron states of significant p and d character near the conduction band minimum can lead to electron trapping and that deep hole trapping should be common to all amorphous oxides. Finally, we demonstrate that bi-electron trapping in a-HfO2 and a-SiO2 weakens Hf(Si)–O bonds and significantly reduces barriers for forming Frenkel defects, neutral O vacancies and O2‑ ions in these materials. These results should be useful for better understanding of electronic properties and structural evolution of thin amorphous films under carrier injection conditions.

Optimization of a model of red blood cells for the study of anti-oxidant drugs, in terms of concentration of oxidant and phosphate buffer.

PubMed

Bureau, A; Lahet, J-J; Lenfant, F; Bouyer, F; Petitjean, M; Chaillot, B; Freysz, M

2005-08-01

The aggression of erythrocytes by an oxidative stress induces hemolysis. This paper aims to valid a model of erythrocytes in terms of composition of the phosphate buffer solution and of concentration of a well-known oxidant, AAPH. Three compositions of phosphate buffer solution are mixed with three concentrations of oxidant. The influence of these two parameters on hemolysis is independently studied by a variance analysis and a Kruskal-Wallis test when ANOVA is not available. The hemolysis rate increases with time at fixed oxidant concentration, but is not influenced by the composition of the buffer solution. The highest hemolysis rate, 90%, was only measured within 2 h with the highest oxidant concentration. If we retain this concentration of oxidant, the lower concentration of the buffer can by eliminated by a significant less hemolysis and the highest concentration of the buffer can by chosen in regard of the better precision for a similar hemolysis compared to the mean buffer. We hope to study the effect of anti-oxidant agent with such a model of erythrocytes.

Electronic Structure Control of Tungsten Oxide Activated by Ni for Ultrahigh-Performance Supercapacitors.

PubMed

Meng, Tian; Kou, Zongkui; Amiinu, Ibrahim Saana; Hong, Xufeng; Li, Qingwei; Tang, Yongfu; Zhao, Yufeng; Liu, Shaojun; Mai, Liqiang; Mu, Shichun

2018-04-17

Tuning the electron structure is of vital importance for designing high active electrode materials. Here, for boosting the capacitive performance of tungsten oxide, an atomic scale engineering approach to optimize the electronic structure of tungsten oxide by Ni doping is reported. Density functional theory calculations disclose that through Ni doping, the density of state at Fermi level for tungsten oxide can be enhanced, thus promoting its electron transfer. When used as electrode of supercapacitors, the obtained Ni-doped tungsten oxide with 4.21 at% Ni exhibits an ultrahigh mass-specific capacitance of 557 F g -1 at the current density of 1 A g -1 and preferable durability in a long-term cycle test. To the best of knowledge, this is the highest supercapacitor performance reported so far in tungsten oxide and its composites. The present strategy demonstrates the validity of the electronic structure control in tungsten oxide via introducing Ni atoms for pseudocapacitors, which can be extended to other related fields as well. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aerobic glycolysis in the human brain is associated with development and neotenous gene expression

PubMed Central

Goyal, Manu S.; Hawrylycz, Michael; Miller, Jeremy A.; Snyder, Abraham Z.; Raichle, Marcus E.

2015-01-01

SUMMARY Aerobic glycolysis (AG), i.e., non-oxidative metabolism of glucose despite the presence of abundant oxygen, accounts for 10–12% of glucose used by the adult human brain. AG varies regionally in the resting state. Brain AG may support synaptic growth and remodeling; however, data supporting this hypothesis are sparse. Here, we report on investigations on the role of AG in the human brain. Meta-analysis of prior brain glucose and oxygen metabolism studies demonstrates that AG increases during childhood, precisely when synaptic growth rates are highest. In resting adult humans, AG correlates with persistence of gene expression typical of infancy (transcriptional neoteny). In brain regions with the highest AG, we find increased gene expression related to synapse formation and growth. In contrast, regions high in oxidative glucose metabolism express genes related to mitochondria and synaptic transmission. Our results suggest that brain AG supports developmental processes, particularly those required for synapse formation and growth. PMID:24411938

Method of separating short half-life radionuclides from a mixture of radionuclides

DOEpatents

Bray, Lane A.; Ryan, Jack L.

1999-01-01

The present invention is a method of removing an impurity of plutonium, lead or a combination thereof from a mixture of radionuclides that contains the impurity and at least one parent radionuclide. The method has the steps of (a) insuring that the mixture is a hydrochloric acid mixture; (b) oxidizing the acidic mixture and specifically oxidizing the impurity to its highest oxidation state; and (c) passing the oxidized mixture through a chloride form anion exchange column whereupon the oxidized impurity absorbs to the chloride form anion exchange column and the 22.sup.9 Th or 2.sup.27 Ac "cow" radionuclide passes through the chloride form anion exchange column. The plutonium is removed for the purpose of obtaining other alpha emitting radionuclides in a highly purified form suitable for medical therapy. In addition to plutonium; lead, iron, cobalt, copper, uranium, and other metallic cations that form chloride anionic complexes that may be present in the mixture; are removed from the mixture on the chloride form anion exchange column.

Method of separating short half-life radionuclides from a mixture of radionuclides

DOEpatents

Bray, L.A.; Ryan, J.L.

1999-03-23

The present invention is a method of removing an impurity of plutonium, lead or a combination thereof from a mixture of radionuclides that contains the impurity and at least one parent radionuclide. The method has the steps of (a) insuring that the mixture is a hydrochloric acid mixture; (b) oxidizing the acidic mixture and specifically oxidizing the impurity to its highest oxidation state; and (c) passing the oxidized mixture through a chloride form anion exchange column whereupon the oxidized impurity absorbs to the chloride form anion exchange column and the {sup 229}Th or {sup 227}Ac ``cow`` radionuclide passes through the chloride form anion exchange column. The plutonium is removed for the purpose of obtaining other alpha emitting radionuclides in a highly purified form suitable for medical therapy. In addition to plutonium, lead, iron, cobalt, copper, uranium, and other metallic cations that form chloride anionic complexes that may be present in the mixture are removed from the mixture on the chloride form anion exchange column. 8 figs.

Thunderstorms Increase Mercury Wet Deposition.

PubMed

Holmes, Christopher D; Krishnamurthy, Nishanth P; Caffrey, Jane M; Landing, William M; Edgerton, Eric S; Knapp, Kenneth R; Nair, Udaysankar S

2016-09-06

Mercury (Hg) wet deposition, transfer from the atmosphere to Earth's surface by precipitation, in the United States is highest in locations and seasons with frequent deep convective thunderstorms, but it has never been demonstrated whether the connection is causal or simple coincidence. We use rainwater samples from over 800 individual precipitation events to show that thunderstorms increase Hg concentrations by 50% relative to weak convective or stratiform events of equal precipitation depth. Radar and satellite observations reveal that strong convection reaching the upper troposphere (where high atmospheric concentrations of soluble, oxidized mercury species (Hg(II)) are known to reside) produces the highest Hg concentrations in rain. As a result, precipitation meteorology, especially thunderstorm frequency and total rainfall, explains differences in Hg deposition between study sites located in the eastern United States. Assessing the fate of atmospheric mercury thus requires bridging the scales of global transport and convective precipitation.

On the Highest Oxidation States of Metal Elements in MO4 Molecules (M = Fe, Ru, Os, Hs, Sm, and Pu).

PubMed

Huang, Wei; Xu, Wen-Hua; Schwarz, W H E; Li, Jun

2016-05-02

Metal tetraoxygen molecules (MO4, M = Fe, Ru, Os, Hs, Sm, Pu) of all metal atoms M with eight valence electrons are theoretically studied using density functional and correlated wave function approaches. The heavier d-block elements Ru, Os, Hs are confirmed to form stable tetraoxides of Td symmetry in (1)A1 electronic states with empty metal d(0) valence shell and closed-shell O(2-) ligands, while the 3d-, 4f-, and 5f-elements Fe, Sm, and Pu prefer partial occupation of their valence shells and peroxide or superoxide ligands at lower symmetry structures with various spin couplings. The different geometric and electronic structures and chemical bonding types of the six iso-stoichiometric species are explained in terms of atomic orbital energies and orbital radii. The variations found here contribute to our general understanding of the periodic trends of oxidation states across the periodic table.

In situ formation of a ZnO/ZnSe nanonail array as a photoelectrode for enhanced photoelectrochemical water oxidation performance

NASA Astrophysics Data System (ADS)

Wang, Liyang; Tian, Guohui; Chen, Yajie; Xiao, Yuting; Fu, Honggang

2016-04-01

In this study, a ZnO/ZnSe nanonail array was prepared via a two-step sequential hydrothermal synthetic route. In this synthetic process, the ZnO nanorod array was first grown on a fluorine-doped tin oxide (FTO) substrate using a seed-mediated growth approach via the hydrothermal process. Then, the ZnO nanonail array was obtained via in situ growth of ZnSe nano caps onto the ZnO nanorod array via a hydrothermal process in the presence of a Se source. The surface morphology and amount of ZnSe grown on the surface of the ZnO nanorods can be regulated by varying the reaction time and reactant concentration. Compared with pure ZnO nanorods, this unique nanonail array heterostructure exhibits enhanced visible light absorption. The transient photocurrent condition, in combination with steady-state and time-resolved photoluminescence spectroscopy, reveals that the ZnO/ZnSe nanonail array electrode has the highest charge separation rate, highest electron injection efficiency, and highest chemical stability. The photocurrent density of the ZnO/ZnSe nanonail array heterostructure reaches 1.01 mA cm-2 at an applied potential of 0.1 V (vs. Ag/AgCl), which is much higher than that of the ZnO/ZnSe nanorod array (0.71 mA cm-2), the pristine ZnO nanorod array (0.39 mA cm-2), and the ZnSe electrode (0.21 mA cm-2), indicating its significant visible light driven activities for photoelectrochemical water oxidation. This unique morphology of nail-capped nanorods might be important for providing better insight into the correlation between heterostructure and photoelectrochemical activity.In this study, a ZnO/ZnSe nanonail array was prepared via a two-step sequential hydrothermal synthetic route. In this synthetic process, the ZnO nanorod array was first grown on a fluorine-doped tin oxide (FTO) substrate using a seed-mediated growth approach via the hydrothermal process. Then, the ZnO nanonail array was obtained via in situ growth of ZnSe nano caps onto the ZnO nanorod array via a hydrothermal process in the presence of a Se source. The surface morphology and amount of ZnSe grown on the surface of the ZnO nanorods can be regulated by varying the reaction time and reactant concentration. Compared with pure ZnO nanorods, this unique nanonail array heterostructure exhibits enhanced visible light absorption. The transient photocurrent condition, in combination with steady-state and time-resolved photoluminescence spectroscopy, reveals that the ZnO/ZnSe nanonail array electrode has the highest charge separation rate, highest electron injection efficiency, and highest chemical stability. The photocurrent density of the ZnO/ZnSe nanonail array heterostructure reaches 1.01 mA cm-2 at an applied potential of 0.1 V (vs. Ag/AgCl), which is much higher than that of the ZnO/ZnSe nanorod array (0.71 mA cm-2), the pristine ZnO nanorod array (0.39 mA cm-2), and the ZnSe electrode (0.21 mA cm-2), indicating its significant visible light driven activities for photoelectrochemical water oxidation. This unique morphology of nail-capped nanorods might be important for providing better insight into the correlation between heterostructure and photoelectrochemical activity. Electronic supplementary information (ESI) available: SEM, EDS, XPS and photocurrent test. See DOI: 10.1039/c6nr01969b

Power generation using spinel manganese-cobalt oxide as a cathode catalyst for microbial fuel cell applications.

PubMed

Mahmoud, Mohamed; Gad-Allah, Tarek A; El-Khatib, K M; El-Gohary, Fatma

2011-11-01

This study focused on the use of spinel manganese-cobalt (Mn-Co) oxide, prepared by a solid state reaction, as a cathode catalyst to replace platinum in microbial fuel cells (MFCs) applications. Spinel Mn-Co oxides, with an Mn/Co atomic ratios of 0.5, 1, and 2, were prepared and examined in an air cathode MFCs which was fed with a molasses-laden synthetic wastewater and operated in batch mode. Among the three Mn-Co oxide cathodes and after 300 h of operation, the Mn-Co oxide catalyst with Mn/Co atomic ratio of 2 (MnCo-2) exhibited the highest power generation 113 mW/m2 at cell potential of 279 mV, which were lower than those for the Pt catalyst (148 mW/m2 and 325 mV, respectively). This study indicated that using spinel Mn-Co oxide to replace platinum as a cathodic catalyst enhances power generation, increases contaminant removal, and substantially reduces the cost of MFCs. Copyright © 2011 Elsevier Ltd. All rights reserved.

The special features of the crystal structure and properties of oxides with mixed conductivity based on lanthanum gallate

NASA Astrophysics Data System (ADS)

Politova, E. D.; Ivanov, S. A.; Kaleva, G. M.; Mosunov, A. V.; Rusakov, V. S.

2008-10-01

The paper presents a review of works on the synthesis, structural composition effects, phase transitions, and electrical conductivity properties of multicomponent solid solutions based on heterosubstituted lanthanum gallate (La,A)(Ga,M)O3 - y . High-temperature phase transitions and structural and charge ordering effects were studied. The presence of iron cations in different valence states was proved; the relative contents of these cations depended on the x parameter and nonstoichiometry parameter y of the base composition. For M = Fe, antiferromagnetic ordering was observed; its temperature interval was determined by the concentration of iron cations in the high-spin state. The total conductivity was found to increase as the concentration of transition metal cations grew because of an increase in the electronic conductivity component. The data on structural parameters and dc and ac conductivity substantiated the conclusion that the highest ionic conductivity and permeability to oxygen were characteristic of iron-containing oxides. The results obtained are evidence that crystal chemical factors play a determining role in the formation of the ion-conducting properties of anion-deficient perovskite-like oxides.

Aqueous vanadium ion dynamics relevant to bioinorganic chemistry: A review.

PubMed

Kustin, Kenneth

2015-06-01

Aqueous solutions of the four highest vanadium oxidation states exhibit four diverse colors, which only hint at the diverse reactions that these ions can undergo. Cationic vanadium ions form complexes with ligands; anionic vanadium ions form complexes with ligands and self-react to form isopolyanions. All vanadium species undergo oxidation-reduction reactions. With a few exceptions, elucidation of the dynamics of these reactions awaited the development of fast reaction techniques before the kinetics of elementary ligation, condensation, reduction, and oxidation of the aqueous vanadium ions could be investigated. As the biological roles played by endogenous and therapeutic vanadium expand, it is appropriate to bring the results of the diverse kinetics studies under one umbrella. To achieve this goal this review presents a systematic examination of elementary aqueous vanadium ion dynamics. Copyright © 2014 Elsevier Inc. All rights reserved.

Handling and Use of Fluorine and Fluorine - Oxygen Mixtures in Rocket Systems,

DTIC Science & Technology

1967-01-01

with nitroso rubber, which could normally be expected to burn when exposed to the flow of liquid fluorine. The materials tested included (1) Nitroso...the system free of contamination. Most common metals of construction are compatible for use in a fluorine environment. Metals can burn with fluorine...conditions of contact), fluorinated compounds in their highest state of oxidation, and a few fluorinated polymers. Even these polymers may burn in fluorine

X-Ray Fluorescence (XRF) to identify chemical analysis of minerals in Buton island, SE Sulawesi, Indonesia

NASA Astrophysics Data System (ADS)

Jamaluddin; Darwis, A.; Massinai, M. A.

2018-02-01

Asbuton as natural rock asphalt consists of a granular material; usually limestone or sandstone. In its natural state, it contains bitumen intimately dispersed throughout its mass, while the remainder of the material is a solid mineral matter. This research was conducted in Sorowalio, Buton Regency, Southeast Sulawesi province, Indonesia. This study aims to determine the content and the percentage of minerals contained in the rocks by using X-Ray Fluorescence (XRF). The method of research is a preliminary survey, sampling and laboratory analysis. XRF reports chemical composition, including Si (quartz) and Ca (calcite). The results indicate the content and the percentage of element dominate the rock sample is Fe2O3, MgO, CaO, and SiO2. Research results using XRF show that there are four metal oxide dominant elements. Hematite (Fe2O3) is dominant in all locations of sampling. Magnesium oxide (MgO) has the highest levels found in sample number six and the lowest is in sample number five. Silicates (SiO) has the highest levels at sample number six and the lowest in sample number seven. Calcium oxide (CaO) is dominant in all sampling locations. The sample of asbuton contains 37.90% asphalt, 43.28% carbonate, and18.82% other minerals.

Nano-structured Platinum-based Catalysts for the Complete Oxidation of Ethylene Glycol and Glycerol

NASA Astrophysics Data System (ADS)

Falase, Akinbayowa

Direct alcohol fuel cells are a viable alternative to the traditional hydrogen PEM fuel cell. Fuel versatility, integration with existing distribution networks, and increased safety when handling these fuels increases their appeal for portable power applications. In order to maximize their utility, the liquid fuel must be fully oxidized to CO2 so as to harvest the full amount of energy. Methanol and ethanol are widely researched as potential fuels to power these devices, but methanol is a toxic substance, and ethanol has a much lower energy density than other liquids such as gasoline or glucose. Oxidation of complex fuels is difficult to realize, due to difficulty in breaking carbon-carbon bonding and poisoning of the catalysts by oxidative byproducts. In order to achieve the highest efficiency, an anode needs to be engineered in such a way as to maximize activity while minimizing poisoning effects of reaction byproducts. We have engineered an anode that uses platinum-based catalysts that is capable of completely oxidizing ethylene glycol and glycerol in neutral and alkaline media with little evidence of CO poisoning. We have constructed a hybrid anode consisting of a nano-structured PtRu electrocatayst with an NAD-dependent alcohol dehydrogenase for improved oxidation of complex molecules. A nano-structured PtRu catalyst was used to oxidize ethylene glycol and glycerol in neutral media. In situ infrared spectroscopy was used to verify complete oxidation via CO2 generation. There was no evidence of poisoning by CO species. A pH study was performed to determine the effect of pH on oxidative current. The peak currents did not trend at 60 mV/pH unit as would be expected from the Nernst equation, suggesting that adsorption of fuel to the surface of the electrode is not an electron-transfer step. We synthesized nano-structured PtRu, PtSn, and PtRuSn catalysts for oxidation of ethylene glycol and glycerol in alkaline media. The PtRu electrocatalyst the highest oxidative currents and highest stability compared to a nano-structured platinum, PtSn, and PtRuSn catalyst. In situ infrared spectroscopy showed complete oxidation of each fuel occurred by the presence of CO 2, with very little poisoning CO species present. In order to increase oxidative performance in neutral media, a hybrid anode based on nano-structured PtRu and a NAD-dependent alcohol dehydrogenase for the oxidation of ethanol and ethylene glycol was developed. Steady state polarization showed that the hybrid anode had higher current densities than the enzyme or the PtRu electrocatalyst alone. The hybrid anode had higher current densities at concentrations up to 3 M while oxidizing ethanol and ethylene glycol. The catalyst synthesis, characterization, and experimental results demonstrate the feasibility of fuel cells that can oxidize higher order fuels that platinum based catalysts or enzymes cannot oxidize alone. The cooperative mechanism from co-catalysis using inorganic and organic catalysts will allow for deep oxidation and improved power generation.

Synthesis of cobalt-containing mesoporous catalysts using the ultrasonic-assisted “pH-adjusting” method: Importance of cobalt species in styrene oxidation

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

Li, Baitao, E-mail: btli@scut.edu.cn; Zhu, Yanrun; Jin, Xiaojing

2015-01-15

Cobalt-containing SBA-15 and MCM-41 (Co-SBA-15 and Co-MCM-41) mesoporous catalysts were prepared via ultrasonic-assisted “pH-adjusting” technique in this study. Their physiochemical structures were comprehensively characterized and correlated with catalytic activity in oxidation of styrene. The nature of cobalt species depended on the type of mesoporous silica as well as pH values. The different catalytic performance between Co-SBA-15 and Co-MCM-41 catalysts originated from cobalt species. Cobalt species were homogenously incorporated into the siliceous framework of Co-SBA-15 in single-site Co(II) state, while Co{sub 3}O{sub 4} particles were loaded on Co-MCM-41 catalysts. The styrene oxidation tests showed that the single-site Co(II) state was moremore » beneficial to the catalytic oxidation of styrene. The higher styrene conversion and benzaldehyde selectivity over Co-SBA-15 catalysts were mainly attributed to single-site Co(II) state incorporated into the framework of SBA-15. The highest conversion of styrene (34.7%) with benzaldehyde selectivity of 88.2% was obtained over Co-SBA-15 catalyst prepared at pH of 7.5, at the mole ratio of 1:1 (styrene to H{sub 2}O{sub 2}) at 70 °C. - Graphical abstract: Cobalt-containing mesoporous silica catalysts were developed via ultrasonic-assisted “pH-adjusting” technique. Compared with Co{sub 3}O{sub 4} in Co-MCM-41, the single-site Co(II) state in Co-SBA-15 was more efficient for the styrene oxidation. - Highlights: • Fast and cost-effective ultrasonic technique for preparing mesoporous materials. • Incorporation of Co via ultrasonic irradiation and “pH-adjusting”. • Physicochemical comparison between Co-SBA-15 and Co-MCM-41. • Correlation of styrene oxidation activity and catalyst structural property.« less

CONCENTRATIONS AND PATTERNS OF PHOTOCHEMICAL OXIDANTS IN THE U.S.

EPA Science Inventory

The report describes ozone and PAN levels at urban sites in the U.S., and of ozone at selected nonurban sites. Sample diurnal curves for ozone at suburban and nonurban sites are presented. Highest concentrations of both oxidants occur in California, where the second-highest 1-hr ...

Thermodynamic analysis of Direct Urea Solid Oxide Fuel Cell in combined heat and power applications

NASA Astrophysics Data System (ADS)

Abraham, F.; Dincer, I.

2015-12-01

This paper presents a comprehensive steady state modelling and thermodynamic analysis of Direct Urea Solid Oxide Fuel Cell integrated with Gas Turbine power cycle (DU-SOFC/GT). The use of urea as direct fuel mitigates public health and safety risks associated with the use of hydrogen and ammonia. The integration scheme in this study covers both oxygen ion-conducting solid oxide fuel cells (SOFC-O) and hydrogen proton-conducting solid oxide fuel cells (SOFC-H). Parametric case studies are carried out to investigate the effects of design and operating parameters on the overall performance of the system. The results reveal that the fuel cell exhibited the highest level of exergy destruction among other system components. Furthermore, the SOFC-O based system offers better overall performance than that with the SOFC-H option mainly due to the detrimental reverse water-gas shift reaction at the SOFC anode as well as the unique configuration of the system.

Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles

PubMed Central

Tvrdy, Kevin; Frantsuzov, Pavel A.; Kamat, Prashant V.

2011-01-01

Quantum dot-metal oxide junctions are an integral part of next-generation solar cells, light emitting diodes, and nanostructured electronic arrays. Here we present a comprehensive examination of electron transfer at these junctions, using a series of CdSe quantum dot donors (sizes 2.8, 3.3, 4.0, and 4.2 nm in diameter) and metal oxide nanoparticle acceptors (SnO2, TiO2, and ZnO). Apparent electron transfer rate constants showed strong dependence on change in system free energy, exhibiting a sharp rise at small driving forces followed by a modest rise further away from the characteristic reorganization energy. The observed trend mimics the predicted behavior of electron transfer from a single quantum state to a continuum of electron accepting states, such as those present in the conduction band of a metal oxide nanoparticle. In contrast with dye-sensitized metal oxide electron transfer studies, our systems did not exhibit unthermalized hot-electron injection due to relatively large ratios of electron cooling rate to electron transfer rate. To investigate the implications of these findings in photovoltaic cells, quantum dot-metal oxide working electrodes were constructed in an identical fashion to the films used for the electron transfer portion of the study. Interestingly, the films which exhibited the fastest electron transfer rates (SnO2) were not the same as those which showed the highest photocurrent (TiO2). These findings suggest that, in addition to electron transfer at the quantum dot-metal oxide interface, other electron transfer reactions play key roles in the determination of overall device efficiency. PMID:21149685

Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles.

PubMed

Tvrdy, Kevin; Frantsuzov, Pavel A; Kamat, Prashant V

2011-01-04

Quantum dot-metal oxide junctions are an integral part of next-generation solar cells, light emitting diodes, and nanostructured electronic arrays. Here we present a comprehensive examination of electron transfer at these junctions, using a series of CdSe quantum dot donors (sizes 2.8, 3.3, 4.0, and 4.2 nm in diameter) and metal oxide nanoparticle acceptors (SnO(2), TiO(2), and ZnO). Apparent electron transfer rate constants showed strong dependence on change in system free energy, exhibiting a sharp rise at small driving forces followed by a modest rise further away from the characteristic reorganization energy. The observed trend mimics the predicted behavior of electron transfer from a single quantum state to a continuum of electron accepting states, such as those present in the conduction band of a metal oxide nanoparticle. In contrast with dye-sensitized metal oxide electron transfer studies, our systems did not exhibit unthermalized hot-electron injection due to relatively large ratios of electron cooling rate to electron transfer rate. To investigate the implications of these findings in photovoltaic cells, quantum dot-metal oxide working electrodes were constructed in an identical fashion to the films used for the electron transfer portion of the study. Interestingly, the films which exhibited the fastest electron transfer rates (SnO(2)) were not the same as those which showed the highest photocurrent (TiO(2)). These findings suggest that, in addition to electron transfer at the quantum dot-metal oxide interface, other electron transfer reactions play key roles in the determination of overall device efficiency.

Microbial utilization of low molecular weight organic substrates in soil depends on their carbon oxidation state

NASA Astrophysics Data System (ADS)

Gunina, Anna; Smith, Andrew; Jones, Davey; Kuzyakov, Yakov

2017-04-01

Removal of low molecular weight organic substances (LMWOS), originating from plants and microorganisms, from soil solution is regulated by microbial uptake. In addition to the concentration of LMWOS in soil solution, the chemical properties of each substance (e.g. C oxidation state, number of C atoms, number of -COOH groups) can affect their uptake and subsequent partitioning of C within the soil microbial community. The aim of this study was to trace the initial fate of three dominant classes of LMWOS in soil (sugars, carboxylic and amino acids), including their removal from solution and utilization by microorganisms, and to reveal the effect of substance chemical properties on these processes. Soil solution, spiked at natural abundance levels with 14C-labelled glucose, fructose, malate, succinate, formate, alanine or glycine, was added to the soil and 14C was traced in the dissolved organic carbon (DOC), CO2, cytosol and soil organic carbon (SOC) over 24 hours. The half-life time of all LMWOS in the DOC (T1 /2-solution) varied between 0.6-5.0 min showing extremely fast initial uptake of LMWOS. The T1 /2-solution of substances was dependent on C oxidation state, indicating that less oxidized organic substances (with C oxidation state "0") were retained longer in soil solution than oxidized substances. The LMWOS-C T1 /2-fast, characterizing the half-life time of 14C in the fast mineralization pool, ranged between 30 and 80 min, with the T1 /2-fast of carboxylic acids (malic acid) being the fastest and the T1 /2-fast of amino acids (glycine) being the slowest. An absence of correlation between T1 /2-fast and either C oxidation state, number of C atoms, or number of -COOH groups suggests that intercellular metabolic pathways are more important for LMWOS transformation in soil than their basic chemical properties. The CO2 release during LMWOS mineralization accounted for 20-90% of 14C applied. Mineralization of LMWOS was the least for sugars and the greatest for carboxylic (formic) acids, whereas the 14C incorporations into cytosol and SOC were opposite. The portion of LMWOS mineralized to CO2 increased with their C oxidation state corresponding to the decrease of C incorporated into the cytosol and SOC pools. The ratio of 14C incorporated into cytosol to 14C incorporated into CO2 pool ranged between 0.03 and 1.19, being the lowest for carboxylic acids and highest for sugars, and decreased with substances C oxidation state. Thus, the C oxidation state is one of the crucial parameter of LMWOS determining their partitioning between two main C fluxes: mineralization and microbial stabilization/immobilization. Our data suggests that the uptake of common LMWOS from soil solution by microorganisms and final LMWOS-C partitioning within microbial biomass may be possible to predict from the physicochemical properties of the substance.

Mechanisms of Mn(II) catalytic oxidation on ferrihydrite surfaces and the formation of manganese (oxyhydr)oxides

NASA Astrophysics Data System (ADS)

Lan, Shuai; Wang, Xiaoming; Xiang, Quanjun; Yin, Hui; Tan, Wenfeng; Qiu, Guohong; Liu, Fan; Zhang, Jing; Feng, Xionghan

2017-08-01

Oxidation of Mn(II) is an important process that controls the mobility and bioavailability of Mn, as well as the formation of Mn (oxyhydr)oxides in natural systems. It was found that the surfaces of minerals, such as iron (oxyhydr)oxides, can accelerate Mn(II) oxidation to a certain degree, but the underlying mechanism has not been clearly understood. This study explores the reaction pathways and mechanisms of Mn(II) oxidation on ferrihydrite surfaces at neutral pH, commonly found in natural environments, by comparisons with montmorillonite, amorphous Al(OH)3, goethite, and magnetite using macroscopic experiments and spectroscopic analyses. Results show that when Mn(II) concentrations are below 4 mM, macroscopic Mn(II) adsorption on the three iron (oxyhydr)oxide surfaces conforms well to the Langmuir equation, with ferrihydrite showing the highest adsorption capacity. With Mn(II) concentrations ranging within 6-24 mM, the adsorbed Mn(II) is mainly oxidized into manganite (γ-MnOOH) and/or feitknechtite (β-MnOOH) by dissolved O2, and Mn(II) removal on a unit mass basis in the presence of magnetite is the highest compared with ferrihydrite and goethite. Ferrihydrite, a semiconductor material, shows stronger catalytic ability for Mn(II) oxidation on the same surface area than insulator minerals (i.e., montmorillonite and amorphous Al(OH)3). Additionally, the products of Mn(II) oxidation in the presence of semiconductor iron (oxyhydr)oxides (i.e., ferrihydrite, goethite, or magnetite) at the same Fe/Mn molar ratio include both manganite and a small amount of Mn(IV) minerals, and the Mn average oxidation states (Mn AOSs) of these products follow the order: magnetite > goethite > ferrihydrite. Magnetite and goethite, with relatively smaller SSAs and lower band gap energies, exhibit greater catalysis for Mn(II) oxidation than ferrihydrite at the same Fe/Mn ratio, which goes against the conventional interfacial effect and is related to the electrochemical properties. Thus, the Mn(II) catalytic oxidation by O2 on ferrihydrite surfaces should include an electrochemical pathway, i.e., electron transfer (ET) in the Mn(II)-Conduction Band (CB)Ferrihydrite-O2 complexes, in addition to the conventional two interfacial catalytic pathways, i.e., ET in the Mn(II)-Fe(II, III)-O2 complexes and direct ET in the Mn(II)-O2 complexes. These results reveal new implications for understanding the processes and mechanisms of Mn(II) oxidation on iron (oxyhydr)oxide surfaces and the abiotic formation of Mn (oxyhydr)oxides in surface environments.

An electrochemical acetylcholine sensor based on lichen-like nickel oxide nanostructure.

PubMed

Sattarahmady, N; Heli, H; Vais, R Dehdari

2013-10-15

Lichen-like nickel oxide nanostructure was synthesized by a simple method and characterized. The nanostructure was then applied to modify a carbon paste electrode and for the fabrication of a sensor, and the electrocatalytic oxidation of acetylcholine (ACh) on the modified electrode was investigated. The electrocatalytic efficiency of the nickel oxide nanostructure was compared with nickel micro- and nanoparticles, and the lichen-like nickel oxide nanostructure showed the highest efficiency. The mechanism and kinetics of the electrooxidation process were investigated by cyclic voltammetry, steady-state polarization curve and chronoamperometry. The catalytic rate constant and the charge transfer coefficient of ACh electrooxidation by the active nickel species, and the diffusion coefficient of ACh were reported. A sensitive and time-saving hydrodynamic amperometry method was developed for the determination of ACh. ACh was determined with a sensitivity of 392.4 mA M⁻¹ cm⁻² and a limit of detection of 26.7 μM. The sensor had the advantages of simple fabrication method without using any enzyme or reagent and immobilization step, high electrocatalytic activity, very high sensitivity, long-term stability, and antifouling surface property toward ACh and its oxidation product. Copyright © 2013 Elsevier B.V. All rights reserved.

Redox Proteomics Applied to the Thiol Secretome.

PubMed

Ghezzi, Pietro; Chan, Philippe

2017-03-01

Secreted proteins are important both as signaling molecules and potential biomarkers. Recent Advances: Protein can undergo different types of oxidation, both in physiological conditions or under oxidative stress. Several redox proteomics techniques have been successfully applied to the identification of glutathionylated proteins, an oxidative post-translational modification consisting in the formation of a mixed disulfide between a protein cysteine and glutathione. Redox proteomics has also been used to study other forms of protein oxidation. Because of the highest proportion of free cysteines in the cytosol, redox proteomics of protein thiols has focused, so far, on intracellular proteins. However, plasma proteins, such as transthyretin and albumin, have been described as glutathionylated or cysteinylated. The present review discusses the redox state of protein cysteines in relation to their cellular distribution. We describe the various approaches used to detect secreted glutathionylated proteins, the only thiol modification studied so far in secreted proteins, and the specific problems presented in the study of the secretome. This review focusses on glutathionylated proteins secreted under inflammatory conditions and that may act as soluble mediators (cytokines). Future studies on the redox secretome (including other forms of oxidation) might identify new soluble mediators and biomarkers of oxidative stress. Antioxid. Redox Signal. 26, 299-312.

An evaluation of the effects of PEO/PEG molecular weights on extruded alumina rods

NASA Astrophysics Data System (ADS)

Bolger, Nancy Beth

1998-12-01

Alumina rods were piston extruded from bodies containing polyethylene glycols (PEGs) and polyethylene oxides (PEOs) with molecular weights ranging from 1,300 to 3,800,000 g/mol. A blend of aluminas possessing different particle size distributions was evaluated with regard to its extrusion pressure by varying the amount of PEG/PEO addition. Behavior exhibited by the alumina blend was dependent upon the additive that was used. The higher molecular weight binders with average molecular weight of 200,000 g/mol and 3,350,000 g/mol displayed the most severe behaviors of near dilatant and dilatant respectively. Physical properties of the green and fired states, as well as the binder burnout, were investigated with the changing additions. Correlation between the green and fired strengths and the changing molecular weights were examined. The additive present influenced the surface properties of the rods, which affected the green strengths. The highest average molecular weight polyethylene glycols showed higher green strengths, while the lowest green strengths were observed for the high molecular weight polyethylene oxides. Fired strengths generally ranged from approximately 12,000 psi to 16,000 psi for additive batches. Alumina pellets containing twelve separate combinations of polyethylene glycol with polyethylene oxide were dry pressed. Physical properties of the green and fired states were examined. Statistical analysis was performed upon the data and seven combinations of polyethylene glycol with polyethylene oxide were deemed significant. These combinations in conjunction with the same alumina blend were then piston extruded. The addition of polyethylene glycol reduced the near dilatant behavior exhibited by the 200,000 g/mol average molecular weight polyethylene oxide. Dilatant behavior was completely eliminated from the 3,350,000 g/mol average molecular weight polyethylene oxide batches. Physical properties of the green and fired states were again investigated with the changing additions. Polyethylene oxide, in combination with polyethylene glycol, did show an increase in green strength versus the polyethylene oxide alone. Strengths were still lower than those displayed by the polyethylene glycols alone. Reductions or degradations in molecular weight of the polymers due to mixing and extrusion processes may account for lower green strength of bodies, especially those containing polyethylene oxides.

Transition-Metal-Controlled Inorganic Ligand-Supported Non-Precious Metal Catalysts for the Aerobic Oxidation of Amines to Imines.

PubMed

Yu, Han; Zhai, Yongyan; Dai, Guoyong; Ru, Shi; Han, Sheng; Wei, Yongge

2017-10-09

Most state-of-art transition-metal catalysts usually require organic ligands, which are essential for controlling the reactivity and selectivity of reactions catalyzed by transition metals. However, organic ligands often suffer from severe problems including cost, toxicity, air/moisture sensitivity, and being commercially unavailable. Herein, we show a simple, mild, and efficient aerobic oxidation procedure of amines using inorganic ligand-supported non-precious metal catalysts 1, (NH 4 ) n [MMo 6 O 18 (OH) 6 ] (M=Cu 2+ ; Fe 3+ ; Co 3+ ; Ni 2+ ; Zn 2+ , n=3 or 4), synthesized by a simple one-step method in water at 100 °C, demonstrating that the catalytic activity and selectivity can be significantly improved by changing the central metal atom. In the presence of these catalysts, the catalytic oxidation of primary and secondary amines, as well as the coupling of alcohols and amines, can smoothly proceed to afford various imines with O 2 (1 atm) as the sole oxidant. In particular, the catalysts 1 have transition-metal ion core, and the planar arrangement of the six Mo VI centers at their highest oxidation states around the central heterometal can greatly enhance the Lewis acidity of catalytically active sites, and also enable the electrons in the center to delocalize onto the six edge-sharing MO 6 units, in the same way as ligands in traditional organometallic complexes. The versatility of this methodology maybe opens a path to catalytic oxidation through inorganic ligand-coordinated metal catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Persulfate activation by iron oxide-immobilized MnO2 composite: identification of iron oxide and the optimum pH for degradations.

PubMed

Jo, Young-Hoon; Do, Si-Hyun; Kong, Sung-Ho

2014-01-01

Iron oxide-immobilized manganese oxide (MnO2) composite was prepared and the reactivity of persulfate (PS) with the composite as activator was investigated for degradation of carbon tetrachloride and benzene at various pH levels. Brunauer-Emmett-Teller (BET) surface area of the composite was similar to that of pure MnO2 while the pore volume and diameter of composite was larger than those of MnO2. Scanning electron microscopy couples with energy dispersive spectroscopy (SEM-EDS) showed that Fe and Mn were detected on the surface of the composite, and X-ray diffraction (XRD) analysis indicated the possibilities of the existence of various iron oxides on the composite surface. Furthermore, the analyses of X-ray photoelectron (XPS) spectra revealed that the oxidation state of iron was identified as 1.74. In PS/composite system, the same pH for the highest degradation rates of both carbon tetrachloride and benzene were observed and the value of pH was 9. Scavenger test was suggested that both oxidants (i.e. hydroxyl radical, sulfate radical) and reductant (i.e. superoxide anion) were effectively produced when PS was activated with the iron-immobilized MnO2. Copyright © 2013 Elsevier Ltd. All rights reserved.

Thermal-Mechanical Stability of Single Crystal Oxide Refractive Concentrators for High-Temperature Solar Thermal Propulsion

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Jacobson, Nathan S.; Miller, Robert A.

1999-01-01

Single crystal oxides such as yttria-stabilized zirconia (Y2O3-ZrO2), yttrium aluminum garnet (Y3Al5O12, or YAG), magnesium oxide (MgO) and sapphire (Al2O3) are candidate refractive secondary concentrator materials for high temperature solar propulsion applications. However, thermo-mechanical reliability of these components in severe thermal environments during the space mission sun/shade transition is of great concern. Simulated mission tests are important for evaluating these candidate oxide materials under a variety of transient and steady-state heat flux conditions, and thus provide vital information for the component design. In this paper, a controlled heat flux thermal shock test approach is established for the single crystal oxide materials using a 3.0 kW continuous wave CO2 laser, with a wavelength 10.6 micron. Thermal fracture behavior and failure mechanisms of these oxide materials are investigated and critical temperature gradients are determined under various temperature and heating conditions. The test results show that single crystal sapphire is able to sustain the highest temperature gradient and heating-cooling rate, and thus exhibit the best thermal shock resistance, as compared to the yttria-stabilized zirconia, yttrium aluminum garnet and magnesium oxide.

Thermal-Mechanical Stability of Single Crystal Oxide Refractive Concentrators for High-Temperature Solar Thermal Propulsion

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Jacobson, Nathan S.; Miller, Robert A.

1999-01-01

Single crystal oxides such as yttria-stabilized zirconia (Y2O3-ZrO2), yttrium aluminum garnet (Y3Al5O12, or YAG), magnesium oxide (MgO) and sapphire (Al2O3) are candidate refractive secondary concentrator materials for high temperature solar propulsion applications. However, thermo-mechanical reliability of these components in severe thermal environments during the space mission sun/shade transition is of great concern. Simulated mission tests are important for evaluating these candidate oxide materials under a variety of transient and steady-state heat flux conditions, and thus provide vital information for the component design. In this paper, a controlled heat flux thermal shock test approach is established for the single crystal oxide materials using a 3.0 kW continuous wave CO2 laser, with a wavelength 10.6 micron. Thermal fracture behavior and failure mechanisms of these oxide materials are investigated and critical temperature gradients are determined under various temperature and heating conditions. The test results show that single crystal sapphire is able to sustain the highest temperature gradient and heating-cooling rate, and thus exhibit the best thermal shock resistance, as compared to the yttria-stabilized zirconia, yttrium aluminum garnet, and magnesium oxide.

In-vitro assessment of oxidative stress generated by orthodontic archwires.

PubMed

Spalj, Stjepan; Mlacovic Zrinski, Magda; Tudor Spalj, Vedrana; Ivankovic Buljan, Zorana

2012-05-01

Several metals undergo redox cycling, producing free radicals and generating oxidative stress. The purpose of this study was to investigate in-vitro oxidative stress of orthodontic archwires made of various alloys. Mouse fibroblast cells L929 were exposed to 6 types of archwires, and the concentration of the oxidative stress marker 8-hydroxy-2'-deoxyguanosine in DNA was evaluated. Trypan blue dye was used in the determination of cell viability and numbers. Standard nickel-titanium archwires generated the highest oxidative stress, significantly higher than all other wires and the controls (P <0.05), and coated nickel-titanium, copper-nickel-titanium, and cobalt-chromium were lower than nickel-titanium (P <0.05), but higher than titanium-molybdenum and the negative and absolute controls (P <0.05). Titanium-molybdenum and stainless steel generated the lowest stress. Nickel-titanium induced the lowest viability, lower than the negative and absolute controls and all other wires (P <0.05) except titanium-molybdenum. Stainless steel showed the highest viability. Nickel-titanium produced the highest inhibition of cell growth, higher than all samples (P <0.05) except the positive control and cobalt-chromium. The lowest inhibition was observed in stainless steel and titanium-molybdenum, lower than nickel-titanium, cobalt-chromium, and the positive control (P <0.05). All orthodontic archwires generate oxidative stress in vitro. Stainless steel archwires have the highest and nickel-titanium the lowest biocompatibility. Copyright © 2012 American Association of Orthodontists. Published by Mosby, Inc. All rights reserved.

Vacuum-Assisted Low-Temperature Synthesis of Reduced Graphene Oxide Thin-Film Electrodes for High-Performance Transparent and Flexible All-Solid-State Supercapacitors.

PubMed

Aytug, Tolga; Rager, Matthew S; Higgins, Wesley; Brown, Forrest G; Veith, Gabriel M; Rouleau, Christopher M; Wang, Hui; Hood, Zachary D; Mahurin, Shannon M; Mayes, Richard T; Joshi, Pooran C; Kuruganti, Teja

2018-04-04

Simple and easily integrated design of flexible and transparent electrode materials affixed to polymer-based substrates hold great promise to have a revolutionary impact on the functionality and performance of energy storage devices for many future consumer electronics. Among these applications are touch sensors, roll-up displays, photovoltaic cells, health monitors, wireless sensors, and wearable communication devices. Here, we report an environmentally friendly, simple, and versatile approach to produce optically transparent and mechanically flexible all-solid-state supercapacitor devices. These supercapacitors were constructed on tin-doped indium oxide coated polyethylene terephthalate substrates by intercalation of a polymer-based gel electrolyte between two reduced graphene oxide (rGO) thin-film electrodes. The rGO electrodes were fabricated simply by drop-casting of graphene oxide (GO) films, followed by a novel low-temperature (≤250 °C) vacuum-assisted annealing approach for the in situ reduction of GO to rGO. A trade-off between the optical transparency and electrochemical performance is determined by the concentration of the GO in the initial dispersion, whereby the highest capacitance (∼650 μF cm -2 ) occurs at a relatively lower optical transmittance (24%). Notably, the all-solid-state supercapacitors demonstrated excellent mechanical flexibility with a capacity retention rate above 90% under various bending angles and cycles. These attributes underscore the potential of the present approach to provide a path toward the realization of thin-film-based supercapacitors as flexible and transparent energy storage devices for a variety of practical applications.

Limits to sustainable muscle performance: interaction between glycolysis and oxidative phosphorylation.

PubMed

Conley, K E; Kemper, W F; Crowther, G J

2001-09-01

This paper proposes a mechanism responsible for setting the sustainable level of muscle performance. Our contentions are that the sustainable work rate is determined (i) at the muscle level, (ii) by the ability to maintain ATP supply and (iii) by the products of glycolysis that may inhibit the signal for oxidative phosphorylation. We argue below that no single factor 'limits' sustainable performance, but rather that the flux through and the interaction between glycolysis and oxidative phosphorylation set the level of sustainable ATP supply. This argument is based on magnetic resonance spectroscopy measurements of the sources and sinks for energy in vivo in human muscle and rattlesnake tailshaker muscle during sustained contractions. These measurements show that glycolysis provides between 20% (human muscle) and 40% (tailshaker muscle) of the ATP supply during sustained contractions in these muscles. We cite evidence showing that this high glycolytic flux does not reflect an O(2) limitation or mitochondria operating at their capacity. Instead, this flux reflects a pathway independent of oxidative phosphorylation for ATP supply during aerobic exercise. The consequence of this high glycolytic flux is accumulation of H(+), which we argue inhibits the rise in the signal activating oxidative phosphorylation, thereby restricting oxidative ATP supply to below the oxidative capacity. Thus, both glycolysis and oxidative phosphorylation play important roles in setting the highest steady-state ATP synthesis flux and thereby determine the sustainable level of work by exercising muscle.

Development of PEGylated KMnF3 nanoparticles as a T1-weighted contrast agent: chemical synthesis, in vivo brain MR imaging, and accounting for high relaxivity

NASA Astrophysics Data System (ADS)

Liu, Zhi-Jun; Song, Xiao-Xia; Tang, Qun

2013-05-01

Magnetic nanoparticles consisting of manganese-based T1-weighted contrast agents have rapidly achieved clinical application, however low proton relaxivity impedes further development. In this report, by analyzing nanoparticles' surface oxidation states we propose the possible reason for the low r1 relaxivity of common MnO nanoparticles and develop PEGylated fluoroperovskite KMnF3 nanoparticles as new T1-weighted contrast agents, which exhibit the highest longitudinal relaxivity (r1 = 23.15 mM-1 s-1) among all the reported manganese-based T1-weighted contrast agents. We, for the first time, illustrate a typical example showing that the surface oxidation states of metal ions exposed on the nanoparticles' surfaces are able to influence not only the optical, magnetic, electronic or catalytic properties but also water proton longitudinal relaxivity when applied as an MRI contrast agent. Cytotoxicity tests demonstrate that the PEGylated KMnF3 nanoparticles are free from toxicity. Further in vivo MRI experiments distinctively depict fine anatomical features in brain imaging at a low dose of 5 mg of Mn per kg and possible removal from the kidneys due to their small size and biocompatibility.Magnetic nanoparticles consisting of manganese-based T1-weighted contrast agents have rapidly achieved clinical application, however low proton relaxivity impedes further development. In this report, by analyzing nanoparticles' surface oxidation states we propose the possible reason for the low r1 relaxivity of common MnO nanoparticles and develop PEGylated fluoroperovskite KMnF3 nanoparticles as new T1-weighted contrast agents, which exhibit the highest longitudinal relaxivity (r1 = 23.15 mM-1 s-1) among all the reported manganese-based T1-weighted contrast agents. We, for the first time, illustrate a typical example showing that the surface oxidation states of metal ions exposed on the nanoparticles' surfaces are able to influence not only the optical, magnetic, electronic or catalytic properties but also water proton longitudinal relaxivity when applied as an MRI contrast agent. Cytotoxicity tests demonstrate that the PEGylated KMnF3 nanoparticles are free from toxicity. Further in vivo MRI experiments distinctively depict fine anatomical features in brain imaging at a low dose of 5 mg of Mn per kg and possible removal from the kidneys due to their small size and biocompatibility. Electronic supplementary information (ESI) available: Experimental procedure for two types of MnO nanoparticles, T1-weighted mapping. See DOI: 10.1039/c3nr00721a

Effects of NOx on the volatility of secondary organic aerosol from isoprene photooxidation

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

Xu, Lu; Kollman, Matthew S.; Song, Chen

2014-01-28

The effects of NOx on the volatility of the secondary organic aerosol (SOA) formed from isoprene photooxidation are investigated in environmental chamber experiments. Two types of experiments are performed. In HO2-dominant experiments, organic peroxy radicals (RO2) primarily react with HO2. In mixed experiments, RO2 reacts through multiple pathways. The volatility and oxidation state of isoprene SOA is sensitive to and displays a non-linear dependence on NOx levels. When initial NO/isoprene ratio is approximately 3 (ppbv:ppbv), SOA are shown to be most oxidized and least volatile, associated with the highest SOA yield. A High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) is appliedmore » to characterize the key chemical properties of aerosols. While the composition of SOA in mixed experiments does not change substantially over time, SOA become less volatile and more oxidized as oxidation progresses in HO2-dominant experiments. Analysis of the SOA composition suggests that the further reactions of organic peroxides and alcohols may produce carboxylic acids, which might play a strong role in SOA aging.« less

Effect of pretreatment on pd/Al2O3 catalyst for catalytic oxidation of o-xylene at low temperature.

PubMed

Huang, Shaoyong; Zhang, Changbin; He, Hong

2013-06-01

The effect of pretreatment on Pd/Al2O3 catalysts for the catalytic oxidation of o-xylene at low temperature was studied by changing the pretreatment and testing conditions. The fresh and pretreated Pd/Al2O3 catalysts were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The results showed that the pretreatment dramatically changed the Pd/PdO ratio and then significantly affected the Pd/Al2O3 activity; while the pretreatment had not much influence on Pd particle size. The Pd/Al2O3 pre-reduced at 300 degrees C/400 degrees C, which has fully reduced Pd species, showed the highest activity; while the fresh Pd/Al2O3, which has fully oxidized Pd species, presented the worst performance, indicating the Pd chemical state plays an important role in the catalytic activity for the o-xylene oxidation. It is concluded that metallic Pd is the active species on the Pd/Al2O3 catalyst for the catalytic oxidation of o-xylene at low temperature.

Friction, wear, and transfer of carbon and graphite to copper, chromium, and aluminum metal surfaces in vacuum

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1973-01-01

Sliding friction experiments were conducted with amorphous and fully graphitized carbons sliding on copper and on films of chromium and aluminum on copper. Auger emission spectroscopy analysis was used to monitor carbon transfer to the metal surfaces. Friction and wear were also measured. Metal surfaces were examined both in the clean state and with normal oxides present. Results indicate that different metals have an important effect on friction, wear, and transfer characteristics. With amorphous carbon, the least chemically active metal gave the highest wear and amount of carbon transfer. Both forms of carbon gave lower friction and wear and lower transfer rates when in contact with clean, as opposed to oxide-covered, chromium surfaces. With copper, the reverse was true; cleaning was detrimental.

Tungsten Incorporation into Gallium Oxide: Crystal Structure, Surface and Interface Chemistry, Thermal Stability and Interdiffusion

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

Rubio, E. J.; Mates, T. E.; Manandhar, S.

Tungsten (W) incorporated gallium oxide (Ga2O3) (GWO) thin films were deposited by radio-frequency magnetron co-sputtering of W-metal and Ga2O3-ceramic targets. Films were produced by varying sputtering power applied to the W-target in order to achieve variable W-content (0-12 at%) into Ga2O3 while substrate temperature was kept constant at 500 °C. Chemical composition, chemical valence states, microstructure and crystal structure of as-deposited and annealed GWO films were evaluated as a function of W-content. The structural and chemical analyses indicate that the samples deposited without any W-incorporation are stoichiometric, nanocrystalline Ga2O3 films, which crystallize in β-phase monoclinic structure. While GWO films alsomore » crystallize in monoclinic β-Ga2O3 phase, W-incorporation induces surface amorphization as revealed by structural studies. The chemical valence state of Ga ions probed by X-ray photoelectron spectroscopic (XPS) analyses is characterized by the highest oxidation state i.e., Ga3+. No changes in Ga chemical state are noted for variable W-incorporation in the range of 0-12 at%. Rutherford backscattering spectrometry (RBS) analyses indicate the uniform distribution of W-content in the GWO films. However, XPS analyses indicate the formation of mixed valence states for W ions, which may be responsible for surface amorphization in GWO films. GWO films were stable up to 900 oC, at which point thermally induced secondary phase (W-oxide) formation was observed. A transition to mesoporous structure coupled with W interdiffusion occurs due to thermal annealing as derived from the chemical analyses at the GWO films’ surface as well as depth-profiling towards the GWO-Si interface. A model has been formulated to account for the mechanism of W-incorporation, thermal stability and interdiffusion via pore formation in GWO films.« less

Effect of proton-conduction in electrolyte on electric efficiency of multi-stage solid oxide fuel cells

PubMed Central

Matsuzaki, Yoshio; Tachikawa, Yuya; Somekawa, Takaaki; Hatae, Toru; Matsumoto, Hiroshige; Taniguchi, Shunsuke; Sasaki, Kazunari

2015-01-01

Solid oxide fuel cells (SOFCs) are promising electrochemical devices that enable the highest fuel-to-electricity conversion efficiencies under high operating temperatures. The concept of multi-stage electrochemical oxidation using SOFCs has been proposed and studied over the past several decades for further improving the electrical efficiency. However, the improvement is limited by fuel dilution downstream of the fuel flow. Therefore, evolved technologies are required to achieve considerably higher electrical efficiencies. Here we present an innovative concept for a critically-high fuel-to-electricity conversion efficiency of up to 85% based on the lower heating value (LHV), in which a high-temperature multi-stage electrochemical oxidation is combined with a proton-conducting solid electrolyte. Switching a solid electrolyte material from a conventional oxide-ion conducting material to a proton-conducting material under the high-temperature multi-stage electrochemical oxidation mechanism has proven to be highly advantageous for the electrical efficiency. The DC efficiency of 85% (LHV) corresponds to a net AC efficiency of approximately 76% (LHV), where the net AC efficiency refers to the transmission-end AC efficiency. This evolved concept will yield a considerably higher efficiency with a much smaller generation capacity than the state-of-the-art several tens-of-MW-class most advanced combined cycle (MACC). PMID:26218470

Effect of proton-conduction in electrolyte on electric efficiency of multi-stage solid oxide fuel cells.

PubMed

Matsuzaki, Yoshio; Tachikawa, Yuya; Somekawa, Takaaki; Hatae, Toru; Matsumoto, Hiroshige; Taniguchi, Shunsuke; Sasaki, Kazunari

2015-07-28

Solid oxide fuel cells (SOFCs) are promising electrochemical devices that enable the highest fuel-to-electricity conversion efficiencies under high operating temperatures. The concept of multi-stage electrochemical oxidation using SOFCs has been proposed and studied over the past several decades for further improving the electrical efficiency. However, the improvement is limited by fuel dilution downstream of the fuel flow. Therefore, evolved technologies are required to achieve considerably higher electrical efficiencies. Here we present an innovative concept for a critically-high fuel-to-electricity conversion efficiency of up to 85% based on the lower heating value (LHV), in which a high-temperature multi-stage electrochemical oxidation is combined with a proton-conducting solid electrolyte. Switching a solid electrolyte material from a conventional oxide-ion conducting material to a proton-conducting material under the high-temperature multi-stage electrochemical oxidation mechanism has proven to be highly advantageous for the electrical efficiency. The DC efficiency of 85% (LHV) corresponds to a net AC efficiency of approximately 76% (LHV), where the net AC efficiency refers to the transmission-end AC efficiency. This evolved concept will yield a considerably higher efficiency with a much smaller generation capacity than the state-of-the-art several tens-of-MW-class most advanced combined cycle (MACC).

Depth-resolved abundance and diversity of arsenite-oxidizing bacteria in the groundwater of Beimen, a blackfoot disease endemic area of southwestern Taiwan.

PubMed

Das, Suvendu; Kar, Sandeep; Jean, Jiin-Shuh; Rathod, Jagat; Chakraborty, Sukalyan; Liu, Hsiao-Sheng; Bundschuh, Jochen

2013-12-01

The role of arsenite oxidizers in natural attenuation of arsenic pollution necessitates studies on their abundance and diversity in arsenic-contaminated aquifers. In this study, most probable number-polymerase chain reaction (MPN-PCR) and denaturing gradient gel electrophoresis (DGGE) was applied to monitor depth-wise abundance and diversity of aerobic arsenite oxidizers in arsenic-enriched groundwater of Beimen, southwestern Taiwan. The results revealed that the abundance of arsenite oxidizers ranged from 0.04 to 0.22, and the lowest ratio was observed in the most arsenic-enriched and comparatively more reduced groundwater (depth 200 m) of Beimen 1. The highest ratio was observed in the less arsenic-enriched and less reduced groundwater (depth 60 m) of Beimen 2B. DGGE profiles showed a shift in diversity of arsenite oxidizers, consisting of members of the Betaproteobacteria (61%), Alphaproteobacteria (28%) and Gammaproteobacteria (11%), depending on mainly arsenic concentration and redox level in groundwater. Groundwater with the lowest arsenic and highest dissolved oxygen at Beimen 2B harbored 78% of the arsenite oxidizers communities, while groundwater with the highest arsenic and lowest dissolved oxygen at Beimen 1 and Beimen-Jinhu harbored 17 and 22% of arsenite oxidizers communities, respectively. Pseudomonas sp. was found only in groundwater containing high arsenic at Beimen 1 and Beimen-Jinhu, while arsenite oxidizers belonging to Alpha- and Betaproteobacteria were dominated in groundwater containing low arsenic. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effect of dynamic surface polarization on the oxidative stability of solvents in nonaqueous Li-O 2 batteries

NASA Astrophysics Data System (ADS)

Khetan, Abhishek; Pitsch, Heinz; Viswanathan, Venkatasubramanian

2017-09-01

Polarization-induced renormalization of the frontier energy levels of interacting molecules and surfaces can cause significant shifts in the excitation and transport behavior of electrons. This phenomenon is crucial in determining the oxidative stability of nonaqueous electrolytes in high-energy density electrochemical systems such as the Li-O2 battery. On the basis of partially self-consistent first-principles Sc G W0 calculations, we systematically study how the electronic energy levels of four commonly used solvent molecules, namely, dimethylsulfoxide (DMSO), dimethoxyethane (DME), tetrahydrofuran (THF), and acetonitrile (ACN), renormalize when physisorbed on the different stable surfaces of Li2O2 , the main discharge product. Using band level alignment arguments, we propose that the difference between the solvent's highest occupied molecular orbital (HOMO) level and the surface's valence-band maximum (VBM) is a refined metric of oxidative stability. This metric and a previously used descriptor, solvent's gas phase HOMO level, agree quite well for physisorbed cases on pristine surfaces where ACN is oxidatively most stable followed by DME, THF, and DMSO. However, this effect is intrinsically linked to the surface chemistry of the solvent's interaction with the surface states and defects, and depends strongly on their nature. We conclusively show that the propensity of solvent molecules to oxidize will be significantly higher on Li2O2 surfaces with defects as compared to pristine surfaces. This suggests that the oxidative stability of a solvent is dynamic and is a strong function of surface electronic properties. Thus, while gas phase HOMO levels could be used for preliminary solvent candidate screening, a more refined picture of solvent stability requires mapping out the solvent stability as a function of the state of the surface under operating conditions.

Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature

PubMed Central

2016-01-01

The direct catalytic conversion of methane to liquid oxygenated compounds, such as methanol or dimethyl ether, at low temperature using molecular oxygen is a grand challenge in C–H activation that has never been met with synthetic, heterogeneous catalysts. We report the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483–498 K). Reaction kinetics studies show sustained catalytic activity and high selectivity for a variety of commercially available zeolite topologies under mild conditions (e.g., 483 K and atmospheric pressure). Transient and steady state measurements with isotopically labeled molecules confirm catalytic turnover. The catalytic rates and apparent activation energies are affected by the zeolite topology, with caged-based zeolites (e.g., Cu-SSZ-13) showing the highest rates. Although the reaction rates are low, the discovery of catalytic sites in copper-exchanged zeolites will accelerate the development of strategies to directly oxidize methane into methanol under mild conditions. PMID:27413787

Optical basicity and polarizability for copper-zinc doped sol-gel glasses

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

Kaur, G., E-mail: gkapds@gmail.com; Pandey, O. P.; Amjotkaur,, E-mail: amjotkaur93@gmail.com

2016-05-06

CaO-SiO{sub 2}-B{sub 2}O{sub 3}-P{sub 2}O{sub 5} glasses have been studied by varying ratios of Copper oxide and Zinc oxide. Glasses were prepared using Sol-Gel technique. Opitical Basicity and oxide ion Polarizability were calculated and discussed in relation with non bridging Oxygen ions (NBOs). Optical basicity is average electron donating capability of an oxide atom. All glasses had a little difference in optical basicity and polarizability values but CZ8 glass (20CaO-60SiO{sub 2}-5B{sub 2}O{sub 3}-5P{sub 2}O{sub 5}-2CuO-8ZnO) came out to show highest optical basicity and polarizability with value 0.5177 and 0.9798 respectively. This showed the highest electron donating tendency of CZ8 glassmore » and highest number of NBOs. These were minimum for CZ2 glass with 8CuO and 2ZnO. In aspect of optical basicity and polarizability glasses follow the series CZ2 < CZ4 < CZ6 < CZ8. Increasing concentration of ZnO and decreasing concentration of CuO lead to higher optical basicity and oxide ion polarizability.« less

Magnetic Hyperthermia and Oxidative Damage to DNA of Human Hepatocarcinoma Cells.

PubMed

Cellai, Filippo; Munnia, Armelle; Viti, Jessica; Doumett, Saer; Ravagli, Costanza; Ceni, Elisabetta; Mello, Tommaso; Polvani, Simone; Giese, Roger W; Baldi, Giovanni; Galli, Andrea; Peluso, Marco E M

2017-04-29

Nanotechnology is addressing major urgent needs for cancer treatment. We conducted a study to compare the frequency of 3-(2-deoxy-β-d-erythro-pentafuranosyl)pyrimido[1,2-α]purin-10(3 H )-one deoxyguanosine (M₁dG) and 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG) adducts, biomarkers of oxidative stress and/or lipid peroxidation, on human hepatocarcinoma HepG2 cells exposed to increasing levels of Fe₃O₄-nanoparticles (NPs) versus untreated cells at different lengths of incubations, and in the presence of increasing exposures to an alternating magnetic field (AMF) of 186 kHz using 32 P-postlabeling. The levels of oxidative damage tended to increase significantly after ≥24 h of incubations compared to controls. The oxidative DNA damage tended to reach a steady-state after treatment with 60 μg/mL of Fe₃O₄-NPs. Significant dose-response relationships were observed. A greater adduct production was observed after magnetic hyperthermia, with the highest amounts of oxidative lesions after 40 min exposure to AMF. The effects of magnetic hyperthermia were significantly increased with exposure and incubation times. Most important, the levels of oxidative lesions in AMF exposed NP treated cells were up to 20-fold greater relative to those observed in nonexposed NP treated cells. Generation of oxidative lesions may be a mechanism by which magnetic hyperthermia induces cancer cell death.

Magnetic Hyperthermia and Oxidative Damage to DNA of Human Hepatocarcinoma Cells

PubMed Central

Cellai, Filippo; Munnia, Armelle; Viti, Jessica; Doumett, Saer; Ravagli, Costanza; Ceni, Elisabetta; Mello, Tommaso; Polvani, Simone; Giese, Roger W.; Baldi, Giovanni; Galli, Andrea; Peluso, Marco E. M.

2017-01-01

Nanotechnology is addressing major urgent needs for cancer treatment. We conducted a study to compare the frequency of 3-(2-deoxy-β-d-erythro-pentafuranosyl)pyrimido[1,2-α]purin-10(3H)-one deoxyguanosine (M1dG) and 8-oxo-7,8-dihydro-2′-deoxyguanosine (8-oxodG) adducts, biomarkers of oxidative stress and/or lipid peroxidation, on human hepatocarcinoma HepG2 cells exposed to increasing levels of Fe3O4-nanoparticles (NPs) versus untreated cells at different lengths of incubations, and in the presence of increasing exposures to an alternating magnetic field (AMF) of 186 kHz using 32P-postlabeling. The levels of oxidative damage tended to increase significantly after ≥24 h of incubations compared to controls. The oxidative DNA damage tended to reach a steady-state after treatment with 60 μg/mL of Fe3O4-NPs. Significant dose–response relationships were observed. A greater adduct production was observed after magnetic hyperthermia, with the highest amounts of oxidative lesions after 40 min exposure to AMF. The effects of magnetic hyperthermia were significantly increased with exposure and incubation times. Most important, the levels of oxidative lesions in AMF exposed NP treated cells were up to 20-fold greater relative to those observed in nonexposed NP treated cells. Generation of oxidative lesions may be a mechanism by which magnetic hyperthermia induces cancer cell death. PMID:28468256

Phase state of ambient aerosol linked with water uptake and chemical aging in the southeastern US

DOE PAGES

Pajunoja, Aki; Hu, Weiwei; Leong, Yu J.; ...

2016-09-09

During the summer 2013 Southern Aerosol and Oxidant Study (SOAS) field campaign in a rural site in the southeastern United States, the effect of hygroscopicity and composition on the phase state of atmospheric aerosol particles dominated by the organic fraction was studied. The analysis is based on hygroscopicity measurements by a Hygroscopic Tandem Differential Mobility Analyzer (HTDMA), physical phase state investigations by an Aerosol Bounce Instrument (ABI) and composition measurements using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). To study the effect of atmospheric aging on these properties, an OH-radical oxidation flow reactor (OFR) was used to simulate longer atmosphericmore » aging times of up to 3 weeks. Hygroscopicity and bounce behavior of the particles had a clear relationship showing higher bounce at elevated relative humidity (RH) values for less hygroscopic particles, which agrees well with earlier laboratory studies. Additional OH oxidation of the aerosol particles in the OFR increased the O:C and the hygroscopicity resulting in liquefying of the particles at lower RH values. At the highest OH exposures, the inorganic fraction starts to dominate the bounce process due to production of inorganics and concurrent loss of organics in the OFR. Our results indicate that at typical ambient RH and temperature, organic-dominated particles stay mostly liquid in the atmospheric conditions in the southeastern US, but they often turn semisolid when dried below ~50 % RH in the sampling inlets. Furthermore, while the liquid phase state suggests solution behavior and equilibrium partitioning for the SOA particles in ambient air, the possible phase change in the drying process highlights the importance of thoroughly considered sampling techniques of SOA particles.« less

Phase state of ambient aerosol linked with water uptake and chemical aging in the southeastern US

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

Pajunoja, Aki; Hu, Weiwei; Leong, Yu J.

During the summer 2013 Southern Aerosol and Oxidant Study (SOAS) field campaign in a rural site in the southeastern United States, the effect of hygroscopicity and composition on the phase state of atmospheric aerosol particles dominated by the organic fraction was studied. The analysis is based on hygroscopicity measurements by a Hygroscopic Tandem Differential Mobility Analyzer (HTDMA), physical phase state investigations by an Aerosol Bounce Instrument (ABI) and composition measurements using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). To study the effect of atmospheric aging on these properties, an OH-radical oxidation flow reactor (OFR) was used to simulate longer atmosphericmore » aging times of up to 3 weeks. Hygroscopicity and bounce behavior of the particles had a clear relationship showing higher bounce at elevated relative humidity (RH) values for less hygroscopic particles, which agrees well with earlier laboratory studies. Additional OH oxidation of the aerosol particles in the OFR increased the O:C and the hygroscopicity resulting in liquefying of the particles at lower RH values. At the highest OH exposures, the inorganic fraction starts to dominate the bounce process due to production of inorganics and concurrent loss of organics in the OFR. Our results indicate that at typical ambient RH and temperature, organic-dominated particles stay mostly liquid in the atmospheric conditions in the southeastern US, but they often turn semisolid when dried below ~50 % RH in the sampling inlets. Furthermore, while the liquid phase state suggests solution behavior and equilibrium partitioning for the SOA particles in ambient air, the possible phase change in the drying process highlights the importance of thoroughly considered sampling techniques of SOA particles.« less

Garnet-type solid-state fast Li ion conductors for Li batteries: critical review.

PubMed

Thangadurai, Venkataraman; Narayanan, Sumaletha; Pinzaru, Dana

2014-07-07

Batteries are electrochemical devices that store electrical energy in the form of chemical energy. Among known batteries, Li ion batteries (LiBs) provide the highest gravimetric and volumetric energy densities, making them ideal candidates for use in portable electronics and plug-in hybrid and electric vehicles. Conventional LiBs use an organic polymer electrolyte, which exhibits several safety issues including leakage, poor chemical stability and flammability. The use of a solid-state (ceramic) electrolyte to produce all-solid-state LiBs can overcome all of the above issues. Also, solid-state Li batteries can operate at high voltage, thus, producing high power density. Various types of solid Li-ion electrolytes have been reported; this review is focused on the most promising solid Li-ion electrolytes based on garnet-type metal oxides. The first studied Li-stuffed garnet-type compounds are Li5La3M2O12 (M = Nb, Ta), which show a Li-ion conductivity of ∼10(-6) at 25 °C. La and M sites can be substituted by various metal ions leading to Li-rich garnet-type electrolytes, such as Li6ALa2M2O12, (A = Mg, Ca, Sr, Ba, Sr0.5Ba0.5) and Li7La3C2O12 (C = Zr, Sn). Among the known Li-stuffed garnets, Li6.4La3Zr1.4Ta0.6O12 exhibits the highest bulk Li-ion conductivity of 10(-3) S cm(-1) at 25 °C with an activation energy of 0.35 eV, which is an order of magnitude lower than that of the currently used polymer, but is chemically stable at higher temperatures and voltages compared to polymer electrolytes. Here, we discuss the chemical composition-structure-ionic conductivity relationship of the Li-stuffed garnet-type oxides, as well as the Li ion conduction mechanism.

Characterization of electro-oxidation catalysts using scanning electrochemical and mass spectral methods

NASA Astrophysics Data System (ADS)

Jambunathan, Krishnakumar

Low temperature fuel cells have many potential benefits, including high efficiency, high energy density and environmental friendliness. However, logistically appealing fuels for this system, such as reformed hydrocarbons or alcohols, exhibit poor performance because of catalyst poisoning that occurs during oxidation at the anode. This research focuses on the analysis of several model fuels and catalyst materials to understand the impact of catalyst poisoning on reactivity. Two novel experimental tools were developed based upon the local measurement of catalyst performance using scanning, reactivity mapping probes. The Scanning Electrochemical Microscope (SECM) was used to directly measure the rate constant for hydrogen oxidation in the presence and absence of dissolved CO. The Scanning Differential Electrochemical Mass Spectrometer (SDEMS) was exploited to measure the partial and complete oxidation products of methanol and ethanol oxidation. The reactivity of Pt and Pt/Ru catalysts towards the hydrogen oxidation reaction in the absence and presence of adsorbed CO was elucidated using the SECM. Steady state rate constant measurements in the absence of CO showed that the rate of hydrogen oxidation reaction exceeded 1 cms-1 . Steady state rate constant measurements in the presence of CO indicated that the platinum surface is completely inactive due to adsorbed CO. Addition of as little as 6% Ru to the Pt electrode was found to significantly improve the activity of the electrode towards CO removal. SDEMS was used to study the electro-oxidation of methanol on Pt xRuy electrodes at different electrode potentials and temperatures. Screening measurements performed with the SDEMS showed that PtxRu y electrodes containing 6--40% Ru had the highest activity for methanol oxidation. Current efficiencies for CO2 were also calculated under different conditions. SDEMS was also used to study the electro-oxidation of ethanol on Pt xRuy electrodes. The reaction was found to occur more slowly than the methanol oxidation reaction. Addition of 22%--40% Ru to the Pt electrode was found to increase the current densities and lower the onset potentials. The reaction was found to occur though a parallel path mechanism, which was confirmed by the detection of ethanol and acetic acid apart from CO2.

Characterisation of [Cu4S], the catalytic site in nitrous oxide reductase, by EPR spectroscopy.

PubMed

Oganesyan, Vasily S; Rasmussen, Tim; Fairhurst, Shirley; Thomson, Andrew J

2004-04-07

The enzyme nitrous oxide reductase (N(2)OR) has a unique tetranuclear copper centre [Cu(4)S], called Cu(Z), at the catalytic site for the two-electron reduction of N(2)O to N(2). The X- and Q-band EPR spectra have been recorded from two forms of the catalytic site of the enzyme N(2)OR from Paracoccus pantotrophus, namely, a form prepared anaerobically, Cu(Z), that undergoes a one-electron redox cycle and Cu(Z)*, prepared aerobically, which cannot be redox cycled. The spectra of both species are axial with that of Cu(Z) showing a rich hyperfine splitting in the g||-region at X-band. DFT calculations were performed to gain insight into the electronic configuration and ground-state properties of Cu(Z) and to calculate EPR parameters. The results for the oxidation state [Cu(+1)(3)Cu(+2)(1)S](3+) are in good agreement with values obtained from the fitting of experimental spectra, confirming the absolute oxidation state of Cu(Z). The unpaired spin density in this configuration is delocalised over four copper ions, thus, Cu(I) 20.1%, Cu(II) 9.5%, Cu(III) 4.8% and Cu(IV) 9.2%, the mu(4)-sulfide ion and oxygen ligand. The three copper ions carrying the highest spin density plus the sulfide ion lie approximately in the same plane while the fourth copper ion is perpendicular to this plane and carries only 4.8% spin density. It is suggested that the atoms in this plane represent the catalytic core of Cu(Z), allowing electron redistribution within the plane during interaction with the substrate, N(2)O.

Electrochemical trapping of metastable Mn3+ ions for activation of MnO2 oxygen evolution catalysts.

PubMed

Morgan Chan, Zamyla; Kitchaev, Daniil A; Nelson Weker, Johanna; Schnedermann, Christoph; Lim, Kipil; Ceder, Gerbrand; Tumas, William; Toney, Michael F; Nocera, Daniel G

2018-06-05

Electrodeposited manganese oxide films are promising catalysts for promoting the oxygen evolution reaction (OER), especially in acidic solutions. The activity of these catalysts is known to be enhanced by the introduction of Mn 3+ We present in situ electrochemical and X-ray absorption spectroscopic studies, which reveal that Mn 3+ may be introduced into MnO 2 by an electrochemically induced comproportionation reaction with Mn 2+ and that Mn 3+ persists in OER active films. Extended X-ray absorption fine structure (EXAFS) spectra of the Mn 3+ -activated films indicate a decrease in the Mn-O coordination number, and Raman microspectroscopy reveals the presence of distorted Mn-O environments. Computational studies show that Mn 3+ is kinetically trapped in tetrahedral sites and in a fully oxidized structure, consistent with the reduction of coordination number observed in EXAFS. Although in a reduced state, computation shows that Mn 3+ states are stabilized relative to those of oxygen and that the highest occupied molecular orbital (HOMO) is thus dominated by oxygen states. Furthermore, the Mn 3+ (T d ) induces local strain on the oxide sublattice as observed in Raman spectra and results in a reduced gap between the HOMO and the lowest unoccupied molecular orbital (LUMO). The confluence of a reduced HOMO-LUMO gap and oxygen-based HOMO results in the facilitation of OER on the application of anodic potentials to the δ-MnO 2 polymorph incorporating Mn 3+ ions.

Skeleton/skin structured (RGO/CNTs)@PANI composite fiber electrodes with excellent mechanical and electrochemical performance for all-solid-state symmetric supercapacitors.

PubMed

Liu, Dong; Du, Pengcheng; Wei, Wenli; Wang, Hongxing; Wang, Qi; Liu, Peng

2018-03-01

Polyaniline coated reduced graphene oxide/carbon nanotube composite fibers ((RGO/CNTs)@PANI, RCP) with skeleton/skin structure are designed as fiber-shaped electrodes for high performance all-solid-state symmetric supercapacitor. The one-dimensional reduced graphene oxide/carbon nanotube composite fibers (RGO/CNTs, RC) are prepared via a simple in-situ reduction of graphene oxide in presence of carbon nanotubes in quartz glass pipes, which exhibit excellent mechanical performance of >193.4 MPa of tensile strength. Then polyaniline is coated onto the RC fibers by electrodepositing technique. The electrochemical properties of the RCP fiber-shaped electrodes are optimized by adjusting the feeding ratio of carbon nanotubes. The optimized one exhibits good electrochemical characteristic such as highest volumetric specific capacitance of 193.1 F cm -3 at 1 A cm -3 , as well as excellent cyclic retention of 92.60% after 2000 cyclic voltammetry cycles. Furthermore, the all-solid-state symmetric supercapacitor, fabricated by using the final composite fiber as both positive and negative electrodes pre-coated with the poly(vinyl alcohol)/H 2 SO 4 gel polyelectrolyte, possesses volumetric capacitance of 36.7 F cm -3 at 0.2 A cm -3 and could light up a red light-emitting diode easily. The excellent mechanical and electrochemical performances make the designed supercapacitor as promising high performance wearable energy storage device. Copyright © 2017 Elsevier Inc. All rights reserved.

Electrochemical Trapping of Metastable Mn3+ Ions for Activation of MnO2 Oxygen Evolution Catalysts

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

Tumas, William; Chan, Zamyla Morgan; Kitchaev, Daniil A.

Electrodeposited manganese oxide films are promising catalysts for promoting the oxygen evolution reaction (OER), especially in acidic solutions. The activity of these catalysts is known to be enhanced by the introduction of Mn3+. We present in situ electrochemical and X-ray absorption spectroscopic studies, which reveal that Mn3+ may be introduced into MnO2 by an electrochemically induced comproportionation reaction with Mn2+ and that Mn3+ persists in OER active films. Extended X-ray absorption fine structure (EXAFS) spectra of the Mn3+-activated films indicate a decrease in the Mn-O coordination number, and Raman microspectroscopy reveals the presence of distorted Mn-O environments. Computational studies showmore » that Mn3+ is kinetically trapped in tetrahedral sites and in a fully oxidized structure, consistent with the reduction of coordination number observed in EXAFS. Although in a reduced state, computation shows that Mn3+ states are stabilized relative to those of oxygen and that the highest occupied molecular orbital (HOMO) is thus dominated by oxygen states. Furthermore, the Mn3+(Td) induces local strain on the oxide sublattice as observed in Raman spectra and results in a reduced gap between the HOMO and the lowest unoccupied molecular orbital (LUMO). The confluence of a reduced HOMO-LUMO gap and oxygen-based HOMO results in the facilitation of OER on the application of anodic potentials to the d-MnO2 polymorph incorporating Mn3+ ions.« less

A series of inorganic solid nitrogen sources for the synthesis of metal nitride clusterfullerenes: the dependence of production yield on the oxidation state of nitrogen and counter ion.

PubMed

Liu, Fupin; Guan, Jian; Wei, Tao; Wang, Song; Jiao, Mingzhi; Yang, Shangfeng

2013-04-01

A series of nitrogen-containing inorganic solid compounds with variable oxidation states of nitrogen and counter ions have been successfully applied as new inorganic solid nitrogen sources toward the synthesis of Sc-based metal nitride clusterfullerenes (Sc-NCFs), including ammonium salts [(NH4)xH(3-x)PO4 (x = 0-2), (NH4)2SO4, (NH4)2CO3, NH4X (X = F, Cl), NH4SCN], thiocyanate (KSCN), nitrates (Cu(NO3)2, NaNO3), and nitrite (NaNO2). Among them, ammonium phosphates ((NH4)xH(3-x)PO4, x = 1-3) and ammonium thiocyanate (NH4SCN) are revealed to behave as better nitrogen sources than others, and the highest yield of Sc-NCFs is achieved when NH4SCN was used as a nitrogen source. The optimum molar ratio of Sc2O3:(NH4)3PO4·3H2O:C and Sc2O3:NH4SCN:C has been determined to be 1:2:15 and 1:3:15, respectively. The thermal decomposition products of these 12 inorganic compounds have been discussed in order to understand their different performances toward the synthesis of Sc-NCFs, and accordingly the dependence of the production yield of Sc-NCFs on the oxidation state of nitrogen and counter ion is interpreted. The yield of Sc3N@C80 (I(h) + D(5h)) per gram Sc2O3 by using the N2-based group of nitrogen sources (thiocyanate, nitrates, and nitrite) is overall much lower than those by using gaseous N2 and NH4SCN, indicating the strong dependence of the yield of Sc-NCFs on the oxidation state of nitrogen, which is attributed to the "in-situ" redox reaction taking place for the N2-based group of nitrogen sources during discharging. For NH3-based group of nitrogen sources (ammonium salts) which exhibits a (-3) oxidation states of nitrogen, their performance as nitrogen sources is found to be sensitively dependent on the anion, and this is understood by considering their difference on the thermal stability and/or decomposition rate. Contrarily, for the N2-based group of nitrogen sources, the formation of Sc-NCFs is independent to both the oxidation state of nitrogen (+3 or +5) and the cation.

Butanol Dehydration over V₂O₅-TiO₂/MCM-41 Catalysts Prepared via Liquid Phase Atomic Layer Deposition.

PubMed

Choi, Hyeonhee; Bae, Jung-Hyun; Kim, Do Heui; Park, Young-Kwon; Jeon, Jong-Ki

2013-04-29

MCM-41 was used as a support and, by using atomic layer deposition (ALD) in the liquid phase, a catalyst was prepared by consecutively loading titanium oxide and vanadium oxide to the support. This research analyzes the effect of the loading amount of vanadium oxide on the acidic characteristics and catalytic performance in the dehydration of butanol. The physical and chemical characteristics of the TiO₂-V₂O₅/MCM-41 catalysts were analyzed using XRF, BET, NH₃-TPD, XRD, Py-IR, and XPS. The dehydration reaction of butanol was performed in a fixed bed reactor. For the samples with vanadium oxide loaded to TiO₂/MCM-41 sample using the liquid phase ALD method, it was possible to increase the loading amount until the amount of vanadium oxide reached 12.1 wt %. It was confirmed that the structural properties of the mesoporous silica were retained well after titanium oxide and vanadium loading. The NH₃-TPD and Py-IR results indicated that weak acid sites were produced over the TiO₂/MCM-41 samples, which is attributed to the generation of Lewis acid sites. The highest activity of the V₂O₅(12.1)-TiO₂/MCM-41 catalyst in 2-butanol dehydration is ascribed to it having the highest number of Lewis acid sites, as well as the highest vanadium dispersion.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Iron Oxide Films Prepared by Rapid Thermal Processing for Solar Energy Conversion

PubMed Central

Wickman, B.; Bastos Fanta, A.; Burrows, A.; Hellman, A.; Wagner, J. B.; Iandolo, B.

2017-01-01

Hematite is a promising and extensively investigated material for various photoelectrochemical (PEC) processes for energy conversion and storage, in particular for oxidation reactions. Thermal treatments during synthesis of hematite are found to affect the performance of hematite electrodes considerably. Herein, we present hematite thin films fabricated via one-step oxidation of Fe by rapid thermal processing (RTP). In particular, we investigate the effect of oxidation temperature on the PEC properties of hematite. Films prepared at 750 °C show the highest activity towards water oxidation. These films show the largest average grain size and the highest charge carrier density, as determined from electron microscopy and impedance spectroscopy analysis. We believe that the fast processing enabled by RTP makes this technique a preferred method for investigation of novel materials and architectures, potentially also on nanostructured electrodes, where retaining high surface area is crucial to maximize performance. PMID:28091573

Solid state ionics: a Japan perspective

NASA Astrophysics Data System (ADS)

Yamamoto, Osamu

2017-12-01

The 70-year history of scientific endeavor of solid state ionics research in Japan is reviewed to show the contribution of Japanese scientists to the basic science of solid state ionics and its applications. The term 'solid state ionics' was defined by Takehiko Takahashi of Nagoya University, Japan: it refers to ions in solids, especially solids that exhibit high ionic conductivity at a fairly low temperature below their melting points. During the last few decades of exploration, many ion conducting solids have been discovered in Japan such as the copper-ion conductor Rb4Cu16I7Cl13, proton conductor SrCe1-xYxO3, oxide-ion conductor La0.9Sr0.9Ga0.9Mg0.1O3, and lithium-ion conductor Li10GeP2S12. Rb4Cu16I7Cl13 has a conductivity of 0.33 S cm-1 at 25 °C, which is the highest of all room temperature ion conductive solid electrolytes reported to date, and Li10GeP2S12 has a conductivity of 0.012 S cm-1 at 25 °C, which is the highest among lithium-ion conductors reported to date. Research on high-temperature proton conducting ceramics began in Japan. The history, the discovery of novel ionic conductors and the story behind them are summarized along with basic science and technology.

Physical Training Status Determines Oxidative Stress and Redox Changes in Response to an Acute Aerobic Exercise

PubMed Central

Damirchi, Arsalan; Farjaminezhad, Manoochehr

2016-01-01

Objective. To assess the influence of different physical training status on exercise-induced oxidative stress and changes in cellular redox state. Methods. Thirty male subjects participated in this study and were assigned as well-trained (WT), moderately trained (MT), and untrained (UT) groups. The levels of cortisol, creatine kinase, plasma reduced glutathione to oxidized glutathione (GSH/GSSG), cysteine/cystine (Cys/CySS), and GSH/GSSG ratio in red blood cells (RBCs) were measured immediately and 10 and 30 min after exercise. Results. Following the exercise, plasma GSH/GSSG (p = 0.001) and Cys/CySS (p = 0.005) were significantly reduced in all groups. Reduction in plasma GSH/GSSG ratio in all groups induced a transient shift in redox balance towards a more oxidizing environment without difference between groups (p = 0.860), while RBCs GSH/GSSG showed significant reduction (p = 0.003) and elevation (p = 0.007) in UT and MT groups, respectively. The highest level of RBCs GSH/GSSG ratio was recorded in MT group, and the lowest one was recorded in the WT group. Conclusion. Long term regular exercise training with moderate intensity shifts redox balance towards more reducing environment, versus intensive exercise training leads to more oxidizing environment and consequently development of related diseases. PMID:27064342

Facile synthesis of birnessite-type manganese oxide nanoparticles as supercapacitor electrode materials.

PubMed

Liu, Lihu; Luo, Yao; Tan, Wenfeng; Zhang, Yashan; Liu, Fan; Qiu, Guohong

2016-11-15

Manganese oxides are environmentally benign supercapacitor electrode materials and, in particular, birnessite-type structure shows very promising electrochemical performance. In this work, nanostructured birnessite was facilely prepared by adding dropwise NH2OH·HCl to KMnO4 solution under ambient temperature and pressure. In order to fully exploit the potential of birnessite-type manganese oxide electrode materials, the effects of specific surface area, pore size, content of K(+), and manganese average oxidation state (Mn AOS) on their electrochemical performance were studied. The results showed that with the increase of NH2OH·HCl, the Mn AOS decreased and the corresponding pore sizes and specific surface area of birnessite increased. The synthesized nanostructured birnessite showed the highest specific capacitance of 245Fg(-1) at a current density of 0.1Ag(-1) within a potential range of 0-0.9V, and excellent cycle stability with a capacitance retention rate of 92% after 3000 cycles at a current density of 1.0Ag(-1). The present work implies that specific capacitance is mainly affected by specific surface area and pore volume, and provides a new method for the facile preparation of birnessite-type manganese oxide with excellent capacitive performance. Copyright © 2016 Elsevier Inc. All rights reserved.

Oxidative stability of sunflower oil supplemented with medicinal split gill mushroom, Schizophyllum commune Fr.:Fr. extract during accelerated storage.

PubMed

Yim, Hip Seng; Chye, Fook Yee; Heng, Pei Ying; Ho, Chun Wai

2011-01-01

The oxidative stability of sunflower oil supplemented with medicinal split gill mushroom, Schizophyllum commune's crude extract (CE), the formic acid (FA) fraction and semipurified subfractions (SF) II and IV were tested, compared to BHA and alpha-tocopherol, by measuring their peroxide value, iodine value, p-anisidine value, thiobarbituric acid-reactive substances, and free fatty acid content. Their total phenolic content (TPC), 2,2-diphenyl-1-picryhydrazyl (DPPH) radical scavenging, and ferric reducing/antioxidant power (FRAP) were also evaluated. FA and CE exhibited highest DPPH* scavenging, while FA and SFIV showed the highest FRAP; TPC was found to be highest in CE, FA, and SFIV. BHA and alpha-tocopherol are more protective in stabilizing the sunflower oil; SFII and SFIV had short-term protective effect in secondary oxidation for 1 year, while CE and FA retarded secondary oxidation and extended the shelf life 1 1/2 years and 2 years, respectively. HPLC-DAD analysis found (+)-catechin in Sch. commune's extracts. Sch. commune's extracts did not show similar retardation of lipid oxidation in sunflower oil as compared to alpha-tocopherol and BHA at the 200 ppm level. However, the higher concentration of Sch. commune's extract that provided the protective effect in stabilizing sunflower oil can be further studied.

Density functional theory molecular modeling and antimicrobial behaviour of selected 1,2,3,4,5,6,7,8-octahydroacridine-N(10)-oxides

NASA Astrophysics Data System (ADS)

Marinescu, Maria; Cinteza, Ludmila Otilia; Marton, George Iuliu; Marutescu, Luminita Gabriela; Chifiriuc, Mariana-Carmen; Constantinescu, Catalin

2017-09-01

A series of 9-substituted 1,2,3,4,5,6,7,8-octahydroacridine-N(10)-oxides is evaluated against 12 bacterial and fungal strains, for their microbicidal and anti-pathogenic features. The largest spectrum of the antibacterial activity is evidenced for the nitro- (2b) and hydroxy- (5b) N-oxides, followed by the amino-N-oxide (3b). Density functional theory (DFT) modeling of the molecular structure and frontier molecular orbitals, i.e. highest occupied/lowest unoccupied molecular orbital (HOMO/LUMO), is accomplished by using the GAMESS 2012 software at M11/ktzvp level of theory in order to find their structural and electronic parameters. We show that the planarity of the molecules and the presence of the electron withdrawing group are advantages for its antimicrobial activity. Finally, we briefly present and discuss results on the processing of such compounds into thin films and hybrid structures by laser-assisted techniques, i.e. matrix-assisted pulsed laser evaporation (MAPLE) or laser-induced forward transfer (LIFT), to provide simple and environmental friendly, state-of-the-art solutions for antimicrobial/medical coatings and devices.

In vitro determination of HT oxidation activity and tritium concentration in soil and vegetation during the chronic HT release experiment at Chalk River

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

Ichimasa, Y.; Ichimasa, M.; Jiang, H.

1995-10-01

The oxidation activity of molecular tritium (HT) in soils and vegetation collected in experimental plots during the 1994 chronic HT release experiment at Chalk River was determined in vitro laboratory experiments after the release. HT oxidation activity was highest in surface soils in the natural plot, about 3-4 times that in soils in the cultivated plots. HT oxidation activity in weeds and Komatsuna leaves was about 2 and 0.4% of that in the cultivated soil, respectively. The number of HT-oxidizing bacteria isolated from soils was highest in the surface soil (0-5 cm) in the natural plot. The viable cell numbersmore » in surface soils in the cultivated and natural plots were almost the same. The total occurrence rates of HT-oxidizing bacteria in the surface soils were 22% in the natural plot, and 7.5% in the cultivated plot. The occurrence rates of HT-oxidizing airborne bacteria during the release on two culture media were 4.2 and 1.9%. 16 refs., 3 figs., 3 tabs.« less

Antibacterial activity of graphite, graphite oxide, graphene oxide, and reduced graphene oxide: membrane and oxidative stress.

PubMed

Liu, Shaobin; Zeng, Tingying Helen; Hofmann, Mario; Burcombe, Ehdi; Wei, Jun; Jiang, Rongrong; Kong, Jing; Chen, Yuan

2011-09-27

Health and environmental impacts of graphene-based materials need to be thoroughly evaluated before their potential applications. Graphene has strong cytotoxicity toward bacteria. To better understand its antimicrobial mechanism, we compared the antibacterial activity of four types of graphene-based materials (graphite (Gt), graphite oxide (GtO), graphene oxide (GO), and reduced graphene oxide (rGO)) toward a bacterial model-Escherichia coli. Under similar concentration and incubation conditions, GO dispersion shows the highest antibacterial activity, sequentially followed by rGO, Gt, and GtO. Scanning electron microscope (SEM) and dynamic light scattering analyses show that GO aggregates have the smallest average size among the four types of materials. SEM images display that the direct contacts with graphene nanosheets disrupt cell membrane. No superoxide anion (O(2)(•-)) induced reactive oxygen species (ROS) production is detected. However, the four types of materials can oxidize glutathione, which serves as redox state mediator in bacteria. Conductive rGO and Gt have higher oxidation capacities than insulating GO and GtO. Results suggest that antimicrobial actions are contributed by both membrane and oxidation stress. We propose that a three-step antimicrobial mechanism, previously used for carbon nanotubes, is applicable to graphene-based materials. It includes initial cell deposition on graphene-based materials, membrane stress caused by direct contact with sharp nanosheets, and the ensuing superoxide anion-independent oxidation. We envision that physicochemical properties of graphene-based materials, such as density of functional groups, size, and conductivity, can be precisely tailored to either reducing their health and environmental risks or increasing their application potentials. © 2011 American Chemical Society

Creatine supplementation and oxidative stress in rat liver

PubMed Central

2013-01-01

Background The objective of this study was to determine the effects of creatine supplementation on liver biomarkers of oxidative stress in exercise-trained rats. Methods Forty 90-day-old adult male Wistar rats were assigned to four groups for the eight-week experiment. Control group (C) rats received a balanced control diet; creatine control group (CCr) rats received a balanced diet supplemented with 2% creatine; trained group (T) rats received a balanced diet and intense exercise training equivalent to the maximal lactate steady state phase; and supplemented-trained (TCr) rats were given a balanced diet supplemented with 2% creatine and subjected to intense exercise training equivalent to the maximal lactate steady state phase. At the end of the experimental period, concentrations of creatine, hydrogen peroxide (H2O2) and thiobarbituric acid reactive substances (TBARS) were measured as well as the enzyme activity of superoxide dismutase (SOD), glutathione peroxidase (GSH-GPx) and catalase (CAT). Liver tissue levels of reduced glutathione (GSH), oxidized glutathione (GSSG) and the GSH/GSSG ratio were also determined. Results Hepatic creatine levels were highest in the CCr and TCr groups with increased concentration of H2O2 observed in the T and TCr animal groups. SOD activity was decreased in the TCr group. GSH-GPx activity was increased in the T and TCr groups while CAT was elevated in the CCr and TCr groups. GSH, GGS and the GSH/GSSG ratio did not differ between all animal subsets. Conclusions Our results demonstrate that creatine supplementation acts in an additive manner to physical training to raise antioxidant enzymes in rat liver. However, because markers of liver oxidative stress were unchanged, this finding may also indicate that training-induced oxidative stress cannot be ameliorated by creatine supplementation. PMID:24325803

Emissions of toxic pollutants from compressed natural gas and low sulfur diesel-fueled heavy-duty transit buses tested over multiple driving cycles.

PubMed

Kado, Norman Y; Okamoto, Robert A; Kuzmicky, Paul A; Kobayashi, Reiko; Ayala, Alberto; Gebel, Michael E; Rieger, Paul L; Maddox, Christine; Zafonte, Leo

2005-10-01

The number of heavy-duty vehicles using alternative fuels such as compressed natural gas (CNG) and new low-sulfur diesel fuel formulations and equipped with after-treatment devices are projected to increase. However, few peer-reviewed studies have characterized the emissions of particulate matter (PM) and other toxic compounds from these vehicles. In this study, chemical and biological analyses were used to characterize the identifiable toxic air pollutants emitted from both CNG and low-sulfur-diesel-fueled heavy-duty transit buses tested on a chassis dynamometer over three transient driving cycles and a steady-state cruise condition. The CNG bus had no after-treatment, and the diesel bus was tested first equipped with an oxidation catalyst (OC) and then with a catalyzed diesel particulate filter (DPF). Emissions were analyzed for PM, volatile organic compounds (VOCs; determined on-site), polycyclic aromatic hydrocarbons (PAHs), and mutagenic activity. The 2000 model year CNG-fueled vehicle had the highest emissions of 1,3-butadiene, benzene, and carbonyls (e.g., formaldehyde) of the three vehicle configurations tested in this study. The 1998 model year diesel bus equipped with an OC and fueled with low-sulfur diesel had the highest emission rates of PM and PAHs. The highest specific mutagenic activities (revertants/microg PM, or potency) and the highest mutagen emission rates (revertants/mi) were from the CNG bus in strain TA98 tested over the New York Bus (NYB) driving cycle. The 1998 model year diesel bus with DPF had the lowest VOCs, PAH, and mutagenic activity emission. In general, the NYB driving cycle had the highest emission rates (g/mi), and the Urban Dynamometer Driving Schedule (UDDS) had the lowest emission rates for all toxics tested over the three transient test cycles investigated. Also, transient emissions were, in general, higher than steady-state emissions. The emissions of toxic compounds from an in-use CNG transit bus (without an oxidation catalyst) and from a vehicle fueled with low-sulfur diesel fuel (equipped with DPF) were lower than from the low-sulfur diesel fueled vehicle equipped with OC. All vehicle configurations had generally lower emissions of toxics than an uncontrolled diesel engine. Tunnel backgrounds (measurements without the vehicle running) were measured throughout this study and were helpful in determining the incremental increase in pollutant emissions. Also, the on-site determination of VOCs, especially 1,3-butadiene, helped minimize measurement losses due to sample degradation after collection.

Effects of Hydrogen-Donating or Metal-Chelating Antioxidants on the Oxidative Stability of Organogels Made of Beeswax and Grapeseed Oil Exposed to Light Irradiation.

PubMed

Hong, Seungmi; Kim, Mi-Ja; Park, Sungkwon; Lee, Suyong; Lee, Jonggil; Lee, JaeHwan

2018-04-01

To enhance the oxidative stability of organogels made from grapeseed oil, the antioxidant effects of sesamol, α-tocopherol, β-carotene, ethylenediaminetetraacetic acid (EDTA), and citric acid were determined in beeswax-based organogels stored under light or in the dark conditions at 25 °C. Without the addition of antioxidants, the organogels rapidly oxidized under light irradiation but not during storage in the dark. Sesamol showed the highest antioxidant activity at concentrations of 10 to 40 ppm, whereas the other compounds exhibited no antioxidant activity at 10 ppm. α-Tocopherol and β-carotene improved the oxidative stability of organogels at concentrations above 40 and 100 ppm, respectively. The addition of sesamol yielded better oxidative stability than the addition of EDTA or a mixture of sesamol and citric acid. Sesamol can improve the oxidative stability of organogels, which could lead to economic benefits for the food industry. Recently, interest in organogels has increased due to their properties of maintaining a solid state at room temperature and composition of trans-free and highly unsaturated fatty acids. However, the addition of antioxidants is necessary due to the high degree of unsaturation in organogels. The results of this study showed that the addition of sesamol significantly enhanced the oxidative stability of organogels under light irradiation. Therefore, the use of sesamol-supplemented organogels could prolong the shelf-life of bakery or meat food products. © 2018 Institute of Food Technologists®.

Electron Source in Photoinduced Hydrogen Production on Pt-supported TiO Particles

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

Perkins, Craig L.; Henderson, Michael A.; McCready, David E.

2001-01-18

Abe et al. illuminated an aqueous suspension of TiO/Pt with a Hg arc lamp and observed H production in the absence of O production. An unspecified elemental analysis excluded carbonaceous contaminants, and the source of the electron donor was concluded to be Ti+ cations. We can suggest at least three more likely (than Ti) sources for their mysterious electron donor: (1)an overlooked inorganic species, (2) Ti, and/or (3)organic impurities. The authors excluded the latter in their paper, but we view this conclusion as suspect given the lack of information on the limits of detection of the carbon assay, and themore » fact that the choice of argon(thermal conductivity= 41.33 x 10-6 cal cm-2s-1 (C cm-1)-1)3 as a carrier gas in their thermal conductivity detector4 probably precluded the observation of CO (thermal conductivity= 37.61 x 10-6 cal cm-2s-1 (C cm-1)-1)3, which is a common product of organic photochemical oxidations. No mention is made of an analysis for inorganic impurities. It is widely accepted that nanometer scale TiO particles can have significant fractions of undercoordinated Ti sites which can be easily oxidized to Ti, the highest valence of Ti observed in condensed phases. Here we point out that oxidation of Ti to Ti is much more physically realistic than oxidation of Ti to Ti. Removal of a fifth electron from titanium requires {approx}56 eV5.Ti, if it were to be generated in a solid oxide, would extract an electron from the valence band composed mainly of oxygen 2s and 2p states rather than remain in the 5 valence state. This unrealistically high oxidation state seems even more unlikely given the fact that at the room temperatures used in the authors' reactions Ti would have been generated and remained at the surface (at room temperature the diffusion of Ti cations in TiO is minimal), and the fact that the surface Madelung potential is smaller than that of the bulk6.« less

Magnetic and transport properties of the spin-state disordered oxide La0.8Sr0.2Co1-xRhxO3-δ

NASA Astrophysics Data System (ADS)

Shibasaki, Soichiro; Terasaki, Ichiro; Nishibori, Eiji; Sawa, Hiroshi; Lybeck, Jenni; Yamauchi, Hisao; Karppinen, Maarit

2011-03-01

We report measurements and analysis of magnetization, resistivity, and thermopower of polycrystalline samples of the perovskite-type Co/Rh oxide La0.8Sr0.2Co1-xRhxO3-δ. This system constitutes a solid solution for a full range of x, in which the crystal structure changes from rhombohedral to orthorhombic symmetry with increasing Rh content x. The magnetization data reveal that the magnetic ground state immediately changes upon Rh substitution from ferromagnetic to paramagnetic with increasing x near 0.25, which is close to the structural phase boundary. We find that one substituted Rh ion diminishes the saturation moment by 9 μB, which implies that one Rh3+ ion makes a few magnetic Co3+ ions nonmagnetic (the low-spin state) and causes disorder in the spin state and the highest occupied orbital. In this disordered composition (0.05⩽x⩽0.75), we find that the thermopower is anomalously enhanced below 50 K. In particular, the thermopower of x=0.5 is larger by a factor of 10 than those of x=0 and 1, and the temperature coefficient reaches 4 μV/K2, which is as large as that of heavy-fermion materials such as CeRu2Si2.

Effects of the Fabrication Process and Thermal Cycling on the Oxidation of Zirconium-Niobium Pressure Tubes

NASA Astrophysics Data System (ADS)

Nam, Cheol

2009-12-01

Pressure tubes made of Zr-2.5%Nb alloy are used to contain fuels and coolant in CANDU nuclear power reactors The pressure tube oxidizes during reactor operation and hydrogen ingress through the oxide grown on the tube limits its lifetime. Little attention was paid to the intermediate tube manufacturing processes in enhancing the oxidation resistance. In addition, the oxide grown on the tube experiences various thermal cycles depending on the reactor shutdown and startup cycles. To address these two aspects and to better understand the oxidation process of the Zr-2.5Nb tube, research was conducted in two parts: (i) effects of tube fabrication on oxidation behavior, and (ii) thermal cycling behaviors of oxides grown on a pressure tube. In the first part, the optimum manufacturing process was pursued to improve the corrosion resistance of Zr-2.5Nb tubes. Experimental micro-tubes were fabricated with various manufacturing routes in the stages of billet preparation, hot extrusion and cold drawing. These were oxidized in air at 400°C and 500°C, and in an autoclave at 360°C lithiated water. Microstructure and texture of the tubes and oxides were characterized with X-ray diffraction, scanning electron microscope and optical microscope. Special emphasis was given to examinations of the metal/oxide interface structures. A correlation between the manufacturing process and oxidation resistance was investigated in terms of tube microstructure and the metal/oxide interface structure. As a result, it was consistently observed that uniform interface structures were formed on the tubes which had a fine distribution of secondary phases. These microstructures were found to be beneficial in enhancing the oxidation resistance as opposed to the tubes that had coarse and continuous beta-Zr phases. Based on these observations, a schematic model of the oxidation process was proposed with respect to the oxidation resistance under oxidizing temperatures of 360°C, 400°C and 500°C. In the second part, the oxides grown on a standard Zr-2.5Nb pressure tube were analyzed by X-ray diffraction peak broadening and line shift. Crystallite size, t-ZrO2 fraction and residual stress of the zirconium oxides were investigated upon several thermal cycles at DeltaT range of 500°C--750°C. The oxide residual stresses measured by the sin2psi method were always compressive around 2 GPa. Different stress-states were noticed with the oxides grown on different sections of pressure tube. The compressive stress was released when the oxide was thermally cycled at the highest DeltaT of 750°C. Discussion was given to the effects of anisotropic nature of thermal expansion coefficients and crystallographic texture on the stress-state of Zr oxides.

Higher Americium Oxidation State Research Roadmap

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

Mincher, Bruce J.; Law, Jack D.; Goff, George S.

2015-12-18

The partitioning of hexavalent Am from dissolved nuclear fuel requires the ability to efficiently oxidize Am(III) to Am(VI) and to maintain that oxidation state for a length of time sufficient to perform the separation. Several oxidants have been, or are being developed. Chemical oxidants include Ag-catalyzed ozone, Ag-catalyzed peroxydisulfate, Cu(III) periodate, and sodium bismuthate. Hexavalent americium has also now successfully been prepared by electrolysis, using functionalized electrodes. So-called auto-reduction rates of Am(VI) are sufficiently slow to allow for separations. However, for separations based on solvent extraction or ion exchange using organic resins, the high valence state must be maintained undermore » the reducing conditions of the organic phase contact, and a holding oxidant is probably necessary. Until now, only Cu(III) periodate and sodium bismuthate oxidation have been successfully combined with solvent extraction separations. Bismuthate oxidation provided the higher DAm, since it acts as its own holding oxidant, and a successful hot test using centrifugal contactors was performed. For the other oxidants, Ag-catalyzed peroxydisulfate will not oxidize americium in nitric acid concentrations above 0.3 M, and it is not being further investigated. Peroxydisulfate in the absence of Ag catalysis is being used to prepare Am(V) in ion exchange work, discussed below. Preliminary work with Ag-catalyzed ozone has been unsuccessful for extractions of Am(VI) from 6.5 M HNO3, and only one attempt at extraction, also from 6.5 M HNO3, using the electrolytic oxidation has been attempted. However, this high acid concentration was based on the highest Am extraction efficiency using the bismuthate oxidant; which is only sparingly soluble, and thus the oxidation yield is based on bismuthate solubility. Lower acid concentrations may be sufficient with alternative oxidants and work with Ag-ozone, Cu(III) and electrolysis is on-going. Two non-solvent-extraction separations are also under investigation. The first would separate Am(VI) by co-crystallization with uranium and the other oxidizable actinides as their nitrate salts. This novel idea has been successful in lab scale testing, and merits further investigation. Similarly, success has been achieved in separations using inorganic or hybrid ion exchange materials to sorb the lanthanides and actinides, while allowing pentavalent americium to elute. This is the only technique currently investigating Am(V), despite the advantages of this oxidation state with regard to its higher stability. The ultimate destination for this roadmap is to develop an americium separation that can be applied under process conditions, preferably affording a co-separation of the actinyl (VI) ions. Toward that end, emphasis is given here to selection of a solvent extraction flowsheet for testing in the INL centrifugal contactor hot test bed during FY16. A solvent extraction process will be tested mainly because solvent extraction separations of Am(VI) are relatively mature and the test bed currently exists in a configuration to support them. Thus, a major goal of FY16 is to select the oxidant/ligand combination to run such a test using the contactors. The only ligands under consideration are DAAP and DEHBA. This is not to say that ion exchange and co-crystallization techniques are unimportant. They merit continued investigation, but are not mature enough for hot test bed testing at this time.« less

Preparation of Graphene-Zinc Oxide Nanostructure Composite for Carbon Monoxide Gas Sensing

NASA Astrophysics Data System (ADS)

Muchtar, Ahmad Rifqi; Septiani, Ni Luh Wulan; Iqbal, Muhammad; Nuruddin, Ahmad; Yuliarto, Brian

2018-03-01

A simple method to synthesize graphene-zinc oxide nanocomposite has been developed. A reduced graphene oxide-ZnO nanocomposite was prepared using a reflux method with ethylene glycol as medium. X-ray diffraction analysis, scanning electron microscopy, energy-dispersive spectrometry, and nitrogen adsorption-desorption measurements were used to characterize the resulting composite materials. The highest response of about 98% was observed when using pure ZnO at 300°C, while the second highest sensor response of about 96% was achieved by graphene-ZnO with 1:3 composition. It was found that the graphene-zinc oxide hybrid has potential to improve sensor performance at low temperature. The graphene-ZnO hybrid with 1:3 composition showed good response of 36% at 125°C, an operating temperature at which pure ZnO showed no response.

Preparation of Graphene-Zinc Oxide Nanostructure Composite for Carbon Monoxide Gas Sensing

NASA Astrophysics Data System (ADS)

Muchtar, Ahmad Rifqi; Septiani, Ni Luh Wulan; Iqbal, Muhammad; Nuruddin, Ahmad; Yuliarto, Brian

2018-07-01

A simple method to synthesize graphene-zinc oxide nanocomposite has been developed. A reduced graphene oxide-ZnO nanocomposite was prepared using a reflux method with ethylene glycol as medium. X-ray diffraction analysis, scanning electron microscopy, energy-dispersive spectrometry, and nitrogen adsorption-desorption measurements were used to characterize the resulting composite materials. The highest response of about 98% was observed when using pure ZnO at 300°C, while the second highest sensor response of about 96% was achieved by graphene-ZnO with 1:3 composition. It was found that the graphene-zinc oxide hybrid has potential to improve sensor performance at low temperature. The graphene-ZnO hybrid with 1:3 composition showed good response of 36% at 125°C, an operating temperature at which pure ZnO showed no response.

Electrospun-sodiumtetrafluoroborate-polyethylene oxide membranes for solvent-free sodium ion transport in solid state sodium ion batteries

NASA Astrophysics Data System (ADS)

Freitag, K. M.; Walke, P.; Nilges, T.; Kirchhain, H.; Spranger, R. J.; van Wüllen, L.

2018-02-01

Electrospinning is used to fabricate sodium ion conducting fiber membranes composed of polyethylene oxide (PEO), sodium tetrafluoroborate (NaBF4), and succinonitrile (SN) as plasticizer. As compared to conventionally prepared lithium electrolyte membranes with identical composition (PEO:SN:LiBF4), those membranes exhibit conductivities up to 10-4 S cm-1 at 328 K (activation energy ∼36 kJ mol-1, 36:8:1 membrane), which favors such systems as a solid-state electrolyte alternative for batteries. The conduction mechanism is evaluated and the ion mobility are examined. We identified the segment mobility of the polyethylene oxide as the main driving force for the enhanced ion mobility in the membranes. The introduction of SN has only a minor influence on the conductivity and segment mobility at room temperature, but extents the anion and cation mobility to temperatures below ambient. For the 36:8:1 (PEO:SN:NaBF4) membrane we found the highest ion mobility of all membranes under investigation. A comparison of the present sodium membranes with lithium systems of the same composition shows that the overall performance of the sodium systems is comparable. Taking plasticizer-free sodium membranes into account they perform even better than the lithium containing counterparts, and plasticizer-modified membranes show only half an order of magnitude lower conductivities than comparable lithium ones.

Origin of and tuning the optical and fundamental band gaps in transparent conducting oxides: The case of M2O3(M =Al ,Ga ,In )

NASA Astrophysics Data System (ADS)

Sabino, Fernando P.; Besse, Rafael; Oliveira, Luiz Nunes; Wei, Su-Huai; Da Silva, Juarez L. F.

2015-11-01

Good transparent conducting oxides (TCOs), such as In2O3 :Sn (ITO), usually combine large optical band gaps, essential for high transparency, with relatively small fundamental band gaps due to low conduction-band minima, which favor n -type doping and enhance the electrical conductivity. It has been understood that the optical band gaps are wider than the fundamental band gaps because optical transitions between the band-edge states are forbidden. The mechanism blocking such transitions, which can play a crucial role in the designing of alternative TCOs, nonetheless remains obscure. Here, based on first-principles density functional theory calculations and symmetry analysis of three oxides, M2O3 (M =Al ,Ga ,In ), we identify the physical origin of the gap disparities. Three conditions are necessary: (1) the crystal structure must have global inversion symmetry; (2) in order to belong to the Ag or A1 g irreducible representations, the states at the conduction-band minimum must have cation and oxygen s character; (3) in order to have g parity, the oxygen p orbitals constituting the states near the valence-band maximum must be strongly coupled to the cation d orbitals. Under these conditions, optical excitations across the fundamental gap will be forbidden. The three criteria explain the trends in the M2O3 (M =Al,Ga,In) sequence, in particular, explaining why In2O3 in the bixbyite structure yields the highest figure of merit. Our study provides guidelines expected to be instrumental in the search for new TCO materials.

Facial muscle activity, Response Entropy, and State Entropy indices during noxious stimuli in propofol-nitrous oxide or propofol-nitrous oxide-remifentanil anaesthesia without neuromuscular block.

PubMed

Aho, A J; Yli-Hankala, A; Lyytikäinen, L-P; Jäntti, V

2009-02-01

Entropy is an anaesthetic EEG monitoring method, calculating two numerical parameters: State Entropy (SE, range 0-91) and Response Entropy (RE, range 0-100). Low Entropy numbers indicate unconsciousness. SE uses the frequency range 0.8-32 Hz, representing predominantly the EEG activity. RE is calculated at 0.8-47 Hz, consisting of both EEG and facial EMG. RE-SE difference (RE-SE) can indicate EMG, reflecting nociception. We studied RE-SE and EMG in patients anaesthetized without neuromuscular blockers. Thirty-one women were studied in propofol-nitrous oxide (P) or propofol-nitrous oxide-remifentanil (PR) anaesthesia. Target SE value was 40-60. RE-SE was measured before and after endotracheal intubation, and before and after the commencement of surgery. The spectral content of the signal was analysed off-line. Appearance of EMG on EEG was verified visually. RE, SE, and RE-SE increased during intubation in both groups. Elevated RE was followed by increased SE values in most cases. In these patients, spectral analysis of the signal revealed increased activity starting from low (<20 Hz) frequency area up to the highest measured frequencies. This was associated with appearance of EMG in raw signal. No spectral alterations or EMG were seen in patients with stable Entropy values. Increased RE is followed by increased SE at nociceptive stimuli in patients not receiving neuromuscular blockers. Owing to their overlapping power spectra, the contribution of EMG and EEG cannot be accurately separated with frequency analysis in the range of 10-40 Hz.

Controlled synthesis of the antiperovskite oxide superconductor Sr3‑x SnO

NASA Astrophysics Data System (ADS)

Hausmann, J. N.; Oudah, M.; Ikeda, A.; Yonezawa, S.; Maeno, Y.

2018-05-01

A large variety of perovskite oxide superconductors are known, including some of the most prominent high-temperature and unconventional superconductors. However, superconductivity among the oxidation state inverted material class, the antiperovskite oxides, was recently reported for the first time. In this superconductor, Sr3‑x SnO, the unconventional ionic state Sn4‑ is realized and possible unconventional superconductivity due to a band inversion has been discussed. Here, we discuss an improved facile synthesis method, making it possible to control the strontium deficiency in Sr3‑x SnO. Additionally, a synthesis method above the melting point of Sr3SnO is presented. We show temperature dependence of magnetization and electrical resistivity for superconducting strontium deficient Sr3‑x SnO (T c ∼ 5 K) and for Sr3SnO without a superconducting transition in alternating current susceptibility down to 0.15 K. Further, we reveal a significant effect of strontium raw material purity on the superconductivity and achieve substantially increased M/M Meissner (∼1) compared to the highest value reported so far. More detailed characterizations utilizing powder x-ray diffraction and energy-dispersive x-ray spectroscopy show that a minor cubic phase, previously suggested to be another Sr3‑x SnO phase with a slightly larger lattice parameter, is SrO. The improved characterization and controlled synthesis reported herein enable detailed investigations on the superconducting nature and its dependency on the strontium deficiency in Sr3‑x SnO.

Toluene decomposition performance and NOx by-product formation during a DBD-catalyst process.

PubMed

Guo, Yufang; Liao, Xiaobin; Fu, Mingli; Huang, Haibao; Ye, Daiqi

2015-02-01

Characteristics of toluene decomposition and formation of nitrogen oxide (NOx) by-products were investigated in a dielectric barrier discharge (DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide (MnOx), iron oxide (FeOx), cobalt oxide (CoOx) and copper oxide (CuO), supported on Al2O3/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO2 selectivity. In addition, NOx was suppressed with the decrease of specific energy density (SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the CuO catalyst showed the best performance in NOx suppression. The MnOx catalyst exhibited the lowest concentration of O3 and highest CO2 selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression. Copyright © 2014. Published by Elsevier B.V.

Coccidian Infection Causes Oxidative Damage in Greenfinches

PubMed Central

Sepp, Tuul; Karu, Ulvi; Blount, Jonathan D.; Sild, Elin; Männiste, Marju; Hõrak, Peeter

2012-01-01

The main tenet of immunoecology is that individual variation in immune responsiveness is caused by the costs of immune responses to the hosts. Oxidative damage resulting from the excessive production of reactive oxygen species during immune response is hypothesized to form one of such costs. We tested this hypothesis in experimental coccidian infection model in greenfinches Carduelis chloris. Administration of isosporan coccidians to experimental birds did not affect indices of antioxidant protection (TAC and OXY), plasma triglyceride and carotenoid levels or body mass, indicating that pathological consequences of infection were generally mild. Infected birds had on average 8% higher levels of plasma malondialdehyde (MDA, a toxic end-product of lipid peroxidation) than un-infected birds. The birds that had highest MDA levels subsequent to experimental infection experienced the highest decrease in infection intensity. This observation is consistent with the idea that oxidative stress is a causative agent in the control of coccidiosis and supports the concept of oxidative costs of immune responses and parasite resistance. The finding that oxidative damage accompanies even the mild infection with a common parasite highlights the relevance of oxidative stress biology for the immunoecological research. PMID:22615772

Kinetic analysis of human CYP24A1 metabolism of vitamin D via the C24-oxidation pathway.

PubMed

Tieu, Elaine W; Tang, Edith K Y; Tuckey, Robert C

2014-07-01

CYP24A1 is the multicatalytic cytochrome P450 responsible for the catabolism of vitamin D via the C23- and C24-oxidation pathways. We successfully expressed the labile human enzyme in Escherichia coli and partially purified it in an active state that permitted detailed characterization of its metabolism of 1,25-dihydroxyvitamin D3 [1,25(OH)2 D3] and the intermediates of the C24-oxidation pathway in a phospholipid-vesicle reconstituted system. The C24-oxidation pathway intermediates, 1,24,25-trihydroxyvitamin D3, 24-oxo-1,25-dihydroxyvitamin D3, 24-oxo-1,23,25-trihydroxyvitamin D3 and tetranor-1,23-dihydroxyvitamin D3, were enzymatically produced from 1,25(OH)2 D3 using rat CYP24A1. Both 1,25(OH)2 D3 and 1,23-dihydroxy-24,25,26,27-tetranorvitamin D3 were found to partition strongly into the phospholipid bilayer when in aqueous medium. Changes to the phospholipid concentration did not affect the kinetic parameters for the metabolism of 1,25(OH)2 D3 by CYP24A1, indicating that it is the concentration of substrates in the membrane phase (mol substrate·mol phospholipid(-1) ) that determines their rate of metabolism. CYP24A1 exhibited Km values for the different C24-intermediates ranging from 0.34 to 15 mmol·mol phospholipid(-1) , with 24-oxo-1,23,25-trihydroxyvitamin D3 [24-oxo-1,23,25(OH)3 D3] displaying the lowest and 1,24,25-trihydroxyvitamin D3 [1,24,25(OH)3 D3] displaying the highest. The kcat values varied by up to 3.8-fold, with 1,24,25(OH)3 D3 displaying the highest kcat (34 min(-1) ) and 24-oxo-1,23,25(OH)3 D3 the lowest. The data show that the cleavage of the side chain of 24-oxo-1,23,25(OH)3 D3 occurs with the highest catalytic efficiency (kcat /Km ) and produces 1-hydroxy-23-oxo-24,25,26,27-tetranorvitamin D3 and not 1,23-dihydroxy-24,25,26,27-tetranorvitamin D3, as the primary product. These kinetic analyses also show that intermediates of the C24-oxidation pathway effectively compete with precursor substrates for binding to the active site of the enzyme, which manifests as an accumulation of intermediates, indicating that they dissociate after each catalytic step. © 2014 FEBS.

Angiotensin-I Converting Enzyme (ACE) Inhibitory and Anti-Oxidant Activities of Sea Cucumber (Actinopyga lecanora) Hydrolysates

PubMed Central

Ghanbari, Raheleh; Zarei, Mohammad; Ebrahimpour, Afshin; Abdul-Hamid, Azizah; Ismail, Amin; Saari, Nazamid

2015-01-01

In recent years, food protein-derived hydrolysates have received considerable attention because of their numerous health benefits. Amongst the hydrolysates, those with anti-hypertensive and anti-oxidative activities are receiving special attention as both activities can play significant roles in preventing cardiovascular diseases. The present study investigated the angiotensin-I converting enzyme (ACE) inhibitory and anti-oxidative activities of Actinopyga lecanora (A. lecanora) hydrolysates, which had been prepared by alcalase, papain, bromelain, flavourzyme, pepsin, and trypsin under their optimum conditions. The alcalase hydrolysate showed the highest ACE inhibitory activity (69.8%) after 8 h of hydrolysis while the highest anti-oxidative activities measured by 2,2-diphenyl 1-1-picrylhydrazyl radical scavenging (DPPH) (56.00%) and ferrous ion-chelating (FIC) (59.00%) methods were exhibited after 24 h and 8 h of hydrolysis, respectively. The ACE-inhibitory and anti-oxidative activities displayed dose-dependent trends, and increased with increasing protein hydrolysate concentrations. Moreover, strong positive correlations between angiotensin-I converting enzyme (ACE) inhibitory and anti-oxidative activities were also observed. This study indicates that A. lecanora hydrolysate can be exploited as a source of functional food owing to its anti-oxidant as well as anti-hypertension functions. PMID:26690117

Synthesis of iron oxides nanoparticles with very high saturation magnetization form TEA-Fe(III) complex via electrochemical deposition for supercapacitor applications

NASA Astrophysics Data System (ADS)

Elrouby, Mahmoud; Abdel-Mawgoud, A. M.; El-Rahman, Rehab Abd

2017-11-01

This work is devoted to the synthesis of magnetic iron oxides nanoparticles with very high saturation magnetization to be qualified for supercapacitor applications using, a simple electrodeposition technique. It is found that the electrochemical reduction process depends on concentration, temperature, deposition potential and the scan rate of potential. The nature of electrodeposition process has been characterized via voltammetric and chronoamperometric techniques. The morphology of the electrodeposits has been investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The structure and phase content of these investigated electrodeposits have been examined and calculated. The obtained iron oxides show a high saturation magnetization (Ms) of about 229 emu g-1. The data exhibited a relation between Ms of electrodeposited iron oxide and specific capacitance. This relation exhibits that the highest Ms value of electrodeposited iron oxides gives also highest specific capacitance of about 725 Fg-1. Moreover, the electrodeposited iron oxides exhibit a very good stability. The new characteristics of the electro synthesized iron oxides at our optimized conditions, strongly qualify them as a valuable material for high-performance supercapacitor applications.

A palladium-doped ceria@carbon core-sheath nanowire network: a promising catalyst support for alcohol electrooxidation reactions

NASA Astrophysics Data System (ADS)

Tan, Qiang; Du, Chunyu; Sun, Yongrong; Du, Lei; Yin, Geping; Gao, Yunzhi

2015-08-01

A novel palladium-doped ceria and carbon core-sheath nanowire network (Pd-CeO2@C CSNWN) is synthesized by a template-free and surfactant-free solvothermal process, followed by high temperature carbonization. This hierarchical network serves as a new class of catalyst support to enhance the activity and durability of noble metal catalysts for alcohol oxidation reactions. Its supported Pd nanoparticles, Pd/(Pd-CeO2@C CSNWN), exhibit >9 fold increase in activity toward the ethanol oxidation over the state-of-the-art Pd/C catalyst, which is the highest among the reported Pd systems. Moreover, stability tests show a virtually unchanged activity after 1000 cycles. The high activity is mainly attributed to the superior oxygen-species releasing capability of Pd-doped CeO2 nanowires by accelerating the removal of the poisoning intermediate. The unique interconnected one-dimensional core-sheath structure is revealed to facilitate immobilization of the metal catalysts, leading to the improved durability. This core-sheath nanowire network opens up a new strategy for catalyst performance optimization for next-generation fuel cells.A novel palladium-doped ceria and carbon core-sheath nanowire network (Pd-CeO2@C CSNWN) is synthesized by a template-free and surfactant-free solvothermal process, followed by high temperature carbonization. This hierarchical network serves as a new class of catalyst support to enhance the activity and durability of noble metal catalysts for alcohol oxidation reactions. Its supported Pd nanoparticles, Pd/(Pd-CeO2@C CSNWN), exhibit >9 fold increase in activity toward the ethanol oxidation over the state-of-the-art Pd/C catalyst, which is the highest among the reported Pd systems. Moreover, stability tests show a virtually unchanged activity after 1000 cycles. The high activity is mainly attributed to the superior oxygen-species releasing capability of Pd-doped CeO2 nanowires by accelerating the removal of the poisoning intermediate. The unique interconnected one-dimensional core-sheath structure is revealed to facilitate immobilization of the metal catalysts, leading to the improved durability. This core-sheath nanowire network opens up a new strategy for catalyst performance optimization for next-generation fuel cells. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03023d

Solid oxide fuel cells fueled with reducible oxides

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

Chuang, Steven S.; Fan, Liang Shih

A direct-electrochemical-oxidation fuel cell for generating electrical energy includes a cathode provided with an electrochemical-reduction catalyst that promotes formation of oxygen ions from an oxygen-containing source at the cathode, a solid-state reduced metal, a solid-state anode provided with an electrochemical-oxidation catalyst that promotes direct electrochemical oxidation of the solid-state reduced metal in the presence of the oxygen ions to produce electrical energy, and an electrolyte disposed to transmit the oxygen ions from the cathode to the solid-state anode. A method of operating a solid oxide fuel cell includes providing a direct-electrochemical-oxidation fuel cell comprising a solid-state reduced metal, oxidizing themore » solid-state reduced metal in the presence of oxygen ions through direct-electrochemical-oxidation to obtain a solid-state reducible metal oxide, and reducing the solid-state reducible metal oxide to obtain the solid-state reduced metal.« less

Solid state ionics: a Japan perspective

PubMed Central

Yamamoto, Osamu

2017-01-01

Abstract The 70-year history of scientific endeavor of solid state ionics research in Japan is reviewed to show the contribution of Japanese scientists to the basic science of solid state ionics and its applications. The term ‘solid state ionics’ was defined by Takehiko Takahashi of Nagoya University, Japan: it refers to ions in solids, especially solids that exhibit high ionic conductivity at a fairly low temperature below their melting points. During the last few decades of exploration, many ion conducting solids have been discovered in Japan such as the copper-ion conductor Rb4Cu16I7Cl13, proton conductor SrCe1–xYxO3, oxide-ion conductor La0.9Sr0.9Ga0.9Mg0.1O3, and lithium-ion conductor Li10GeP2S12. Rb4Cu16I7Cl13 has a conductivity of 0.33 S cm–1 at 25 °C, which is the highest of all room temperature ion conductive solid electrolytes reported to date, and Li10GeP2S12 has a conductivity of 0.012 S cm–1 at 25 °C, which is the highest among lithium-ion conductors reported to date. Research on high-temperature proton conducting ceramics began in Japan. The history, the discovery of novel ionic conductors and the story behind them are summarized along with basic science and technology. PMID:28804526

MitoQ10 induces adipogenesis and oxidative metabolism in myotube cultures.

PubMed

Nierobisz, Lidia S; McFarland, Douglas C; Mozdziak, Paul E

2011-02-01

Coenzyme Q(10) (CoQ(10)) plays an essential role in determination of mitochondrial membrane potential and substrate utilization in all metabolically important tissues. The objective of the present study was to investigate the effect of Coenzyme Q analog (MitoQ(10)) on oxidative phenotype and adipogenesis in myotubes derived from fast-glycolytic Pectoralis major (PM) and slow-oxidative Anterior latissimus dorsi (ALD) muscles of the turkey (Meleagris gallopavo). The myotubes were subjected to the following treatments: fusion media alone, fusion media+125 nM MitoQ(10), and 500 nM MitoQ(10). Lipid accumulation was visualized by Oil Red O staining and quantified by measuring optical density of extracted lipid at 500 nm. Quantitative Real-Time PCR was utilized to quantify the expression levels of peroxisome proliferator-activated receptor (PPARγ) and PPARγ co-activator-1α (PGC-1α). MitoQ(10) treatment resulted in the highest (P<0.05) lipid accumulation in PM myotubes. MitoQ(10) up-regulated genes controlling oxidative mitochondrial biogenesis and adipogenesis in PM myotube cultures. In contrast, MitoQ(10) had a limited effect on adipogenesis and down-regulated oxidative metabolism in ALD myotube cultures. Differential response to MitoQ(10) treatment may be dependent on the cellular redox state. MitoQ(10) likely controls a range of metabolic pathways through its differential regulation of gene expression levels in myotubes derived from fast-glycolytic and slow-oxidative muscles. Published by Elsevier Inc.

Effect of Nanoparticles on Complement System in Cell Culture Model

DTIC Science & Technology

2006-09-15

case complement activation considerably differs between nanoparticles , being the highest in case of fullerene, ferric oxide and aluminium oxide ... oxide (CdO; 1 µm), manganese oxide (MnO2; 1-2 µm), and tungsten (W; 27 µm) were assessed. Additionally the effects of nanoparticles coated with...using in vitro system. Obtained results indicate that: 1. Nanoparticles toxicity in vitro can’t be measured using methods which were designed

Development of PEGylated KMnF3 nanoparticles as a T1-weighted contrast agent: chemical synthesis, in vivo brain MR imaging, and accounting for high relaxivity.

PubMed

Liu, Zhi-jun; Song, Xiao-xia; Tang, Qun

2013-06-07

Magnetic nanoparticles consisting of manganese-based T1-weighted contrast agents have rapidly achieved clinical application, however low proton relaxivity impedes further development. In this report, by analyzing nanoparticles' surface oxidation states we propose the possible reason for the low r1 relaxivity of common MnO nanoparticles and develop PEGylated fluoroperovskite KMnF3 nanoparticles as new T1-weighted contrast agents, which exhibit the highest longitudinal relaxivity (r1 = 23.15 mM(-1) s(-1)) among all the reported manganese-based T1-weighted contrast agents. We, for the first time, illustrate a typical example showing that the surface oxidation states of metal ions exposed on the nanoparticles' surfaces are able to influence not only the optical, magnetic, electronic or catalytic properties but also water proton longitudinal relaxivity when applied as an MRI contrast agent. Cytotoxicity tests demonstrate that the PEGylated KMnF3 nanoparticles are free from toxicity. Further in vivo MRI experiments distinctively depict fine anatomical features in brain imaging at a low dose of 5 mg of Mn per kg and possible removal from the kidneys due to their small size and biocompatibility.

Colour changes by laser irradiation of reddish building limestones

NASA Astrophysics Data System (ADS)

Grossi, C. M.; Benavente, D.

2016-10-01

We have used X-ray photoelectron spectroscopy (XPS) as a novel method to investigate the causes of colour changes in a reddish limestone under irradiation by a Q-switched Nd:YAG 1064 nm laser. We irradiated clean dry and wet surfaces of Pidramuelle Roja, a building stone frequently used in the Asturian heritage, at fluences ranging from 0.12 to 1.47 J cm-2. We measured the colour coordinates and undertook XPS analysis of the state of oxidation of iron both before and after irradiation. Visible colour changes and potential aesthetic damage occurred on dry surfaces from a fluence of 0.31 J cm-2, with the stone showing a greening effect and very intense darkening. The colour change on dry surfaces was considerably higher than on wet surfaces, which at the highest fluence (1.47 J cm-2) was also above the human visual detection threshold. The use of XPS demonstrated that the change in colour (chroma and hue) is associated with a reduction in the iron oxidation state on dry surfaces during laser irradiation. This points out to a potential routinary use of XPS to analyse causes of colour changes during laser cleaning in other types of coloured building stones.

X-ray Absorption Near Edge Structure Spectroscopy to Resolve the in Vivo Chemistry of the Redox-Active Indazolium trans-[Tetrachlorobis(1H-indazole)ruthenate(III)] (KP1019)

PubMed Central

2013-01-01

Indazolium trans-[tetrachlorobis(1H-indazole)ruthenate(III)] (1, KP1019) and its analogue sodium trans-[tetrachlorobis(1H-indazole)ruthenate(III)] (2, KP1339) are promising redox-active anticancer drug candidates that were investigated with X-ray absorption near edge structure spectroscopy. The analysis was based on the concept of the coordination charge and ruthenium model compounds representing possible coordinations and oxidation states in vivo. 1 was investigated in citrate saline buffer (pH 3.5) and in carbonate buffer (pH 7.4) at 37 °C for different time intervals. Interaction studies on 1 with glutathione in saline buffer and apo-transferrin in carbonate buffer were undertaken, and the coordination of 1 and 2 in tumor tissues was studied too. The most likely coordinations and oxidation states of the compound under the above mentioned conditions were assigned. Microprobe X-ray fluorescence of tumor thin sections showed the strong penetration of ruthenium into the tumor tissue, with the highest concentrations near blood vessels and in the edge regions of the tissue samples. PMID:23282017

Nitrous oxide pollution from aircraft to increase by 2050

NASA Astrophysics Data System (ADS)

Bhattacharya, Atreyee

2012-09-01

The transportation industry is not only one of the biggest sources of air pollution and a significant player in greenhouse gas-induced global warming, but, as a new study shows, the industry could also be responsible for episodes of ozone (O3 ) pollution, particularly over the United States and northern Europe. Combustion of fuel in cars, shipping vessels, and low-flying aircraft produce nitrogen oxides (NOx), which not only decrease the lifetime of greenhouse gases such as methane but also react with other molecules in the atmosphere to form tropospheric O3, another, more lethal, air pollutant. Hauglustaine and Koff used a global three-dimensional chemistry-climate model to investigate how different components of the transportation industry—cars, ships, and low-flying aircraft—would contribute to NOx pollution over the next few decades under several projected emission scenarios. They found that as road transportation stagnates or even declines due to stricter regulations and congestion, NOx emissions from cars will decrease over time. However, aircraft will increase in number and could contribute between 25% and 48% of NOx emissions, which will be most severe over the United States and Europe—two regions with the highest growth rate in commercial aviation.

Role of order and disorder on the electronic performances of oxide semiconductor thin film transistors

NASA Astrophysics Data System (ADS)

Martins, R.; Barquinha, P.; Ferreira, I.; Pereira, L.; Gonçalves, G.; Fortunato, E.

2007-02-01

The role of order and disorder on the electronic performances of n-type ionic oxides such as zinc oxide, gallium zinc oxide, and indium zinc oxide used as active (channel) or passive (drain/source) layers in thin film transistors (TFTs) processed at room temperature are discussed, taking as reference the known behavior observed in conventional covalent semiconductors such as silicon. The work performed shows that while in the oxide semiconductors the Fermi level can be pinned up within the conduction band, independent of the state of order, the same does not happen with silicon. Besides, in the oxide semiconductors the carrier mobility is not bandtail limited and so disorder does not affect so strongly the mobility as it happens in covalent semiconductors. The electrical properties of the oxide films (resistivity, carrier concentration, and mobility) are highly dependent on the oxygen vacancies (source of free carriers), which can be controlled by changing the oxygen partial pressure during the deposition process and/or by adding other metal ions to the matrix. In this case, we make the oxide matrix less sensitive to the presence of oxygen, widening the range of oxygen partial pressures that can be used and thus improving the process control of the film resistivity. The results obtained in fully transparent TFT using polycrystalline ZnO or amorphous indium zinc oxide (IZO) as channel layers and highly conductive poly/nanocrystalline ZGO films or amorphous IZO as drain/source layers show that both devices work in the enhancement mode, but the TFT with the highest electronic saturation mobility and on/off ratio 49.9cm2/Vs and 4.3×108, respectively, are the ones in which the active and passive layers are amorphous. The ZnO TFT whose channel is based on polycrystalline ZnO, the mobility and on/off ratio are, respectively, 26cm2/Vs and 3×106. This behavior is attributed to the fact that the electronic transport is governed by the s-like metal cation conduction bands, not significantly affected by any type of angular disorder promoted by the 2p O states related to the valence band, or small amounts of incorporated metal impurities that lead to a better control of vacancies and of the TFT off current.

The effect of diet composition on weight gain and pyruvate dehydrogenase activity in heart muscle in the gold thioglucose obese mouse.

PubMed

Steinbeck, K; Caterson, I D; Astbury, L; Turtle, J R

1987-01-01

Pyruvate dehydrogenase complex activity is the major determinant of glucose oxidation in animal cells. Tissue glucose oxidation is reduced in obesity and states of insulin resistance and alternate fuels are utilized for energy and pyruvate dehydrogenase activity is reduced in cardiac muscle in obesity. The effect of four different diets (standard laboratory chow, high-carbohydrate, high-protein and high-fat) on weight gain, cardiac pyruvate dehydrogenase activity (PDHa) and serum insulin, glucose and free fatty acids was studied in the gold thioglucose obese mouse. All four diets produced significant weight gain in the gold thioglucose injected animal. Cardiac PDHa was influenced by both obesity and diet composition. The obese chow-fed animals had significantly reduced PDHa. On high-carbohydrate and high-protein feeding lean controls had a significant decrease in cardiac PDHa compared to chow-fed controls, but only in high-carbohydrate-fed animals was this further reduced by obesity. High-fat feeding produced a rapid and almost complete suppression of PDHa in both lean and obese animals. Serum insulin, glucose and free fatty acids were also affected by diet as well as obesity. The highest serum insulins were found in chow-fed obese animals whereas the highest serum glucoses were in high-carbohydrate-fed obese animals. Hyperinsulinaemia did not develop in the high-fat-fed obese animal, but the highest serum free fatty acids were found in high-fat feeding. It is concluded that both diet composition and obesity affect cardiac PDHa and therefore glucose utilization in this tissue. Insulin resistance in the acute stages of obesity development is also affected by diet composition.

Sensor materials for an intravascular fiber optic nitric oxide sensor

NASA Astrophysics Data System (ADS)

Soller, Babs R.; Parikh, Bhairavi R.; Stahl, Russell F.

1996-04-01

Nitric oxide (NO) is an important regulatory molecule in physiological processes including neurotransmission and the control of blood pressure. It is produced in excess during septic shock, the profound hypotensive state which accompanies severe infections. In-vivo measurement of NO would enhance the understanding of its varied biological roles. Our goal is the development of an intravascular fiber-optic sensor for the continuous measurement of NO. This study evaluated nitric oxide sensitive compounds as potential sensing materials in the presence and absence of oxygen. Using absorption spectroscopy we studied both the Fe II and Fe III forms of three biologically active hemes known to rapidly react with NO: hemoglobin, myoglobin, and cytochrome-c. The Fe II forms of hemoglobin and myoglobin and the Fe III form of cytochrome-c were found to have the highest sensitivity to NO. Cytochrome c (Fe III) is selective for NO even at high oxygen levels, while myoglobin is selective only under normal oxygen levels. NO concentrations as low as 1 (mu) M can be detected with our fiber-optic spectrometer using cytochrome c, and as low as 300 nM using myoglobin. Either of these materials would be adequate to monitor the increase in nitric oxide production during the onset of septic shock.

Platinum nanocatalysts prepared with different surfactants for C1-C3 alcohol oxidations and their surface morphologies by AFM

NASA Astrophysics Data System (ADS)

Ertan, Salih; Şen, Fatih; Şen, Selda; Gökağaç, Gülsün

2012-06-01

In this study, platinum nanoparticle catalysts have been prepared using PtCl4 as a starting material and 1-octanethiol, 1-decanethiol, 1-dodecanethiol, and 1-hexadecanethiol as surfactants for methanol, ethanol, and 2-propanol oxidation reactions. The structure, particle sizes, and surface morphologies of the catalysts were characterized by X-ray diffraction (XRD), atomic force microscopy and transmission electron microscopy (TEM). XRD and TEM results indicate that all prepared catalysts have a face-centered cubic structure and are homogeneously dispersed on the carbon support with a narrow size distribution (2.0-1.3 nm). X-ray photoelectron spectra of the catalysts were examined and it is found that platinum has two different oxidation states, Pt (0) and Pt(IV), oxygen and sulfur compounds are H2Oads and OHads, bound and unbound thiols. The electrochemical and electrocatalytic properties of these catalysts were investigated with respect to C1-C3 alcohol oxidations by cyclic voltammetry and chronoamperometry. The highest electrocatalytic activity was obtained from catalyst I which was prepared with 1-octanethiol. This may be attributed to a decrease in the ratio of bound to unbound thiol species increase in Pt (0)/Pt(IV), H2Oads/OHads ratios, electrochemical surface area, CO tolerance and percent platinum utility.

Determination of the oxidation states of metals and metalloids: An analytical review

NASA Astrophysics Data System (ADS)

Vodyanitskii, Yu. N.

2013-12-01

The hazard of many heavy metals/metalloids in the soil depends on their oxidation state. The problem of determining the oxidation state has been solved due to the use of synchrotron radiation methods with the analysis of the X-ray absorption near-edge structure (XANES). The determination of the oxidation state is of special importance for some hazardous heavy elements (arsenic, antimony, selenium, chromium, uranium, and vanadium). The mobility and hazard of each of these elements depend on its oxidation state. The mobilities are higher at lower oxidation states of As, Cr, V, and Se and at higher oxidation states of Sb and U. The determination of the oxidation state of arsenic has allowed revealing its fixation features in the rhizosphere of hydrophytes. The known oxidation states of chromium and uranium are used for the retention of these elements on geochemical barriers. Different oxidation states have been established for vanadium displacing iron in goethite. The determination of the oxidation state of manganese in the rhizosphere and the photosynthetic apparatus of plants is of special importance for agricultural chemists.

Reconstituted High-Density Lipoprotein Containing Human Growth Hormone-1 Shows Potent Tissue Regeneration Activity with Enhancement of Anti-Oxidant and Anti-Atherosclerotic Activities.

PubMed

Lee, Eun-Young; Kim, So-Hee; Cho, Kyung-Hyun

2015-06-01

Human growth hormone-1 (GH-1), somatotropin, is a peptide hormone that stimulates cell division in tissues such as bone and cartilage. To compare physiological activities in lipid-free and lipid-bound states, we expressed and incorporated GH-1 in reconstituted high-density lipoprotein (rHDL). GH-1 was expressed and purified using the pET30(a) vector and an Escherichia coli expression system. Purified GH-1 (at least 98% purity, 23 kD) was characterized and synthesized with apolipoproteinA-I (apoA-I), 1-palmitoyl-2-oleoyl-phosphatidylcholine (POPC), and cholesterol. Secondary structure analysis of GH-1 revealed 54% α-helical content in a lipid-free state and 65% α-helical content in a lipid-bound state along with blue-shifted tryptophan movement (around 2 nm). GH-1 caused less uptake of oxidized low-density lipoprotein (oxLDL) into macrophages and inhibited senescence of dermal cells in a dose-dependent manner. GH-1 in a lipid-bound state exerted stronger inhibitory activity than in a lipid-free state, indicating improved anti-atherosclerotic activity due to the lipid formulation. In a fin regeneration experiment using zebrafish (17 weeks old, n=9), GH-1 showed its highest regeneration speed without any side effects. GH-1-rHDL containing apoA-I showed 2.3-fold and 1.6-fold higher regeneration speeds than lipid-free GH-1 (in native state) and lipid-bound GH-1, respectively. Incorporation of GH-1 and apoA-I in HDL enhanced tissue regeneration activity of amputated tail fin, indicating a synergetic effect between GH-1 and apoA-I in a lipid-bound state.

Bioleaching mechanism of Co and Li from spent lithium-ion battery by the mixed culture of acidophilic sulfur-oxidizing and iron-oxidizing bacteria.

PubMed

Xin, Baoping; Zhang, Di; Zhang, Xian; Xia, Yunting; Wu, Feng; Chen, Shi; Li, Li

2009-12-01

The bioleaching mechanism of Co and Li from spent lithium-ion batteries by mixed culture of sulfur-oxidizing and iron-oxidizing bacteria was investigated. It was found that the highest release of Li occurred at the lowest pH of 1.54 with elemental sulfur as an energy source, the lowest occurred at the highest pH of 1.69 with FeS(2). In contrast, the highest release of Co occurred at higher pH and varied ORP with S + FeS(2), the lowest occurred at almost unchanged ORP with S. It is suggested that acid dissolution is the main mechanism for Li bioleaching independent of energy matters types, however, apart from acid dissolution, Fe(2+) catalyzed reduction takes part in the bioleaching process as well. Co(2+) was released by acid dissolution after insoluble Co(3+) was reduced into soluble Co(2+) by Fe(2+) in both FeS(2) and FeS(2) + S systems. The proposed bioleaching mechanism mentioned above was confirmed by the further results obtained from the experiments of bioprocess-stimulated chemical leaching and from the changes in structure and component of bioleaching residues characterized by XPS, SEM and EDX.

Iron Pentapyridyl Complexes as Molecular Water Oxidation Catalysts: Strong Influence of a Chloride Ligand and pH in Altering the Mechanism.

PubMed

Das, Biswanath; Orthaber, Andreas; Ott, Sascha; Thapper, Anders

2016-05-23

The development of molecular water oxidation catalysts based on earth-abundant, non-noble metals is essential for artificial photosynthesis research. Iron, which is the most abundant transition metal in the earth's crust, is a prospective candidate for this purpose. Herein, we report two iron complexes based on the polypyridyl ligand Py5OH (Py5OH=pyridine-2,6-diylbis [di(pyridin-2-yl)methanol]) that can catalyse water oxidation to produce O2 in Ru(III) -induced (at pH 8, highest turnover number (TON)=26.5; turnover frequency (TOF)=2.2 s(-1) ), Ce(IV) -induced (at pH≈1.5 highest TON=16; TOF=0.75 s(-1) ) and photo-induced (at pH 8, highest TON=43.5; TOF=0.6 s(-1) ) reactions. A chloride ligand in one of the iron complexes is shown to affect the activity strongly, improve stability and, thereby, the performance at pH 8 but it inhibits oxygen evolution at pH≈1.5. The observations are consistent with a change in mechanism for catalytic water oxidation with the Fe(Py5OH) complexes between acidic (Ce(IV) ) and near-neutral pH (Ru(III) ). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

XPS studies of Mg doped GDC (Ce0.8Gd0.2O2-δ) for IT-SOFC

NASA Astrophysics Data System (ADS)

Tyagi, Deepak; Rao, P. Koteswara; Wani, B. N.

2018-04-01

Fuel Cells have gained much attention as efficient and environment friendly device for both stationary as well as mobile applications. For intermediate temperature SOFC (IT-SOFC), ceria based electrolytes are the most promising one, due to their higher ionic conductivity at relatively lower temperatures. Gd doped ceria is reported to be having the highest ionic conductivity. In the present work, Mg is codoped along with Gd and the electronic structure of the constituents is studied by XPS. XPS confirm that the Cerium is present in +4 oxidation state only which indicates that electronic conduction can be completely avoided.

Carbon nanotube-supported Au-Pd alloy with cooperative effect of metal nanoparticles and organic ketone/quinone groups as a highly efficient catalyst for aerobic oxidation of amines.

PubMed

Deng, Weiping; Chen, Jiashu; Kang, Jincan; Zhang, Qinghong; Wang, Ye

2016-05-21

Functionalised carbon nanotube (CNT)-supported Au-Pd alloy nanoparticles were highly efficient catalysts for the aerobic oxidation of amines. We achieved the highest turnover frequencies (>1000 h(-1)) for the oxidative homocoupling of benzylamine and the oxidative dehydrogenation of dibenzylamine. We discovered a cooperative effect between Au-Pd nanoparticles and ketone/quinone groups on CNTs.

Production of Oxidative and Hydrolytic Enzymes by Coprinus cinereus (Schaeff.) Gray from Sisal Wastes Supplemented with Cow Dung Manure

PubMed Central

Raymond, Prosper; Mshandete, Anthony Manoni; Kajumulo Kivaisi, Amelia

2015-01-01

The activity of oxidative and hydrolytic enzymes of the edible and medicinal white rot fungi Coprinus cinereus (Schaeff.) Gray mushroom was observed during mycelia growth and fruiting body development in solid substrate fermentation using sisal waste fractions amended with cow dung manure as supplement. Laccase had the highest titre value among the five detected enzymes. Its activity was higher during mycelia growth compared to fruiting phase, with 10% supplemented substrate formulation unmixed sisal leaf decortication residues [abbreviated SL : SB (100 : 0)] displaying the highest activity of 39.45 ± 12.05 Ug−1. Lignin peroxidase (LiP) exhibited a characteristic wave-like pattern with the highest peaks found either during full mycelia colonization or soon after first flush harvest; the highest activity of 1.93 ± 0.62 Ug−1 was observed on unsupplemented SL : SB (100 : 0) substrate formulation during mycelia colonization. For hydrolytic enzymes, the highest carboxymethyl cellulase (CMCase) activity of 2.03 ± 0.70 Ug−1 was observed on 20% supplemented SL : SB (0 : 100) after first flush; that of pectinase (1.90 ± 0.32 Ug−1) was revealed after third flush on 10% supplemented SL : SB (0 : 100) substrate formulation while 10% supplemented SL : SB (25 : 75) exhibited the highest xylanase activity (1.23 ± 0.12 Ug−1) after first flush. These findings show that the activities of both oxidative and hydrolytic enzymes were regulated in line with developmental phase of growth of Coprinus cinereus. PMID:26664748

Secondary Organic Aerosol Formation and Aging in a Flow Reactor in the Forested Southeast US during SOAS

NASA Astrophysics Data System (ADS)

Hu, W.; Palm, B. B.; Hacker, L.; Campuzano Jost, P.; Day, D. A.; de Sá, S. S.; Ayres, B. R.; Draper, D.; Fry, J.; Ortega, A. M.; Kiendler-Scharr, A.; Pajunoja, A.; Virtanen, A.; Krechmer, J.; Canagaratna, M. R.; Thompson, S.; Yatavelli, R. L. N.; Stark, H.; Worsnop, D. R.; Martin, S. T.; Farmer, D.; Brown, S. S.; Jimenez, J. L.

2015-12-01

A major field campaign (Southern Oxidant and Aerosol Study, SOAS) was conducted in summer 2013 in a forested area in Centreville Supersite, AL (SEARCH network) in the southeast U.S. To investigate secondary organic aerosol (SOA) formation from biogenic volatile organic compounds (BVOCs), 3 oxidation flow reactors (OFR) were used to expose ambient air to oxidants and their output was analyzed by state-of-the-art gas and aerosol instruments including a High-Resolution Aerosol Mass Spectrometer (HR-AMS), a HR Proton-Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOFMS), and Two HR-TOF Chemical Ionization Mass Spectrometers (HRToF-CIMS). Ambient air was exposed 24/7 to variable concentrations of each of the 3 main atmospheric oxidants (OH, NO3 radicals and O3) to investigate the oxidation of BVOCs (including isoprene derived epoxydiols, IEPOX) and SOA formation and aging. Effective OH exposures up to 1×1013 molec cm-3 s were achieved, equivalent to over a month of aging in the atmosphere. Multiple oxidation products from isoprene and monoterpenes including small gas-phase acids were observed in OH OFR. High SOA formation of up to 12 μg m-3 above ambient concentrations of 5 μg m-3 was observed under intermediate OH exposures, while very high OH exposures led to destruction of ~30% of ambient OA, indicating shifting contributions of functionalization vs. fragmentation, consistent with results from urban and terpene-dominated environments. The highest SOA enhancements were 3-4 times higher than ambient OA. More SOA is typically formed during nighttime when terpenes are higher and photochemistry is absent, and less during daytime when isoprene is higher, although the IEPOX pathway is suppressed in the OFR. SOA is also observed after exposure of ambient air to O3 or NO3, although the amounts and oxidation levels were lower than for OH. Formation of organic nitrates in the NO3 reaction will also be discussed.A major field campaign (Southern Oxidant and Aerosol Study, SOAS) was conducted in summer 2013 in a forested area in Centreville Supersite, AL (SEARCH network) in the southeast U.S. To investigate secondary organic aerosol (SOA) formation from biogenic volatile organic compounds (BVOCs), 3 oxidation flow reactors (OFR) were used to expose ambient air to oxidants and their output was analyzed by state-of-the-art gas and aerosol instruments including a High-Resolution Aerosol Mass Spectrometer (HR-AMS), a HR Proton-Transfer Reaction Time-of-Flight Mass Spectrometer (PTR-TOFMS), and two HR-TOF Chemical Ionization Mass Spectrometers (HRToF-CIMS). Ambient air was exposed 24/7 to variable concentrations of each of the 3 main atmospheric oxidants (OH, NO3 radicals and O3) to investigate the oxidation of BVOCs (including ambient isoprene-derived epoxydiols, IEPOX) and SOA formation and aging. Effective OH exposures up to 1×1013 molec cm-3 s were achieved, equivalent to over a month of aging in the atmosphere. Multiple oxidation products from isoprene and monoterpenes including small gas-phase acids were observed in OH OFR. High SOA formation of up to 12 μg m-3 above ambient concentrations of 5 μg m-3 was observed under intermediate OH exposures, while very high OH exposures led to destruction of ~30% of ambient OA, indicating shifting contributions of functionalization vs. fragmentation, consistent with results from urban and terpene-dominated environments. The highest SOA enhancements were 3-4 times higher than ambient OA. More SOA is typically formed during nighttime when terpenes are higher and photochemistry is absent, and less during daytime when isoprene is higher, although the IEPOX pathway is suppressed in the OFR. SOA is also observed after exposure of ambient air to O3 or NO3, although the amounts and oxidation levels were lower than for OH. Formation of organic nitrates in the NO3 reaction will also be discussed.

Copper Oxide Nanoparticles Impact Several Toxicological Endpoints and Cause Neurodegeneration in Caenorhabditis elegans

PubMed Central

Zanon, Tyler; Kappell, Anthony D.; Petrella, Lisa N.; Andersen, Erik C.; Hristova, Krassimira R.

2016-01-01

Engineered nanoparticles are becoming increasingly incorporated into technology and consumer products. In 2014, over 300 tons of copper oxide nanoparticles were manufactured in the United States. The increased production of nanoparticles raises concerns regarding the potential introduction into the environment or human exposure. Copper oxide nanoparticles commonly release copper ions into solutions, which contribute to their toxicity. We quantified the inhibitory effects of both copper oxide nanoparticles and copper sulfate on C. elegans toxicological endpoints to elucidate their biological effects. Several toxicological endpoints were analyzed in C. elegans, including nematode reproduction, feeding behavior, and average body length. We examined three wild C. elegans isolates together with the Bristol N2 laboratory strain to explore the influence of different genotypic backgrounds on the physiological response to copper challenge. All strains exhibited greater sensitivity to copper oxide nanoparticles compared to copper sulfate, as indicated by reduction of average body length and feeding behavior. Reproduction was significantly reduced only at the highest copper dose, though still more pronounced with copper oxide nanoparticles compared to copper sulfate treatment. Furthermore, we investigated the effects of copper oxide nanoparticles and copper sulfate on neurons, cells with known vulnerability to heavy metal toxicity. Degeneration of dopaminergic neurons was observed in up to 10% of the population after copper oxide nanoparticle exposure. Additionally, mutants in the divalent-metal transporters, smf-1 or smf-2, showed increased tolerance to copper exposure, implicating both transporters in copper-induced neurodegeneration. These results highlight the complex nature of CuO nanoparticle toxicity, in which a nanoparticle-specific effect was observed in some traits (average body length, feeding behavior) and a copper ion specific effect was observed for other traits (neurodegeneration, response to stress). PMID:27911941

Understanding the Intrinsic Electrochemistry of Ni-Rich Layered Cathodes

NASA Astrophysics Data System (ADS)

Sallis, Shawn

The demand for energy is continually increasing overtime and the key to meeting future demand in a sustainable way is with energy storage. Li-ion batteries employing layered transition metal oxide cathodes are one of the most technologically important energy storage technologies. However, current Li-ion batteries are unable to access their full theoretical capacity and suffer from performance limiting degradation over time partially originating from the cathode and partially from the interface with the electrolyte. Understanding the fundamental limitations of layered transition metal oxide cathodes requires a complete understanding of the surface and bulk of the materials in their most delithiated state. In this thesis, we employ LiNi0.8Co0.15Al 0.05O2 (NCA) as a model system for Ni-rich layered oxide cathodes. Unlike its parent compound, LiCoO2, NCA is capable of high states of delithiation with minimal structural transitions. Furthermore, commercially available NCA has little to no transition metals in the Li layer. X-ray spectroscopies are an ideal tool for studying cathodes at high states of delithiation due their elemental selectivity, range of probing depths, and sensitivity to both chemical and electronic state information. The oxidation state of the transition metals at the surface can be probed via X-ray photoelectron spectroscopy (XPS) while both bulk and surface oxidation states as well as changes in metal oxygen bonding can be probed using X-ray absorption spectroscopy (XAS). Using X-ray spectroscopy in tandem with electrochemical, transport and microscopy measurements of the same materials, the impedance growth with increasing delithiation was correlated with the formation of a disordered NiO phase on the surface of NCA which was precipitated by the release of oxygen. Furthermore, the surface degradation was strongly impacted by the type of Li salt used in the electrolyte, with the standard commercial salt LiPF6 suffering from exothermic decomposition at high voltages and temperatures. Substituting LiPF6with LiBF4 suppressed NCA surface degradation and the dissolution of the transition metals into the electrolyte which is responsible for the impedance growth. Even in the most extreme conditions (4.75V vs Li +/Li0 at 60 °C for > 100 hrs) the degradation (i.e. metal reduction) was restricted to the first 10-30 nm and no evidence of oxygen loss was observed in the bulk. However, the transition metal ions were found to cease oxidizing above 4.25 V vs Li+/Li0 despite it being possible to extract 20% more lithium. Using a newly developed high efficiency resonant inelastic x-ray scattering (RIXS) spectrometer to probe the O K-edge of NCA electrodes at various conditions, it was concluded that oxygen participates in the charge compensation at the highest states of delithiation instead of the transition metals. These results are intrinsic to the physical and electronic structure of NCA and appear general to the other layered transition metal oxides currently under consideration for use as cathodes in Li-ion batteries.

Conductivity enhancement of surface-polymerized polyaniline films via control of processing conditions

NASA Astrophysics Data System (ADS)

Park, Chung Hyoi; Jang, Sung Kyu; Kim, Felix Sunjoo

2018-01-01

We investigate a fast and facile approach for the simultaneous synthesis and coating of conducting polyaniline (PANI) onto a substrate and the effects of processing conditions on the electrical properties of the fabricated films. Simultaneous polymerizing and depositing on the substrate forms a thin film with the average thickness of 300 nm and sheet resistance of 304 Ω/sq. Deposition conditions such as polymerization time (3-240 min), temperature (-10 to 40 °C), concentrations of monomer and oxidant (0.1-0.9 M), and type of washing solvents (acetone, water, and/or HCl solution) affect the film thickness, doping state, absorption characteristics, and solid-state nanoscale morphology, therefore affecting the electrical conductivity. Among the conditions, the surface-polymerized PANI film deposited at room temperature with acetone washing showed the highest conductivity of 22.2 S/cm.

Baseline and post-stress seasonal changes in immunocompetence and redox state maintenance in the fishing bat Myotis vivesi.

PubMed

Hernández-Arciga, Ulalume; Herrera M, L Gerardo; Ibáñez-Contreras, Alejandra; Miranda-Labra, Roxana U; Flores-Martínez, José Juan; Königsberg, Mina

2018-01-01

Little is known of how the stress response varies when animals confront seasonal life-history processes. Antioxidant defenses and damage caused by oxidative stress and their link with immunocompetence are powerful biomarkers to assess animal´s physiological stress response. The aim of this study was A) to determine redox state and variation in basal (pre-acute stress) immune function during summer, autumn and winter (spring was not assessed due to restrictions in collecting permit) in the fish-eating Myotis (Myotis vivesi; Chiroptera), and B) to determine the effect of acute stress on immunocompetence and redox state during each season. Acute stress was stimulated by restricting animal movement for 6 and 12 h. The magnitude of the cellular immune response was higher during winter whilst that of the humoral response was at its highest during summer. Humoral response increased after 6 h of movement restriction stress and returned to baseline levels after 12 h. Basal redox state was maintained throughout the year, with no significant changes in protein damage, and antioxidant activity was modulated mainly in relation to variation to environment cues, increasing during high temperatures and decreasing during windy nights. Antioxidant activity increased after the 6 h of stressful stimuli especially during summer and autumn, and to a lesser extent in early winter, but redox state did not vary. However, protein damage increased after 12 h of stress during summer. Prolonged stress when the bat is engaged in activities of high energy demand overcame its capacity to maintain homeostasis resulting in oxidative damage.

Baseline and post-stress seasonal changes in immunocompetence and redox state maintenance in the fishing bat Myotis vivesi

PubMed Central

Ibáñez-Contreras, Alejandra; Miranda-Labra, Roxana U.; Flores-Martínez, José Juan

2018-01-01

Little is known of how the stress response varies when animals confront seasonal life-history processes. Antioxidant defenses and damage caused by oxidative stress and their link with immunocompetence are powerful biomarkers to assess animal´s physiological stress response. The aim of this study was A) to determine redox state and variation in basal (pre-acute stress) immune function during summer, autumn and winter (spring was not assessed due to restrictions in collecting permit) in the fish-eating Myotis (Myotis vivesi; Chiroptera), and B) to determine the effect of acute stress on immunocompetence and redox state during each season. Acute stress was stimulated by restricting animal movement for 6 and 12 h. The magnitude of the cellular immune response was higher during winter whilst that of the humoral response was at its highest during summer. Humoral response increased after 6 h of movement restriction stress and returned to baseline levels after 12 h. Basal redox state was maintained throughout the year, with no significant changes in protein damage, and antioxidant activity was modulated mainly in relation to variation to environment cues, increasing during high temperatures and decreasing during windy nights. Antioxidant activity increased after the 6 h of stressful stimuli especially during summer and autumn, and to a lesser extent in early winter, but redox state did not vary. However, protein damage increased after 12 h of stress during summer. Prolonged stress when the bat is engaged in activities of high energy demand overcame its capacity to maintain homeostasis resulting in oxidative damage. PMID:29293551

Technology breakthroughs in high performance metal-oxide-semiconductor devices for ultra-high density, low power non-volatile memory applications

NASA Astrophysics Data System (ADS)

Hong, Augustin Jinwoo

Non-volatile memory devices have attracted much attention because data can be retained without power consumption more than a decade. Therefore, non-volatile memory devices are essential to mobile electronic applications. Among state of the art non-volatile memory devices, NAND flash memory has earned the highest attention because of its ultra-high scalability and therefore its ultra-high storage capacity. However, human desire as well as market competition requires not only larger storage capacity but also lower power consumption for longer battery life time. One way to meet this human desire and extend the benefits of NAND flash memory is finding out new materials for storage layer inside the flash memory, which is called floating gate in the state of the art flash memory device. In this dissertation, we study new materials for the floating gate that can lower down the power consumption and increase the storage capacity at the same time. To this end, we employ various materials such as metal nanodot, metal thin film and graphene incorporating complementary-metal-oxide-semiconductor (CMOS) compatible processes. Experimental results show excellent memory effects at relatively low operating voltages. Detailed physics and analysis on experimental results are discussed. These new materials for data storage can be promising candidates for future non-volatile memory application beyond the state of the art flash technologies.

One-step synthesis of vertically aligned anatase thornbush-like TiO2 nanowire arrays on transparent conducting oxides for solid-state dye-sensitized solar cells.

PubMed

Roh, Dong Kyu; Chi, Won Seok; Ahn, Sung Hoon; Jeon, Harim; Kim, Jong Hak

2013-08-01

Herein, we report a facile synthesis of high-density anatase-phase vertically aligned thornbush-like TiO2 nanowires (TBWs) on transparent conducting oxide glasses. Morphologically controllable TBW arrays of 9 μm in length are generated through a one-step hydrothermal reaction at 200 °C over 11 h using potassium titanium oxide oxalate dehydrate, diethylene glycol (DEG), and water. The TBWs consist of a large number of nanoplates or nanorods, as confirmed by SEM and TEM imaging. The morphologies of TBWs are controllable by adjusting DEG/water ratios. TBW diameters gradually decrease from 600 (TBW600) to 400 (TBW400) to 200 nm (TBW200) and morphologies change from nanoplates to nanorods with an increase in DEG content. TBWs are utilized as photoanodes for quasi-solid-state dye-sensitized solar cells (qssDSSCs) and solid-state DSSCs (ssDSSCs). The energy-conversion efficiency of qssDSSCs is in the order: TBW200 (5.2%)>TBW400 (4.5%)>TBW600 (3.4%). These results can be attributed to the different surface areas, light-scattering effects, and charge transport rates, as confirmed by dye-loading measurements, reflectance spectroscopy, and incident photon-to-electron conversion efficiency and intensity-modulated photovoltage spectroscopy/intensity-modulated photocurrent spectroscopy analyses. TBW200 is further treated with a graft-copolymer-directed organized mesoporous TiO2 to increase the surface area and interconnectivity of TBWs. As a result, the energy-conversion efficiency of the ssDSSC increases to 6.7% at 100 mW cm(-2) , which is among the highest values for N719-dye-based ssDSSCs. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetism and superconductivity of some Tl-Cu oxides

NASA Technical Reports Server (NTRS)

Datta, Timir

1990-01-01

Many copper oxide based Thallium compounds have now been discovered. In comparison to the Bi-compounds, the Tl-system shows a richer diversity; viz., High Temperature Superconductors (HTSC) can be obtained with either one or two Tl-0 layers (m = 1,2); also, the triple-digit phases are easier to synthesize. The value of d, oxygen stoichiometry, is critical to achieving superconductivity. The Tl system is robust to oxygen loss; Tl may be lost or incorporated by diffusion. A diffusion coefficient equal to 10 ms at 900 C was determined. Both ortho-rhombic and tetragonal structures are evidenced, but HTSC behavior is indifferent to the crystal symmetry. This system has the highest T(sub c) confirmed. T(sub c) generally increases with p, the number of CuO layers, but tends to saturate at p = 3. Zero resistance as high as 125K has been observed. Most of these HTSC's are hole type, but the Ce-doped specimens may be electronic. The magnetic aspects were studied; because in addition to defining the perfectly diamagnetic ground state as in the conventional superconductors, magnetism of the copper oxides show a surprising variety. This is true of both the normal and the superconducting states. Also, due to the large phonon contribution to the specific heat at the high T(sub c) accurate thermal measurement of important parameters such as the sp. heat jump, electronic density of states, D(Ef) and coherence length are uncertain, and thus, are estimated from the magnetic results. Results from the Tl-system CuO, LaBaCuO, 120 and the Bi-CuO compounds are discussed. The emphasis is on the role of magnetism in the TlCuO HTSC, but technological aspects are also pointed out.

Magnetism and superconductivity of some Tl-Cu oxides

NASA Technical Reports Server (NTRS)

Datta, Timir

1991-01-01

Many copper oxide based Thallium compounds are now known. In comparison to the Bi-compounds, the Tl-system shows a richer diversity; i.e., High Temperature Superconductors (HTSC) can be obtained with either one or two Tl-0 layers (m = 1,2); also, the triple-digit phases are easier to synthesize. The value of d, oxygen stoichiometry, is critical to achieving superconductivity. The Tl system is robust to oxygen loss; Tl may be lost or incorporated by diffusion. A diffusion coefficient equal to 10 ms at 900 C was determined. Both ortho-rhombic and tetragonal structures are found, but HTSC behavior is indifferent to the crystal symmetry. This system has the highest T(sub c) confirmed. T(sub c) generally increases with p, the number of CuO layers, but tends to saturate at p = 3. Zero resistance was observed at temperatures as great as 125 K. Most of these HTSC's are hole type, but the Ce-doped specimens may be electronic. The magnetic aspects were studied; because in addition to defining the perfectly diamagnetic ground state as in conventional superconductors, magnetism of the copper oxides show a surprising variety. This is true of both the normal and the superconducting states. Also, due to the large phonon contribution to the specific heat at the high T(sub c) jump, electronic density of states, D(Ef), and coherence length are uncertain, and thus, are estimated from the magnetic results. Results from the Tl-system CuO, LaBaCuO,120 and the Bi-CuO compounds are discussed. The emphasis is on the role of magnetism in the Tl-CuO HTSC, but technological aspects are also pointed out.

Chlorination of bromide-containing waters: enhanced bromate formation in the presence of synthetic metal oxides and deposits formed in drinking water distribution systems.

PubMed

Liu, Chao; von Gunten, Urs; Croué, Jean-Philippe

2013-09-15

Bromate formation from the reaction between chlorine and bromide in homogeneous solution is a slow process. The present study investigated metal oxides enhanced bromate formation during chlorination of bromide-containing waters. Selected metal oxides enhanced the decay of hypobromous acid (HOBr), a requisite intermediate during the oxidation of bromide to bromate, via (i) disproportionation to bromate in the presence of nickel oxide (NiO) and cupric oxide (CuO), (ii) oxidation of a metal to a higher valence state in the presence of cuprous oxide (Cu2O) and (iii) oxygen formation by NiO and CuO. Goethite (α-FeOOH) did not enhance either of these pathways. Non-charged species of metal oxides seem to be responsible for the catalytic disproportionation which shows its highest rate in the pH range near the pKa of HOBr. Due to the ability to catalyze HOBr disproportionation, bromate was formed during chlorination of bromide-containing waters in the presence of CuO and NiO, whereas no bromate was detected in the presence of Cu2O and α-FeOOH for analogous conditions. The inhibition ability of coexisting anions on bromate formation at pH 8.6 follows the sequence of phosphate > sulfate > bicarbonate/carbonate. A black deposit in a water pipe harvested from a drinking water distribution system exerted significant residual oxidant decay and bromate formation during chlorination of bromide-containing waters. Energy dispersive spectroscopy (EDS) analyses showed that the black deposit contained copper (14%, atomic percentage) and nickel (1.8%, atomic percentage). Cupric oxide was further confirmed by X-ray diffraction (XRD). These results indicate that bromate formation may be of concern during chlorination of bromide-containing waters in distribution systems containing CuO and/or NiO. Copyright © 2013 Elsevier Ltd. All rights reserved.

Nitrite oxidation in the upper water column and oxygen minimum zone of the eastern tropical North Pacific Ocean

PubMed Central

Beman, J Michael; Leilei Shih, Joy; Popp, Brian N

2013-01-01

Nitrogen (N) is an essential nutrient in the sea and its distribution is controlled by microorganisms. Within the N cycle, nitrite (NO2−) has a central role because its intermediate redox state allows both oxidation and reduction, and so it may be used by several coupled and/or competing microbial processes. In the upper water column and oxygen minimum zone (OMZ) of the eastern tropical North Pacific Ocean (ETNP), we investigated aerobic NO2− oxidation, and its relationship to ammonia (NH3) oxidation, using rate measurements, quantification of NO2−-oxidizing bacteria via quantitative PCR (QPCR), and pyrosequencing. 15NO2− oxidation rates typically exhibited two subsurface maxima at six stations sampled: one located below the euphotic zone and beneath NH3 oxidation rate maxima, and another within the OMZ. 15NO2− oxidation rates were highest where dissolved oxygen concentrations were <5 μM, where NO2− accumulated, and when nitrate (NO3−) reductase genes were expressed; they are likely sustained by NO3− reduction at these depths. QPCR and pyrosequencing data were strongly correlated (r2=0.79), and indicated that Nitrospina bacteria numbered up to 9.25% of bacterial communities. Different Nitrospina groups were distributed across different depth ranges, suggesting significant ecological diversity within Nitrospina as a whole. Across the data set, 15NO2− oxidation rates were decoupled from 15NH4+ oxidation rates, but correlated with Nitrospina (r2=0.246, P<0.05) and NO2− concentrations (r2=0.276, P<0.05). Our findings suggest that Nitrospina have a quantitatively important role in NO2− oxidation and N cycling in the ETNP, and provide new insight into their ecology and interactions with other N-cycling processes in this biogeochemically important region of the ocean. PMID:23804152

In vitro effects of nonesterified fatty acids on bovine neutrophils oxidative burst and viability.

PubMed

Scalia, D; Lacetera, N; Bernabucci, U; Demeyere, K; Duchateau, L; Burvenich, C

2006-01-01

An in vitro study was conducted to examine the influence of nonesterified fatty acids (NEFA) on bovine polymorphonuclear leukocytes (PMN). Eight healthy, midlactating Holstein cows were used as blood donors. Blood PMN were isolated and incubated with a mixture of NEFA, reflecting composition of bovine plasma NEFA at concentrations that were intended to mimic those found in blood of cows undergoing high, moderate, or low lipomobilization intensity (2, 1, 0.5, 0.25, 0.125, and 0.0625 mM). Control samples were incubated in absence of NEFA. Phagocytosis and oxidative burst activities were assessed by a 2-color flow cytometric method, which was based on oxidation of intracellular dihydrorhodamine 123 to green fluorescent rhodamine 123. Oxidative burst products were generated by incubating PMN with Staphylococcus aureus labeled with propidium iodide. A flow cytometric technique was used to detect PMN viability, necrosis, and apoptosis using fluorescein isothiocyanate-labeled annexin-V and propidium iodide. Phagocytic activity was not affected by NEFA. The highest concentration of NEFA (2 mM) was associated with a dramatic increase of phagocytosis-associated oxidative burst activities with a reduction in cell viability (48.0 vs. 97.5% in control samples) and with a marked increase of necrosis (49.4 vs. 0.5% in control samples). Conversely, the mixture of NEFA did not affect the occurrence of apoptosis. Enhancement of the oxidative burst associated with the highest concentration of NEFA might explain the reduced viability and higher percentage of necrosis observed under the same conditions. This study demonstrated a substantial resistance of bovine PMN to an overload of fatty acids. However, observation that the highest concentration of NEFA regulated some PMN functions encourages the possibility of in vivo studies to assess the relationships between intensity of lipomobilization, plasma NEFA, and bovine PMN functions.

Effects of muscle fiber type on glycolytic potential and meat quality traits in different Tibetan pig muscles and their association with glycolysis-related gene expression.

PubMed

Shen, L Y; Luo, J; Lei, H G; Jiang, Y Z; Bai, L; Li, M Z; Tang, G Q; Li, X W; Zhang, S H; Zhu, L

2015-11-13

The myosin heavy chain (MyHC) composition, glycolytic potential, mitochondrial content, and gene expression related to energy metabolism were analyzed in eight muscles from Tibetan pigs, to study how meat quality develops in different muscle tissues. The muscles were classified into three clusters, based on MyHC composition: masseter, trapezius, and latissimus dorsi as 'slow-oxidative-type'; psoas major and semimembranosus as 'intermediate-type'; and longissimus dorsi, obliquus externus abdominis, and semitendinosus as 'fast-glycolytic-type'. The 'slow-oxidative-type' muscles had the highest MyHC I and MyHC IIA content (P < 0.01); 'intermediate-type' muscles, the highest MyHC IIx content (P < 0.01); and 'fast-glycolytic-type' muscles, the highest MyHC IIb content (P < 0.01). The pH values measured in 'slow-oxidative-type' muscles were higher than those in the other clusters were; however, the color of 'fast-glycolytic-type' muscles was palest (P < 0.01). Mitochondrial content increased in the order: fast-glycolytic-type < intermediate-type < slow-oxidative-type. In the 'slow-oxidative-type' muscles, the expression levels of genes related to ATP synthesis were higher, but were lower for those related to glycogen synthesis and glycolysis. Mitochondrial content was significantly positively correlated with MyHC I content, but negatively correlated with MyHC IIb content. MyHC I and mitochondrial content were both negatively correlated with glycolytic potential. Overall, muscles used frequently in exercise had a higher proportion of type I fibers. 'Slow-oxidative-type' muscles, rich in type I fibers with higher mitochondrial and lower glycogen and glucose contents, had a higher ATP synthesis efficiency and lower glycolytic capacity, which contributed to their superior meat quality.

Compositional investigation of ∼2 μm luminescence of Ho{sup 3+}-doped lead silicate glass

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

Liu, Xueqiang; Huang, Feifei; Gao, Song

2015-11-15

Graphical abstract: Ho{sup 3+}-doped lead silicate glass with lowest maximum phonon energy possesses highest ∼2 μm luminescence intensity. - Highlights: • With increment of lead oxide, maximum phonon energy in lead silicate glass decreased. • ∼2 μm luminescent intensity of Ho{sup 3+} increased with increment of lead oxide. • Lowest lead oxide content glass possesses highest quantum efficiency due to low maximum phonon energy. - Abstract: Lead silicate glass samples with varying lead oxide content were prepared in this study, and their luminescent properties were examined and analyzed. It was found that with increasing lead oxide content, the maximum phononmore » energies of the glass samples decreased, while their spontaneous transition probabilities first increased and then decreased. The influence of the spontaneous transition rate, A{sub 10}, and the multi-phonon relaxation rate, W{sub 10}, on the sample luminescent properties was analyzed using rate equations. As a result, it was found that with increasing lead oxide content, W{sub 10}/A{sub 10} decreased, while the quantum efficiency increased. Thus, the luminescent intensity at ∼2 μm increased in the glass samples with increased lead oxide content. The high luminescent intensity and long lifetime indicate that silicate glasses containing high levels of lead oxide could potentially be used in ∼2 μm lasers.« less

Nanomaterial induction of oxidative stress in lung epithelial cells and macrophages

NASA Astrophysics Data System (ADS)

Wang, Lin; Pal, Anoop K.; Isaacs, Jacqueline A.; Bello, Dhimiter; Carrier, Rebecca L.

2014-09-01

Oxidative stress in the lung epithelial A549 cells and macrophages J774A.1 due to contact with commercially important nanomaterials [i.e., nano-silver (nAg), nano-alumina (nAl2O3), single-wall carbon nanotubes (CNT), and nano-titanium oxide anatase (nTiO2)] was evaluated. Nanomaterial-induced intracellular oxidative stress was analyzed by both H2DCFDA fluorescein probe and GSH depletion, extracellular oxidative stress was assessed by H2HFF fluorescein probes, and the secretion of chemokine IL-8 by A549 cells due to elevation of cellular oxidative stress was also monitored, in order to provide a comprehensive in vitro study on nanomaterial-induced oxidative stress in lung. In addition, results from this study were also compared with an acellular "ferric reducing ability of serum" (FRAS) assay and a prokaryotic cell-based assay in evaluating oxidative damage caused by the same set of nanomaterials, for comparison purposes. In general, it was found that nanomaterial-induced oxidative stress is highly cell-type dependent. In A549 lung epithelial cells, nAg appeared to induce highest level of oxidative stress and cell death followed by CNT, nTiO2, and nAl2O3. Different biological oxidative damage (BOD) assays' (i.e., H2DCFA, GSH, and IL-8 release) results generally agreed with each other, and the same trends of nanomaterial-induced BOD were also observed in acellular FRAS and prokaryotic E. coli K12-based assay. In macrophage J774A.1 cells, nAl2O3 and nTiO2 appeared to induce highest levels of oxidative stress. These results suggest that epithelial and macrophage cell models may provide complimentary information when conducting cell-based assays to evaluate nanomaterial-induced oxidative damage in lung.

The potential of cashew gum functionalization as building blocks for layer-by-layer films.

PubMed

Leite, Álvaro J; Costa, Rui R; Costa, Ana M S; Maciel, Jeanny S; Costa, José F G; de Paula, Regina C M; Mano, João F

2017-10-15

Cashew gum (CG), an exudate polysaccharide from Anacardium occidentale trees, was carboxymethylated (CGCm) and oxidized (CGO). These derivatives were characterized by FTIR and zeta potential measurements confirming the success of carboxymethylation and oxidation reactions. Nanostructured multilayered films were then produced through layer-by-layer (LbL) assembly in conjugation with chitosan via electrostatic interactions or Schiff bases covalent bonds. The films were analyzed by QCM-D and AFM. CG functionalization increased the film thickness, with the highest thickness being achieved for the lowest oxidation degree. The roughest surface was obtained for the CGO with the highest oxidation degree due to the predominance of covalent Schiff bases. This work shows that nanostructured films can be assembled and stabilized by covalent bonds in alternative to the conventional electrostatic ones. Moreover, the functionalization of CG can increase its feasibility in multilayers films, widening its potential in biomedical, food industry, or environmental applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ethanol oxidation on Pt single-crystal electrodes: surface-structure effects in alkaline medium.

PubMed

Busó-Rogero, Carlos; Herrero, Enrique; Feliu, Juan M

2014-07-21

Ethanol oxidation in 0.1 M NaOH on single-crystal electrodes has been studied using electrochemical and FTIR techniques. The results show that the activity order is the opposite of that found in acidic solutions. The Pt(111) electrode displays the highest currents and also the highest onset potential of all the electrodes. The onset potential for the oxidation of ethanol is linked to the adsorption of OH on the electrode surface. However, small (or even negligible) amounts of CO(ads) and carbonate are detected by FTIR, which implies that cleavage of the C-C bond is not favored in this medium. The activity of the electrodes diminishes quickly upon cycling. The diminution of the activity is proportional to the measured currents and is linked to the formation and polymerization of acetaldehyde, which adsorbs onto the electrode surface and prevents further oxidation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

State variation in rates of cesarean and VBAC delivery: 1989 and 1993.

PubMed

Clarke, S C; Taffel, S M

1996-01-01

There is wide variation among states in rates of cesarean and vaginal births after cesarean (VBAC) deliveries. In general, states in the South have the highest cesarean rates, states in the West have the lowest, and states in the Northeast and Midwest are intermediate. Louisiana had the highest overall rate in 1993 (27.7 per 100 births) while Alaska had the lowest rate (15.2). The majority of states had declines in their cesarean rate between 1989 and 1993. Patterns in primary cesarean rates are similar to those of the overall rate-states in the South generally have the highest rates while states in the West have the lowest rates. Primary cesarean rates ranged between a high of 19.6 in Louisiana to a low of 10.6 in Wisconsin. In general, states with low cesarean rates have among the highest rates of VBAC delivery. Alaska had the highest VBAC rate (40.0), which was almost quadruple the rate of Louisiana (11.2), the state with the lowest rate. Most states had substantial increases in VBAC rates between 1989 and 1993. When examining cesarean rates by maternal age and birth order, states with the highest overall rates also have among the highest age/birth order-specific rates. Cesarean rates were lowest for mothers under 25 years of age having a second or higher order birth in Alaska, 10.4, and highest for mothers 35 years of age or over having a first birth in Mississippi, 51.3. Standardized cesarean rates which were adjusted for differences between states in maternal age and birth order distributions did not diminish the variation among areas.

A predictive model of iron oxide nanoparticles flocculation tuning Z-potential in aqueous environment for biological application

NASA Astrophysics Data System (ADS)

Baldassarre, Francesca; Cacciola, Matteo; Ciccarella, Giuseppe

2015-09-01

Iron oxide nanoparticles are the most used magnetic nanoparticles in biomedical and biotechnological field because of their nontoxicity respect to the other metals. The investigation of iron oxide nanoparticles behaviour in aqueous environment is important for the biological applications in terms of polydispersity, mobility, cellular uptake and response to the external magnetic field. Iron oxide nanoparticles tend to agglomerate in aqueous solutions; thus, the stabilisation and aggregation could be modified tuning the colloids physical proprieties. Surfactants or polymers are often used to avoid agglomeration and increase nanoparticles stability. We have modelled and synthesised iron oxide nanoparticles through a co-precipitation method, in order to study the influence of surfactants and coatings on the aggregation state. Thus, we compared experimental results to simulation model data. The change of Z-potential and the clusters size were determined by Dynamic Light Scattering. We developed a suitable numerical model to predict the flocculation. The effects of Volume Mean Diameter and fractal dimension were explored in the model. We obtained the trend of these parameters tuning the Z-potential. These curves matched with the experimental results and confirmed the goodness of the model. Subsequently, we exploited the model to study the influence of nanoparticles aggregation and stability by Z-potential and external magnetic field. The highest Z-potential is reached up with a small external magnetic influence, a small aggregation and then a high suspension stability. Thus, we obtained a predictive model of Iron oxide nanoparticles flocculation that will be exploited for the nanoparticles engineering and experimental setup of bioassays.

Polarity determination of polar and semipolar (112¯2) InN and GaN layers by valence band photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Skuridina, D.; Dinh, D. V.; Lacroix, B.; Ruterana, P.; Hoffmann, M.; Sitar, Z.; Pristovsek, M.; Kneissl, M.; Vogt, P.

2013-11-01

We demonstrate that the polarity of polar (0001), (0001¯) and semipolar (112¯2) InN and GaN thin layers can be determined by valence band X-ray photoemission spectroscopy (XPS). The polarity of the layers has been confirmed by wet etching and convergent beam electron diffraction. Unlike these two techniques, XPS is a non-destructive method and unaffected by surface oxidation or roughness. Different intensities of the valence band states in spectra recorded by using AlKα X-ray radiation are observed for N-polar and group-III-polar layers. The highest intensity of the valence band state at ≈3.5 eV for InN and ≈5.2 eV for GaN correlates with the group-III polarity, while the highest intensity at ≈6.7 eV for InN and ≈9.5 eV for GaN correlates with the N-polarity. The difference between the peaks for the group-III- and N-polar orientations was found to be statistically significant at the 0.05 significance level. The polarity of semipolar (112¯2) InN and GaN layers can be determined by recording valence band photoelectrons emitted along the [000 ± 1] direction.

Graphene Oxide Membranes with Heterogeneous Nanodomains for Efficient CO2 Separations.

PubMed

Wang, Shaofei; Xie, Yu; He, Guangwei; Xin, Qingping; Zhang, Jinhui; Yang, Leixin; Li, Yifan; Wu, Hong; Zhang, Yuzhong; Guiver, Michael D; Jiang, Zhongyi

2017-11-06

Achieving high membrane performance in terms of gas permeance and carbon dioxide selectivity is an important target in carbon capture. Aiming to manipulate the channel affinity towards CO 2 to implement efficient separations, gas separation membranes containing CO 2 -philic and non-CO 2 -philic nanodomains in the interlayer channels of graphene oxide (GO) were formed by intercalating poly(ethylene glycol) diamines (PEGDA). PEGDA reacts with epoxy groups on the GO surface, constructing CO 2 -philic nanodomains and rendering a high sorption capacity, whereas unreacted GO surfaces give non-CO 2 -philic nanodomains, rendering low-friction diffusion. Owing to the orderly stacking of nanochannels through cross-linking and the heterogeneous nanodomains with moderate CO 2 affinity, a GO-PEGDA500 membrane exhibits a high CO 2 permeance of 175.5 GPU and a CO 2 /CH 4 selectivity of 69.5, which is the highest performance reported for dry-state GO-stacking membranes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reaching the Ionic Current Detection Limit in Silicon-Based Nanopores

NASA Astrophysics Data System (ADS)

Puster, Matthew; Rodriguez-Manzo, Julio Alejandro; Nicolai, Adrien; Meunier, Vincent; Drndic, Marija

2015-03-01

Solid-state nanopores act as single-molecule sensors whereby passage of an individual molecule in aqueous electrolyte through a nanopore is registered as a change in ionic conductance (ΔG). Future nanopore applications such as DNA sequencing at high bandwidth require high ΔG for optimal signal-to-noise ratio. Reducing the nanopore diameter and thickness increase ΔG. Molecule size limits the diameter, thus efforts concentrate on minimizing the thickness by thinning oxide/nitride films or using 2D materials. Weighted by electrolyte conductivity the highest ΔG reported to date for DNA translocations were obtained with nanopores made in oxide/nitride films. We present a controlled electron irradiation technique to thin such films to the limit of their stability, producing nanopores tailored to molecule size in amorphous Si with thicknesses less than 2 nm. We compare ΔG values with results found in the literature for DNA translocation through these nanopores, where access resistance becomes comparable to the resistance through the nanopore itself.

Integrated, Step-Wise, Mass-Isotopomeric Flux Analysis of the TCA Cycle.

PubMed

Alves, Tiago C; Pongratz, Rebecca L; Zhao, Xiaojian; Yarborough, Orlando; Sereda, Sam; Shirihai, Orian; Cline, Gary W; Mason, Graeme; Kibbey, Richard G

2015-11-03

Mass isotopomer multi-ordinate spectral analysis (MIMOSA) is a step-wise flux analysis platform to measure discrete glycolytic and mitochondrial metabolic rates. Importantly, direct citrate synthesis rates were obtained by deconvolving the mass spectra generated from [U-(13)C6]-D-glucose labeling for position-specific enrichments of mitochondrial acetyl-CoA, oxaloacetate, and citrate. Comprehensive steady-state and dynamic analyses of key metabolic rates (pyruvate dehydrogenase, β-oxidation, pyruvate carboxylase, isocitrate dehydrogenase, and PEP/pyruvate cycling) were calculated from the position-specific transfer of (13)C from sequential precursors to their products. Important limitations of previous techniques were identified. In INS-1 cells, citrate synthase rates correlated with both insulin secretion and oxygen consumption. Pyruvate carboxylase rates were substantially lower than previously reported but showed the highest fold change in response to glucose stimulation. In conclusion, MIMOSA measures key metabolic rates from the precursor/product position-specific transfer of (13)C-label between metabolites and has broad applicability to any glucose-oxidizing cell. Copyright © 2015 Elsevier Inc. All rights reserved.

Advanced smart tungsten alloys for a future fusion power plant

NASA Astrophysics Data System (ADS)

Litnovsky, A.; Wegener, T.; Klein, F.; Linsmeier, Ch; Rasinski, M.; Kreter, A.; Tan, X.; Schmitz, J.; Mao, Y.; Coenen, J. W.; Bram, M.; Gonzalez-Julian, J.

2017-06-01

The severe particle, radiation and neutron environment in a future fusion power plant requires the development of advanced plasma-facing materials. At the same time, the highest level of safety needs to be ensured. The so-called loss-of-coolant accident combined with air ingress in the vacuum vessel represents a severe safety challenge. In the absence of a coolant the temperature of the tungsten first wall may reach 1200 °C. At such a temperature, the neutron-activated radioactive tungsten forms volatile oxide which can be mobilized into atmosphere. Smart tungsten alloys are being developed to address this safety issue. Smart alloys should combine an acceptable plasma performance with the suppressed oxidation during an accident. New thin film tungsten-chromium-yttrium smart alloys feature an impressive 105 fold suppression of oxidation compared to that of pure tungsten at temperatures of up to 1000 °C. Oxidation behavior at temperatures up to 1200 °C, and reactivity of alloys in humid atmosphere along with a manufacturing of reactor-relevant bulk samples, impose an additional challenge in smart alloy development. First exposures of smart alloys in steady-state deuterium plasma were made. Smart tungsten-chroimium-titanium alloys demonstrated a sputtering resistance which is similar to that of pure tungsten. Expected preferential sputtering of alloying elements by plasma ions was confirmed experimentally. The subsequent isothermal oxidation of exposed samples did not reveal any influence of plasma exposure on the passivation of alloys.

High rate sodium ion battery anodes from block copolymer templated mesoporous nickel–cobalt carbonates and oxides

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

Bhaway, Sarang M.; Tangvijitsakul, Pattarasai; Lee, Jeongwoo

2015-09-16

Micelle-templated ordered mesoporous nickel–cobalt carbonates and oxides are fabricated using a metal nitrate–citric acid strategy, which avoids the hydrolysis and aging requirements associated with sol–gel chemistry. A series of mesoporous Ni xCo (3-x)(CO 3) y and Ni xCo (3-x)O 4 films with varying Ni–Co compositions and 14 ± 4 nm mesopores are fabricated with the same block copolymer template. AFM and GISAXS analysis indicates that the mesostructure is maintained through the formation of the carbonate and oxide, while GIXD profiles confirm formation of pure spinel phases of semi-crystalline Ni xCo (3-x)O 4. The micelle templated mesopores are interconnected and providemore » transport paths for the electrolyte to minimize the solid-state diffusion requirements associated with battery electrodes. These materials exhibit good performance as sodium ion battery anodes even at high current densities of 4 A g -1. Amongst the mixed-metal oxides, Ni 2CoO 4 exhibits the highest specific capacity of 239 mA h g -1 after galvanostatic cycling at a current density of 1 A g -1 for 10 cycles. We attribute the superior performance of Ni 2CoO 4 at high rates to the high surface area and short ion-diffusion paths of the nanoporous anode architecture, while the higher nickel content in the mixed metal oxide provides enhanced stability during oxide formation along with enhanced electronic conductivity, leading to improved cycling stability of the anode. This micelle template metal nitrate–citric acid method enables new possibilities for fabricating variety of ordered mesoporous mixed-metal carbonates and oxides that could be used in a wide range of applications.« less

Particulate matter (PM) episodes at a suburban site in Hong Kong: evolution of PM characteristics and role of photochemistry in secondary aerosol formation

NASA Astrophysics Data System (ADS)

Qin, Yi Ming; Jie Li, Yong; Wang, Hao; Lee, Berto Paul Yok Long; Huang, Dan Dan; Keung Chan, Chak

2016-11-01

Episodes with high concentrations of particulate matter (PM) across the seasons were investigated during four 1-month campaigns at a suburban site in Hong Kong. High-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) measurements revealed that both regional transport and secondary formation contributed to high PM levels during the episodes at this site. Based on distinct meteorological conditions, episodes were categorized into three types: liquid water content (LWC), solar irradiance (IR), and long-range transport (LRT). Despite the difference in meteorological conditions, all episodes were characterized by a high fraction of sulfate (45-56 %) and organics (23-34 %). However, aerosols in LWC episodes were less aged, consisting of the lowest fraction of secondary organic aerosol (SOA) and the highest fraction of small particles. Large particles mixed internally while freshly formed small particles mixed externally in LWC episodes. Aerosols in LRT episodes, by contrast, were the most aged and consisted of the highest proportion of low-volatility oxygenated organic aerosol (LVOOA) and the lowest proportion of small particles. Both small and large particles mixed externally in LRT episodes. The highest proportion of semi-volatile oxygenated organic aerosol (SVOOA) and a medium proportion of small particles were observed in IR episodes. Both small and large particles were likely externally mixed during IR episodes. Furthermore, aerosols experienced the most dramatic size increase and diurnal variation, with a time lag between SVOOA and LVOOA and a gradual increase in carbon oxidation state (OSc ≈ 2 × O : C - H : C). Five out of 10 episodes were of the IR type, further reflecting the importance of this type of episode. The evolution of aerosol components in one particular episode of the IR type, which exhibited a clear land-sea breeze pattern, was examined in detail. Sulfate and SOA due to photochemical aging were very efficiently produced during the course of 6 h. The "less-oxidized" SOA (SVOOA) was initially formed at a higher rate than the "more-oxidized" SOA (LVOOA). The SVOOA transformed to LVOOA at the later stage of photochemical aging. This transformation was further supported by mass spectral analysis, which showed an increase in the most oxidized ion (CO2+) and decreases in moderately oxidized ones (C2H3O+, C3H3O+ and C3H5O+). By measuring the physical and chemical properties of PM in a highly time-resolved manner, the current study was able to demonstrate the dynamic and complex nature of PM transformation during high-PM episodes.

Nitrous oxide flux under changing temperature and CO2

EPA Science Inventory

We are investigating nitrous oxide flux seasonal trends and response to temperature and CO2 increases in a boreal peatland. Peatlands located in boreal regions make up a third of global wetland area and are expected to have the highest temperature increases in response to climat...

Chlorpyrifos-induced oxidative damage is reduced under warming and predation risk: Explaining antagonistic interactions with a pesticide.

PubMed

Janssens, Lizanne; Stoks, Robby

2017-07-01

Interactions with pollutants and environmental factors are poorly studied for physiological traits. Yet physiological traits are important for explaining and predicting interactions at higher levels of organization. We investigated the single and combined impact of the pesticide chlorpyrifos, predation risk and warming on endpoints related to oxidative stress in the damselfly Enallagma cyathigerum. We thereby integrated information on reactive oxygen species (ROS), antioxidant enzymes and oxidative damage. All three treatments impacted the oxidative stress levels and for most traits the pesticide interacted antagonistically with warming or predation risk. Chlorpyrifos exposure resulted in increased ROS levels, decreased antioxidant defence and increased oxidative damage compared to the control situation. Under warming, the pesticide-induced increase in oxidative stress was less strong and the investment in antioxidant defence higher. Although both the pesticide and predation risk increased oxidative damage, the effects of the pesticide on oxidative damage were less strong in the presence of predator cues (at 20 °C). Despite the weaker pesticide-induced effects under predation risk, the combination of the pesticide and predator cues consistently caused the highest ROS levels, the lowest antioxidant defence and the highest oxidative damage, indicating the importance of cumulative stressor effects for impairing fitness. Our results provide the first evidence for antagonistic interactions of warming and predation risk with a pollutant for physiological traits. We identified two general mechanisms that may generate antagonistic interactions for oxidative stress: cross-tolerance and the maximum cumulative levels of damage. Copyright © 2017 Elsevier Ltd. All rights reserved.

Depth distribution of microbial production and oxidation of methane in northern boreal peatlands.

PubMed

Sundh, I; Nilsson, M; Granberg, G; Svensson, B H

1994-05-01

The depth distributions of anaerobic microbial methane production and potential aerobic microbial methane oxidation were assessed at several sites in both Sphagnum- and sedge-dominated boreal peatlands in Sweden, and compared with net methane emissions from the same sites. Production and oxidation of methane were measured in peat slurries, and emissions were measured with the closed-chamber technique. Over all eleven sites sampled, production was, on average, highest 12 cm below the depth of the average water table. On the other hand, highest potential oxidation of methane coincided with the depth of the average water table. The integrated production rate in the 0-60 cm interval ranged between 0.05 and 1.7 g CH4 m (-2) day(-) and was negatively correlated with the depth of the average water table (linear regression: r (2) = 0.50, P = 0.015). The depth-integrated potential CH4-oxidation rate ranged between 3.0 and 22.1 g CH4 m(-2) day(-1) and was unrelated to the depth of the average water table. A larger fraction of the methane was oxidized at sites with low average water tables; hence, our results show that low net emission rates in these environments are caused not only by lower methane production rates, but also by conditions more favorable for the development of CH4-oxidizing bacteria in these environments.

Oil-structuring characterization of natural waxes in canola oil oleogels: Rheological, thermal, and oxidative properties

USDA-ARS?s Scientific Manuscript database

Natural waxes (candelilla wax, carnauba wax, and beeswax) were utilized as canola oil structurants to produce oleogels and their physicochemical properties were evaluated from rheological, thermal, and oxidative points of view. The oleogels with candelilla wax exhibited the highest hardness, followe...

The Role of Work Function and Band Gap in Resistive Switching Behaviour of ZnTe Thin Films

NASA Astrophysics Data System (ADS)

Rowtu, Srinu; Sangani, L. D. Varma; Krishna, M. Ghanashyam

2018-02-01

Resistive switching behavior by engineering the electrode work function and band gap of ZnTe thin films is demonstrated. The device structures Au/ZnTe/Au, Au/ZnTe/Ag, Al/ZnTe/Ag and Pt/ZnTe/Ag were fabricated. ZnTe was deposited by thermal evaporation and the stoichiometry and band gap were controlled by varying the source-substrate distance. Band gap could be varied between 1.0 eV to approximately 4.0 eV with the larger band gap being attributed to the partial oxidation of ZnTe. The transport characteristics reveal that the low-resistance state is ohmic in nature which makes a transition to Poole-Frenkel defect-mediated conductivity in the high-resistance states. The highest R off-to- R on ratio achieved is 109. Interestingly, depending on stoichiometry, both unipolar and bipolar switching can be realized.

Graphene saturable absorber mirror for ultra-fast-pulse solid-state laser.

PubMed

Xu, Jin-Long; Li, Xian-Lei; Wu, Yong-Zhong; Hao, Xiao-Peng; He, Jing-Liang; Yang, Ke-Jian

2011-05-15

High-quality graphene sheets with lateral size over 20 μm have been obtained by bath sonicating after subjecting the wormlike graphite marginally to mixed oxidizer. To date, to our knowledge, they are the largest graphene sheets prepared by exfoliation in the liquid phase. A saturable absorber mirror was fabricated based on these sheets. We exploited it to realize mode-locking operation in a diode-pumped Nd:GdVO(4) laser. A pulse duration of 16 ps was produced with an average power of 360 mW and a highest pulse energy of 8.4 nJ for a graphene mode-locked laser. © 2011 Optical Society of America

Reduction in the Band Gap of Manganese-Doped Zinc Oxide: Role of the Oxidation State

NASA Astrophysics Data System (ADS)

Sharma, Sonia; Ramesh, Pranith; Swaminathan, P.

2015-12-01

Manganese-doped zinc oxide powders were synthesized by solid state reaction of the respective oxides. The high-temperature conditions were chosen such that multiple valence states of manganese were doped in the host zinc oxide lattice. Structural characterization was carried out to confirm the doping and to find the maximum amount of manganese that can be incorporated. Diffuse reflectance spectroscopy was used to measure the optical band gap of the doped sample and the lowering with respect to pure ZnO was attributed to the presence of higher oxidation states of manganese. The presence of these oxidation states was confirmed using x-ray photoelectron spectroscopy. The study shows that a solid state reaction is a viable route for synthesizing doped metal oxides with desired optical properties.

Assessing genetic structure, diversity of bacterial aerosol from aeration system in an oxidation ditch wastewater treatment plant by culture methods and bio-molecular tools.

PubMed

Li, Lin; Han, Yunping; Liu, Junxin

2013-01-01

Airborne bacteria emissions from oxidation ditch with rotating aeration brushes were investigated in a municipal wastewater treatment plant in Beijing, China. Microbial samples were collected at different distances from the rotating brushes, different heights above the water surface, and different operation state over a 3-month period (April, May, and June) in order to estimate the seasonal variation and site-related distribution characteristics of the microorganisms present. The concentration of bacterial aerosol was analyzed by culture methods, while their dominant species, genetic structure and diversity were assayed using bio-molecular tools. Results showed that total microbial concentrations were highest in June and lowest in April. The mechanical rotation caused remarkable variation in concentration and diversity of culturable airborne bacteria before and after the rotating brushes. The highest concentration was observed near the rotating brushes (931 ± 129-3,952 ± 730 CFU/m(3)), with concentration decreasing as distance and height increased. Bacterial community polymerase chain reaction and denaturing gradient gel electrophoresis indicated that diversity decreased gradually with increasing height above the water surface but remained relatively constant at the same height. All dominant bacteria identified by DNA sequence analysis belonged to Firmicutes. Pathogenic species such as Moraxella nonliquefaciens and Flavobacterium odoratum were isolated from the bioaerosols. Due to the serious health risks involved, exposure of sewage workers to airborne microorganisms caused by brush aerators should be monitored and controlled.

High-performance flexible supercapacitors based on electrochemically tailored three-dimensional reduced graphene oxide networks.

PubMed

Purkait, Taniya; Singh, Guneet; Kumar, Dinesh; Singh, Mandeep; Dey, Ramendra Sundar

2018-01-12

A simple approach for growing porous electrochemically reduced graphene oxide (pErGO) networks on copper wire, modified with galvanostatically deposited copper foam is demonstrated. The as-prepared pErGO networks on the copper wire are directly used to fabricate solid-state supercapacitor. The pErGO-based supercapacitor can deliver a specific capacitance (C sp ) as high as 81±3 F g -1 at 0.5 A g -1 with polyvinyl alcohol/H 3 PO 4 gel electrolyte. The C sp per unit length and area are calculated as 40.5 mF cm -1 and 283.5 mF cm -2 , respectively. The shape of the voltammogram retained up to high scan rate of 100 V s -1 . The pErGO-based supercapacitor device exhibits noticeably high charge-discharge cycling stability, with 94.5% C sp retained even after 5000 cycles at 5 A g -1 . Nominal change in the specific capacitance, as well as the shape of the voltammogram, is observed at different bending angles of the device even after 5000 cycles. The highest energy density of 11.25 W h kg -1 and the highest power density of 5 kW kg -1 are also achieved with this device. The wire-based supercapacitor is scalable and highly flexible, which can be assembled with/without a flexible substrate in different geometries and bending angles for illustrating promising use in smart textile and wearable device.

Diurnal patterns of methane flux from a seasonal wetland: mechanisms and methodology

USGS Publications Warehouse

Bansal, Sheel; Tangen, Brian; Finocchiaro, Raymond

2018-01-01

Methane emissions from wetlands are temporally dynamic. Few chamber-based studies have explored diurnal variation in methane flux with high temporal replication. Using an automated sampling system, we measured methane flux every 2.5 to 4 h for 205 diel cycles during three growing seasons (2013–2015) from a seasonal wetland in the Prairie Pothole Region of North America. During ponded conditions, fluxes were generally positive (i.e., methanogenesis dominant, 10.1 ± 0.8 mg m−2 h−1), had extreme range of variation (from −1 to 70 mg m−2 h−1), and were highest during late day. In contrast, during dry conditions fluxes were very low and primarily negative (i.e., oxidation dominant, −0.05 ± 0.002 mg m−2 h−1), with the highest (least negative) fluxes occurring at pre-dawn. During semi-saturated conditions, methane fluxes also were very low, oscillated between positive and negative values (i.e., balanced between methanogenesis and methane oxidation), and exhibited no diel pattern. Methane flux was positively correlated with air temperature during ponded conditions (r = 0.57) and negatively during dry conditions (r = −0.42). Multiple regression analyses showed that temperature, light and water-filled pore space explained 72% of variation in methane flux. Methane fluxes are highly temporally dynamic and follow contrasting diel patterns that are dependent on dominant microbial processes influenced by saturation state.

In vitro potential cytogenetic and oxidative stress effects of roxithromycin.

PubMed

Arslan, Mehmet; Timocin, Taygun; Ila, Hasan B

2017-10-01

Macrolide antibiotic roxithromycin was evaluated in terms of its genotoxic, cytotoxic and oxidative stress effects. For this purpose; 25, 50, 100 and 200 μg/mL concentrations of roxithromycin were dissolved in dimethyl sulfoxide and treated to human peripheral blood lymphocytes for two different treatment periods (24 and 48 h). In chromosome aberration (CA) and micronucleus (MN) tests, roxithromycin did not show genotoxic effect. But it induced sister chromatid exchange (SCE) at the highest concentration (200 μg/mL) for the 24-h treatment period and at all concentrations (except 25 μg/mL) for the 48-h treatment period. Looking at cytotoxic effect of roxithromycin, statistically insignificant decreases on mitotic index and proliferation index were observed. Roxithromycin decreased nuclear division index (NDI) at highest two concentrations (100 and 200 μg/mL) for the 24-h treatment period and at all concentrations (expect 25 μg/mL) for the 48-h treatment period. Total oxidant values, total antioxidant values and oxidative stress index did not change with roxithromycin treatment. Eventually, roxithromycin did not have genotoxic and oxidative stress effects in human-cultured lymphocytes.

Designed catalysts from Pt nanoparticles supported on macroporous oxides for selective isomerization of n-hexane.

PubMed

An, Kwangjin; Alayoglu, Selim; Musselwhite, Nathan; Na, Kyungsu; Somorjai, Gabor A

2014-05-14

Selective isomerization toward branched hydrocarbons is an important catalytic process in oil refining to obtain high-octane gasoline with minimal content of aromatic compounds. Colloidal Pt nanoparticles with controlled sizes of 1.7, 2.7, and 5.5 nm were deposited onto ordered macroporous oxides of SiO2, Al2O3, TiO2, Nb2O5, Ta2O5, and ZrO2 to investigate Pt size- and support-dependent catalytic selectivity in n-hexane isomerization. Among the macroporous oxides, Nb2O5 and Ta2O5 exhibited the highest product selectivity, yielding predominantly branched C6 isomers, including 2- or 3-methylpentane, as desired products of n-hexane isomerization (140 Torr n-hexane and 620 Torr H2 at 360 °C). In situ characterizations including X-ray diffraction and ambient-pressure X-ray photoelectron spectroscopy showed that the crystal structures of the oxides in Pt/oxide catalysts were not changed during the reaction and oxidation states of Nb2O5 were maintained under both H2 and O2 conditions. Fourier transform infrared spectra of pyridine adsorbed on the oxides showed that Lewis sites were the dominant acidic site of the oxides. Macroporous Nb2O5 and Ta2O5 were identified to play key roles in the selective isomerization by charge transfer at Pt-oxide interfaces. The selectivity was revealed to be Pt size-dependent, with improved isomer production as Pt sizes increased from 1.7 to 5.5 nm. When 5.5 nm Pt nanoparticles were supported on Nb2O5 or Ta2O5, the selectivity toward branched C6 isomers was further increased, reaching ca. 97% with a minimum content of benzene, due to the combined effects of the Pt size and the strong metal-support interaction.

Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

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

Jernigan, Glenn Geoffrey

1994-10-01

Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu 2O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu 2O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/molmore » < Cu 2O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N 2 and CO 2. At the end of each reaction, the catalyst was found to be Cu 2O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.« less

A toxicological study of inhalable particulates in an industrial region of Lanzhou City, northwestern China: Results from plasmid scission assay

NASA Astrophysics Data System (ADS)

Xiao, Zhenghui; Shao, Longyi; Zhang, Ning; Wang, Jing; Chuang, Hsiao-Chi; Deng, Zhenzhen; Wang, Zhen; BéruBé, Kelly

2014-09-01

The city of Lanzhou in northwestern China experiences serious air pollution episodes in the form of PM10 that is characterized by having high levels of heavy metals. The Xigu District represents the industrial core area of Lanzhou City and is denoted by having the largest petrochemical bases in western China. This study investigates heavy metal compositions and oxidative potential of airborne PM10 (particulate matter with aerodynamic diameter of 10 μm or less) collected in Xigu District in the summer and winter of 2010. An in vitro plasmid scission assay (PSA) was employed to study the oxidative potential of airborne PM10 and inductively coupled plasma-mass spectrometry (ICP-MS) was used to examine heavy metal compositions. Transmission electron microscopy coupled with energy-dispersive X-ray spectrometry (TEM/EDX) was used to investigate elemental compositions and mixing states of PM10. The average mass concentrations of PM10 collected in Xigu District were generally higher than the national standard for daily PM10 (150 μg/m3). Cr, Zn, Pb and Mn were the most abundant metals in the intact whole particles of PM10. Zn, Mn and As was the most abundant metal in the water-soluble fraction, while Cr, Pb, and V existed primarily in insoluble forms. TD20 values (i.e. toxic dosage of PM10 causing 20% of plasmid DNA damage) varied considerably in both winter and summer (from 19 μg/mL to >1000 μg/mL) but were typically higher in summer, suggesting that the winter PM10 exhibited greater bioreactivity. In addition, the PM10 collected during a dust storm episode had a highest TD20 value and thus the least oxidative damage to supercoiled plasmid DNA, while the particles collected on a hazy day had a lowest TD20 value and thus the highest oxidative damage to supercoiled plasmid DNA. The particles collected on the first day after snow fall and on a day of cold air intrusion exhibited minor oxidative potential (i.e. caused limited DNA damage). The water-soluble Zn, Mn, As, and Cu displayed a significant negative correlation with TD20 values, suggesting that these heavy metals were responsible for the increase of oxidative potential. The high mass concentration of PM10 and resulting high oxidative potential in Xigu District may be due to the constant low wind speed and high relative humidity, particularly in winter. Finally, TEM analysis suggested that the oxidative potential of PM10 may be associated with its degree of internal mixing, whereby the heterogeneous assortment of soot, mineral and metals created a highly reactive moiety.

High-resolution crystal structures of the photoreceptor glyceraldehyde 3-phosphate dehydrogenase (GAPDH) with three and four-bound NAD molecules

PubMed Central

Baker, Bo Y; Shi, Wuxian; Wang, Benlian; Palczewski, Krzysztof

2014-01-01

Glyceraldehyde-3-phosphate dehydrogenase (GAPDH) catalyzes the oxidative phosphorylation of d-glyceraldehyde 3-phosphate (G3P) into 1,3-diphosphoglycerate (BGP) in the presence of the NAD cofactor. GAPDH is an important drug target because of its central role in glycolysis, and nonglycolytic processes such as nuclear RNA transport, DNA replication/repair, membrane fusion and cellular apoptosis. Recent studies found that GAPDH participates in the development of diabetic retinopathy and its progression after the cessation of hyperglycemia. Here, we report two structures for native bovine photoreceptor GAPDH as a homotetramer with differing occupancy by NAD, bGAPDH(NAD)4, and bGAPDH(NAD)3. The bGAPDH(NAD)4 was solved at 1.52 Å, the highest resolution for GAPDH. Structural comparison of the bGAPDH(NAD)4 and bGAPDH(NAD)3 models revealed novel details of conformational changes induced by cofactor binding, including a loop region (residues 54–56). Structure analysis of bGAPDH confirmed the importance of Phe34 in NAD binding, and demonstrated that Phe34 was stabilized in the presence of NAD but displayed greater mobility in its absence. The oxidative state of the active site Cys149 residue is regulated by NAD binding, because this residue was found oxidized in the absence of dinucleotide. The distance between Cys149 and His176 decreased upon NAD binding and Cys149 remained in a reduced state when NAD was bound. These findings provide an important structural step for understanding the mechanism of GAPDH activity in vision and its pathological role in retinopathies. PMID:25176140

Changes in Non-Enzymatic Antioxidants in the Blood Following Anaerobic Exercise in Men and Women

PubMed Central

Wiecek, Magdalena; Kantorowicz, Malgorzata

2015-01-01

Purpose The aim of this study was to compare changes in total oxidative status (TOS), total antioxidative capacity (TAC) and the concentration of VitA, VitE, VitC, uric acid (UA), reduced (GSH) and oxidized glutathione (GSSG) in blood within 24 hours following anaerobic exercise (AnEx) among men and women. Methods 10 women and 10 men performed a 20-second bicycle sprint (AnEx). Concentrations of oxidative stress indicators were measured before AnEx and 3, 15 and 30 minutes and 1 hour afterwards. UA, GSH and GSSH were also measured 24 hours after AnEx. Lactate and H+ concentrations were measured before and 3 minutes after AnEx. Results The increase in lactate and H+ concentrations following AnEx was similar in both sexes. Changes in the concentrations of all oxidative stress indicators were significant and did not differ between men and women. In both sexes, TOS, TAC, TOS/TAC and VitA and VitE concentrations were the highest 3 minutes, VitC concentration was the highest 30 minutes, and UA concentration was the highest 1 hour after AnEx. GSH concentration was significantly lower than the initial concentration from 15 minutes to 24 hour after AnEx. GSSG concentration was significantly higher, while the GSH/GSSG ratio was significantly lower than the initial values 1 hour and 24 hour after AnEx. Conclusions With similar changes in lactate and H+ concentrations, AnEx induces the same changes in TAC, TOS, TOS/TAC and non-enzymatic antioxidants of low molecular weight in men and women. Oxidative stress lasted at least 24 hours after AnEx. PMID:26600020

Changes in Non-Enzymatic Antioxidants in the Blood Following Anaerobic Exercise in Men and Women.

PubMed

Wiecek, Magdalena; Maciejczyk, Marcin; Szymura, Jadwiga; Szygula, Zbigniew; Kantorowicz, Malgorzata

2015-01-01

The aim of this study was to compare changes in total oxidative status (TOS), total antioxidative capacity (TAC) and the concentration of VitA, VitE, VitC, uric acid (UA), reduced (GSH) and oxidized glutathione (GSSG) in blood within 24 hours following anaerobic exercise (AnEx) among men and women. 10 women and 10 men performed a 20-second bicycle sprint (AnEx). Concentrations of oxidative stress indicators were measured before AnEx and 3, 15 and 30 minutes and 1 hour afterwards. UA, GSH and GSSH were also measured 24 hours after AnEx. Lactate and H+ concentrations were measured before and 3 minutes after AnEx. The increase in lactate and H+ concentrations following AnEx was similar in both sexes. Changes in the concentrations of all oxidative stress indicators were significant and did not differ between men and women. In both sexes, TOS, TAC, TOS/TAC and VitA and VitE concentrations were the highest 3 minutes, VitC concentration was the highest 30 minutes, and UA concentration was the highest 1 hour after AnEx. GSH concentration was significantly lower than the initial concentration from 15 minutes to 24 hour after AnEx. GSSG concentration was significantly higher, while the GSH/GSSG ratio was significantly lower than the initial values 1 hour and 24 hour after AnEx. With similar changes in lactate and H+ concentrations, AnEx induces the same changes in TAC, TOS, TOS/TAC and non-enzymatic antioxidants of low molecular weight in men and women. Oxidative stress lasted at least 24 hours after AnEx.

Combining Bayesian methods and aircraft observations to constrain the HO. + NO2 reaction rate

EPA Science Inventory

Tropospheric ozone is the third strongest greenhouse gas, and has the highest uncertainty in radiative forcing of the top five greenhouse gases. Throughout the troposphere, ozone is produced by radical oxidation of nitrogen oxides (NO,_x =NO+NO₂). In the uppe...

[Effect of temperature on the rate of oxidation of pyrrhotite-rich sulfide ore flotation concentrate and the structure of the acidophilic chemolithoautotrophic microbial community].

PubMed

Moshchanetskii, P V; Pivovarova, T A; Belyi, A V; Kondrat'eva, T F

2014-01-01

Oxidation of flotation concentrate of a pyrrhotite-rich sulfide ore by acidophilic chemolithoautotrophic microbial communities at 35, 40, and 45 degrees C was investigated. According to the physicochemical parameters of the liquid phase of the pulp, as well as the results of analysis of the solid residue after biooxidation and cyanidation, the community developed at 40 degrees C exhibited the highest rate of oxidation. The degree of gold recovery at 35, 40, and 45 degrees C was 89.34, 94.59, and 83.25%, respectively. At 40 degrees C, the highest number of microbial cells (6.01 x 10(9) cells/mL) was observed. While temperature had very little effect on the species composition of microbial communities, except for the absence of Leptospirillum ferriphilum at 35 degrees C, the shares of individual species in the communities varied with temperature. Relatively high numbers of Sulfobacillus thermosulfidooxidans, the organism oxidizing iron and elemental sulfur at higher rates than other acidophilic chemolithotrophic species, were observed at 40 degrees C.

Arsenic release from Fe/Mn oxide-rich (model) soils/sediments - A comparison of single extraction procedures

NASA Astrophysics Data System (ADS)

Vanek, A.; Komarek, M.; Galuskova, I.

2012-04-01

Arsenic extractability in As-modified Fe(III) and Mn(III,IV) oxide-coated sands was tested using five widely used 2-h single extraction procedures: deionised water, 0.01 M CaCl2, 1 M NH4NO3, 0.1 M Na2HPO4 and 0.005 DTPA. In general, the highest As recoveries reaching 39-50% of total As concentration were observed for all extracting media in the birnessite (delta-MnO2) system, indicating relatively weak adsorption of As onto the Mn oxides. The Na2HPO4 extracts from the Fe oxide systems (i.e., associated with ferrihydrite and goethite) were highest in As, accounting for up to 34% of total As amount. Surprisingly, comparable recoveries of As (14-20%) yielded deionised water, CaCl2, NH4NO3, DTPA as extracting media for both ferrihydrite and goethite coatings. Deionised water and Na2HPO4 extractions are suggested for quick estimation of easily soluble, exchangeable and/or specifically adsorbed As in real soil/sediment samples.

Ozone response to emission reductions in the southeastern United States

NASA Astrophysics Data System (ADS)

Blanchard, Charles L.; Hidy, George M.

2018-06-01

Ozone (O3) formation in the southeastern US is studied in relation to nitrogen oxide (NOx) emissions using long-term (1990s-2015) surface measurements of the Southeastern Aerosol Research and Characterization (SEARCH) network, U.S. Environmental Protection Agency (EPA) O3 measurements, and EPA Clean Air Status and Trends Network (CASTNET) nitrate deposition data. Annual fourth-highest daily peak 8 h O3 mixing ratios at EPA monitoring sites in Georgia, Alabama, and Mississippi exhibit statistically significant (p < 0.0001) linear correlations with annual NOx emissions in those states between 1996 and 2015. The annual fourth-highest daily peak 8 h O3 mixing ratios declined toward values of ˜ 45-50 ppbv and monthly O3 maxima decreased at rates averaging ˜ 1-1.5 ppbv yr-1. Mean annual total oxidized nitrogen (NOy) mixing ratios at SEARCH sites declined in proportion to NOx emission reductions. CASTNET data show declining wet and dry nitrate deposition since the late 1990s, with total (wet plus dry) nitrate deposition fluxes decreasing linearly in proportion to reductions of NOx emissions by ˜ 60 % in Alabama and Georgia. Annual nitrate deposition rates at Georgia and Alabama CASTNET sites correspond to 30 % of Georgia emission rates and 36 % of Alabama emission rates, respectively. The fraction of NOx emissions lost to deposition has not changed. SEARCH and CASTNET sites exhibit downward trends in mean annual nitric acid (HNO3) concentrations. Observed relationships of O3 to NOz (NOy-NOx) support past model predictions of increases in cycling of NO and increasing responsiveness of O3 to NOx. The study data provide a long-term record that can be used to examine the accuracy of process relationships embedded in modeling efforts. Quantifying observed O3 trends and relating them to reductions in ambient NOy species concentrations offers key insights into processes of general relevance to air quality management and provides important information supporting strategies for reducing O3 mixing ratios.

Using X-ray absorption to probe sulfur oxidation states in complex molecules

NASA Astrophysics Data System (ADS)

Vairavamurthy, A.

1998-10-01

X-ray absorption near-edge structure (XANES) spectroscopy offers an important non-destructive tool for determining oxidation states and for characterizing chemical speciation. The technique was used to experimentally verify the oxidation states of sulfur in different types of complex molecules because there are irregularities and uncertainties in assigning the values traditionally. The usual practice of determining oxidation states involves using a set of conventional rules. The oxidation state is an important control in the chemical speciation of sulfur, ranging from -2 to +6 in its different compounds. Experimental oxidation-state values for various types of sulfur compounds, using their XANES peak-energy positions, were assigned from a scale in which elemental sulfur and sulfate are designated as 0 and +6, respectively. Because these XANES-based values differed considerably from conventionally determined oxidation states for most sulfur compounds, a new term 'oxidation index' was coined to describe them. The experimental values were closer to those conventional values obtained by assigning shared electrons to the more electronegative atoms than to those based on other customary rules for assigning them. Because the oxidation index is distinct and characteristic for each different type of sulfur functionality, it becomes an important parameter for characterizing sulfur species, and for experimentally verifying uncertain oxidation states.

Surface chemistry and catalytic properties of VOX/Ti-MCM-41 catalysts for dibenzothiophene oxidation in a biphasic system

NASA Astrophysics Data System (ADS)

González, J.; Chen, L. F.; Wang, J. A.; Manríquez, Ma.; Limas, R.; Schachat, P.; Navarrete, J.; Contreras, J. L.

2016-08-01

A series of vanadium oxide supported on Ti-MCM-41 catalysts was synthesized via the incipient impregnation method by varying the vanadia loading from 5 wt% to 10, 15, 20 and 25 wt%. These catalysts were characterized by a variety of advanced techniques for investigating their crystalline structure, textural properties, and surface chemistry information including surface acidity, reducibility, vanadium oxidation states, and morphological features. The catalytic activities of the catalysts were evaluated in a biphasic reaction system for oxidative desulfurization (ODS) of a model diesel containing 300 ppm of dibenzothiophene (DBT) where acetonitrile was used as extraction solvent and H2O2 as oxidant. ODS activity was found to be proportional to the V5+/(V4+ + V5+) values of the catalysts, indicating that the surface vanadium pentoxide (V2O5) was the active phase. Reaction temperature would influence significantly the ODS efficiency; high temperature, i.e., 80 °C, would lead to low ODS reaction due to the partial decomposition of oxidant. All the catalysts contained both Lewis and Brønsted acid sites but the former was predominant. The catalysts with low vanadia loading (5 or 10 wt%V2O5) had many Lewis acid sites and could strongly adsorb DBT molecule via the electron donation/acceptance action which resulted in an inhibition for the reaction of DBT with the surface peroxometallic species. The catalyst with high vanadia loading (25wt%V2O5/Ti-MCM-41) showed the highest catalytic activity and could remove 99.9% of DBT at 60 °C within 60 min.

Efficiency of bimetallic PtPd on polydopamine modified on various carbon supports for alcohol oxidations

NASA Astrophysics Data System (ADS)

Pinithchaisakula, A.; Ounnunkad, K.; Themsirimongkon, S.; Promsawan, N.; Waenkaew, P.; Saipanya, S.

2017-02-01

In this work, the preparation, characterization, and electrocatalytic analysis of the catalysts on various carbon substrates for direct alcohol fuel cells were studied. Selected carbons were modified with/without polydopamine (labelled as PDA-C and C) and further metal electrodeposited incorporated onto the glassy carbon (labelled as 5Pt1Pd/PDA-C and 5Pt1Pd/C). Four various carbon materials were used e.g. graphite (G), carbon nanotube (CNT), graphene (GP) and graphene oxide (GO) and the carbons were modified with PDA denoted as PDA-G, PDA-CNT, PDA-GP and PDA-GO, respectively. The transmission electron microscopy (TEM) and scanning electron microscopy (SEM) experimental observation showed narrow size distribution of metal anchored on the PDA-C and C materials. Chemical compositions and oxidation states of the catalysts were determined by X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX). The catalytic performances for small organic electro-oxidation (e.g. methanol and ethanol) were measured by cyclic voltammetry (CV). Among different PDA-C and C catalysts, monometallic Pt showed less activity than the bimetallic catalysts. Among catalysts with PDA, the 5Pt1Pd/PDA-GO catalyst facilitated methanol and ethanol oxidations with high oxidation currents and If/Ib value and stability with low potentials while among catalysts without PDA, the 5Pt1Pd/CNT provides highest activity and stability. It was found that the catalysts with PDA provided high activity and stability than the catalysts without PDA. The improved catalytic performance of the prepared catalysts could be related to the higher active surface area from polymer modification and bimetallic catalyst system in the catalyst composites.

Survival and Recovery of Methanotrophic Bacteria Starved Under Oxic and Anoxic Conditions

NASA Technical Reports Server (NTRS)

Roslev, Peter; King, Gary M.

1994-01-01

The effects of carbon deprivation on survival of methanotrophic bacteria were compared in cultures incubated in the presence and absence of oxygen in the starvation medium. Survival and recovery of the examined methanotrophs were generally highest for cultures starved under anoxic conditions as indicated by poststarvation measurements of methane oxidation, tetrazolium salt reduction, plate counts, and protein synthesis. Methylosinus trichosporium OB3b survived up to 6 weeks of carbon deprivation under anoxic conditions while maintaining a physiological state that allowed relatively rapid (hours) methane oxidation after substrate addition. A small fraction of cells starved under oxic and anoxic conditions (4 and 10%, respectively) survived more than 10 weeks but required several days for recovery on plates and in liquid medium. A non-spore-forming methanotroph, strain WP 12, displayed 36 to 118% of its initial methane oxidation capacity after 5 days of carbon deprivation. Oxidation rates varied with growth history prior to the experiments as well as with starvation conditions. Strain WP 12 starved under anoxic conditions showed up to 90% higher methane oxidation activity and 46% higher protein production after starvation than did cultures starved under oxic conditions. Only minor changes in biomass and niorpholow were seen for methanotrophic bacteria starved tinder anoxic conditions. In contrast, starvation under oxic conditions resulted in morphology changes and an initial 28 to 35% loss of cell protein. These data suggest that methanotrophic bacteria can survin,e carbon deprivation under anoxic conditions by using maintenance energy derived Solelyr from an anaerobic endogenous metabolism. This capability could partly explain a significant potential for methane oxidation in environments not continuously, supporting aerobic methanotrophic growth.

Technology of GaAs metal-oxide-semiconductor solar cells

NASA Technical Reports Server (NTRS)

Stirn, R. J.; Yeh, Y. C. M.

1977-01-01

The growth of an oxide interfacial layer was recently found to increase the open-circuit voltage (OCV) and efficiency by up to 60 per cent in GaAs metal-semiconductor solar cells. Details of oxidation techniques to provide the necessary oxide thickness and chemical structure and using ozone, water-vapor-saturated oxygen, or oxygen gas discharges are described, as well as apparent crystallographic orientation effects. Preliminary results of the oxide chemistry obtained from X-ray, photoelectron spectroscopy are given. Ratios of arsenic oxide to gallium oxide of unity or less seem to be preferable. Samples with the highest OVC predominantly have As(+3) in the arsenic oxide rather than As(+5). A major difficulty at this time is a reduction in OCV by 100-200 mV when the antireflection coating is vacuum deposited.

Polymer/graphite oxide composites as high-performance materials for electric double layer capacitors

NASA Astrophysics Data System (ADS)

Tien, Chien-Pin; Teng, Hsisheng

A single graphene sheet represents a carbon material with the highest surface area available to accommodating molecules or ions for physical and chemical interactions. Here we demonstrate in an electric double layer capacitor the outstanding performance of graphite oxide for providing a platform for double layer formation. Graphite oxide is generally the intermediate compound for obtaining separated graphene sheets. Instead of reduction with hydrazine, we incorporate graphite oxide with a poly(ethylene oxide)-based polymer and anchor the graphene oxide sheets with poly(propylene oxide) diamines. This polymer/graphite oxide composite shows in a "dry" gel-electrolyte system a double layer capacitance as high as 130 F g -1. The polymer incorporation developed here can significantly diversify the application of graphene-based materials in energy storage devices.

Characterization of a transient +2 sulfur oxidation state intermediate from the oxidation of aqueous sulfide

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

Vairavmurthy, M.A.; Zhou, Weiqing

1995-04-01

The oxidation H{sub 2}S to sulfate involves a net transfer of eight electrons and occurs through the formation of several partially oxidized intermediates with oxidation states ranging from {minus}1 to +5. Known intermediates include elemental sulfur (oxidation state 0), polysulfides (outer sulfur: {minus}1, inner sulfur: 0), sulfite (+4) and thiosulfate (outer sulfur: {minus}1, inner sulfur: +5). A noticeable gap in this series of intermediates is that of a +2 sulfur oxidation state oxoacid/oxoanion species, which was never detected experimentally. Here, we present evidence of the transient existence of +2 oxidation state intermediate in the Ni(II)-catalyzed oxidation of aqueous sulfide. X-raymore » absorption near-edge structure (XANES) spectroscopy and Fourier-transform-infrared (FT-IR) spectroscopy were used to characterize this species; they suggest that it has a sulfoxylate ion (SO{sub 2}{sup 2{minus}}) structure.« less

Production of Oxygen from Lunar Regolith by Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Curreri, Peter A.

2009-01-01

This paper describes the use of the molten oxide electrolysis (MOE) process for the extraction of oxygen for life support and propellant, and silicon and metallic elements for use in fabrication on the Moon. The Moon is rich in mineral resources, but it is almost devoid of chemical reducing agents, therefore, molten oxide electrolysis is ideal for extraction, since the electron is the only practical reducing agent. MOE has several advantages over other extraction methods. First, electrolytic processing offers uncommon versatility in its insensitivity to feedstock composition. Secondly, oxide melts boast the twin key attributes of highest solubilizing capacity for regolith and lowest volatility of any candidate electrolytes. The former is critical in ensuring high productivity since cell current is limited by reactant solubility, while the latter simplifies cell design by obviating the need for a gas-tight reactor to contain evaporation losses as would be the case with a gas or liquid phase fluoride reagent operating at such high temperatures. Alternatively, MOE requires no import of consumable reagents (e.g. fluorine and carbon) as other processes do, and does not rely on interfacing multiple processes to obtain refined products. Electrolytic processing has the advantage of selectivity of reaction in the presence of a multi-component feed. Products from lunar regolith can be extracted in sequence according to the stabilities of their oxides as expressed by the values of the free energy of oxide formation (e.g. chromium, manganese, Fe, Si, Ti, Al, magnesium, and calcium). Previous work has demonstrated the viability of producing Fe and oxygen from oxide mixtures similar in composition to lunar regolith by molten oxide electrolysis (electrowinning), also called magma electrolysis having shown electrolytic extraction of Si from regolith simulant. This paper describes recent advances in demonstrating the MOE process by a joint project with participation by NASA KSC and MSFC, and Ohio State University and MIT. Progress in measuring cell efficiency for oxygen production, development of non reacting electrodes, and cell feeding and withdrawal will be discussed.

Chemical bonding analysis on amphoteric hydrogen - alkaline earth ammine borohydrides

NASA Astrophysics Data System (ADS)

Kiruthika, S.; Ravindran, P.

2018-04-01

Usually the ions in solid are in the positive oxidation states or in the negative oxidation state depending upon the chemical environment. It is highly unusual for an ion having both positive as well as negative oxidation state in a particular compound. Structural analysis suggest that the alkaline earth ammine borohydrides (AABH) with the chemical formula M (BH4)2(NH3)2 (M = Mg, Ca, or Sr) where hydrogen is present in +1 and -1 oxidation states. In order to understand the oxidation states of hydrogen and also the character of chemical bond present in AABH we have made charge density, electron localization function, Born effective charge, Bader effective charge, and density of states analyses using result from the density functional calculations. Our detailed analyses show that hydrogen is in amphoteric behavior with hydrogen closer to boron is in negative oxidation state and that closer to nitrogen is in the positive oxidation state. Due to the presence of finite covalent bonding between the consitutents in AABH the oxidation state of hydrogen is non-interger value. The confirmation of the presence of amphtoric behavior of hydrogen in AABH has implication in hydrogen storage applications.

La and Al co-doped CaMnO 3 perovskite oxides: From interplay of surface properties to anion exchange membrane fuel cell performance

DOE PAGES

Dzara, Michael J.; Christ, Jason M.; Joghee, Prabhuram; ...

2017-09-01

This work reports the first account of perovskite oxide and carbon composite oxygen reduction reaction (ORR) catalysts integrated into anion exchange membrane fuel cells (AEMFCs). Perovskite oxides with a theoretical stoichiometry of Ca 0.9La 0.1Al 0.1Mn 0.9O 3-δ are synthesized by an aerogel method and calcined at various temperatures, resulting in a set of materials with varied surface chemistry and surface area. Material composition is evaluated by X-ray diffraction, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The perovskite oxide calcined at 800 degrees C shows the importance of balance between surface area, purity of the perovskite phase, and surfacemore » composition, resulting in the highest ORR mass activity when evaluated in rotating disk electrodes. Integration of this catalyst into AEMFCs reveals that the best AEMFC performance is obtained when using composites with 30:70 perovskite oxide:carbon composition. Doubling the loading leads to an increase in the power density from 30 to 76 mW cm -2. The AEMFC prepared with a composite based on perovskite oxide and N-carbon achieves a power density of 44 mW cm -2, demonstrating an ~50% increase when compared to the highest performing composite with undoped carbon at the same loading.« less

La and Al co-doped CaMnO3 perovskite oxides: From interplay of surface properties to anion exchange membrane fuel cell performance

NASA Astrophysics Data System (ADS)

Dzara, Michael J.; Christ, Jason M.; Joghee, Prabhuram; Ngo, Chilan; Cadigan, Christopher A.; Bender, Guido; Richards, Ryan M.; O'Hayre, Ryan; Pylypenko, Svitlana

2018-01-01

This work reports the first account of perovskite oxide and carbon composite oxygen reduction reaction (ORR) catalysts integrated into anion exchange membrane fuel cells (AEMFCs). Perovskite oxides with a theoretical stoichiometry of Ca0.9La0.1Al0.1Mn0.9O3-δ are synthesized by an aerogel method and calcined at various temperatures, resulting in a set of materials with varied surface chemistry and surface area. Material composition is evaluated by X-ray diffraction, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The perovskite oxide calcined at 800 °C shows the importance of balance between surface area, purity of the perovskite phase, and surface composition, resulting in the highest ORR mass activity when evaluated in rotating disk electrodes. Integration of this catalyst into AEMFCs reveals that the best AEMFC performance is obtained when using composites with 30:70 perovskite oxide:carbon composition. Doubling the loading leads to an increase in the power density from 30 to 76 mW cm-2. The AEMFC prepared with a composite based on perovskite oxide and N-carbon achieves a power density of 44 mW cm-2, demonstrating an ∼50% increase when compared to the highest performing composite with undoped carbon at the same loading.

The local structure and ferromagnetism in Fe-implanted SrTiO3 single crystals

NASA Astrophysics Data System (ADS)

Lobacheva, O.; Chavarha, M.; Yiu, Y. M.; Sham, T. K.; Goncharova, L. V.

2014-07-01

We report a connection between the local structure of low-level Fe impurities and vacancies as the cause of ferromagnetic behavior observed in strontium titanate single crystals (STO), which were implanted with Fe and Si ions at different doses then annealed in oxygen. The effects of Fe doping and post-implantation annealing of STO were studied by X-ray Absorption Near Edge Structure (XANES) spectroscopy and Superconducting Quantum Interference Device magnetometry. XANES spectra for Fe and Ti K- and L-edge reveal the changes in the local environment of Fe and Ti following the implantation and annealing steps. The annealing in oxygen atmosphere partially healed implantation damages and changed the oxidation state of the implanted iron from metallic Fe0 to Fe2+/Fe3+ oxide. The STO single crystals were weak ferromagnets prior to implantation. The maximum saturation moment was obtained after our highest implantation dose of 2 × 1016 Fe atom/cm2, which could be correlated with the metallic Fe0 phases in addition to the presence of O/Ti vacancies. After recrystallization annealing, the ferromagnetic response disappears. Iron oxide phases with Fe2+ and Fe3+ corresponding to this regime were identified and confirmed by calculations using Real Space Multiple Scattering program (FEFF9).

Impact of oxygen stoichiometry on electroforming and multiple switching modes in TiN/TaOx/Pt based ReRAM

NASA Astrophysics Data System (ADS)

Sharath, S. U.; Joseph, M. J.; Vogel, S.; Hildebrandt, E.; Komissinskiy, P.; Kurian, J.; Schroeder, T.; Alff, L.

2016-10-01

We have investigated the material and electrical properties of tantalum oxide thin films (TaOx) with engineered oxygen contents grown by RF-plasma assisted molecular beam epitaxy. The optical bandgap and the density of the TaOx films change consistently with oxygen contents in the range of 3.63 to 4.66 eV and 12.4 to 9.0 g/cm3, respectively. When exposed to atmosphere, an oxidized Ta2O5-y surface layer forms with a maximal thickness of 1.2 nm depending on the initial oxygen deficiency of the film. X-ray photoelectron spectroscopy studies show that multiple sub-stoichiometric compositions occur in oxygen deficient TaOx thin films, where all valence states of Ta including metallic Ta are possible. Devices of the form Pt/Ta2O5-y/TaOx/TiN exhibit highly tunable forming voltages of 10.5 V to 1.5 V with decreasing oxygen contents in TaOx. While a stable bipolar resistive switching (BRS) occurs in all devices irrespective of oxygen content, unipolar switching was found to coexist with BRS only at higher oxygen contents, which transforms to a threshold switching behaviour in the devices grown under highest oxidation.

Systemic oxidative stress could predict assisted reproductive technique outcome.

PubMed

Ahelik, A; Mändar, R; Korrovits, P; Karits, P; Talving, E; Rosenstein, K; Jaagura, M; Salumets, A; Kullisaar, T

2015-05-01

Previous studies have indicated that OxS (oxidative stress) may appear as a possible reason for poor ART outcome. Our aim was to study OxS levels in both partners of couples seeking Assisted reproduction Technology (ART). Altogether 79 couples were recruited. Oxidative DNA damage (8-OHdG) and lipid peroxidation (8-EPI) were measured, and clinical background and ART outcomes were recorded. Both OxS markers accurately reflected clinical conditions with prominent negative effects attributable to genital tract infections, endometriosis, uterine myoma and smoking. Furthermore, the level of OxS was also affected by partner's state of health. The highest 8-EPI levels were detected in both partners when biochemically detectable pregnancies did not develop into clinically detectable pregnancies (in women, 97,8 ± 16,7 vs 72.9 ± 22,9, p = 0.007; in men, 89.6 ± 20,4 vs 72,1 ± 22,6, p = 0.049). To conclude, high grade systemix OxS in both partners may negatively affect the maintenance and outcome of pregnancy. Applying the detection of OxS in ART patients may select patients with higher success rate and/or those who require antioxidant therapy. This would lead to improvement of ART outcome as well as natural fertility.

Low molecular weight hyaluronic acid effects on murine macrophage nitric oxide production.

PubMed

Lyle, Daniel B; Breger, Joyce C; Baeva, Larissa F; Shallcross, Jonathan C; Durfor, Charles N; Wang, Nam Sun; Langone, John J

2010-09-01

Hyaluronic acid (HA) is increasingly used for a number of medical device applications. Since the chemical structure of HA is identical no matter its bacterial or animal origin, it should be the ideal biomaterial. However, short term transient inflammatory reactions are common, while rare long-term adverse events may correlate with subclinical chronic inflammation. Concern has been raised that low molecular weight components or degradation fragments from implanted HA may directly stimulate inflammatory reactions. This study examined a panel of HA molecular weights from the unitary disaccharide up to 1.7 x 10(6) Dalton lengths, in which endotoxin was assayed at a very low level (less than 0.03 EU/mg). The murine cell line RAW 264.7, rat splenocytes, and rat adherent differentiated primary macrophages were assayed for nitric oxide production under a variety of inflammatory conditions plus or minus HA. Under the highest inflammatory states, nitric oxide production was mildly suppressed by HMW-HA while slightly augmented by LMW-HA at mg/mL concentrations. However, at micromolar concentrations fragments below 5000 Daltons, thought to have drug-like qualities, were without effect. These data support the hypothesis that if endotoxin is reduced to an extremely low level, LMW-HA may not directly provoke normal tissue macrophage-mediated inflammatory reactions. (c) 2010 Wiley Periodicals, Inc.

Systems and methods for separation and purification of products

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

Weiss, Michael Joseph; Gilliam, Ryan J.; Self, Kyle

There are provided methods and systems for an electrochemical cell including an anode and a cathode where the anode is contacted with a metal ion that converts the metal ion from a lower oxidation state to a higher oxidation state. The metal ion in the higher oxidation state is reacted with an unsaturated hydrocarbon and/or a saturated hydrocarbon to form products. Separation and/or purification of the products as well as of the metal ions in the lower oxidation state and the higher oxidation state, is provided herein.

Interactions between nitrogen cycling and methane oxidation in the pelagic waters of the Gulf of Mexico.

NASA Astrophysics Data System (ADS)

Joye, S. B.; Weber, S.; Battles, J.; Montoya, J. P.

2014-12-01

Methane is an important greenhouse gas that plays a critical role in climate variation. Although a variety of marine methane sources and sinks have been identified, key aspects of the fate of methane in the ocean remain poorly constrained. At cold seeps in the Gulf of Mexico and elsewhere, methane is introduced into the overlying water column via fluid escape from the seabed. We quantified the fate of methane in the water column overlying seafloor cold seeps, in a brine basin, and at several control sites. Our goals were to determine the factors that regulated methane consumption and assimilation and to explore how these controlling factors varied among and between sites. In particular, we examined the impact of nitrogen availability on methane oxidation and studied the ability of methane oxidizing bacteria to fix molecular nitrogen. Methane oxidation rates were highest in the methane rich bottom waters of natural hydrocabron seeps. At these sites, inorganic nitrogen addition stimulated methane oxidation in laboratory experiments. In vitro shipboard experiments revealed that rates of methane oxidation and nitrogen fixation were correlated strongly, suggesting that nitrogen fixation may have been mediated by methanotrophic bacteria. The highest rates of methane oxidation and nitrogen fixation were observed in the deepwater above at natural hydrocarbon seeps. Rates of methane oxidation were substantial along the chemocline of a brine basin but in these ammonium-rich brines, addition of inorganic nitrogen had little impact on methane oxidation suggesting that methanotrophy in these waters were not nitrogen limited. Control sites exhibited the lowest methane concentrations and methane oxidation rates but even these waters exhibited substantial potential for methane oxidation when methane and inorganic nitrogen concentrations were increased. Together, these data suggest that the availability of inorganic nitrogen plays a critical role in regulating methane oxidation in pelagic ocean waters. Some methanotrophs may obtain a competitive advantage in nitrogen-limited oceanic environments by fixing molecular nitrogen. The importance of such "methano-diazotrophy" on a global scale warrants further investigation.

Antioxidant, Antityrosinase, Anticholinesterase, and Nitric Oxide Inhibition Activities of Three Malaysian Macaranga Species

PubMed Central

Abas, Faridah; Ahmad, Syahida; Shaari, Khozirah; Khamis, Shamsul; Lajis, N. H.

2013-01-01

The methanol extracts of three Macaranga species (M. denticulata, M. pruinosa, and M. gigantea) were screened to evaluate their total phenolic contents and activities as cholinesterase inhibitors, nitric oxide (NO) production inhibitors, tyrosinase inhibitors, and antioxidants. The bark of M. denticulata showed the highest total phenolic content (2682 mg gallic acid equivalent (GAE)/100 g) and free radical scavenging activity (IC50 = 0.063 mg/mL). All of the samples inhibited linoleic acid peroxidation by greater than 80%, with the leaves of M. gigantea exhibiting the highest inhibition of 92.21%. Most of the samples exhibited significant antioxidant potential. The bark of M. denticulata and the leaves of both M. pruinosa and M. gigantea exhibited greater than 50% tyrosinase inhibition, with the bark of M. denticulata having the highest percentage of inhibition (68.7%). The bark and leaves of M. denticulata exhibited greater than 50% inhibition (73.82% and 54.50%, resp.) of the acetylcholinesterase enzyme (AChE), while none of the samples showed any significant inhibition of butyrylcholinesterase (BChE). Only the bark of M. denticulata and M. gigantea displayed greater than 50% inhibition of nitric oxide production in cells (81.79% and 56.51%, resp.). These bioactivities indicate that some Macaranga spp. have therapeutic potential in medicinal research. PMID:24319356

Antioxidant, antityrosinase, anticholinesterase, and nitric oxide inhibition activities of three malaysian macaranga species.

PubMed

Mazlan, Nor Aishah; Mediani, Ahmed; Abas, Faridah; Ahmad, Syahida; Shaari, Khozirah; Khamis, Shamsul; Lajis, N H

2013-01-01

The methanol extracts of three Macaranga species (M. denticulata, M. pruinosa, and M. gigantea) were screened to evaluate their total phenolic contents and activities as cholinesterase inhibitors, nitric oxide (NO) production inhibitors, tyrosinase inhibitors, and antioxidants. The bark of M. denticulata showed the highest total phenolic content (2682 mg gallic acid equivalent (GAE)/100 g) and free radical scavenging activity (IC50 = 0.063 mg/mL). All of the samples inhibited linoleic acid peroxidation by greater than 80%, with the leaves of M. gigantea exhibiting the highest inhibition of 92.21%. Most of the samples exhibited significant antioxidant potential. The bark of M. denticulata and the leaves of both M. pruinosa and M. gigantea exhibited greater than 50% tyrosinase inhibition, with the bark of M. denticulata having the highest percentage of inhibition (68.7%). The bark and leaves of M. denticulata exhibited greater than 50% inhibition (73.82% and 54.50%, resp.) of the acetylcholinesterase enzyme (AChE), while none of the samples showed any significant inhibition of butyrylcholinesterase (BChE). Only the bark of M. denticulata and M. gigantea displayed greater than 50% inhibition of nitric oxide production in cells (81.79% and 56.51%, resp.). These bioactivities indicate that some Macaranga spp. have therapeutic potential in medicinal research.

Antimutagenic and free radical scavenger effects of leaf extracts from Accacia salicina

PubMed Central

2011-01-01

Background Three extracts were prepared from the leaves of Accacia salicina; ethyl acetate (EA), chloroform (Chl) and petroleum ether (PE) extracts and was designed to examine antimutagenic, antioxidant potenty and oxidative DNA damage protecting activity. Methods Antioxidant activity of A. salicina extracts was determined by the ability of each extract to protect against plasmid DNA strand scission induced by hydroxyl radicals. An assay for the ability of these extracts to prevent mutations induced by various oxidants in Salmonella typhimurium TA102 and TA 104 strains was conducted. In addition, nonenzymatic methods were employed to evaluate anti-oxidative effects of tested extracts. Results These extracts from leaf parts of A. salicina showed no mutagenicity either with or without the metabolic enzyme preparation (S9). The highest protections against methylmethanesulfonate induced mutagenicity were observed with all extracts and especially chloroform extract. This extract exhibited the highest inhibitiory level of the Ames response induced by the indirect mutagen 2- aminoanthracene. All extracts exhibited the highest ability to protect plasmid DNA against hydroxyl radicals induced DNA damages. The ethyl acetate (EA) and chloroform (Chl) extracts showed with high TEAC values radical of 0.95 and 0.81 mM respectively, against the ABTS.+. Conclusion The present study revealed the antimutagenic and antioxidant potenty of plant extract from Accacia salicina leaves. PMID:22132863

Evaluating toxicity of copper(II) oxide nanoparticles (CuO-NPs) through waterborne exposure to tilapia (Oreochromis mossambicus) by tissue accumulation, oxidative stress, histopathology, and genotoxicity.

PubMed

Shahzad, Khurram; Khan, Muhammad Naeem; Jabeen, Farhat; Kosour, Nasreen; Chaudhry, Abdul Shakoor; Sohail, Muhammad

2018-06-01

Metal oxide nanoparticles are widely used in industries, and peak level can be confirmed in their surroundings. In the present study, the sub-lethal effects of CuO-NPs from low to high concentration as 0.5 to 1.5 mg/L were observed in tilapia (Oreochromis mossambicus). Accumulation of copper from CuO-NPs was increased with the increase in doses, and maximum accumulation was found in the gill than liver and muscles. The increased lipid peroxidation level was observed in the gill as compared to liver, and the similar results were obtained in catalase and glutathione while superoxide dismutase level was higher in the liver than gills. In histological alterations, gill edema, curved tips, fusion of gill lamellae, and thickening of primary and secondary gill lamellae were observed. Necrosis and apoptosis with condensed nuclear bodies and pyknotic nuclei were observed in the liver at the highest dose concentration. In a genotoxic study, the highest value of % tail DNA and olive tail movement was observed with increasing concentrations. Copper oxide nanoparticles has greater potential to accumulate in the soft tissues, which may cause respiratory distress such as oxidative stress, induction of antioxidant defense by raising glutathione, organ pathology, and genotoxicity.

Graphene oxide/alginate beads as adsorbents: Influence of the load and the drying method on their physicochemical-mechanical properties and adsorptive performance.

PubMed

Platero, Emiliano; Fernandez, Maria Emilia; Bonelli, Pablo Ricardo; Cukierman, Ana Lea

2017-04-01

Graphene oxide/alginate beads were prepared from lab-synthesized graphene oxide, varying its content within the beads (0.05, 0.125, and 0.25wt.%). Ethanol-drying and lyophilization were compared as drying methods to obtain suitable adsorbents which were later tested to the removal of a model organic molecule (methylene blue). The morphological and textural properties of all the beads were characterized by scanning electron microscopy and N 2 adsorption/desorption isotherms at -196°C, respectively. Limited porosity was obtained for all cases (S BET <60m 2 /g). Uniaxial compression tests were performed to assess the mechanical properties of the beads. Ethanol-dried ones exhibited higher Young's elasticity modulus (E=192kPa) than the lyophilized samples (twice at 0.25wt.% graphene oxide loading), which disclosed breakage points at lower deformation percentages. Adsorption experiments were conducted and dye adsorption isotherms were obtained for the beads with the best removal performance. The experimental data were better fitted by the Langmuir model. The highest maximum adsorption capacity (4.25mmol/g) was obtained for the lyophilized beads with the highest graphene oxide content. Mechanical properties were found to be affected also by the dye adsorption. Copyright © 2016 Elsevier Inc. All rights reserved.

An oxidized liquid metal-based microfluidic platform for tunable electronic device applications.

PubMed

Li, Guangyong; Parmar, Mitesh; Lee, Dong-Weon

2015-02-07

Easy movement of oxidized Galinstan in microfluidic channels is a promising way for the wide application of the non-toxic liquid metal. In this paper, two different surface modification techniques (physical and chemical) are reported, which dramatically improve the non-wetting characteristics of oxidized Galinstan in the microfluidic channel. In the physical technique, normal paper textures are transferred to the inner wall of polydimethylsiloxane (PDMS) channels and four types of nanoparticles are then coated on the surface of the wall for further improvement of the non-wetting characteristics. Highest advancing angle of 167° and receding angle of 151° are achieved on the paper-textured PDMS with titanium oxide (TiO2) nanoparticles. In the chemical technique, three types of inorganic acids are employed to generate dual-scale structures on the PDMS surface. The inner wall surface treated with sulfuric acid (H2SO4) shows the highest contact angle of 167° and a low hysteresis of ~14° in the dynamic measurement. Creating, transporting, separating and merging of oxidized Galinstan droplets are successfully demonstrated in the fabricated PDMS microfluidic channels. After optimization of these modification techniques, the potential application of tunable capacitors and electronic filters is realized by using liquid metal-based microfluidic devices.

Electrocatalysis using transition metal carbide and oxide nanocrystals

NASA Astrophysics Data System (ADS)

Regmi, Yagya N.

Carbides are one of the several families of transition metal compounds that are considered economic alternatives to catalysts based on noble metals and their compounds. Phase pure transition metal carbides of group 4-6 metals, in the first three periods, were synthesized using a common eutectic salt flux synthesis method, and their electrocatalytic activities compared under uniform electrochemical conditions. Mo2C showed highest hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) activities among the nine metal carbides investigated, but all other metal carbides also showed substantial activities. All the metal carbides showed remarkable enhancement in catalytic activities as supports, when compared to traditional graphitic carbon as platinum support. Mo2C, the most active transition metal carbide electrocatalyst, was prepared using four different synthesis routes, and the synthesis route dependent activities compared. Bifunctional Mo 2C that is HER as well as oxygen evolution reaction (OER) active, was achieved when the carbide was templated on a multiwalled carbon nanotube using carbothermic reduction method. Bimetallic carbides of Fe, Co, and Ni with Mo or W were prepared using a common carbothermic reduction method. Two different stoichiometries of bimetallic carbides were obtained for each system within a 60 °C temperature window. While the bimetallic carbides showed relatively lower electrocatalytic activities towards HER and ORR in comparison to Mo2C and WC, they revealed remarkably higher OER activities than IrO2 and RuO2, the state-of-the-art OER catalysts. Bimetallic oxides of Fe, Co, and Ni with Mo and W were also prepared using a hydrothermal synthesis method and they also revealed OER activities that are much higher than RuO2 and IrO2. Additionally, the OER activities were dependent on the degree and nature of hydration in the bimetallic oxide crystal lattice, with the completely hydrated, as synthesized, cobalt molybdate and nickel molybdate showing the highest OER activities.

Stress Exacerbates Infectivity and Pathogenicity of Blastocystis hominis: In Vitro and In Vivo Evidences

PubMed Central

Chandramathi, Samudi; Suresh, Kumar; Sivanandam, Sinnadurai; Kuppusamy, Umah Rani

2014-01-01

Background Stress alters the oxidant-antioxidant state and immune cell responses which disrupts its function to combat infection. Blastocystis hominis, a common intestinal protozoan has been reported to be opportunistic in immunocompromised patients namely cancer. B. hominis infectivity in other altered immune system conditions especially stress is unknown. We aimed to demonstrate the stress effects towards the susceptibility and pathogenicity of B. hominis infection. Methods/Findings Three-week-old Wistar rats were divided into four groups: (a)control; (b)stress-induced; (c)B. hominis infected; (d)stress-induced with B. hominis infection; (n = 20 respectively). Stress was induced for an hour daily (30 days) using a Belly Dancer Shaker. Weight gain was monitored, stool samples were collected for B. hominis screening and blood for the determination of differential count, levels of immunoglobulin, oxidative damage, and peripheral blood mononuclear cell (PBMC) proliferation upon induction with solubilized antigen of B. hominis (Blasto-Ag). Group (b) exhibited the highest level of weight gain. Group (d) had higher levels of parasite cyst count in stools, serum IgE, oxidized protein and lipid compared to the group (c). Levels of monocyte and antioxidant in group (d) were decreased and their PBMCs showed highest inhibition of proliferation level when exposed to Blasto-Ag. Monocyte level in Group (b) showed insignificant difference compared to group (a) but was significantly lower compared to group (c). Antioxidant levels in group (c) were generally lower compared to group (a) and (b). Inhibition level exhibited by Blasto-Ag treated PBMCs of group (c) was higher compared to group (a) and (b). Conclusion The pathogenicity and augmentation of B. hominis infection is enhanced when stress is present. Lifestyles today are becoming increasingly stressed and the present findings suggest that the parasite which has been reported to be one of the most common organisms seen in stool surveys, namely in developing countries, may tend to be more pathogenic in stressful situations. PMID:24788756

Electrochemical preparation of single-crystalline Cr 2O 3 from molten salts

NASA Astrophysics Data System (ADS)

Abe, Hideki; Nishida, Kenji; Imai, Motoharu; Kitazawa, Hideaki

2004-06-01

Single crystals of Cr 2O 3 have been grown by means of electrolysis on a 1:100 stoichiometric mixture of CrO 3 and cesium molybdate, Cs 2MoO 4, fused at 1000°C in an ambient atmosphere. Potentiometric measurements on the molten salts have shown the existence of a critical voltage of -320 mV below which hexagonal platelets-shaped single-crystalline Cr 2O 3 is grown on the surface of the working electrode. Coulometry measurements have revealed that the Cr ions are at their highest oxidation state of Cr +6 in the molten electrolyte, which suggests that the electric reduction of Cr +6 to Cr +3 drives the single-crystal growth of Cr 2O 3.

Electronic structures of AlMoO(y)(-) (y = 1-4) determined by photoelectron spectroscopy and density functional theory calculations.

PubMed

Waller, Sarah E; Mann, Jennifer E; Hossain, Ekram; Troyer, Mary; Jarrold, Caroline C

2012-07-14

Vibrationally-resolved photoelectron spectra of AlMoO(y)(-) (y = 1-4) are presented and analyzed in conjunction with density functional theory computational results. The structures determined for the AlMoO(y) anion and neutral clusters suggest ionic bonding between Al(+) and a MoO(y)(-) or MoO(y)(-2) moiety, and point to the relative stability of Mo=O versus Al=O bonds. The highest occupied and partially occupied orbitals in the anions and neutrals can be described as Mo atomic-like orbitals, so while the Mo is in a higher oxidation state than Al, the most energetically accessible electrons are localized on the molybdenum center.

Effect of Cobalt Particle Size on Acetone Steam Reforming

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

Sun, Junming; Zhang, He; Yu, Ning

2015-06-11

Carbon-supported cobalt nanoparticles with different particle sizes were synthesized and characterized by complementary characterization techniques such as X-ray diffraction, N-2 sorption, acetone temperature-programmed desorption, transmission electron microscopy, and CO chemisorption. Using acetone steam reforming reaction as a probe reaction, we revealed a volcano-shape curve of the intrinsic activity (turnover frequency of acetone) and the CO2 selectivity as a function of the cobalt particle size with the highest activity and selectivity observed at a particle size of approximately 12.8nm. Our results indicate that the overall performance of acetone steam reforming is related to a combination of particle-size-dependent acetone decomposition, water dissociation,more » and the oxidation state of the cobalt nanoparticles.« less

Association between oxidative status and the composition of intestinal microbiota along the gastrointestinal tract.

PubMed

Gyuraszova, Marianna; Kovalcikova, Alexandra; Gardlik, Roman

2017-06-01

Studies have shown that the microbiota along the gastrointestinal tract (GIT) plays an important role when it comes to the maintenance of its proper functions. Many studies exist that have analyzed the composition of the bacterial community in the different regions of the GIT of humans and model animals. Microbial imbalance leads to several systemic disorders, including cardiovascular and renal disease. The imbalance between the production of reactive oxygen species (ROS) and their elimination by antioxidants leads to oxidative stress. Oxidative stress plays an important role in a variety of physiological processes, as well as disease. The continuous formation of ROS in the GIT is the result of the interaction between intestinal mucosa, symbiotic bacteria and dietary factors. It has also been proven that ROS play a role in the pathogenesis of several GI disorders, including IBD. We hypothesized that the levels of advanced glycation end products (AGEs) would be the highest in the ileum, caecum or colon, where the microbiota mostly consist of butyrate producing bacteria, Bacterioides, Clostridium, Ruminococcus or Bifidobacterium, which derive energy through carbohydrate fermentation. We also assumed that advanced oxidation protein products (AOPP) mostly act in the segments, where bacteria reside and which are responsible for the amino acid fermentation, such as caecum or colon. Lipid hydroxyperoxides are generated during digestion in the stomach, which contains absorbed oxygen and has a low pH. According to this we hypothesized that the highest concentration of thiobarbituric acid reacting substances (TBARS) could be in the stomach, which, however, has not been confirmed. Because Lactobacilli are able to produce catalase, an endogenous antioxidant, and are abundant in the small intestine, we hypothesized that antioxidant capacity (measured by ferric reducing ability) would be the highest here. The highest levels of AGEs were found in the caecum. The highest level of TBARS was found in the jejunum of the rats. The assessment of our hypothesis also revealed high levels of AOPP in the caecum. It has been shown that AOPP contributes to the progression of IBD. The ferric reducing ability of tissue was the lowest in the colon of the experimental animals, which is in accordance with previous studies that show that rat colon has a lower total antioxidant capacity than the small bowel. In summary, we offer some insight into the differences between the oxidative status along the GIT of rats and some advice concerning supportive antioxidant therapy of gastrointestinal diseases. Copyright © 2017 Elsevier Ltd. All rights reserved.

Syzyguim guineense Extracts Show Antioxidant Activities and Beneficial Activities on Oxidative Stress Induced by Ferric Chloride in the Liver Homogenate

PubMed Central

Pieme, Constant Anatole; Ngoupayo, Joseph; Khou-Kouz Nkoulou, Claude Herve; Moukette Moukette, Bruno; Njinkio Nono, Borgia Legrand; Ama Moor, Vicky Jocelyne; Ze Minkande, Jacqueline; Yonkeu Ngogang, Jeanne

2014-01-01

The aim of this study was to determine the in vitro antioxidant activity, free radical scavenging property and the beneficial effects of extracts of various parts of Syzygium guineense in reducing oxidative stress damage in the liver. The effects of extracts on free radicals were determined on radicals DPPH, ABTS, NO and OH followed by the antioxidant properties using Ferric Reducing Antioxidant Power assay (FRAP) and hosphomolybdenum (PPMB). The phytochemical screening of these extracts was performed by determination of the phenolic content. The oxidative damage inhibition in the liver was determined by measuring malondialdehyde (MDA) as well as the activity of the antioxidant enzymes superoxide dismutase (SOD), catalase (CAT) and peroxidase. Overall, the bark extract of the ethanol/water or methanol showed the highest radical scavenging activities against DPPH, ABTS and OH radicals compared to the other extracts. This extract also contained the highest phenolic content implying the potential contribution of phenolic compounds towards the antioxidant activities. However, the methanol extract of the root demonstrated the highest protective effects of SOD and CAT against ferric chloride while the hydro-ethanol extract of the leaves exhibited the highest inhibitory effects on lipid peroxidation. These findings suggest that antioxidant properties of S. guineense extracts could be attributed to phenolic compounds revealed by phytochemical studies. Thus, the present results indicate clearly that the extracts of S. guineense possess antioxidant properties and could serve as free radical inhibitors or scavengers, acting possibly as primary antioxidants. The antioxidant properties of the bark extract may thus sustain its various biological activities. PMID:26785075

Spatial variation of charge and sulfur oxidation state in a surface gradient affects plasma proteins adsorption

PubMed Central

Ding, Yong-Xue; Streitmatter, Seth; Wright, Bryon E.; Hlady, Vladimir

2010-01-01

A gradient of negative surface charge based on 1-D spatial variation from surface sulfhydryl to mixed sulfhydryl-sulfonate moities was prepared by controlled UV oxidation of 3-mercaptopropylsilane monolayer on fused silica. Adsorption of three human plasma proteins, albumin (HSA), immunoglobulin G (IgG), and fibrinogen (Fgn) onto such surface gradient was studied using spatially-resolved total internal reflection fluorescence (TIRF) and autoradiography. Adsorption was measured from dilute solutions equivalent to 1/100 (TIRF, autoradiography), and 1/500 and 1/1000 (autoradiography) of protein’s physiological concentrations in plasma. All three proteins adsorbed more to the non-oxidized sulfhydryl region than to the oxidized, mixed sulfhydryl-sulfonate region of the gradient. In the case of HSA the adsorption contrast along the gradient was largest when the adsorption took place from more dilute protein solutions. Increasing the concentration to 1/100 of protein plasma concentration eliminated the effect of the gradient on HSA adsorption and to the lesser extent on IgG adsorption. In the case of Fgn the greatest adsorption contrast was observed at the highest concentration used. Based on adsorption kinetics, the estimated binding affinity of HSA for the sulfhydryl region what twice the affinity for the mixed sulfhydryl-sulfonate region of the gradient. For IgG and Fgn the initial adsorption was transport-limited and the initial adsorption rates approached the computed flux of the protein to the surface. PMID:20568822

Biosynthesis of Pyocyanine by a Paraffin Hydrocarbon-oxidizing Strain of Pseudomonas aeruginosa

PubMed Central

Lee, E. G.-H.; Walden, C. C.

1969-01-01

A paraffin-oxidizing bacterium, designated as Pseudomonas aeruginosa ATS-14, was isolated from soil samples obtained from the Athabasca “tar sands.” This strain utilized kerosene as the only carbon source of energy and produced a high concentration of pyocyanine in the culture medium. Aromatic carbons were not attacked, but C10 to C17n-alkanes were readily oxidized by the pseudomonad and formed pyocyanine. The highest yield of the pigment was obtained from hexadecane and heptadecane. PMID:4977219

Evidence for Weakly Correlated Oxygen Holes in the Highest-Tc Cuprate Superconductor HgBa2 Ca2 Cu3 O8 +δ

NASA Astrophysics Data System (ADS)

Chainani, A.; Sicot, M.; Fagot-Revurat, Y.; Vasseur, G.; Granet, J.; Kierren, B.; Moreau, L.; Oura, M.; Yamamoto, A.; Tokura, Y.; Malterre, D.

2017-08-01

We study the electronic structure of HgBa2 Ca2 Cu3 O8 +δ (Hg1223; Tc=134 K ) using photoemission spectroscopy (PES) and x -ray absorption spectroscopy (XAS). Resonant valence band PES across the O K edge and Cu L edge identifies correlation satellites originating in O 2 p and Cu 3 d two-hole final states, respectively. Analyses using the experimental O 2 p and Cu 3 d partial density of states show quantitatively different on-site Coulomb energy for the Cu site (Ud d=6.5 ±0.5 eV ) and O site (Up p=1.0 ±0.5 eV ). Cu2 O7 -cluster calculations with nonlocal screening explain the Cu 2 p core level PES and Cu L -edge XAS spectra, confirm the Ud d and Up p values, and provide evidence for the Zhang-Rice singlet state in Hg1223. In contrast to other hole-doped cuprates and 3 d -transition metal oxides, the present results indicate weakly correlated oxygen holes in Hg1223.

Factors affecting sodium hypochlorite extraction of CCA from treated wood.

PubMed

Gezer, E D; Cooper, P A

2009-12-01

Significant amounts of chromated copper arsenate (CCA) treated wood products, such as utility poles and residential construction wood, remain in service. There is increasing public concern about environmental contamination from CCA-treated wood when it is removed from service for reuse or recycling, placed in landfills or burned in commercial incinerators. In this paper, we investigated the effects of time, temperature and sodium hypochlorite concentration on chromium oxidation and extraction of chromated copper arsenate from CCA-treated wood (Type C) removed from service. Of the conditions evaluated, reaction of milled wood with sodium hypochlorite for one hour at room temperature followed by heating at 75 degrees C for two hours gave the highest extraction efficiency. An average of 95% Cr, 99% Cu and 96% As could be removed from CCA-treated, milled wood by this process. Most of the extracted chromium was oxidized to the hexavalent state and could therefore be recycled in a CCA treating solution. Sodium hypochlorite extracting solutions could be reused several times to extract CCA components from additional treated wood samples.

Investigation of the High-Energy Oxidation of FiberForm from DSMC Analysis of Molecular Beam Experiments

NASA Technical Reports Server (NTRS)

Borner, A.; Swaminathan-Gopalan, K.; Stephani, Kelly; Poovathingal, S.; Murray, V. J.; Minton, T. K.; Panerai, F.; Mansour, N. N.

2017-01-01

A collaborative effort between the University of Illinois at Urbana-Champaign (UIUC), NASA Ames Research Center (ARC) and Montana State University (MSU) succeeded at developing a new finite-rate carbon oxidation model from molecular beam scattering experiments on vitreous carbon (VC). We now aim to use the direct simulation Monte Carlo (DSMC) code SPARTA to apply the model to each fiber of the porous fibrous Thermal Protection Systems (TPS) material FiberForm (FF). The detailed micro-structure of FF was obtained from X-ray micro-tomography and then used in DSMC. Both experiments and simulations show that the CO/O products ratio increased at all temperatures from VC to FF. We postulate this is due to the larger number of collisions an O atom encounters inside the porous FF material compared to the flat surface of VC. For the simulations, we particularly focused on the lowest and highest temperatures studied experimentally, 1023 K and 1823 K, and found good agreement between the finite-rate DSMC simulations and experiments.

A palladium-doped ceria@carbon core-sheath nanowire network: a promising catalyst support for alcohol electrooxidation reactions.

PubMed

Tan, Qiang; Du, Chunyu; Sun, Yongrong; Du, Lei; Yin, Geping; Gao, Yunzhi

2015-08-28

A novel palladium-doped ceria and carbon core-sheath nanowire network (Pd-CeO2@C CSNWN) is synthesized by a template-free and surfactant-free solvothermal process, followed by high temperature carbonization. This hierarchical network serves as a new class of catalyst support to enhance the activity and durability of noble metal catalysts for alcohol oxidation reactions. Its supported Pd nanoparticles, Pd/(Pd-CeO2@C CSNWN), exhibit >9 fold increase in activity toward the ethanol oxidation over the state-of-the-art Pd/C catalyst, which is the highest among the reported Pd systems. Moreover, stability tests show a virtually unchanged activity after 1000 cycles. The high activity is mainly attributed to the superior oxygen-species releasing capability of Pd-doped CeO2 nanowires by accelerating the removal of the poisoning intermediate. The unique interconnected one-dimensional core-sheath structure is revealed to facilitate immobilization of the metal catalysts, leading to the improved durability. This core-sheath nanowire network opens up a new strategy for catalyst performance optimization for next-generation fuel cells.

Organic aerosol in the summertime southeastern United States: components and their link to volatility distribution, oxidation state and hygroscopicity

NASA Astrophysics Data System (ADS)

Kostenidou, Evangelia; Karnezi, Eleni; Hite, James R., Jr.; Bougiatioti, Aikaterini; Cerully, Kate; Xu, Lu; Ng, Nga L.; Nenes, Athanasios; Pandis, Spyros N.

2018-04-01

The volatility distribution of the organic aerosol (OA) and its sources during the Southern Oxidant and Aerosol Study (SOAS; Centreville, Alabama) was constrained using measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a thermodenuder (TD). Positive matrix factorization (PMF) analysis was applied on both the ambient and thermodenuded high-resolution mass spectra, leading to four factors: more oxidized oxygenated OA (MO-OOA), less oxidized oxygenated OA (LO-OOA), an isoprene epoxydiol (IEPOX)-related factor (isoprene-OA) and biomass burning OA (BBOA). BBOA had the highest mass fraction remaining (MFR) at 100 °C, followed by the isoprene-OA, and the LO-OOA. Surprisingly the MO-OOA evaporated the most in the TD. The estimated effective vaporization enthalpies assuming an evaporation coefficient equal to unity were 58 ± 13 kJ mol-1 for the LO-OOA, 89 ± 10 kJ mol-1 for the MO-OOA, 55 ± 11 kJ mol-1 for the BBOA, and 63 ± 15 kJ mol-1 for the isoprene-OA. The estimated volatility distribution of all factors covered a wide range including both semi-volatile and low-volatility components. BBOA had the lowest average volatility of all factors, even though it had the lowest O : C ratio among all factors. LO-OOA was the more volatile factor and its high MFR was due to its low enthalpy of vaporization according to the model. The isoprene-OA factor had intermediate volatility, quite higher than suggested by a few other studies. The analysis suggests that deducing the volatility of a factor only from its MFR could lead to erroneous conclusions. The oxygen content of the factors can be combined with their estimated volatility and hygroscopicity to provide a better view of their physical properties.

Selected oxidative stress markers in a South American crocodilian species.

PubMed

Furtado-Filho, Orlando V; Polcheira, Cássia; Machado, Daniel P; Mourão, Guilherme; Hermes-Lima, Marcelo

2007-01-01

Crocodilians and other diving vertebrates experience hypoperfusion and hypoxia of several internal organs during long dives. At the end of a dive, reperfusion of aerated blood may cause a physiologically relevant oxidative stress. In this study, we analyzed selected markers of oxidative stress in eight organs of normoxic Paraguayan caiman (Caiman yacare) captured in the Brazilian Pantanal wetlands during the winter of 2001 (six mature-adult males and eight young-adult males; AD-1 and YA-1 groups, respectively), and during the summer of 2002 (six young-adult males (YA-2 group), ten hatchlings and five embryos). Lipid peroxidation products determined by three different assays were generally highest in brain, liver and kidney (in comparison with all other organs), and lowest in white muscles from the tail and hind legs. Liver and kidney showed the highest levels of carbonyl protein, while brain showed low levels. Intermediate levels of oxidative stress markers were mostly found in the heart ventricles and lung. Differences in oxidative stress markers between AD-1 and YA-1 were organ-specific, showing no age-related correlation. However, most oxidative stress markers in YA-2 organs were either higher than (by 1.4- to 3.7-fold) or not significantly different from respective values in hatchlings organs. This pattern (hatchlings versus young-adults) was confirmed using correlation analysis of individual caiman size versus levels of oxidative damage markers in four organs. The higher level of oxidative stress markers in young-adults possibly relates to the fast growth rate (and thus, increased oxidative metabolic rate) of C. yacare in the first years of life. Differences in oxidative stress markers between YA-1 and YA-2 were also observed and were ascribed to seasonal changes in free radical metabolism. These results in normoxic C. yacare represent the first step towards understanding the age-related physiological oxidative stress of a diving reptile from a seasonally changing wetland environment.

Solid-state rechargeable magnesium battery

DOEpatents

Shao, Yuyan; Liu, Jun; Liu, Tianbiao; Li, Guosheng

2016-09-06

Embodiments of a solid-state electrolyte comprising magnesium borohydride, polyethylene oxide, and optionally a Group IIA or transition metal oxide are disclosed. The solid-state electrolyte may be a thin film comprising a dispersion of magnesium borohydride and magnesium oxide nanoparticles in polyethylene oxide. Rechargeable magnesium batteries including the disclosed solid-state electrolyte may have a coulombic efficiency .gtoreq.95% and exhibit cycling stability for at least 50 cycles.

Microstructural modifications induced by accelerated aging and lipid absorption in remelted and annealed UHMWPEs for total hip arthroplasty

PubMed Central

Puppulin, Leonardo; Zhu, Wenliang; Sugano, Nobuhiko

2014-01-01

Three types of commercially available ultra-high molecular weight polyethylene (UHMWPE) acetabular cups currently used in total hip arthroplasty have been studied by means of Raman micro-spectroscopy to unfold the microstructural modification induced by the oxidative degradation after accelerated aging with and without lipid absorption. The three investigated materials were produced by three different manufacturing procedures, as follows: irradiation followed by remelting, one-step irradiation followed by annealing, 3-step irradiation and annealing. Clear microstructural differences were observed in terms of phase contents (i.e. amorphous, crystalline and intermediate phase fraction). The three-step annealed material showed the highest crystallinity fraction in the bulk, while the remelted polyethylene is clearly characterized by the lowest content of crystalline phase and the highest content of amorphous phase. After accelerated aging either with or without lipids, the amount of amorphous phase decreased in all the samples as a consequence of the oxidation-induced recrystallization. The most remarkable variations of phase contents were detected in the remelted and in the single-step annealed materials. The presence of lipids triggered oxidative degradation especially in the remelted polyethylene. Such experimental evidence might be explained by the highest amount of amorphous phase in which lipids can be absorbed prior to accelerated aging. The results of these spectroscopic characterizations help to rationalize the complex effect of different irradiation and post-irradiation treatments on the UHMWPE microstructure and gives useful information on how significantly any single step of the manufacturing procedures might affect the oxidative degradation of the polymer. PMID:25179830

Mesoporous xEr 2O 3·CoTiO 3 composite oxide catalysts for low temperature dehydrogenation of ethylbenzene to styrene using CO 2 as a soft oxidant

DOE PAGES

Yue, Yanfeng; Zhang, Li; Chen, Jihua; ...

2016-01-01

A series of mesoporous xEr 2O 3·CoTiO 3 composite oxide catalysts have been prepared using template method and tested as a new type of catalyst for the oxidative dehydrogenation of ethylbenzene to styrene by using CO 2 as a soft oxidant. Among the catalysts tested, the 0.25Er 2O 3 CoTiO 3 sample with a ratio of 1:4:4 content and calcined at 600 oC exhibited the highest ethylbenzene conversion (58%) and remarkable styrene selectivity (95%) at low temperature (450 °C).

Ceo2 Based Catalysts for the Treatment of Propylene in Motorcycle’s Exhaust Gases

PubMed Central

Pham, Phuong Thi Mai; Le Minh, Thang; Nguyen, Tien The; Van Driessche, Isabel

2014-01-01

In this work, the catalytic activities of several single metallic oxides were studied for the treatment of propylene, a component in motorcycles’ exhaust gases, under oxygen deficient conditions. Amongst them, CeO2 is one of the materials that exhibit the highest activity for the oxidation of C3H6. Therefore, several mixtures of CeO2 with other oxides (SnO2, ZrO2, Co3O4) were tested to investigate the changes in catalytic activity (both propylene conversion and CO2 selectivity). Ce0.9Zr0.1O2, Ce0.8Zr0.2O2 solid solutions and the mixtures of CeO2 and Co3O4 was shown to exhibit the highest propylene conversion and CO2 selectivity. They also exhibited good activities when tested under oxygen sufficient and excess conditions and with the presence of co-existing gases (CO, H2O). PMID:28788253

Effects of Different Lipophilized Ferulate Esters in Fish Oil-Enriched Milk: Partitioning, Interaction, Protein, and Lipid Oxidation.

PubMed

Qiu, Xujian; Jacobsen, Charlotte; Villeneuve, Pierre; Durand, Erwann; Sørensen, Ann-Dorit Moltke

2017-11-01

Antioxidant effects of ferulic acid and lipophilized ferulate esters were investigated in fish oil-enriched milk. Methyl ferulate (C1) and ethyl ferulate (C2) more efficiently prevented lipid oxidation than dodecyl ferulate (C12) did, followed by ferulic acid (C0). The combination of C1 or C2 with C12 could have a "synergistic" effect indicated by peroxide value, hexanal, and 1-penten-3-ol analysis results. These antioxidants also showed protein oxidation inhibition effects. The most effective antioxidants (C1 and C2) had the highest concentration in the precipitate phase but the lowest concentration in the aqueous phase, which was the opposite of the partitioning of C0. C12 had the highest concentration in the oil and emulsion phase. In particular, the interaction between ferulates esterified with short and medium alkyl chain lengths could lead to their "synergistic" effects in fish oil-enriched milk, which could be caused by the change in their partitioning or localization at the interface.

Study of Traverse Speed Effects on Residual Stress State and Cavitation Erosion Behavior of Arc-Sprayed Aluminum Bronze Coatings

NASA Astrophysics Data System (ADS)

Hauer, Michél; Henkel, Knuth Michael; Krebs, Sebastian; Kroemmer, Werner

2017-01-01

Within a research project regarding cavitation erosion-resistant coatings, arc spraying was used with different traverse speeds to influence heat transfer and the resulting residual stress state. The major reason for this study is the lack of knowledge concerning the influence of residual stress distribution on mechanical properties and coating adhesion, especially with respect to heterogeneous aluminum bronze alloys. The materials used for spray experiments were the highly cavitation erosion-resistant propeller alloys CuAl9Ni5Fe4Mn (Ni-Al-Bronze) and CuMn13Al8Fe3Ni2 (Mn-Al-Bronze). Analyses of cavitation erosion behavior were carried out to evaluate the suitability for use in marine environments. Further microstructural, chemical and mechanical analyses were realized to examine adhesive and cohesive coating properties. Residual stress distribution was measured by modified hole drilling method using electronic speckle pattern interferometry (ESPI). It was found that the highest traverse speed led to higher tensile residual stresses near the surface and less cavitation erosion resistance of the coatings. Moreover, high oxygen affinity of main alloying element aluminum was identified to severely influence the microstructures by the formation of large oxides and hence the coating properties. Overall, Mn-Al-Bronze coatings showed lower residual stresses, a more homogeneous pore and oxide distribution and less material loss by cavitation than Ni-Al-Bronze coatings.

Comparative Studies on Thermal, Mechanical, and Flame Retardant Properties of PBT Nanocomposites via Different Oxidation State Phosphorus-Containing Agents Modified Amino-CNTs.

PubMed

Zhu, San-E; Wang, Li-Li; Chen, Hao; Yang, Wei; Yuen, Anthony Chun-Yin; Chen, Timothy Bo-Yuan; Luo, Cheng; Bi, Wen-Mei; Hu, En-Zhu; Zhang, Jian; Si, Jing-Yu; Lu, Hong-Dian; Hu, Kun-Hong; Chan, Qing Nian; Yeoh, Guan Heng

2018-01-26

High-performance poly(1,4-butylene terephthalate) (PBT) nanocomposites have been developed via the consideration of phosphorus-containing agents and amino-carbon nanotube (A-CNT). One-pot functionalization method has been adopted to prepare functionalized CNTs via the reaction between A-CNT and different oxidation state phosphorus-containing agents, including chlorodiphenylphosphine (DPP-Cl), diphenylphosphinic chloride (DPP(O)-Cl), and diphenyl phosphoryl chloride (DPP(O₃)-Cl). These functionalized CNTs, DPP(O x )-A-CNTs ( x = 0, 1, 3), were, respectively, mixed with PBT to obtain the CNT-based polymer nanocomposites through a melt blending method. Scanning electron microscope observations demonstrated that DPP(O x )-A-CNT nanoadditives were homogeneously distributed within PBT matrix compared to A-CNT. The incorporation of DPP(O x )-A-CNT improved the thermal stability of PBT. Moreover, PBT/DPP(O₃)-A-CNT showed the highest crystallization temperature and tensile strength, due to the superior dispersion and interfacial interactions between DPP(O₃)-A-CNT and PBT. PBT/DPP(O)-A-CNT exhibited the best flame retardancy resulting from the excellent carbonization effect. The radicals generated from decomposed polymer were effectively trapped by DPP(O)-A-CNT, leading to the reduction of heat release rate, smoke production rate, carbon dioxide and carbon monoxide release during cone calorimeter tests.

Pirin-like proteins are regulated by oxidative stress and iron in bacteroides fragilis and involved in the modulation of central energy metabolism and metronidazole susceptibility

USDA-ARS?s Scientific Manuscript database

Bacteroides fragilis is the most frequent anaerobe isolated from human infections. Clinical isolates of B. fragilis are among the highest aerotolerant anaerobic bacteria. The oxidative stress response (OSR) in B. fragilis induces an array of genes enabling them to survive prolonged oxygen exposure i...

In vitro tensile bond strength of adhesive cements to new post materials.

PubMed

O'Keefe, K L; Miller, B H; Powers, J M

2000-01-01

The purpose of this study was to measure the in vitro tensile bond strength of 3 types of adhesive resin cements to stainless steel, titanium, carbon fiber-reinforced resin, and zirconium oxide post materials. Disks of post materials were polished to 600 grit, air abraded, and ultrasonically cleaned. Zirconium oxide bonding surfaces were pretreated with hydrofluoric acid and silanated. Bis-Core, C&B Metabond, and Panavia cements were bonded to the post specimens and placed in a humidor for 24 hours. Post specimens were debonded in tension. Means and standard deviations (n = 5) were analyzed by 2-way analysis of variance. Tukey-Kramer intervals at the 0.05 significance level were calculated. Failure modes were observed. Panavia 21 provided the highest bond strengths for all types of post materials, ranging from 22 MPa (zirconium oxide) to 37 MPa (titanium). C&B Metabond bonded significantly more strongly to stainless steel (27 MPa) and titanium (22 MPa) than to zirconium oxide (7 MPa). Bis-Core results were the lowest, ranging from 16 MPa (stainless steel) to 8 MPa (zirconium oxide). In most cases, bonds to carbon fiber post materials were weaker than to stainless steel and titanium, but stronger than to zirconium oxide. In general, higher bond strengths resulted in a higher percentage of cohesive failures within the cement. Panavia 21 provided the highest bond strengths to all post materials, followed by C&B Metabond. In most cases, adhesive resins had higher bond strengths to stainless steel, titanium, and carbon fiber than to zirconium oxide.

Nitrification and the ammonia-oxidizing communities in the central Baltic Sea water column

NASA Astrophysics Data System (ADS)

Jäntti, Helena; Ward, Bess B.; Dippner, Joachim W.; Hietanen, Susanna

2018-03-01

The redoxclines that form between the oxic and anoxic water layers in the central Baltic Sea are sites of intensive nitrogen cycling. To gain better understanding of nitrification, we measured the biogeochemical properties along with potential nitrification rates and analyzed the assemblages of ammonia-oxidizing bacteria and archaea using functional gene microarrays. To estimate nitrification in the entire water column, we constructed a regression model for the nitrification rates and applied it to the conditions prevailing in the area in 2008-2012. The highest ammonia oxidation rates were found in a thin layer at the top of the redoxcline and the rates quickly decreased below detection limit when oxygen was exhausted. This is probably because extensive suboxic layers, which are known to harbor pelagic nitrification, are formed only for short periods after inflows in the Baltic Sea. The nitrification rates were some of the highest measured in the water columns, but the thickness of the layer where conditions were favorable for nitrification, was very small and it remained fairly stable between years. However, the depth of the nitrification layer varied substantially between years, particularly in the eastern Gotland Basin (EGB) due to turbulence in the water column. The ammonia oxidizer communities clustered differently between the eastern and western Gotland Basin (WGB) and the composition of ammonia-oxidizing assemblages correlated with the environmental variables. The ammonia oxidizer community composition was more even in the EGB, which may be related to physical instability of the redoxcline that does not allow predominance of a single archetype, whereas in the WGB, where the position of the redoxcline is more constant, the ammonia-oxidizing community was less even. Overall the ammonia-oxidizing communities in the Baltic Sea redoxclines were very evenly distributed compared to other marine environments where microarrays have been applied previously.

Resveratrol modulates apoptosis and oxidation in human blood mononuclear cells.

PubMed

Losa, G A

2003-09-01

We examined the effect of resveratrol (RS), a nonflavonoid polyphenolic phytoalexin found in grapes and red wine, and RS coincubated with the oxidant 2-deoxy-D-ribose (dR), on apoptosis and on the oxidative metabolic status of normal human peripheral blood mononuclear cells (PBMNCs) isolated ex vivo from healthy donors. Apoptosis was measured by changes of membrane permeability to propidium iodide (PI), plasma membrane exposure of phosphatidylserine (PS) and intracellular caspase activity. Oxidative status was assessed by recording the intracellular glutathione concentration (GSH), the activities of the enzymes y-glutamyltransferase (y-GT) and glutathione-S-transferase (GST), and intracellular lipid peroxidation (MDA). Neither apoptotic nor oxidative parameters were affected by culturing PBMNCs in medium containing RS up to 20 micro M for 5 days, while the frequency of cells with intermediate permeability to PI (17% +/- 5) increased at 50 micro M of RS. Thus resveratrol was slightly toxic, but there was little apoptosis in these cells. Peripheral blood mononuclear cells were also grown first in medium plus RS for 24 h and then for 96 h in medium containing RS plus 10 mM of dR, an oxidant sugar that is apoptogenic for human lymphocytes. The apoptotic changes triggered by dR were counteracted by the phytoalexin in a dose-dependent manner, but RS activity was absent at the lowest concentration (5 micro M) and significantly reduced at the highest concentration used (50 micro M). In PBMNCs coincubated with 20 micro M of RS and 10 mM of dR the antioxidant effect of RS manifested with a significant reduction of caspases-3, -8, y-GT, GST activities and MDA content. Peripheral blood mononuclear cells acquire antioxidant capacity when treated with RS. Grape resveratrol may make a useful dietary supplement for minimizing oxidative injury in immune-perturbed states and human chronic degenerative diseases.

Mechanism of Oxidation of Ethane to Ethanol at Iron(IV)-Oxo Sites in Magnesium-Diluted Fe2(dobdc).

PubMed

Verma, Pragya; Vogiatzis, Konstantinos D; Planas, Nora; Borycz, Joshua; Xiao, Dianne J; Long, Jeffrey R; Gagliardi, Laura; Truhlar, Donald G

2015-05-06

The catalytic properties of the metal-organic framework Fe2(dobdc), containing open Fe(II) sites, include hydroxylation of phenol by pure Fe2(dobdc) and hydroxylation of ethane by its magnesium-diluted analogue, Fe0.1Mg1.9(dobdc). In earlier work, the latter reaction was proposed to occur through a redox mechanism involving the generation of an iron(IV)-oxo species, which is an intermediate that is also observed or postulated (depending on the case) in some heme and nonheme enzymes and their model complexes. In the present work, we present a detailed mechanism by which the catalytic material, Fe0.1Mg1.9(dobdc), activates the strong C-H bonds of ethane. Kohn-Sham density functional and multireference wave function calculations have been performed to characterize the electronic structure of key species. We show that the catalytic nonheme-Fe hydroxylation of the strong C-H bond of ethane proceeds by a quintet single-state σ-attack pathway after the formation of highly reactive iron-oxo intermediate. The mechanistic pathway involves three key transition states, with the highest activation barrier for the transfer of oxygen from N2O to the Fe(II) center. The uncatalyzed reaction, where nitrous oxide directly oxidizes ethane to ethanol is found to have an activation barrier of 280 kJ/mol, in contrast to 82 kJ/mol for the slowest step in the iron(IV)-oxo catalytic mechanism. The energetics of the C-H bond activation steps of ethane and methane are also compared. Dehydrogenation and dissociation pathways that can compete with the formation of ethanol were shown to involve higher barriers than the hydroxylation pathway.

Maceral distributions in Illinois coals and their paleoenvironmental implications

USGS Publications Warehouse

Harvey, R.D.; Dillon, J.W.

1985-01-01

For purposes of assessing the maceral distribution of Illinois (U.S.A.) coals analyses were assembled for 326 face channel and drill core samples from 24 coal members of the Pennsylvanian System. The inertinite content of coals from the Missourian and Virgilian Series averages 16.1% (mineral free), compared to 9.4% for older coals from the Desmoinesian and older Series. This indicates there was generally a higher state of oxidation in the peat that formed the younger coals. This state probably resulted from greater exposure of these peats to weathering as the climate became drier and the water table lower than was the case for the older coals, although oxidation during allochthonous deposition of inertinite components is a genetic factor that needs further study to confirm the importance of the climate. Regional variation of the vitrinite-inertinite ratio (V-I), on a mineral- and micrinite-free basis, was observed in the Springfield (No. 5) and Herrin (No. 6) Coal Members to be related to the geographical position of paleochannel (river) deposits known to have been contemporaneous with the peats that formed these two coal strata. The V-I ratio is highest (generally 12-27) in samples from areas adjacent to the channels, and lower (5-11) some 10-20 km away. We interpret the V-I ratio to be an inverse index of the degree of oxidation to which the original peat was exposed. High V-I ratio coal located near the channels probably formed under more anoxic conditions than did the lower V-I ratio coal some distance away from the channels. The low V-I ratio coal probably formed in areas of the peat swamp where the watertable was generally lower than the channel areas. ?? 1986.

Plant hemoglobins may be maintained in functional form by reduced flavins in the nuclei, and confer differential tolerance to nitro-oxidative stress.

PubMed

Sainz, Martha; Pérez-Rontomé, Carmen; Ramos, Javier; Mulet, Jose Miguel; James, Euan K; Bhattacharjee, Ujjal; Petrich, Jacob W; Becana, Manuel

2013-12-01

The heme of bacteria, plant and animal hemoglobins (Hbs) must be in the ferrous state to bind O(2) and other physiological ligands. Here we have characterized the full set of non-symbiotic (class 1 and 2) and 'truncated' (class 3) Hbs of Lotus japonicus. Class 1 Hbs are hexacoordinate, but class 2 and 3 Hbs are pentacoordinate. Three of the globins, Glb1-1, Glb2 and Glb3-1, are nodule-enhanced proteins. The O(2) affinity of Glb1-1 (50 pm) was the highest known for any Hb, and the protein may function as an O(2) scavenger. The five globins were reduced by free flavins, which transfer electrons from NAD(P)H to the heme iron under aerobic and anaerobic conditions. Class 1 Hbs were reduced at very fast rates by FAD, class 2 Hbs at slower rates by both FMN and FAD, and class 3 Hbs at intermediate rates by FMN. The members of the three globin classes were immunolocalized predominantly in the nuclei. Flavins were quantified in legume nodules and nuclei, and their concentrations were sufficient to maintain Hbs in their functional state. All Hbs, except Glb1-1, were expressed in a flavohemoglobin-deficient yeast mutant and found to confer tolerance to oxidative stress induced by methyl viologen, copper or low temperature, indicating an anti-oxidative role for the hemes. However, only Glb1-2 and Glb2 afforded protection against nitrosative stress induced by S-nitrosoglutathione. Because this compound is specifically involved in transnitrosylation reactions with thiol groups, our results suggest a contribution of the single cysteine residues of both proteins in the stress response. © 2013 The Authors The Plant Journal © 2013 John Wiley & Sons Ltd.

Bioavailability of Compounds Susceptible to Enzymatic Oxidation Enhances Growth of Shiitake Medicinal Mushroom (Lentinus edodes) in Solid-State Fermentation with Vineyard Prunings.

PubMed

Cabrera, Rosina; López-Peña, Damian; Asaff, Ali; Esqueda, Martín; Valenzuela-Soto, Elisa M

2018-01-01

Grapes are widely produced in northwestern Mexico, generating many wood trimmings (vineyard prunings) that have no further local use. This makes vineyard prunings a very attractive alternative for the cultivation of white-rot medicinal mushrooms such as Lentinus edodes. This type of wood can also offer a model for the evaluation of oxidative enzyme production during the fermentation process. We tested the effect of wood from vineyard prunings on the vegetative growth of and production of ligninolytic enzymes in L. edodes in solid-state fermentation and with wheat straw as the control substrate. The specific growth rate of the fungus was 2-fold higher on vineyard pruning culture (μM = 0.95 day-1) than on wheat straw culture (μM = 0.47 day-1). Laccase-specific production was 4 times higher in the vineyard prunings culture than on wheat straw (0.34 and 0.08 mU · mg protein-1 · ppm CO2-1, respectively), and manganese peroxidase production was 3.7 times higher on wheat straw culture than on vineyard prunings (2.21 and 0.60 mU · mg protein-1 · ppm CO2-1, respectively). To explain accurately these differences in growth and ligninolytic enzyme activity, methanol extracts were obtained from each substrate and characterized. Resveratrol and catechins were the main compounds identified in vineyard prunings, whereas epigallocatechin was the only one detected in wheat straw. Compounds susceptible to enzymatic oxidation are more bioavailable in vineyard prunings than in wheat straw, and thus the highest L. edodes growth rate is associated with the presence of these compounds.

On the annealing-induced enhancement of the interface properties of NiO:Cu/wet-SiOx/n-Si tunnelling junction solar cells

NASA Astrophysics Data System (ADS)

Yang, Xueliang; Liu, Wei; Chen, Jingwei; Sun, Yun

2018-04-01

Using metal oxides to form a carrier-selective interface on crystalline silicon (c-Si) has recently generated considerable interest for use with c-Si photovoltaics because of the potential to reduce cost. n-type oxides, such as MoO3, V2O5, and WO3, have been widely studied. In this work, a p-type oxide, Cu-doped NiO (NiO:Cu), is explored as a transparent hole-selective contact to n-Si. An ultrathin SiOx layer, fabricated by a wet-chemical method (wet-SiOx), is introduced at the NiO:Cu/n-Si interface to achieve a tunnelling junction solar cell. Interestingly, it was observed that the interface quality of the NiO:Cu/wet-SiOx/n-Si heterojunction was dramatically enhanced by post-deposition annealing (PDA) at a temperature of 200 °C. Our device exhibits an improved power conversion efficiency of 10.8%, which is the highest efficiency among NiO/Si heterojunction photo-electric devices to date. It is demonstrated that the 200 °C PDA treatment enhances the built-in field by a reduction in the interface density of states (Dit) but does not influence the work function of the NiO:Cu thin layer. This stable work function after the PDA treatment is in conflict with the changed built-in field according to the Schottky model. Thus, the Bardeen model is introduced for this physical insight: the enhancement of the built-in field originates from the unpinning of the Fermi levels of NiO:Cu and n-Si by the interface state reduction.

Biodegradability of fluoxetine, mefenamic acid, and metoprolol using different microbial consortiums.

PubMed

Velázquez, Yolanda Flores; Nacheva, Petia Mijaylova

2017-03-01

The biodegradation of fluoxetine, mefenamic acid, and metoprolol using ammonium-nitrite-oxidizing consortium, nitrite-oxidizing consortium, and heterotrophic biomass was evaluated in batch tests applying different retention times. The ammonium-nitrite-oxidizing consortium presented the highest biodegradation percentages for mefenamic acid and metoprolol, of 85 and 64% respectively. This consortium was also capable to biodegrade 79% of fluoxetine. The heterotrophic consortium showed the highest ability to biodegrade fluoxetine reaching 85%, and it also had a high potential for biodegrading mefenamic acid and metoprolol, of 66 and 58% respectively. The nitrite-oxidizing consortium presented the lowest biodegradation of the three pharmaceuticals, of less than 48%. The determination of the selected pharmaceuticals in the dissolved phase and in the biomass indicated that biodegradation was the major removal mechanism of the three compounds. Based on the obtained results, the biodegradation kinetics was adjusted to pseudo-first-order for the three pharmaceuticals. The values of k biol for fluoxetine, mefenamic acid, and metoprolol determined with the three consortiums indicated that ammonium-nitrite-oxidizing and heterotrophic biomass allow a partial biodegradation of the compounds, while no substantial biodegradation can be expected using nitrite-oxidizing consortium. Metoprolol was the less biodegradable compound. The sorption of fluoxetine and mefenamic acid onto biomass had a significant contribution for their removal (6-14%). The lowest sorption coefficients were obtained for metoprolol indicating that the sorption onto biomass is poor (3-4%), and the contribution of this process to the global removal can be neglected.

Strongly-correlated crystal-field approach to heavy-fermion compounds and to 3d oxides

NASA Astrophysics Data System (ADS)

Radwanski, Ryszard; Ropka, Zofia

2005-03-01

The description of electronic and magnetic properties of real compounds like LaMnO3, LaCoO3, Na2V3O7, FeO, NdAl2 and ErNi5 as well as heavy-fermion superconductor UPd2Al3 and heavy-fermion metal YbRh2Si2, both zero-temperature ground state properties and thermodynamics, will be presented pointing out the existence of a discrete atomic-like low-energy, in the meV scale, electronic structure. This low-energy many-electron discrete atomic-like electronic structure is governed by very strong electron correlations, predominantly on-site, by the intra-atomic spin-orbit coupling and by details of the local surrounding (crystal-field interactions), but later is modified by inter-site interactions. Our studies indicate that there is the highest time to ``unquench'' the orbital moment in solid state physics in description of 3d-/4f-/5f-atom containing compounds and that heavy-fermion phenomena are of the relativistic origin.

Occurrence of alachlor and its sulfonated metabolite in rivers and reservoirs of the midwestern United States: The importance of sulfonation in the transport of chloroacetanilide herbicides

USGS Publications Warehouse

Thurman, E.M.; Goolsby, D.A.; Aga, D.S.; Pomes, M.L.; Meyer, M.T.

1996-01-01

Alachlor and its metabolite, 2-[(2',6'-diethylphenyl)- (methoxymethyl)amino]-2-oxoethanesulfonate (ESA), were identified in 76 reservoirs in the midwestern United States using immunoassay, liquid chromatography, and gas chromatography/mass spectrometry. The median concentration of ESA (0.48 ??g/L) exceeded the median concentration of alachlor (<0.05 ??g/L), with highest values in the upper Midwest. ESA also was detected in the Mississippi River from the mouth to the headwaters at concentrations of 0.2-1.5 ??g/L, exceeding the concentration of alachlor. In a field runoff study, alachlor rapidly formed ESA. It is hypothesized that a glutathione conjugate forms, which later oxidizes in soil to ESA. The removal of the chlorine atom lessens the toxicity of the parent compound and increases runoff potential. It is hypothesized further that sulfonic acid metabolites of other chloroacetanilides, including acetochlor, butachlor, metolachlor, and propachlor, also occur in surface water.

Genistein modulates oxidative stress in breast cancer cell lines according to ERα/ERβ ratio: effects on mitochondrial functionality, sirtuins, uncoupling protein 2 and antioxidant enzymes.

PubMed

Nadal-Serrano, Mercedes; Pons, Daniel Gabriel; Sastre-Serra, Jorge; Blanquer-Rosselló, M del Mar; Roca, Pilar; Oliver, Jordi

2013-09-01

Genistein is a biologically active isoflavone with estrogenic activity and can be found in a variety of soy products. This natural compound displays a wide array of biological activities, but it is best known for its ability to inhibit cancer progression, especially for hormone-related ones such as breast cancer. Genistein has been shown to bind both the estrogen receptor alpha (ERα) and the estrogen receptor beta (ERβ), although it has a higher affinity for the ERβ. The ERα/ERβ ratio is a prognostic marker for breast tumors, and ERβ expression could indicate the presence of tumors more benign in state, whereas ERα indicates malignant tumors. The objective of the present study was to investigate the effects of genistein on oxidative stress and mitochondrial functionality through its interaction with the estrogen receptor in breast cancer cell lines with different ERα/ERβ ratios. The lower ERα/ERβ ratio T47D cell line showed lower oxidative stress and greater mitochondrial functionality, along with an up-regulation of uncoupling protein 2 and sirtuins. On the other hand, genistein-treated MCF-7 cell line, with the highest ERα/ERβ ratio, reported no changes for the control situation. On the whole, our results show different genistein effects depending on ERα/ERβ ratio for oxidative stress regulation, mitochondrial functionality, and modulation of UCPs, antioxidant enzymes and sirtuins in breast cancer cell lines. Effects of genistein on oxidative stress and mitochondria could be due at least in part, to a higher ERβ presence, but could also be due to up-regulation of ERβ caused by the genistein treatment. Copyright © 2013 Elsevier Ltd. All rights reserved.

Antimutagenic and free radical scavenger effects of leaf extracts from Accacia salicina.

PubMed

Boubaker, Jihed; Mansour, Hedi Ben; Ghedira, Kamel; Chekir-Ghedira, Leila

2011-12-01

Three extracts were prepared from the leaves of Accacia salicina; ethyl acetate (EA), chloroform (Chl) and petroleum ether (PE) extracts and was designed to examine antimutagenic, antioxidant potenty and oxidative DNA damage protecting activity. Antioxidant activity of A. salicina extracts was determined by the ability of each extract to protect against plasmid DNA strand scission induced by hydroxyl radicals. An assay for the ability of these extracts to prevent mutations induced by various oxidants in Salmonella typhimurium TA102 and TA 104 strains was conducted. In addition, nonenzymatic methods were employed to evaluate anti-oxidative effects of tested extracts. These extracts from leaf parts of A. salicina showed no mutagenicity either with or without the metabolic enzyme preparation (S9). The highest protections against methylmethanesulfonate induced mutagenicity were observed with all extracts and especially chloroform extract. This extract exhibited the highest inhibitiory level of the Ames response induced by the indirect mutagen 2- aminoanthracene. All extracts exhibited the highest ability to protect plasmid DNA against hydroxyl radicals induced DNA damages. The ethyl acetate (EA) and chloroform (Chl) extracts showed with high TEAC values radical of 0.95 and 0.81 mM respectively, against the ABTS(.+). The present study revealed the antimutagenic and antioxidant potenty of plant extract from Accacia salicina leaves. © 2011 Boubaker et al; licensee BioMed Central Ltd.

Process parameter-growth environment-film property relationships for reactive sputter deposited metal (V, Nb, Zr, Y, Au) oxide, nitride, and oxynitride films. Final report, 1 January 1989-30 June 1993

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

Aita, C.R.

1993-09-30

The research developed process parameter-growth environment-film property relations (phase maps) for model sputter-deposited transition metal oxides, nitrides, and oxynitrides grown by reactive sputter deposition at low temperature. Optical emission spectrometry was used for plasma diagnostics. The results summarized here include the role of sputtered metal-oxygen molecular flux in oxide film growth; structural differences in highest valence oxides including conditions for amorphous growth; and using fundamental optical absorption edge features to probe short range structural disorder. Eight appendices containing sixteen journal articles are included.

Effect of mass density on surface morphology of electrodeposited manganese oxide films

NASA Astrophysics Data System (ADS)

Singh, Avtar; Kumar, Davinder; Thakur, Anup; Kaur, Raminder

2018-05-01

This work focus on high surface area morphology of manganese oxide films which are currently required for electrochemical capacitor electrode to enhance their performance. Electrodeposition of manganese oxide films was carried out using Chronoamperometry for different deposition time ranging from 30 to 120 sec. Cronoamperomertic I-T integrated data have been used to analyze active mass of all electrodeposited films. Morphological study of the deposited films with different mass was carried out through scanning electron microscopy. Film deposited for 30 sec time show highest porous morphology than others. Manganese oxide films with high porosity are suitable for electrochemical capacitor electrode.

Corrosion-induced release of the main alloying constituents of manganese-chromium stainless steels in different media.

PubMed

Herting, Gunilla; Wallinder, Inger Odnevall; Leygraf, Christofer

2008-09-01

The main focus of this paper is the assessment of release rates of chromium, nickel, iron and manganese from manganese-chromium stainless steel grades of low nickel content. The manganese content varied between 9.7 and 1.5 wt% and the corresponding nickel content between 1 and 5 wt%. All grades were exposed to artificial rain and two were immersed in a synthetic body fluid of similar pH but of different composition and exposure conditions. Surface compositional studies were performed using X-ray photoelectron spectroscopy (XPS) in parallel to correlate the metal release process with changes in surface oxide properties. All grades, independent of media, revealed a time-dependent metal release process with a preferential low release of iron and manganese compared to nickel and chromium while the chromium content of the surface oxide increased slightly. Manganese was detected in the surface oxide of all grades, except the grade of the lowest manganese bulk content. No nickel was observed in the outermost surface oxide. Stainless steel grades of the lowest chromium content (approximately 16 wt%) and highest manganese content (approximately 7-9 wt%), released the highest quantity of alloy constituents in total, and vice versa. No correlation was observed between the release rate of manganese and the alloy composition. Released main alloy constituents were neither proportional to the bulk alloy composition nor to the surface oxide composition.

Modelling of nitrogen oxides distribution in the hearth of gas-fired industrial furnace

NASA Astrophysics Data System (ADS)

Zhubrin, S.; Glazov, V.; Guzhov, S.

2017-11-01

A model is proposed for calculating the formation and transportation of nitrogen oxides in the combustion chamber of an industrial furnace heated by gaseous fuels burning. The calculations use a three-dimensional stationary description of turbulent flow and mixing of fuel and oxidizer flows in the presence of heat transfer, mass transfer, and momentum between them transfer. Simulation of the spatial pattern of nitrogen oxides formation in the working space of the furnace is performed in the programming and computing suite SCAN. It is shown that the temperature non-uniformity over the hearth surface is not too pronounced due to the organization of the inclined flow inlet in the direction of the hearth, which is a desirable feature of the furnace operation. The highest concentration of combustion products is observed in the zone of maximum temperatures. In addition, the existence of two zones of the highest generation of oxides has been determined. The first zone is located approximately in the center of the hearth, and the second is located on the far external surface of the furnace. The possibility of using the developed model in the SCAN complex for carrying out parametric studies and engineering calculations, as well as for modification in the direction of adjusting and adapting the model to the regime-constructive features of specific energy technological devices, is noted.

Weatherability and leach resistance of wood impregnated with nano-zinc oxide

Treesearch

Carol A. Clausen; Frederick Green; S. Nami Kartal

2010-01-01

Southern pine specimens vacuum-treated with nano-zinc oxide (nano-ZnO) dispersions were evaluated for leach resistance and UV protection. Virtually, no leaching occurred in any of the nano-ZnO–treated specimens in a laboratory leach test, even at the highest retention of 13 kg/m3. However, specimens treated with high concentrations of nano-ZnO...

Approaches to Determining the Oxidation State of Nitrogen and Carbon Atoms in Organic Compounds for High School Students

ERIC Educational Resources Information Center

Jurowski, Kamil; Krzeczkowska, Malgorzata Krystyna; Jurowska, Anna

2015-01-01

The concept of oxidation state (or oxidation number) and related issues have always been difficult for students. In addition, there are misunderstandings and obscurities, which can cause improper balancing of the chemical equations (mostly in organic reactions). In particular, these problems are related to determination of the oxidation state of…

Solid state electrochemical current source

DOEpatents

Potanin, Alexander Arkadyevich; Vedeneev, Nikolai Ivanovich

2002-04-30

A cathode and a solid state electrochemical cell comprising said cathode, a solid anode and solid fluoride ion conducting electrolyte. The cathode comprises a metal oxide and a compound fluoride containing at least two metals with different valences. Representative compound fluorides include solid solutions of bismuth fluoride and potassium fluoride; and lead fluoride and potassium fluoride. Representative metal oxides include copper oxide, lead oxide, manganese oxide, vanadium oxide and silver oxide.

Apparatus and method for two-stage oxidation of wastes

DOEpatents

Fleischman, Scott D.

1995-01-01

An apparatus and method for oxidizing wastes in a two-stage process. The apparatus includes an oxidation device, a gas-liquid contacting column and an electrocell. In the first stage of the process, wastes are heated in the presence of air to partially oxidize the wastes. The heated wastes produce an off-gas stream containing oxidizable materials. In the second stage, the off-gas stream is cooled and flowed through the contacting column, where the off-gas stream is contacted with an aqueous acid stream containing an oxidizing agent having at least two positive valence states. At least a portion of the oxidizable materials are transferred to the acid stream and destroyed by the oxidizing agent. During oxidation, the valence of the oxidizing agent is decreased from its higher state to its lower state. The acid stream is flowed to the electrocell, where an electric current is applied to the stream to restore the oxidizing agent to its higher valence state. The regenerated acid stream is recycled to the contacting column.

Inhibitory properties of bambara groundnut protein hydrolysate and peptide fractions against angiotensin-converting enzymes, renin and free radicals.

PubMed

Arise, Abimbola K; Alashi, Adeola M; Nwachukwu, Ifeanyi D; Malomo, Sunday A; Aluko, Rotimi E; Amonsou, Eric O

2017-07-01

An increased rate of high blood pressure has led to critical human hypertensive conditions in most nations. In the present study, bambara protein hydrolysates (BPHs) obtained using three different proteases (alcalase, trypsin and pepsin) and their peptide fractions (molecular weight: 10, 5, 3 and 1 kDa) were investigated for antihypertensive and antioxidant activities. Alcalase hydrolysate contained the highest amount of low molecular weight (LMW) peptides compared to pepsin and trypsin hydrolysates. LMW peptides fractions (<1 kDa) exhibited the highest inhibitory activity against angiotensin-converting enzyme (ACE) for all the enzymes hydrolysates. For renin inhibition, alcalase hydrolysate showed the highest inhibition at 59% compared to other hydrolysates and their corresponding membrane fractions. The antioxidant power of bambara protein hydrolysates and peptide fractions was evaluated through the inhibition of linoleic acid peroxidation and ABTS scavenging activity. Among the hydrolysates, alcalase exhibited the highest inhibition of linoleic acid oxidation. Furthermore, all BPHs were able to scavenge ABTS •+ to a three-fold greater extent compared to the isolate. BPH and LMW peptide fractions could potentially serve as useful ingredients in the formulation of functional foods and nutraceuticals against high blood pressure and oxidative stress. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Sulfate turpentine: a resource of tick repellent compounds.

PubMed

Schubert, Fredrik; Pålsson, Katinka; Santangelo, Ellen; Borg-Karlson, Anna-Karin

2017-07-01

Compounds with tick (Ixodes ricinus) repellent properties were isolated from sulfate turpentine consisting of Norway spruce (80%) and Scots pine (20%) from southern Sweden. The turpentine was divided into two fractions by distillation under reduced pressure resulting in one monoterpene hydrocarbon fraction and a residual containing higher boiling terpenoids. The monoterpene fraction was further oxidized with SeO 2 to obtain oxygenated monoterpenes with potential tick repellent properties. The oxidized fraction and the high boiling distillation residual were each separated by medium pressure liquid chromatography. The fractions were tested for tick repellency and the compounds in those with highest tick repellency were identified by GC-MS. The fractions with highest repellency contained, mainly (-)-borneol, and mixtures of (+)- and (-)-1-terpineol and terpinen-4-ol. The enantiomers of borneol showed similar tick repellent properties.

EROD activity, chromosomal damage, and oxidative stress in response to contaminants exposure in tree swallow (Tachycineta bicolor) nestlings from Great Lakes Areas of Concern

USGS Publications Warehouse

Custer, Thomas W.; Custer, Christine M.; Dummer, Paul; Bigorgne, Emilie; Oziolor, Elias; Karouna-Renier, Natalie K.; Schultz, Sandra; Erickson, Richard A.; Aagaard, Kevin; Matson, Cole W.

2017-01-01

Tree swallow, Tachycineta bicolor, nestlings were collected from 60 sites in the Great Lakes, which included multiple sites within 27 Areas of Concern (AOCs) and six sites not listed as AOCs from 2010 to 2014. Nestlings, approximately 12 days-of-age, were evaluated for ethoxyresorufin-O-dealkylase (EROD) activity, chromosomal damage, and six measures of oxidative stress. Data on each of these biomarkers were divided into four equal numbered groups from the highest to lowest values and the groups were compared to contaminant concentrations using multivariate analysis. Contaminant concentrations, from the same nestlings, included polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), perfluorinated compounds (PFCs), and 17 elements. Alkylated polycyclic aromatic hydrocarbons (aPAHs) and parent PAHs (pPAHs) were measured in pooled nestling dietary samples. Polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and pesticides were measured in sibling eggs. Concentrations of aPAHs, pPAHs, chlordane, dieldrin, heptachlor, and PCBs, in that order, were the major contributors to the significant differences between the lowest and highest EROD activities; PFCs, PBDEs, the remaining pesticides, and all elements were of secondary importance. The four categories of chromosomal damage did not separate out well based on the contaminants measured. Concentrations of aPAHs, pPAHs, heptachlor, PCBs, chlordane, and dieldrin were the major contributors to the significant differences between the lowest and highest activities of two oxidative stress measures, total sulfhydryl (TSH) activity and protein bound sulfhydryl (PBSH) activity. The four categories of thiobarbituric acid reacting substances (TBARS), oxidized glutathione (GSSG), reduced glutathione (GSH), and the ratio of GSSG/GSH did not separate well based on the contaminants measured.

EROD activity, chromosomal damage, and oxidative stress in response to contaminants exposure in tree swallow (Tachycineta bicolor) nestlings from Great Lakes Areas of Concern.

PubMed

Custer, Thomas W; Custer, Christine M; Dummer, Paul M; Bigorgne, Emilie; Oziolor, Elias M; Karouna-Renier, Natalie; Schultz, Sandra; Erickson, Richard A; Aagaard, Kevin; Matson, Cole W

2017-12-01

Tree swallow, Tachycineta bicolor, nestlings were collected from 60 sites in the Great Lakes, which included multiple sites within 27 Areas of Concern (AOCs) and six sites not listed as AOCs from 2010 to 2014. Nestlings, approximately 12 days-of-age, were evaluated for ethoxyresorufin-O-dealkylase (EROD) activity, chromosomal damage, and six measures of oxidative stress. Data on each of these biomarkers were divided into four equal numbered groups from the highest to lowest values and the groups were compared to contaminant concentrations using multivariate analysis. Contaminant concentrations, from the same nestlings, included polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), perfluorinated compounds (PFCs), and 17 elements. Alkylated polycyclic aromatic hydrocarbons (aPAHs) and parent PAHs (pPAHs) were measured in pooled nestling dietary samples. Polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and pesticides were measured in sibling eggs. Concentrations of aPAHs, pPAHs, chlordane, dieldrin, heptachlor, and PCBs, in that order, were the major contributors to the significant differences between the lowest and highest EROD activities; PFCs, PBDEs, the remaining pesticides, and all elements were of secondary importance. The four categories of chromosomal damage did not separate out well based on the contaminants measured. Concentrations of aPAHs, pPAHs, heptachlor, PCBs, chlordane, and dieldrin were the major contributors to the significant differences between the lowest and highest activities of two oxidative stress measures, total sulfhydryl (TSH) activity and protein bound sulfhydryl (PBSH) activity. The four categories of thiobarbituric acid reacting substances (TBARS), oxidized glutathione (GSSG), reduced glutathione (GSH), and the ratio of GSSG/GSH did not separate well based on the contaminants measured.

Growth control of the oxidation state in vanadium oxide thin films

DOE PAGES

Lee, Shinbuhm; Meyer, Tricia L.; Park, Sungkyun; ...

2014-12-05

Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research, but also technological applications that utilize the subtle change in the physical properties originating from the metalinsulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase puremore » epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V₂⁺²O₃, V⁺⁴O₂, and V₂⁺⁵O₅. A well pronounced MIT was only observed in VO₂ films grown in a very narrow range of oxygen partial pressure P(O₂). The films grown either in lower (< 10 mTorr) or higher P(O₂) (> 25 mTorr) result in V₂O₃ and V₂O₅ phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO₂ thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an 3 improved MIT behavior.« less

Growth control of the oxidation state in vanadium oxide thin films

NASA Astrophysics Data System (ADS)

Lee, Shinbuhm; Meyer, Tricia L.; Park, Sungkyun; Egami, Takeshi; Lee, Ho Nyung

2014-12-01

Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research but also technological applications that utilize the subtle change in the physical properties originating from the metal-insulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase pure epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V2 + 3 O 3 , V + 4 O 2 , and V2 + 5 O 5 . A well pronounced MIT was only observed in VO2 films grown in a very narrow range of oxygen partial pressure P(O2). The films grown either in lower (<10 mTorr) or higher P(O2) (>25 mTorr) result in V2O3 and V2O5 phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO2 thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an improved MIT behavior.

Growth control of the oxidation state in vanadium oxide thin films

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

Lee, Shinbuhm; Meyer, Tricia L.; Lee, Ho Nyung, E-mail: hnlee@ornl.gov

2014-12-01

Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research but also technological applications that utilize the subtle change in the physical properties originating from the metal-insulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase puremore » epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V{sub 2}{sup +3}O{sub 3}, V{sup +4}O{sub 2}, and V{sub 2}{sup +5}O{sub 5}. A well pronounced MIT was only observed in VO{sub 2} films grown in a very narrow range of oxygen partial pressure P(O{sub 2}). The films grown either in lower (<10 mTorr) or higher P(O{sub 2}) (>25 mTorr) result in V{sub 2}O{sub 3} and V{sub 2}O{sub 5} phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO{sub 2} thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an improved MIT behavior.« less

The redox state of endogenous pyridine nucleotides can determine both the degree of mitochondrial oxidative stress and the solute selectivity of the permeability transition pore.

PubMed

Zago, E B; Castilho, R F; Vercesi, A E

2000-07-28

Acetoacetate, an NADH oxidant, stimulated the ruthenium red-insensitive rat liver mitochondrial Ca(2+) efflux without significant release of state-4 respiration, disruption of membrane potential (Deltapsi) or mitochondrial swelling. This process is compatible with the opening of the currently designated low conductance state of the permeability transition pore (PTP) and, under our experimental conditions, was associated with a partial oxidation of the mitochondrial pyridine nucleotides. In contrast, diamide, a thiol oxidant, induced a fast mitochondrial Ca(2+) efflux associated with a release of state-4 respiration, a disruption of Deltapsi and a large amplitude mitochondrial swelling. This is compatible with the opening of the high conductance state of the PTP and was associated with extensive oxidation of pyridine nucleotides. Interestingly, the addition of carbonyl cyanide p-(trifluoromethoxy)phenylhydrazone to the acetoacetate experiment promoted a fast shift from the low to the high conductance state of the PTP. Both acetoacetate and diamide-induced mitochondrial permeabilization were inhibited by exogenous catalase. We propose that the shift from a low to a high conductance state of the PTP can be promoted by the oxidation of NADPH. This impairs the antioxidant function of the glutathione reductase/peroxidase system, strongly strengthening the state of mitochondrial oxidative stress.

Facilitating Proton Transport in Nafion-Based Membranes at Low Humidity by Incorporating Multifunctional Graphene Oxide Nanosheets.

PubMed

He, Xueyi; He, Guangwei; Zhao, Anqi; Wang, Fei; Mao, Xunli; Yin, Yongheng; Cao, Li; Zhang, Bei; Wu, Hong; Jiang, Zhongyi

2017-08-23

Nafion, as a state-of-the-art solid electrolyte for proton exchange membrane fuel cells (PEMFCs), suffers from drastic decline in proton conductivity with decreasing humidity, which significantly restricts the efficient and stable operation of the fuel cell system. In this study, the proton conductivity of Nafion at low relative humidity (RH) was remarkably enhanced by incorporating multifunctional graphene oxide (GO) nanosheets as multifunctional fillers. Through surface-initiated atom transfer radical polymerization of sulfopropyl methacrylate (SPM) and poly(ethylene glycol) methyl ether methacrylate, the copolymer-grafted GO was synthesized and incorporated into the Nafion matrix, generating efficient paths at the Nafion-GO interface for proton conduction. The Lewis basic oxygen atoms of ethylene oxide (EO) units and sulfonated acid groups of SPM monomers served as additional proton binding and release sites to facilitate the proton hopping through the membrane. Meanwhile, the hygroscopic EO units enhanced the water retention property of the composite membrane, conferring a dramatic increase in proton conductivity under low humidity. With 1 wt % filler loading, the composite membrane displayed the highest proton conductivity of 2.98 × 10 -2 S cm -1 at 80 °C and 40% RH, which was 10 times higher than that of recast Nafion. Meanwhile, the Nafion composite exhibited a 135.5% increase in peak power density at 60 °C and 50% RH, indicating its great application potential in PEMFCs.

Investigation of hydrogen evolution activity for the nickel, nickel-molybdenum nickel-graphite composite and nickel-reduced graphene oxide composite coatings

NASA Astrophysics Data System (ADS)

Jinlong, Lv; Tongxiang, Liang; Chen, Wang

2016-03-01

The nickel, nickel-molybdenum alloy, nickel-graphite and nickel-reduced graphene oxide composite coatings were obtained by the electrodeposition technique from a nickel sulfate bath. Nanocrystalline molybdenum, graphite and reduced graphene oxide in nickel coatings promoted hydrogen evolution reaction in 0.5 M H2SO4 solution at room temperature. However, the nickel-reduced graphene oxide composite coating exhibited the highest electrocatalytic activity for the hydrogen evolution reaction in 0.5 M H2SO4 solution at room temperature. A large number of gaps between 'cauliflower' like grains could decrease effective area for hydrogen evolution reaction in slight amorphous nickel-molybdenum alloy. The synergistic effect between nickel and reduced graphene oxide promoted hydrogen evolution, moreover, refined grain in nickel-reduced graphene oxide composite coating and large specific surface of reduced graphene oxide also facilitated hydrogen evolution reaction.

Charge transfer in rectifying oxide heterostructures and oxide access elements in ReRAM

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

Stefanovich, G. B.; Pergament, A. L.; Boriskov, P. P.

2016-05-15

The main aspects of the synthesis and experimental research of oxide diode heterostructures are discussed with respect to their use as selector diodes, i.e., access elements in oxide resistive memory. It is shown that charge transfer in these materials differs significantly from the conduction mechanism in p–n junctions based on conventional semiconductors (Si, Ge, A{sup III}–B{sup V}), and the model should take into account the electronic properties of oxides, primarily the low carrier drift mobility. It is found that an increase in the forward current requires an oxide with a small band gap (<1.3 eV) in the heterostructure composition. Heterostructuresmore » with Zn, In–Zn (IZO), Ti, Ni, and Cu oxides are studied; it is found that the CuO–IZO heterojunction has the highest forward current density (10{sup 4} A/cm{sup 2}).« less

Role of vitamin B6 status on antioxidant defenses, glutathione, and related enzyme activities in mice with homocysteine-induced oxidative stress.

PubMed

Hsu, Cheng-Chin; Cheng, Chien-Hsiang; Hsu, Chin-Lin; Lee, Wan-Ju; Huang, Shih-Chien; Huang, Yi-Chia

2015-01-01

Vitamin B6 may directly or indirectly play a role in oxidative stress and the antioxidant defense system. The purpose of this study was to examine the associations of vitamin B6 status with cysteine, glutathione, and its related enzyme activities in mice with homocysteine-induced oxidative stress. Four-week-old male BALB/c mice were weighed and divided into one of four dietary treatment groups fed either a normal diet (as a control group and a homocysteine group), a vitamin B6-deficient diet (as a B6-deficient group), or a B6-supplemented diet (a pyridoxine-HCl-free diet supplemented with 14 mg/kg of pyridoxine-HCl, as a B6 supplement group) for 28 days. Homocysteine thiolactone was then added to drinking water in three groups for 21 days to induce oxidative stress. At the end of the study, mice were sacrificed by decapitation and blood and liver samples were obtained. Mice with vitamin B6-deficient diet had the highest homocysteine concentration in plasma and liver among groups. Significantly increased hepatic malondialdehyde levels were observed in the vitamin B6-deficient group. Among homocysteine-treated groups, mice with vitamin B6-deficient diet had the highest plasma glutathione concentration and relatively lower hepatic glutathione concentration. The glutathione peroxidase activities remained relatively stable in plasma and liver whether vitamin B6 was adequate, deficient, or supplemented. Mice with deficient vitamin B6 intakes had an aggravate effect under homocysteine-induced oxidative stress. The vitamin B6-deficient status seems to mediate the oxidative stress in connection with the redistribution of glutathione from liver to plasma, but not further affect glutathione-related enzyme activities in mice with homocysteine-induced oxidative stress.

Thermionic converter performance with oxide collectors

NASA Technical Reports Server (NTRS)

Lieb, D.; Goodale, D.; Briere, T.; Balestra, C.

1977-01-01

Thermionic converters using a variety of metal oxide collector surfaces have been fabricated and tested. Both work function and power output data are presented and evaluated. Oxides of barium, strontium, zinc, tungsten and titanium have been incorporated into a variable spacing converter. Tungsten oxide was found to give the highest converter performance and to furnish oxygen for the emitter at the same time. Oxygenated emitters operate at reduced cesium pressure with an increase in electrode spacing. Electron spectroscopy for chemical analysis (ESCA) performed on several tungsten oxide collectors showed cesium penetration of the oxide layer, possibly forming a cesium tungstate bronze. Titanium oxide showed high performance but did not furnish oxygen for the emitter; strontium oxide, in the form of a sprayed layer, appeared to dissociate in the presence of cesium. Sprayed coatings of barium and zinc oxides produced collector work functions of about 1.3 eV, but had excessive series resistance. Lanthanum hexaboride, in combination with oxygen introduced through a silver tube, and cesium produced a low work function collector and better than average performance.

Synthesis and superconductivity of highly underdoped HgBa2CuO4+δ

NASA Astrophysics Data System (ADS)

Edwards, P. P.; Gameson, I.; Fletcher, A.; Peacock, G. B.

1998-05-01

The highest transition temperature superconductors are found within the complex homologous series HgBa2Can-1CunO2n+2+δ (n=1-7), with the third member, HgBa2Ca2Cu3O8+δ possessing the record-high transition temperature (Tc) of 135 K at room pressure. The first member of this family, HgBa2CuO4+δ having a Tc of up to 97 K, displays the highest transition temperature for any analogous compounds with a single copper-layer. The chemical reaction for the formation of this material is intrinsically complex due to the natural high volatility of mercury-bearing compounds; chemical synthesis has been postulated to proceed via a solid-vapour reaction. With this in mind, we have developed a mixed solid/vapour phase synthesis for HgBa2CuO4+δ using what one might term a `remote' source of mercury, in this case elemental Hg itself. Interestingly, because of the zero oxidation state of elemental mercury in the reagent mixture, the synthesis reaction proceeds under reducing conditions. By this route, a highly underdoped state (Tc<=35 K) of the superconducting phase HgBa2CuO4+δ is readily obtained. This level of underdoping is extremely difficult to achieve by more conventional synthetic routes. We comment on the unusually high oxygen affinity of the resulting underdoped compound, in relation to other cuprate superconductors, and the implied mobility of oxygen defects within the crystal structure.

GHG emissions and mitigation potential in Indian agriculture

NASA Astrophysics Data System (ADS)

Vetter, Sylvia; Feliciano, Diana; Sapkota, Tek; Hillier, Jon; Smith, Pete; Stirling, Clare

2016-04-01

India is one of the world's largest greenhouse gas (GHG) emitter, accounting for about 5% of global emissions with further increases expected in the future. The Government of India aims to reduce emission intensities by 20-25% by 2020 compared with the 2005 level. In a recent departure from past practice the reconvened Council on Climate Change stated that climate change in agriculture would include a component that would focus on reducing emissions in agriculture, particularly methane and nitrous oxide emissions. To develop recommendations for mitigation in agriculture in India, a baseline study is presented to analyse the GHG emissions from agriculture for current management (Directorate of Economics and Statistics of the government of India). This analysis is done for the two states Bihar and Haryana, which differ in their management and practises based on different climate and policies. This first analysis shows were the highest GHG emissions in agriculture is produced and were the highest mitigation potential might be. The GHG emissions and mitigation potential are calculated using the CCAFS Mitigation Option Tool (CCAFS-MOT) (https://ccafs.cgiar.org/mitigation-option-tool-agriculture#.VpTnWL826d4) with modifications for the special modelling. In a second step, stakeholder meetings provided a wide range of possible and definite scenarios (management, policy, technology, costs, etc.) for the future to mitigate emissions in agriculture as well as how to increase productivity. These information were used to create scenarios to give estimates for the mitigation potential in agriculture for India in 2020.

Non-equilibrium oxidation states of zirconium during early stages of metal oxidation

DOE PAGES

Ma, Wen; Senanayake, Sanjaya D.; Herbert, F. William; ...

2015-03-11

The chemical state of Zr during the initial, self-limiting stage of oxidation on single crystal zirconium (0001), with oxide thickness on the order of 1 nm, was probed by synchrotron x-ray photoelectron spectroscopy. Quantitative analysis of the Zr 3d spectrum by the spectrum reconstruction method demonstrated the formation of Zr 1+, Zr 2+, and Zr 3+ as non-equilibrium oxidation states, in addition to Zr 4+ in the stoichiometric ZrO 2. This finding resolves the long-debated question of whether it is possible to form any valence states between Zr 0 and Zr 4+ at the metal-oxide interface. As a result, themore » presence of local strong electric fields and the minimization of interfacial energy are assessed and demonstrated as mechanisms that can drive the formation of these non-equilibrium valence states of Zr.« less

CuCo 2O 4 ORR/OER Bi-functional catalyst: Influence of synthetic approach on performance

DOE PAGES

Serov, Alexey; Andersen, Nalin I.; Roy, Aaron J.; ...

2015-02-07

A series of CuCo 2O 4 catalysts were synthesized by pore forming, sol-gel, spray pyrolysis and sacrificial support methods. Catalysts were characterized by XRD, SEM, XPS and BET techniques. The electrochemical activity for the oxygen reduction and oxygen evolution reactions (ORR and OER) was evaluated in alkaline media by RRDE. Density Functional Theory was used to identify two different types of active sites responsible for ORR/OER activity of CuCo 2O 4 and it was found that CuCo 2O 4 can activate the O-O bond by binding molecular oxygen in bridging positions between Co or Co and Cu atoms. It wasmore » found that the sacrificial support method (SSM) catalyst has the highest performance in both ORR and OER and has the highest content of phase-pure CuCo 2O 4. It was shown that the presence of CuO significantly decreases the activity in oxygen reduction and oxygen evolution reactions. As a result, the half-wave potential (E 1/2) of CuCo 2O 4-SSM was found as 0.8 V, making this material a state-of-the-art, unsupported oxide catalyst.« less

Fabrication of transparent TiO2 nanotube-based photoanodes for CdS/CdTe quantum co-sensitized solar cells

NASA Astrophysics Data System (ADS)

Gualdrón-Reyes, A. F.; Cárdenas-Arenas, A.; Martínez, C. A.; Kouznetsov, V. V.; Meléndez, A. M.

2017-01-01

In order to fabricate a solar cell, ordered TiO2 nanotube (TNT) arrays were prepared by double anodization. TNT arrays with variable lengths were obtained by changing the duration of the anodizing process of up to 3h. TNT membranes were transferred to indium tin oxide substrates and attached with a B-TiO2 sol. TNT photoanode with the best photoelectrochemical performance was sensitized with CdS by SILAR method. On other hand, CdTe quantum dots prepared via colloidal synthesis were deposited on TNT photoanodes for 2h, 4h and 6h. In addition, TNT/CdS was loaded with CdTe quantum dots for 4 h. Morphology and chemical modification of TiO2 were characterized by FESEM and XPS, while their photoelectrochemical performance was measured by open-circuit photopotential and photovoltammetry under visible light. TiO2 nanotubes grown during 2.5h showed the highest photocurrent due to presence of Ti3+ donor states by N and F co-doping, increasing the number of photogenerated electrons transported to back collector. TNT/CdS/CdTe photoanode reach the highest conversion efficiency under AM 1.5G simulated solar illumination.

Large sulfur-isotope anomaly in nonvolcanic sulfate aerosol and its implications for the Archean atmosphere.

PubMed

Shaheen, Robina; Abaunza, Mariana M; Jackson, Teresa L; McCabe, Justin; Savarino, Joël; Thiemens, Mark H

2014-08-19

Sulfur-isotopic anomalies have been used to trace the evolution of oxygen in the Precambrian atmosphere and to document past volcanic eruptions. High-precision sulfur quadruple isotope measurements of sulfate aerosols extracted from a snow pit at the South Pole (1984-2001) showed the highest S-isotopic anomalies (Δ(33)S = +1.66‰ and Δ(36)S = +2‰) in a nonvolcanic (1998-1999) period, similar in magnitude to Pinatubo and Agung, the largest volcanic eruptions of the 20th century. The highest isotopic anomaly may be produced from a combination of different stratospheric sources (sulfur dioxide and carbonyl sulfide) via SOx photochemistry, including photoexcitation and photodissociation. The source of anomaly is linked to super El Niño Southern Oscillation (ENSO) (1997-1998)-induced changes in troposphere-stratosphere chemistry and dynamics. The data possess recurring negative S-isotope anomalies (Δ(36)S = -0.6 ± 0.2‰) in nonvolcanic and non-ENSO years, thus requiring a second source that may be tropospheric. The generation of nonvolcanic S-isotopic anomalies in an oxidizing atmosphere has implications for interpreting Archean sulfur deposits used to determine the redox state of the paleoatmosphere.

Greenhouse gas microbiology in wet and dry straw crust covering pig slurry.

PubMed

Hansen, Rikke R; Nielsen, Daniel Aa; Schramm, Andreas; Nielsen, Lars P; Revsbech, Niels P; Hansen, Martin N

2009-01-01

Liquid manure (slurry) storages are sources of gases such as ammonia (NH(3)) and methane (CH(4)). Danish slurry storages are required to be covered to reduce NH(3) emissions and often a floating crust of straw is applied. This study investigated whether physical properties of the crust or crust microbiology had an effect on the emission of the potent greenhouse gases CH(4) and nitrous oxide (N(2)O) when crust moisture was manipulated ("dry", "moderate", and "wet"). The dry crust had the deepest oxygen penetration (45 mm as compared to 20 mm in the wet treatment) as measured with microsensors, the highest amounts of nitrogen oxides (NO(2)(-) and NO(3)(-)) (up to 36 mumol g(-1) wet weight) and the highest emissions of N(2)O and CH(4). Fluorescent in situ hybridization and gene-specific polymerase chain reaction (PCR) were used to detect occurrence of bacterial groups. Ammonia-oxidizing bacteria (AOB) were abundant in all three crust types, whereas nitrite-oxidizing bacteria (NOB) were undetectable and methane-oxidizing bacteria (MOB) were only sparsely present in the wet treatment. A change to anoxia did not affect the CH(4) emission indicating the virtual absence of aerobic methane oxidation in the investigated 2-mo old crusts. However, an increase in N(2)O emission was observed in all crusted treatments exposed to anoxia, and this was probably a result of denitrification based on NO(x)(-) that had accumulated in the crust during oxic conditions. To reduce overall greenhouse gas emissions, floating crust should be managed to optimize conditions for methanotrophs.

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

PubMed

Blewett, Tamzin A; Wood, Chris M

2015-02-01

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

Highly Sensitive Sensors Based on Metal-Oxide Nanocolumns for Fire Detection.

PubMed

Lee, Kwangjae; Shim, Young-Seok; Song, Young Geun; Han, Soo Deok; Lee, Youn-Sung; Kang, Chong-Yun

2017-02-07

A fire detector is the most important component in a fire alarm system. Herein, we present the feasibility of a highly sensitive and rapid response gas sensor based on metal oxides as a high performance fire detector. The glancing angle deposition (GLAD) technique is used to make the highly porous structure such as nanocolumns (NCs) of various metal oxides for enhancing the gas-sensing performance. To measure the fire detection, the interface circuitry for our sensors (NiO, SnO₂, WO₃ and In₂O₃ NCs) is designed. When all the sensors with various metal-oxide NCs are exposed to fire environment, they entirely react with the target gases emitted from Poly(vinyl chlorides) (PVC) decomposed at high temperature. Before the emission of smoke from the PVC (a hot-plate temperature of 200 °C), the resistances of the metal-oxide NCs are abruptly changed and SnO₂ NCs show the highest response of 2.1. However, a commercial smoke detector did not inform any warning. Interestingly, although the NiO NCs are a p -type semiconductor, they show the highest response of 577.1 after the emission of smoke from the PVC (a hot-plate temperature of 350 °C). The response time of SnO₂ NCs is much faster than that of a commercial smoke detector at the hot-plate temperature of 350 °C. In addition, we investigated the selectivity of our sensors by analyzing the responses of all sensors. Our results show the high potential of a gas sensor based on metal-oxide NCs for early fire detection.

SNC Oxygen Fugacity Recorded in Pyroxenes and its Implications for the Oxidation State of the Martian Interior: An Experimental and Analytical Study

NASA Technical Reports Server (NTRS)

McCanta, M. C.; Rutherford, M. J.

2003-01-01

Knowledge of the oxidation state of a magma is critical as it is one of the parameters which controls the nature and composition of the resulting crystals. In terrestrial magmatic systems, oxygen fugacity (fo2) is known to vary by over nine orders of magnitude. With variations of this magnitude, understanding the compositional differences, phase changes, and crystallization sequence variations, caused by the magma fo2, is essential in deciphering the origin of all igneous rocks. Magmatic oxidation state is of great importance in that it reflects the degree of oxidation of the source region and can provide insight into magmatic processes, such as metasomatism, degassing, and assimilation, which may have changed them. Carmichael [1991] argues that most magmas are unlikely to have their redox states altered from those of their source region. This assumption allows for estimation of the oxidation state of planetary interiors. Conversely, it is known that the fo2 of the magma can be affected by other processes, which occur outside of the source region and therefore, the oxidation state may record those too. Processes which could overprint source region fugacities include melt dehydrogenation or other volatile loss, water or melt infiltration, or assimilation of oxidized or reduced wallrock. Understanding which of these processes is responsible for the redox state of a magma can provide crucial information regarding igneous processes and other forces active in the region. The composition of the SNC basalts and their widely varying proposed oxidation states raise some interesting questions. Do the SNC meteorites have an oxidized or reduced signature? What was the oxygen fugacity of the SNC source region at the time of melt generation? Is the fugacity calculated for the various SNC samples the fugacity of the magma source region or was it overprinted by later events? Are there different oxidation states in the Martian interior or a single one? This proposal seeks to address all of these questions.

Effects of biochar and wood pellets amendments added to landfill cover soil on microbial methane oxidation: A laboratory column study.

PubMed

Yargicoglu, Erin N; Reddy, Krishna R

2017-05-15

Alternate landfill covers designed to enhance microbial methane (CH 4 ) oxidation and reduce the negative impacts of landfill gas emissions on global climate have recently been proposed and investigated. In this study, the use of biochar as a soil amendment is examined in order to assess the feasibility and effectiveness for enhanced CH 4 removal in landfill covers when incorporated under high compaction conditions and relatively low soil moisture. Four different cover configurations were tested in large soil columns for ∼510 days and potential CH 4 oxidation rates were determined following long-term incubation in small batch assays. Cover designs tested include: a thin biochar layer at 15-18 cm; 2% mixed soil-biochar layer at 20-40 cm; 2% mixed soil-uncharred wood pellets at 20-40 cm; and soil obtained from intermediate cover at an active landfill site. The placement of a thin biochar layer in the cover significantly impacted moisture distribution and infiltration, which in turn affected CH 4 oxidation potential with depth. An increase in CH 4 removal rates was observed among all columns over the 500 day incubation period, with steady-state CH 4 removal efficiencies ranging from ∼60 to 90% in the final stages of incubation (inlet load ∼80 g CH 4  m -2  d -1 ). The thin biochar layer had the lowest average removal efficiency as a result of reduced moisture availability below the biochar layer. The addition of 2% biochar to soil yielded similar CH 4 oxidation rates in terminal assays as the 2% uncharred wood pellet amendment. CH 4 oxidation rates in terminal assays were positively correlated with soil moisture, which was affected by the materials' water holding capacity. The high water holding capacity of biochar led to higher oxidation rates within the thin biochar layer, supporting the initial hypothesis that biochar may confer more favorable physical conditions for methanotrophy. Ultimate performance was apparently affected by soil type and CH 4 exposure history, with the highest oxidation rates observed in the unamended field soil with higher initial methanotrophic activity. Copyright © 2017 Elsevier Ltd. All rights reserved.

Computer modeling of obesity links theoretical energetic measures with experimental measures of fuel use for lean and obese men.

PubMed

Rossow, Heidi A; Calvert, C Chris

2014-10-01

The goal of this research was to use a computational model of human metabolism to predict energy metabolism for lean and obese men. The model is composed of 6 state variables representing amino acids, muscle protein, visceral protein, glucose, triglycerides, and fatty acids (FAs). Differential equations represent carbohydrate, amino acid, and FA uptake and output by tissues based on ATP creation and use for both lean and obese men. Model parameterization is based on data from previous studies. Results from sensitivity analyses indicate that model predictions of resting energy expenditure (REE) and respiratory quotient (RQ) are dependent on FA and glucose oxidation rates with the highest sensitivity coefficients (0.6, 0.8 and 0.43, 0.15, respectively, for lean and obese models). Metabolizable energy (ME) is influenced by ingested energy intake with a sensitivity coefficient of 0.98, and a phosphate-to-oxygen ratio by FA oxidation rate and amino acid oxidation rate (0.32, 0.24 and 0.55, 0.65 for lean and obese models, respectively). Simulations of previously published studies showed that the model is able to predict ME ranging from 6.6 to 9.3 with 0% differences between published and model values, and RQ ranging from 0.79 to 0.86 with 1% differences between published and model values. REEs >7 MJ/d are predicted with 6% differences between published and model values. Glucose oxidation increases by ∼0.59 mol/d, RQ increases by 0.03, REE increases by 2 MJ/d, and heat production increases by 1.8 MJ/d in the obese model compared with lean model simulations. Increased FA oxidation results in higher changes in RQ and lower relative changes in REE. These results suggest that because fat mass is directly related to REE and rate of FA oxidation, body fat content could be used as a predictor of RQ. © 2014 American Society for Nutrition.

Phenolic Content of Hypodaphnis Zenkeri and Its Antioxidant Effects against Fenton Reactions’ Mediated Oxidative Injuries on Liver Homogenate

PubMed Central

Moukette Moukette, Bruno; Pieme, Constant Anatole; Nya Biapa, Prosper Cabral; Njimou, Jacques Romain; Ama Moor, Vicky Jocelyne; Stoller, Marco; Bravi, Marco; Ngogang, Jeanne Yonkeu

2014-01-01

Under oxidative stress conditions, endogenous antioxidant defenses are unable to completely inactivate the free radicals generated by an excessive production of reactive oxygen species (ROS). This state causes serious cell damage leading to a variety of human diseases. Natural antioxidants can protect cells against oxidative stress. Hypaodaphnis zenkeri (H. zenkiri) is a plant consumed as a spice in the Cameroonian diet, and its bark has been used in traditional medicine for the treatment of several diseases. The present study aims at investigating the antioxidant activity, which includes free radical scavenging and protective properties of an extract from H. Zenkiri against oxidative damage on a liver homogenate. The free radical assays determined the scavenging activities of 2,2-diphenyl-1-picrylhydrazyl (DPPH), hydroxyl (OH), nitrite oxide (NO) and 2,2-azinobis(3-ethylbenzthiazoline)-6-sulfonic acid (ABTS) radicals and the enzymes, whose protection was to be considered in the liver homogenate, including superoxide dismutase, catalase, and peroxidase. The antioxidative activities were studied using the ferric reducing antioxidant power (FRAP), reductive activity, and phosphomolybdenum antioxidant power (PAP) methods. In addition, the phenolic contents of the extracts were examined. The results showed that these extracts demonstrated significant scavenging properties and antioxidant activities, with the hydro-ethanolic extract of the bark of H. zenkeri (EEH) being the most potent. This extract had the highest total polyphenol (21.77 ± 0.05 mg caffeic acid (CAE)/g dried extract (DE)) and flavonoids (3.34 ± 0.13 mg quercetin (QE)/g dried extract) content. The same extract had significantly greater protective effects on enzyme activities compared to other extracts. The high performance liquied chromatography (HPLC) profile showed higher levels of caffeic acid, OH-tyrosol acid, and rutin in the leaves compared to the bark of H. zenkeri. In conclusion, the ethanolic and hydro-ethanolic extracts of the bark and leaves from H. zenkeri showed an antioxidant and protective potential against oxidative damage. PMID:26785245

The influence of coating solution and calcination condition on the durability of Ir1-xSnxO2/Ti anodes for oxygen evolution

NASA Astrophysics Data System (ADS)

Kato, Zenta; Kashima, Ryo; Tatsumi, Kohei; Fukuyama, Shinnosuke; Izumiya, Koichi; Kumagai, Naokazu; Hashimoto, Koji

2016-12-01

For oxygen formation without forming chlorine in seawater electrolysis for hydrogen production we have been using the anode consisting of three layers of MnO2-type multiple oxide catalyst, intermediate layer and titanium substrate. The intermediate layer was used for prevention of oxidation of the titanium substrate during anodic polarization for oxygen evolution and was prepared by calcination of butanol solutions of H2IrCl6 and SnCl4 coated on titanium. The protectiveness of Ir1-xSnxO2 layer formed was directly examined using Ir1-xSnxO2/Ti anodes in H2SO4 solution changing the preparation conditions of the layer. When the sum of Ir4+ and Sn4+ was 0.1 M, the highest protectiveness was observed at 0.06 M Sn4+. Although an increase in calcination temperature led to the formation of Ir1-x-ySnxTiyO2 triple oxide with a slightly lower catalytic activity for oxygen evolution, the anode calcined at 450 °C showed the highest protectiveness.

Antioxidant potential of curry (Murraya koenigii L.) and mint (Mentha spicata) leaf extracts and their effect on colour and oxidative stability of raw ground pork meat during refrigeration storage.

PubMed

Biswas, A K; Chatli, M K; Sahoo, J

2012-07-15

The aim of this study was to investigate the antioxidant activity of different solvent extracts of curry and mint leaf and their effect on colour and oxidative stability of raw ground pork meat stored at 4 ± 1°C. The results indicated that among the two individual leaf categories, the ethanol extract of curry leaf (EHEC) and the water extract of mint leaf (WEM) showed higher DPPH and ABTS(+) activity. EHEC also exhibited the highest total phenolic contents while these were the lowest for WEM. WEM showed the highest superoxide anionic scavenging activity (%). The pork meat samples treated with EHEC and WEM showed a decrease in the Hunter L- and a-values and a increase in b-value during storage at 4°C. However, the pH and TBARS values were higher in control samples irrespective of storage periods. In conclusion, EHEC and WEM have the potential to be used as natural antioxidants to minimise lipid oxidation of pork products. Copyright © 2012 Elsevier Ltd. All rights reserved.

The effect of hydrophilicity of graphene oxide as additive towards performance of polysulfone membrane

NASA Astrophysics Data System (ADS)

Jamalludin, Mohd Riduan; Harun, Zawati; Zakaria, M. S.; Rahim, Wan Mohd Faizal Wan Abd; Khor, C. Y.; Rosli, M. U.; Ishak, Muhammad Ikman; Nawi, M. A. M.; Shahrin, Suhaimi

2017-09-01

This study investigates the effect of hydrophilicity of graphene oxide as additive towards properties and performance on polysulfone (PSf) membrane. A polysulfone (PSf) membrane containing graphene oxide (GO) with different content was prepared via phase inversion technique. Characterization on the fabricated membrane were water contact angle measurement, porosity and mean pore size. The effects of PSf/GO were further investigated in terms of permeation test, rejection test and antifouling test. Based on the result obtained, PSf membrane incorporating with GO additive shows better capability to permeate more water compared to unfilled PSf membrane. The PSf/GO membrane were able to increase the permeate rate rapidly with the highest value is given by sample 4 (consist of 0.7 g of GO) at 571.78 J/m2h. Furthermore, water contact angle confirmed the hydrophilicity of this membrane at 62°. The transmembrane fouling activity showed that GO embedded in PSf membrane has improved tremendously. In addition, this study revealed that 0.7g of GO had the highest permeation test, rejection test and antifouling test.

Nanocylindrical confinement imparts highest structural order in molecular self-assembly of organophosphonates on aluminum oxide.

PubMed

Pathak, Anshuma; Bora, Achyut; Braunschweig, Björn; Meltzer, Christian; Yan, Hongdan; Lemmens, Peter; Daum, Winfried; Schwartz, Jeffrey; Tornow, Marc

2017-05-18

We report the impact of geometrical constraint on intramolecular interactions in self-assembled monolayers (SAMs) of alkylphosphonates grown on anodically oxidized aluminum (AAO). Molecular order in these films was determined by sum frequency generation (SFG) spectroscopy, a more sensitive measure of order than infrared absorption spectroscopy. Using SFG we show that films grown on AAO are, within detection limits, nearly perfectly ordered in an all-trans alkyl chain configuration. In marked contrast, films formed on planar, plasma-oxidized aluminum oxide or α-Al 2 O 3 (0001) are replete with gauche defects. We attribute these differences to the nanocylindrical structure of AAO, which enforces molecular confinement.

Oxidation of ethanol on NaX zeolite modified with transition metals

NASA Astrophysics Data System (ADS)

Mirzai, J. I.; Nadirov, P. A.; Velieva, A. D.; Muradkhanli, V. G.

2017-06-01

NaLaX, NaX + Co, and NaPdX catalysts are synthesized by modification of NaX zeolite with transition metals (La, Co, Pd). The activity of the prepared materials in catalytic ethanol oxidation is studied in the temperature range of 423-723 K. It is shown that NaPdX and NaX + Co accelerate the reactions of partial and complete oxidation of ethanol as the temperature rises. NaLaX accelerates both intramolecular and intermolecular dehydration of alcohol. It is shown that the NaPdX (1.0% Pd) sample has the highest activity in the complete oxidation of alcohol with the formation of CO2.

Synchrotron Micro-XANES Measurements of Vanadium Oxidation State in Glasses as a Function of Oxygen Fugacity: Experimental Calibration of Data Relevant to Partition Coefficient Determination

NASA Technical Reports Server (NTRS)

Delaney, J. S.; Sutton, S. R.; Newville, M.; Jones, J. H.; Hanson, B.; Dyar, M. D.; Schreiber, H.

2000-01-01

Oxidation state microanalyses for V in glass have been made by calibrating XANES spectral features with optical spectroscopic measurements. The oxidation state change with fugacity of O2 will strongly influence partitioning results.

pH regulates genes for flagellar motility, catabolism, and oxidative stress in Escherichia coli K-12.

PubMed

Maurer, Lisa M; Yohannes, Elizabeth; Bondurant, Sandra S; Radmacher, Michael; Slonczewski, Joan L

2005-01-01

Gene expression profiles of Escherichia coli K-12 W3110 were compared as a function of steady-state external pH. Cultures were grown to an optical density at 600 nm of 0.3 in potassium-modified Luria-Bertani medium buffered at pH 5.0, 7.0, and 8.7. For each of the three pH conditions, cDNA from RNA of five independent cultures was hybridized to Affymetrix E. coli arrays. Analysis of variance with an alpha level of 0.001 resulted in 98% power to detect genes showing a twofold difference in expression. Normalized expression indices were calculated for each gene and intergenic region (IG). Differential expression among the three pH classes was observed for 763 genes and 353 IGs. Hierarchical clustering yielded six well-defined clusters of pH profiles, designated Acid High (highest expression at pH 5.0), Acid Low (lowest expression at pH 5.0), Base High (highest at pH 8.7), Base Low (lowest at pH 8.7), Neutral High (highest at pH 7.0, lower in acid or base), and Neutral Low (lowest at pH 7.0, higher at both pH extremes). Flagellar and chemotaxis genes were repressed at pH 8.7 (Base Low cluster), where the cell's transmembrane proton potential is diminished by the maintenance of an inverted pH gradient. High pH also repressed the proton pumps cytochrome o (cyo) and NADH dehydrogenases I and II. By contrast, the proton-importing ATP synthase F1Fo and the microaerophilic cytochrome d (cyd), which minimizes proton export, were induced at pH 8.7. These observations are consistent with a model in which high pH represses synthesis of flagella, which expend proton motive force, while stepping up electron transport and ATPase components that keep protons inside the cell. Acid-induced genes, on the other hand, were coinduced by conditions associated with increased metabolic rate, such as oxidative stress. All six pH-dependent clusters included envelope and periplasmic proteins, which directly experience external pH. Overall, this study showed that (i) low pH accelerates acid consumption and proton export, while coinducing oxidative stress and heat shock regulons; (ii) high pH accelerates proton import, while repressing the energy-expensive flagellar and chemotaxis regulons; and (iii) pH differentially regulates a large number of periplasmic and envelope proteins.

The Highest State of Being and Knowing.

ERIC Educational Resources Information Center

Clarken, Rodney H.

This paper identifies the most influential paradigmatic individuals in human history, Socrates, Confucius, Buddha, Jesus, Muhammad, and Baha'u'llah, and presents their individual conceptions of the highest state of being and knowing, comparing the commonalities of those conceptualizations. Each proposes a state that might be described as…

Effect of Pr Valence State on Interfacial Structure and Electrical Properties of Pr Oxide/PrON/Ge Gate Stack Structure

NASA Astrophysics Data System (ADS)

Kato, Kimihiko; Sakashita, Mitsuo; Takeuchi, Wakana; Kondo, Hiroki; Nakatsuka, Osamu; Zaima, Shigeaki

2011-04-01

In this study, we investigated the valence state and chemical bonding state of Pr in a Pr oxide/PrON/Ge structure. We clarified the relationship between the valence state of Pr and the Pr oxide/Ge interfacial reaction using Pr oxide/Ge and Pr oxide/PrON/Ge samples. We found the formation of three Pr oxide phases in Pr oxide films; hexagonal Pr2O3 (h-Pr2O3) (Pr3+), cubic Pr2O3 (c-Pr2O3) (Pr3+), and c-PrO2 (Pr4+). We also investigated the effect of a nitride interlayer on the interfacial reaction in Pr oxide/Ge gate stacks. In a sample with a nitride interlayer (Pr oxide/PrON/Ge), metallic Pr-Pr bonds are also formed in the c-Pr2O3 film. After annealing in H2 ambient, the diffusion of Ge into Pr oxide is not observed in this sample. Pr-Pr bonds probably prevent the interfacial reaction and Ge oxide formation, considering that the oxygen chemical potential of this film is lower than that of a GeO2/Ge system. On the other hand, the rapid thermal oxidation (RTO) treatment terminates the O vacancies and defects in c-Pr2O3. As a result, c-PrO2 with tetravalent Pr is formed in the Pr oxide/PrON/Ge sample with RTO. In this sample, the leakage current density is effectively decreased in comparison with the sample without RTO. Hydrogen termination works effectively in Pr oxide/PrON/Ge samples with and without RTO, and we can achieve an interface state density of as low as 4 ×1011 eV-1·cm-2.

Dependence of nitrite oxidation on nitrite and oxygen in low-oxygen seawater

NASA Astrophysics Data System (ADS)

Sun, Xin; Ji, Qixing; Jayakumar, Amal; Ward, Bess B.

2017-08-01

Nitrite oxidation is an essential step in transformations of fixed nitrogen. The physiology of nitrite oxidizing bacteria (NOB) implies that the rates of nitrite oxidation should be controlled by concentration of their substrate, nitrite, and the terminal electron acceptor, oxygen. The sensitivities of nitrite oxidation to oxygen and nitrite concentrations were investigated using 15N tracer incubations in the Eastern Tropical North Pacific. Nitrite stimulated nitrite oxidation under low in situ nitrite conditions, following Michaelis-Menten kinetics, indicating that nitrite was the limiting substrate. The nitrite half-saturation constant (Ks = 0.254 ± 0.161 μM) was 1-3 orders of magnitude lower than in cultivated NOB, indicating higher affinity of marine NOB for nitrite. The highest rates of nitrite oxidation were measured in the oxygen depleted zone (ODZ), and were partially inhibited by additions of oxygen. This oxygen sensitivity suggests that ODZ specialist NOB, adapted to low-oxygen conditions, are responsible for apparently anaerobic nitrite oxidation.

Facile Co-Electrodeposition Method for High-Performance Supercapacitor Based on Reduced Graphene Oxide/Polypyrrole Composite Film.

PubMed

Chen, Junchen; Wang, Yaming; Cao, Jianyun; Liu, Yan; Zhou, Yu; Ouyang, Jia-Hu; Jia, Dechang

2017-06-14

A facile co-electrodeposition method has been developed to fabricate reduced graphene oxide/polypyrrole (rGO/PPy) composite films, with sodium dodecyl benzene sulfonate as both a surfactant and supporting electrolyte in the precursor solution. The introduction of rGO into the PPy films forms porous structure and enhances the conductivity across the film, leading to superior electrochemical performance. By controlling the deposition time and rGO concentration, the highest area capacitance can reach 411 mF/cm 2 (0.2 mA/cm 2 ) for rGO/PPy films, whereas optimized specific capacitance is as high as 361 F/g (0.2 mA/cm 2 ). All of the composite films exhibit excellent rate capability (at least 175 F/g at the current density of 12 mA/cm 2 ) compared with pure PPy film (only 12 F/g at the current density of 12 mA/cm 2 ). The rGO/PPy composite exhibits excellent cycling stability that maintains 104% of its initial capacitance after cycling for 2000 cycles and 80% for 5000 cycles. The two-electrode solid-state supercapacitor (SC) based on rGO/PPy composite electrodes demonstrates good rate performance, excellent cycling stability, as well as a high area capacitance of 222 mF/cm 2 . The solid-state planar SC based on the rGO/PPy composite exhibits an area capacitance of 9.4 mF/cm 2 , demonstrating great potential for fabrication of microsupercapacitors.

A GdAlO3 Perovskite Oxide Electrolyte-Based NOx Solid-State Sensor.

PubMed

Xiao, Yihong; Wang, Dongmei; Cai, Guohui; Zheng, Yong; Zhong, Fulan

2016-11-25

NO x is a notorious emission from motor vehicles and chemical factories as the precursor of acid rain and photochemical smog. Although zirconia-based NO x sensors have been developed and showed high sensitivity and selectivity at a high temperature of above 800 °C, they fail to show good performance, and even don't work at the typical work temperature window of the automotive engine (<500 °C). It still is a formidable challenge for development of mild-temperature NO x detector or sensor. Herein, a novel amperometric solid-state NO x sensor was developed using perovskite-type oxide Gd 1-x Ca x AlO 3-δ (GCA) as the electrolyte and NiO as the sensing electrode. NO x sensing properties of the device were investigated at the temperature region of 400-500 °C. The response current value at -300 mV was almost linearly proportional to the NO x concentration between 300 and 500 ppm at 500 °C. At such a temperature, the optimal sensor gave the highest NO 2 sensitivity of 20.15 nA/ppm, and the maximum response current value reached 5.57 μA. Furthermore, a 90% response and 90% recover time to 500 ppm NO 2 were about 119 and 92 s, respectively. The excellent selectivity and stability towards NO x sensing showed the potential application of the sensor in motor vehicles.

A GdAlO3 Perovskite Oxide Electrolyte-Based NOx Solid-State Sensor

NASA Astrophysics Data System (ADS)

Xiao, Yihong; Wang, Dongmei; Cai, Guohui; Zheng, Yong; Zhong, Fulan

2016-11-01

NOx is a notorious emission from motor vehicles and chemical factories as the precursor of acid rain and photochemical smog. Although zirconia-based NOx sensors have been developed and showed high sensitivity and selectivity at a high temperature of above 800 °C, they fail to show good performance, and even don’t work at the typical work temperature window of the automotive engine (<500 °C). It still is a formidable challenge for development of mild-temperature NOx detector or sensor. Herein, a novel amperometric solid-state NOx sensor was developed using perovskite-type oxide Gd1-xCaxAlO3-δ(GCA) as the electrolyte and NiO as the sensing electrode. NOx sensing properties of the device were investigated at the temperature region of 400-500 °C. The response current value at -300 mV was almost linearly proportional to the NOx concentration between 300 and 500 ppm at 500 °C. At such a temperature, the optimal sensor gave the highest NO2 sensitivity of 20.15 nA/ppm, and the maximum response current value reached 5.57 μA. Furthermore, a 90% response and 90% recover time to 500 ppm NO2 were about 119 and 92 s, respectively. The excellent selectivity and stability towards NOx sensing showed the potential application of the sensor in motor vehicles.

Anti-oxidant properties and polyphenolic profile screening of Vitis vinifera stems and leaves crude extracts grown in Perlis, Malaysia

NASA Astrophysics Data System (ADS)

Zakaria, Nursyahda; Zulkifli, Razauden Mohamed; Akhir, Fazrena Nadia Md; Basar, Norazah

2014-03-01

Grape has become a fast growing agricultural sector in Malaysia producing between 0.62 kg to 2.03 kg waste per vinestock. This study aims to generate useful information on anti-oxidative properties as well as polyphenolic composition of grapevine waste. Stems and leaves of Vitis vinifera cultivated in Perlis, Malaysia were extracted using methanol, ethyl acetate and petroleum ether. Ethyl acetate stems extract exhibited highest total phenolic content. While in DPPH assay, methanolic stems extract show the highest antioxidant activities. This result indicates that total phenolic content in the extracts may not contribute directly to the antioxidant activities. Thin Layer Chromatograms of all crude extracts exhibited good separation under solvent system petroleum ether-ethyl acetate (2:3) resulted in detection of resveratrol in ethyl acetate stems crude extract.

Antioxidant Activities and Oxidative Stabilities of Some Unconventional Oilseeds.

PubMed

Uluata, Sibel; Ozdemir, Nurhayat

2012-04-01

The oils of some unconventional oilseeds (hemp, radish, terebinth, stinging nettle, laurel) were obtained by a cold-press method in which the total oil content, fatty acids, tocopherol isomers, some metal contents (Ca, Mg, Fe, Cu), antioxidant activity and oxidative stability were determined. The total oil content was determined ranging between 30.68 and 43.12%, and the oil samples had large amounts of unsaturated fatty acids, with oleic acid and linoleic acid. Of all the oils, terebinth seed oil had the highest α-tocopherol content (102.21 ± 1.01 mg/kg oil). Laurel oilseed had the highest antiradical activity in both the DPPH and ABTS assays. The peroxide value of the non-oxidized oils ranged between 0.51 and 3.73 mequiv O(2)/kg oil. The TBARS value of the non-oxidized oils ranged between 0.68 ± 0.02 and 6.43 ± 0.48 mmol MA equiv/g oil. At 110 °C, the Rancimat induction period of the oils ranged between 1.32 and 43.44 h. The infrared spectra of the samples were recorded by FTIR spectroscopy. The absorbance values of the spectrum bands were observed and it was determined that some of the chemical groups of oxidized oils caused changes in absorbance. As a result of the present research, the analyzed oils could be evaluated as an alternative to traditionally consumed vegetable oils or as additives to them.

Precision-Cut Liver Slices of Salmo salar as a tool to investigate the oxidative impact of CYP1A-mediated PCB 126 and 3-methylcholanthrene metabolism.

PubMed

Lemaire, Benjamin; Beck, Michaël; Jaspart, Mélanie; Debier, Cathy; Calderon, Pedro Buc; Thomé, Jean-Pierre; Rees, Jean-François

2011-02-01

Fish isolated cell systems have long been used to predict in vivo toxicity of man-made chemicals. In present study, we tested the suitability of Precision-Cut Liver Slices (PCLS) as an alternative to these models that allows the evaluation of a global tissue response to toxicants, to investigate oxidative stress response to cytochrome P450 1A (CYP1A) induction in fish liver. PCLS of Salmo salar were exposed for 21 h to increasing doses of 3-methylcholanthrene (3-MC) and Polychlorobiphenyl 126 (PCB 126). 3-MC (25 μM) strongly induced CYP1A transcription. In dose-response analysis (25-100 μM), EROD activity was strongly increased at intermediate 3-MC concentrations. We found the counter-intuitive decline of EROD at the highest 3-MC doses to result from reversible competition with ethoxyresorufin. No increases of H(2)O(2) production, antioxidant enzymes activities or oxidative damage to lipids were found with 3-MC treatments. PCLS subjected to PCB 126 (2-200 nM) showed increased contamination levels and a parallel increased CYP1A mRNA synthesis and EROD activity. H(2)O(2) production tended to increase but no oxidative damage to lipids was found. As antioxidant enzymes activities declined at the highest PCB 126 dose, it is suggested that longer incubation periods could be required to generate oxidative stress in PCLS. Copyright © 2010 Elsevier Ltd. All rights reserved.

Improved Sp1 and Betaine Homocysteine-S-Methyltransferase Expression and Homocysteine Clearance Are Involved in the Effects of Zinc on Oxidative Stress in High-Fat-Diet-Pretreated Mice.

PubMed

Wu, Li; Zhou, Xihong; Li, Tiejun; He, Juyun; Huang, Linli; Ouyang, Zicheng; He, Liuqin; Wei, Tao; He, Qinghua

2017-12-04

Zinc plays a role in alleviating oxidative stress. However, the related mechanisms remain to be further elucidated. The present study was conducted to investigate whether the recovery of oxidative stress in high-fat-diet (HFD)-pretreated mice was affected by zinc. Male mice received either an HFD or a low-fat-diet (LFD) for 8 weeks. Then, the mice fed with HFD and LFD were both assigned to either a control diet (30 mg zinc, ZD) or a no-added zinc diet (NZD) for an additional 4 weeks. The results showed that after feeding with NZD for 4 weeks, the HFD-pretreated mice had the highest plasma glucose and insulin concentrations, while had the lowest CuZn-SOD and glutathione concentrations. Moreover, after feeding with NZD for 4 weeks, the HFD-pretreated mice had the highest hepatic ROS and homocysteine concentrations, while had the lowest glutathione and methionine concentrations. Furthermore, the HFD-pretreated mice fed with NZD for 4 weeks had the lowest gene and protein expression of betaine homocysteine-S-methyltransferase (BHMT), cystathionine β-synthase, and Sp1. The results suggested that zinc was critical for oxidative stress alleviation and homocysteine clearance in HFD-pretreated mice. It was further elucidated that improved Sp1 and BHMT expression are involved in the effects of zinc on oxidative stress.

[Effect of occupational stress on oxidation/antioxidant capacity in nurses].

PubMed

Cao, Lili; Tian, Honger; Zhang, Qingdong; Zhu, Xinyun; Zhan, Yongguo; Su, Jingguo; Xu, Tian; Zhu, Huabin; Liu, Ling

2014-02-01

To investigate the effect of occupational stress on the oxidation/antioxidant capacity in nurses. A total of 131 nurses were included as study subjects. The occupational health information collection system (based on the Internet of things) was used for measurement of occupational stress. Levels of hydroxyl free radicals and antioxidant enzymes were determined. The serum level of superoxide dismutase (SOD) was the highest in nurses under the age of 30 and the lowest in those over 45 (P < 0.05). The serum levels of glutathione peroxidase (GSH-Px) and peroxidase (POD) were the highest in nurses of working age less than 5 years, followed by those of 5-15 years, and nurses with more than 25 years' working experience showed the lowest GSH-Px and POD levels (P < 0.05). Furthermore, nurses with a university (college) degree had a higher GSH-Px level and a lower POD level compared with those with junior and senior high school degrees (P < 0.05). Job prospects and job control were positive occupational stress factors for SOD. Job hazards were negative occupational stress factors for POD. Psychological satisfaction was negative occupational stress reaction for hydroxyl free radicals. Calmness was positive occupational stress reaction for SOD, and daily stress was a negative one. The positive occupational stress reactions for GSH-Px were psychological satisfaction and job satisfaction, and daily stress was negative reaction. Nurses with higher occupational stress have stronger oxidation and weaker antioxidant capacity, which intensifies oxidant-antioxidant imbalance and leads to oxidative stress damage.

Role of oxidants in enhancing dewaterability of anaerobically digested sludge through Fe (II) activated oxidation processes: hydrogen peroxide versus persulfate

PubMed Central

Song, Kang; Zhou, Xu; Liu, Yiqi; Gong, Yanyan; Zhou, Beibei; Wang, Dongbo; Wang, Qilin

2016-01-01

Improving dewaterability of sludge is important for the disposal of sludge in wastewater treatment plants (WWTPs). This study, for the first time, investigated the Fe(II) activated oxidization processes in improving anaerobically digested sludge (ADS) dewaterability. The combination of Fe(II) (0–100 mg/g total solids (TS)) and persulfate (0–1,000 mg/g TS) under neutral pH as well as the combination of Fe(II) (0–100 mg/g TS) and hydrogen peroxide (HP) (0–1,000 mg/g TS) under pH 3.0 were used to examine and compare their effect on the ADS dewaterability enhancement. The highest ADS dewaterability enhancement was attained at 25 mg Fe(II)/g TS and 50 mg HP/g TS, when the CST (CST: the capillary suction time, a sludge dewaterability indicator) was reduced by 95%. In contrast, the highest CST reduction in Fe(II)-persulfate conditioning was 90%, which was obtained at 50 mg Fe(II)/g TS and 250 mg persulfate/g TS. The results showed that Fe(II)-HP conditioning was comparable with Fe(II)-persulfate conditioning in terms of highest CST reduction. Economic analysis suggested that the Fe(II)-HP conditioning was more promising for improving ADS dewaterability compared with Fe(II)-persulfate conditioning, with the saving being up to $65,000 per year in a WWTP with a population equivalent of 100,000. PMID:27109500

Bacterial oxidation of methyl bromide in Mono Lake, California

USGS Publications Warehouse

Connell, T.L.; Joye, S.B.; Miller, L.G.; Oremland, R.S.

1997-01-01

The oxidation of methyl bromide (MeBr) in the water column of Mono Lake, CA, was studied by measuring the formation of H14CO3 from [14C]MeBr. Potential oxidation was detected throughout the water column, with highest rates occurring in the epilimnion (5-12 m depth). The oxidation of MeBr was eliminated by filter-sterilization, thereby demonstrating the involvement of bacteria. Vertical profiles of MeBr activity differed from those obtained for nitrification and methane oxidation, indicating that MeBr oxidation is not simply a co-oxidation process by either nitrifiers or methanotrophs. Furthermore, specific inhibitors of methane oxidation and/or nitrification (e.g., methyl fluoride, acetylene, allyl sulfide) had no effect upon the rate of MeBr oxidation in live samples. Of a variety of potential electron donors added to Mono Lake water, only trimethylamine resulted in the stimulation of MeBr oxidation. Cumulatively, these results suggest that the oxidation of MeBr in Mono Lake waters is attributable to trimethylamine-degrading methylotrophs. Neither methyl chloride nor methanol inhibited the oxidation of [14C]MeBr in live samples, indicating that these bacteria directly oxidized MeBr rather than the products of MeBr nucleophilic substitution reactions.

METHOD OF MAINTAINING PLUTONIUM IN A HIGHER STATE OF OXIDATION DURING PROCESSING

DOEpatents

Thompson, S.G.; Miller, D.R.

1959-06-30

This patent deals with the oxidation of tetravalent plutonium contained in an aqueous acid solution together with fission products to the hexavalent state, prior to selective fission product precipitation, by adding to the solution bismuthate or ceric ions as the oxidant and a water-soluble dichromate as a holding oxidant. Both oxidant and holding oxidant are preferably added in greater than stoichiometric quantities with regard to the plutonium present.

Effect of Adding SiO2-Al2O3 Sol into Anodizing Bath on Corrosion Resistance of Oxidation Film on Magnesium Alloy

NASA Astrophysics Data System (ADS)

Liu, Huicong; Zhu, Liqun; Li, Weiping

Due to the widely use in automobile and construction field, AZ91D magnesium alloy need to be protected more effectively for its high chemical activity. In this paper, three kinds of films were formed on magnesium alloy. The first kind of film, named as anodic oxidation film, was prepared by anodic oxidation in the alkaline solution. The processes for preparing the second kind of film, named as multiple film, involved coating sol-gel on the samples and heat-treating before anodic oxidation. The third kind of film was prepared by anodic oxidation in the alkaline oxidation solution containning 5% (vol) SiO2-Al2O3 sol, named as modified oxidation film. The corrosion resistance of the three different films was investigated. The results showed that the modified oxidation film had the highest corrosion resistance due to the largest thickness and most dense surface morphology. Sol was discussed to react during the film forming process, which leaded to the difference between modified oxidation film and anodic oxidation film.

Fundamentals of Passive Oxidation In SiC and Si3N4

NASA Technical Reports Server (NTRS)

Thomas-Ogbuji, Linus U.

1998-01-01

The very slow oxidation kinetics of silicon carbide and silicon nitride, which derive from their adherent and passivating oxide films, has been explored at length in a broad series of studies utilizing thermogravimetric analysis, electron and optical micrography, energy dispersive spectrometry, x-ray diffractometry, micro-analytical depth profiling, etc. Some interesting microstructural phenomena accompanying the process of oxidation in the two materials will be presented. In Si3N4 the oxide is stratified, with an SiO2 topscale (which is relatively impervious to O2)underlain by a coherent subscale of silicon oxynitride which is even less permeable to O2- Such "defence in depth" endows Si3N4 with what is perhaps the highest oxidation resistance of any material, and results in a unique set of oxidation processes. In SiC the oxidation reactions are much simpler, yet new issues still emerge; for instance, studies involving controlled devitrification of the amorphous silica scale confirmed that the oxidation rate of SiC drops by more than an order of magnitude when the oxide scale fully crystallizes.

Factors affecting the partitioning of Cu, Zn and Pb in boulder coatings and stream sediments in the vicinity of a polymetallic sulfide deposit

USGS Publications Warehouse

Filipek, L.H.; Chao, T.T.; Carpenter, R.H.

1981-01-01

A sequential extraction scheme is utilized to determine the geochemical partitioning of Cu, Zn and Pb among hydrous Mn- and Fe-oxides, organics and residual crystalline silicates and oxides in the minus-80-mesh ( Fe-oxides > Mn-oxides; Zn, Mn-oxides {reversed tilde equals} organics > Fe-oxides; Pb, Fe-oxides > organics > Mn-oxides. In the sediments, organics are the most efficient scavengers of all three ore metals. These results emphasize the importance of organics as sinks for the ore metals, even in environments with high concentrations of Mn- and Fe-oxides. Of the ore metals, Zn appears to be the most mobile, and is partitioned most strongly into the coatings. However, anomaly contrast for hydromorphic Zn, normalized to the MnFe-oxide or organic content, is similar in sediments and coatings. Cu shows the highest anomaly on the boulder coatings, probably due to precipitation of a secondary Cu mineral. In contrast, detrital Pb in the pan concentrates shows a better anomaly than any hydromorphic Pb component. ?? 1981.

Behaviour of non-oxidized and oxidized flaxseed oils, as models of omega-3 rich lipids, during in vitro digestion. Occurrence of epoxidation reactions.

PubMed

Nieva-Echevarría, Bárbara; Goicoechea, Encarnación; Guillén, María D

2017-07-01

Fresh and partially oxidized flaxseed oil, as models of omega-3 rich lipids, were submitted to in vitro gastrointestinal digestion. Hydrolysis level, lipid composition and oxidative status of the samples before and after digestion were studied by Proton Nuclear Magnetic Resonance ( 1 H NMR) and Solid Phase Microextraction-Gas Chromatography/Mass Spectrometry (SPME-GC/MS). Although a great degree of lipolysis was reached in both kinds of samples after digestion, it was somewhat lower in the digests of oxidized flaxseed oil. The occurrence of lipid oxidation during digestion was evidenced by decreased unsaturated lipids and increased primary and secondary oxidation products, especially in oxidized samples. In these latter, linolenic-derived monoepoxy-octadecadienoates were the main oxidation products generated. SPME-GC/MS study showed the highest abundances of highly reactive alkadienals (C5-C10), alkatrienals (C9-C10) and linolenic-derived 4,5-epoxy-2-heptenals in the headspace of oxidized flaxseed oil digests. Volatile markers of Maillard-type reactions were also detected. Copyright © 2017 Elsevier Ltd. All rights reserved.

In Situ Characterization of Mesoporous Co/CeO 2 Catalysts for the High-Temperature Water-Gas Shift

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

Vovchok, Dimitriy; Guild, Curtis J.; Dissanayake, Shanka

Here, mesoporous Co/CeO 2 catalysts were found to exhibit significant activity for the high-temperature water-gas shift (WGS) reaction with cobalt loadings as low as 1 wt %. The catalysts feature a uniform dispersion of cobalt within the CeO 2 fluorite type lattice with no evidence of discrete cobalt phase segregation. In situ XANES and ambient pressure XPS experiments were used to elucidate the active state of the catalysts as partially reduced cerium oxide doped with oxidized cobalt atoms. In situ XRD and DRIFTS experiments suggest facile cerium reduction and oxygen vacancy formation, particularly with lower cobalt loadings. In situ DRIFTSmore » analysis also revealed the presence of surface carbonate and bidentate formate species under reaction conditions, which may be associated with additional mechanistic pathways for the WGS reaction. Deactivation behavior was observed with higher cobalt loadings. XANES data suggest the formation of small metallic cobalt clusters at temperatures above 400 °C may be responsible. Notably, this deactivation was not observed for the 1% cobalt loaded catalyst, which exhibited the highest activity per unit of cobalt.« less

Liquidus temperature and chemical durability of selected glasses to immobilize rare earth oxides waste

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

Mohd Fadzil, Syazwani Binti; Hrma, Pavel R.; Schweiger, Michael J.

Pyroprocessing is a reprocessing method for managing and reusing used nuclear fuel (UNF) by dissolving it in an electrorefiner with a molten alkali or alkaline earth chloride salt mixture while avoiding wet reprocessing. Pyroprocessing UNF with a LiCl-KCl eutectic salt releases the fission products from the fuel and generates a variety of metallic and salt-based species, including rare earth (RE) chlorides. If the RE-chlorides are converted to oxides, borosilicate glass is a prime candidate for their immobilization because of its durability and ability to dissolve almost any RE waste component into the matrix at high loadings. Crystallization that occurs inmore » waste glasses as the waste loading increases may complicate glass processing and affect the product quality. This work compares three types of borosilicate glasses in terms of liquidus temperature (TL): the International Simple Glass designed by the International Working Group, sodium borosilicate glass developed by Korea Hydro and Nuclear Power, and the lanthanide aluminoborosilicate (LABS) glass established in the United States. The LABS glass allows the highest waste loadings (over 50 mass% RE2O3) while possessing an acceptable chemical durability.« less

Liquidus temperature and chemical durability of selected glasses to immobilize rare earth oxides waste

NASA Astrophysics Data System (ADS)

Mohd Fadzil, Syazwani; Hrma, Pavel; Schweiger, Michael J.; Riley, Brian J.

2015-10-01

Pyroprocessing is are processing method for managing and reusing used nuclear fuel (UNF) by dissolving it in an electrorefiner with a molten alkali or alkaline earth chloride salt mixture while avoiding wet reprocessing. Pyroprocessing UNF with a LiCl-KCl eutectic salt releases the fission products from the fuel and generates a variety of metallic and salt-based species, including rare earth (RE) chlorides. If the RE-chlorides are converted to oxides, borosilicate glass is a prime candidate for their immobilization because of its durability and ability to dissolve almost any RE waste component into the glass matrix at high loadings. Crystallization that occurs in waste glasses as the waste loading increases may complicate glass processing and affect the product quality. This work compares three types of borosilicate glasses in terms of liquidus temperature (TL): the International Simple Glass designed by the International Working Group, sodium borosilicate glass developed by Korea Hydro and Nuclear Power, and the lanthanide aluminoborosilicate (LABS) glass established in the United States. The LABS glass allows the highest waste loadings (over 50 mass% RE2O3) while possessing an acceptable chemical durability.

Changes in growth, biochemical components, and antioxidant activity in aquatic plant Wolffia arrhiza (Lemnaceae) exposed to cadmium and lead.

PubMed

Piotrowska, Alicja; Bajguz, Andrzej; Godlewska-Zyłkiewicz, Beata; Zambrzycka, Elzbieta

2010-04-01

The present study investigated the biochemical response of aquatic plant Wolffia arrhiza (Lemnaceae) treated with lead (Pb) and cadmium (Cd) at a range of concentrations from 1 to 1000 microM. W. arrhiza has been identified as good scavenger of heavy metals from aqueous solution. Pb and Cd accumulation was found to be increased in a concentration- and duration-dependent manner. However, the highest biosorption of heavy metals was found in plants exposed to low levels (10 microM) of Cd and Pb in the nutrient medium. In observing the response to heavy-metal stress, we noted inhibited plant growth and decreased photosynthetic pigments, monosaccharides, and proteins. In addition, Cd was found to be more toxic to plants than Pb. Heavy metals also induced oxidative damage as evidenced by increased lipid peroxidation and hydrogen peroxide levels. In contrast, the deleterious effects resulting from the cellular oxidative state can be alleviated by enzymatic (catalase, ascorbate peroxidase, nicotinamide dinucleotide [NADH] peroxidase) and nonenzymatic (ascorbate, glutathione) antioxidant mechanisms activated in W. arrhiza plants exposed to Cd and Pb, especially at 10 microM. These results suggest that W. arrhiza is a promising bioindicator of heavy-metal toxicity.

In Situ Characterization of Mesoporous Co/CeO 2 Catalysts for the High-Temperature Water-Gas Shift

DOE PAGES

Vovchok, Dimitriy; Guild, Curtis J.; Dissanayake, Shanka; ...

2018-04-04

Here, mesoporous Co/CeO 2 catalysts were found to exhibit significant activity for the high-temperature water-gas shift (WGS) reaction with cobalt loadings as low as 1 wt %. The catalysts feature a uniform dispersion of cobalt within the CeO 2 fluorite type lattice with no evidence of discrete cobalt phase segregation. In situ XANES and ambient pressure XPS experiments were used to elucidate the active state of the catalysts as partially reduced cerium oxide doped with oxidized cobalt atoms. In situ XRD and DRIFTS experiments suggest facile cerium reduction and oxygen vacancy formation, particularly with lower cobalt loadings. In situ DRIFTSmore » analysis also revealed the presence of surface carbonate and bidentate formate species under reaction conditions, which may be associated with additional mechanistic pathways for the WGS reaction. Deactivation behavior was observed with higher cobalt loadings. XANES data suggest the formation of small metallic cobalt clusters at temperatures above 400 °C may be responsible. Notably, this deactivation was not observed for the 1% cobalt loaded catalyst, which exhibited the highest activity per unit of cobalt.« less

Characterization of poly methyl methaacrylate and reduced graphene oxide composite for application as electrolyte in dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Shrivatsav, Roshan; Mahalingam, Vignesh; Lakshmi Narayanan, E. R.; Naveen Balaji, N.; Balu, Murali; Krishna Prasad, R.; Kumaresan, Duraisamy

2018-04-01

Quasi-solid state iodide/triiodide redox electrolyte containing reduced graphene oxide and poly (methyl methaacrylate) (RGO-PMMA) composites for the fabrication of more durable, high performance dye sensitized solar cells are prepared. The morphological analysis of prepared RGO-PMMA composites showed formation of spherical like morphologies of RGO dispersed PMMA particles with their macroscopic inter-particle networks having voids. The x ray diffraction and electrical conductivity studies showed the addition of 1 wt% of filler RGO into amorphous PMMA matrix increased the electrical conductivity of the polymer composite about three orders of magnitude from 10‑7 and 10‑4 S cm‑1. Further, the photovoltaic current-voltage analysis of DSSCs with different RGO-PMMA composite based iodide/triiodide redox electrolytes showed the highest power conversion efficiency of 5.38% and the fill factor 0.63 for 2% RGO-PMMA electrolyte. The EIS analysis showed an increased recombination resistance (Rct2) at TiO2 electrode/dye/electrolyte interface due to the better electrical conductivity of RGO with good ionic conductivity in 2% RGO-PMMA composite based redox electrolyte boosted the generation of a high current density and fill factor in their DSSCs.

Catalytic process for formaldehyde oxidation

NASA Technical Reports Server (NTRS)

Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); D'Ambrosia, Christine M. (Inventor)

1996-01-01

Disclosed is a process for oxidizing formaldehyde to carbon dioxide and water without the addition of energy. A mixture of formaldehyde and an oxidizing agent (e.g., ambient air containing formaldehyde) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.

Electrical characterization of plasma-grown oxides on gallium arsenide

NASA Technical Reports Server (NTRS)

Hshieh, F. I.; Bhat, K. N.; Ghandhi, S. K.; Borrego, J. M.

1985-01-01

Plasma-grown GaAs oxides and their interfaces have been characterized by measuring the electrical properties of metal-oxide-semiconductor capacitors and of Schottky junctions. The current transport mechanism in the oxide at high electrical field was found to be Frankel-Poole emission, with an electron trap center at 0.47 eV below the conduction band of the oxide. The interface-state density, evaluated from capacitance and conductance measurements, exhibits a U-shaped interface-state continuum extending over the entire band gap. Two discrete deep states with high concentration are superimposed on this continuum at 0.40 and 0.70 eV below the conduction band. The results obtained from measurements on Schottky junctions have excluded the possibility that these two deep states originate from plasma damage. Possible origins of these states are discussed in this paper.

Role of Al in Zn bath on the formation of the inhibition layer during hot-dip galvanizing for a 1.2Si-1.5Mn transformation-induced plasticity steel

NASA Astrophysics Data System (ADS)

Wang, Kuang-Kuo; Hsu, Chiung-Wen; Chang, Liuwen; Gan, Dershin; Yang, Kuo-Cheng

2013-11-01

This study investigated the interaction between the Al in the Zn bath and the surface oxides formed by selective oxidation on a 1.2Si-1.5Mn TRIP steel during hot-dip galvanizing. XPS and TEM were employed for characterization. The results indicated that the amorphous xMnO·SiO2 oxide could react with Al to form a Si-Mn-Al-containing oxide. The crystalline MnSiO3 and Mn2SiO4 oxides could be largely reduced by Al to form holes in the oxide film. Consequently, the steel covered by a layer of mixed xMnO·SiO2 and MnSiO3 could form a continuous Fe2Al5 inhibition layer and showed the highest galvanizability among the three samples examined.

Corrosion evaluation of zirconium doped oxide coatings on aluminum formed by plasma electrolytic oxidation.

PubMed

Bajat, Jelena; Mišković-Stanković, Vesna; Vasilić, Rastko; Stojadinović, Stevan

2014-01-01

The plasma electrolytic oxidation (PEO) of aluminum in sodium tungstate (Na(2)WO(4) · (2)H(2)O) and Na(2)WO(4) · (2)H(2)O doped with Zr was analyzed in order to obtain oxide coatings with improved corrosion resistance. The influence of current density in PEO process and anodization time was investigated, as well as the influence of Zr, with the aim to find out how they affect the chemical content, morphology, surface roughness, and corrosion stability of oxide coatings. It was shown that the presence of Zr increases the corrosion stability of oxide coatings for all investigated PEO times. Evolution of EIS spectra during the exposure to 3% NaCl, as a strong corrosive agent, indicated the highest corrosion stability for PEO coating formed on aluminum at 70 mA/cm(2) for 2 min in a zirconium containing electrolyte.

Moessbauer spectra of ferrite catalysts used in oxidative dehydrogenation

NASA Technical Reports Server (NTRS)

Cares, W. R.; Hightower, J. W.

1971-01-01

Room temperature Mossbauer spectroscopy was used to examine bulk changes which occur in low surface area CoFe2O4 and CuFe2O4 catalysts as a result of contact with various mixtures of trans-2-butene and O2 during oxidative dehydrogenation reactions at about 420 C. So long as there was at least some O2 in the gas phase, the CoFe2O4 spectrum was essentially unchanged. However, the spectrum changed from a random spinel in the oxidized state to an inverse spinel as it was reduced by oxide ion removal. The steady state catalyst lies very near the fully oxidized state. More dramatic solid state changes occurred as the CuFe2O4 underwent reduction. Under severe reduction, the ferrite was transformed into Cu and Fe3O4, but it could be reversibly recovered by oxidation. An intense doublet located near zero velocity persisted in all spectra of CuFe2O4 regardless of the state of reduction.

Short-term nitrous oxide profile dynamics and emissions response to water, nitrogen and carbon additions in two tropical soils

Treesearch

A. D. Nobre; M. Keller; P. M. Crill; R. C. Harriss

2001-01-01

Tropical soils are potentially the highest and least studied nitrous oxide (N2O) production areas in the world. The effect of water, nitrate and glucose additions on profile concentrations and episodic emissions of N2O for two volcanic soils in Costa Rica was examined. Magnitudes of episodic N2O pulses, as well as overall N2O emissions, varied considerably and...

[Impact of environmental pollution with variable valence metals on the pediatric population's provision with vitamins in an agroindustrial region].

PubMed

Krasikov, S I; Kuz'micheva, N A; Alekhina, E M

2009-01-01

The urinary and serum levels of vitamins B1, B2, B3, A, E, and C were analyzed in 300 children aged 2 to 7 years, who lived in the Orenburg Regions areas having a varying oxidative load. The most severe deficiency of vitamins was observed in the children residing in the regional area characterized by the highest oxidative load.

The impact of degassing on the oxidation state of basaltic magmas: A case study of Kīlauea volcano

NASA Astrophysics Data System (ADS)

Moussallam, Yves; Edmonds, Marie; Scaillet, Bruno; Peters, Nial; Gennaro, Emanuela; Sides, Issy; Oppenheimer, Clive

2016-09-01

Volcanic emissions link the oxidation state of the Earth's mantle to the composition of the atmosphere. Whether the oxidation state of an ascending magma follows a redox buffer - hence preserving mantle conditions - or deviates as a consequence of degassing remains under debate. Thus, further progress is required before erupted basalts can be used to infer the redox state of the upper mantle or the composition of their co-emitted gases to the atmosphere. Here we present the results of X-ray absorption near-edge structure (XANES) spectroscopy at the iron K-edge carried out for a series of melt inclusions and matrix glasses from ejecta associated with three eruptions of Kīlauea volcano (Hawai'i). We show that the oxidation state of these melts is strongly correlated with their volatile content, particularly in respect of water and sulfur contents. We argue that sulfur degassing has played a major role in the observed reduction of iron in the melt, while the degassing of H2O and CO2 appears to have had a negligible effect on the melt oxidation state under the conditions investigated. Using gas-melt equilibrium degassing models, we relate the oxidation state of the melt to the composition of the gases emitted at Kīlauea. Our measurements and modelling yield a lower constraint on the oxygen fugacity of the mantle source beneath Kīlauea volcano, which we infer to be near the nickel nickel-oxide (NNO) buffer. Our findings should be widely applicable to other basaltic systems and we predict that the oxidation state of the mantle underneath most hotspot volcanoes is more oxidised than that of the associated lavas. We also suggest that whether the oxidation states of a basalt (in particular MORB) reflects that of its source, is primarily determined by the extent of sulfur degassing.

Removal of PCBs in contaminated soils by means of chemical reduction and advanced oxidation processes.

PubMed

Rybnikova, V; Usman, M; Hanna, K

2016-09-01

Although the chemical reduction and advanced oxidation processes have been widely used individually, very few studies have assessed the combined reduction/oxidation approach for soil remediation. In the present study, experiments were performed in spiked sand and historically contaminated soil by using four synthetic nanoparticles (Fe(0), Fe/Ni, Fe3O4, Fe3 - x Ni x O4). These nanoparticles were tested firstly for reductive transformation of polychlorinated biphenyls (PCBs) and then employed as catalysts to promote chemical oxidation reactions (H2O2 or persulfate). Obtained results indicated that bimetallic nanoparticles Fe/Ni showed the highest efficiency in reduction of PCB28 and PCB118 in spiked sand (97 and 79 %, respectively), whereas magnetite (Fe3O4) exhibited a high catalytic stability during the combined reduction/oxidation approach. In chemical oxidation, persulfate showed higher PCB degradation extent than hydrogen peroxide. As expected, the degradation efficiency was found to be limited in historically contaminated soil, where only Fe(0) and Fe/Ni particles exhibited reductive capability towards PCBs (13 and 18 %). In oxidation step, the highest degradation extents were obtained in presence of Fe(0) and Fe/Ni (18-19 %). The increase in particle and oxidant doses improved the efficiency of treatment, but overall degradation extents did not exceed 30 %, suggesting that only a small part of PCBs in soil was available for reaction with catalyst and/or oxidant. The use of organic solvent or cyclodextrin to improve the PCB availability in soil did not enhance degradation efficiency, underscoring the strong impact of soil matrix. Moreover, a better PCB degradation was observed in sand spiked with extractable organic matter separated from contaminated soil. In contrast to fractions with higher particle size (250-500 and <500 μm), no PCB degradation was observed in the finest fraction (≤250 μm) having higher organic matter content. These findings may have important practical implications to promote successively reduction and oxidation reactions in soils and understand the impact of soil properties on remediation performance.

Metal oxidation states in biological water splitting.

PubMed

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

2015-03-01

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

Total Observed Organic Carbon (TOOC): A Synthesis of North American Observations

NASA Technical Reports Server (NTRS)

Heald, C. L.; Goldstein, A. H.; Allan, J. D.; Aiken, A. C.; Apel, E.; Atlas, E. L.; Baker, A. K.; Bates, T. S.; Beyersdorf, A. J.; Blake, D. R.;

Experiments with Unusual Oxidation States

ERIC Educational Resources Information Center

Kauffman, G. B.

1975-01-01

Describes four synthesis experiments, adapted for the general chemistry laboratory, in which compounds in unusual oxidation are prepared. The abnormal oxidation states involved in the synthesis products are: silver (II), chromium (II), lead (IV), and bromine (I). (MLH)

Free radical scavenging, antidiarrheal and anthelmintic activity of Pistia stratiotes L. extracts and its phytochemical analysis.

PubMed

Bin Karim, Mohammed Faisal; Imam, Hasan; Sarker, Md Moklesur-Rahman; Uddin, Nizam; Hasan, Nahid; Paul, Nirmala; Haque, Tahmina

2015-05-01

In this phyto-pharmacological screening of Pistia stratiotes L leaf and root extracts each separately in two different solvents demonstrated its potential medicinal value. Apparent antioxidant value is demonstrated by DPPH, Nitric oxide scavenging and Ferric ion reducing method. Additionally, total flavonoid and phenolic compounds were measured. The leaf methanolic extract scavenged both nitric oxide (NO) and DPPH radical with a dose dependent manner. But the pet ether fraction of root was found to have highest efficacy in Fe(3±) reducing power assay. Flavonoid was found to contain highest in the pet ether fraction of root (411.35mg/g) in terms of quercetin equivalent, similarly highest amount (34.96mg/g) of total phenolic compounds (assayed as gallic acid equivalents) were found to contain in the same fraction. The methanolic fractions appeared less cytotoxic compared to pet ether extracts. The plant extracts caused a dose dependent decrease in faecal droppings in both castor oil and magnesium sulphate induced diarrhea, where as leaf extracts in each solvent appeared most effective. Also, the plant extracts showed anthelmintic activity in earthworm by inducing paralysis and death in a dose dependent manner. At highest doses (50 mg/ml) all fractions were almost effective as the positive control piperazine citrate (10 mg/ml). Thus, besides this cytotoxic effect it's traditional claim for therapeutic use can never be overlooked.

Anodic behavior of uranium in AlCl3-1-ethyl-3-methyl-imidazolium chloride ionic liquid

NASA Astrophysics Data System (ADS)

Jiang, Yidong; Luo, Lizhu; Wang, Shaofei; Bin, Ren; Zhang, Guikai; Wang, Xiaolin

2018-01-01

The oxidation state of metals unambiguously affects its anodic behavior in ionic liquid. We systematically investigated the anodic behavior of uranium with different surface oxidation states by electrochemical measurements, spectroscopic methods and surface analysis techniques. In the anodic process, metal uranium can be oxidized to U3+. The corresponding products accumulated on the metal/ILs interface will form a viscous layer. The anodic behavior of uranium is also strongly dependent upon the surface oxide states including thickness and homogeneity of the oxide film. With an increase in the thickness of oxide film, it will be breached at potentials in excess of a critical value. A uniform oxide on uranium surface can be breached evenly, and then the underlying metal starts to dissolve forming a viscous layer which can facilitate uniformly stripping of oxide, thus giving an oxide-free surface. Otherwise, a nonuniform oxide can result in a severe pitted surface with residue oxygen.

Old and stable soil organic matter is not necessarily chemically recalcitrant: Implications for modeling concepts and temperature sensitivity

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

Kleber, M.; Nico, P.S.; Plante, A.

2010-03-01

Soil carbon turnover models generally divide soil carbon into pools with varying intrinsic decomposition rates. Although these decomposition rates are modified by factors such as temperature, texture, and moisture, they are rationalized by assuming chemical structure is a primary controller of decomposition. In the current work, we use near edge X-ray absorption fine structure (NEXAFS) spectroscopy in combination with differential scanning calorimetry (DSC) and alkaline cupric oxide (CuO) oxidation to explore this assumption. Specifically, we examined material from the 2.3-2.6 kg L{sup -1} density fraction of three soils of different type (Oxisol, Alfisol, Inceptisol). The density fraction with the youngestmore » {sup 14}C age (Oxisol, 107 years) showed the highest relative abundance of aromatic groups and the lowest O-alkyl C/aromatic C ratio as determined by NEXAFS. Conversely, the fraction with the oldest C (Inceptisol, 680 years) had the lowest relative abundance of aromatic groups and highest O-alkyl C/aromatic C ratio. This sample also had the highest proportion of thermally labile materials as measured by DSC, and the highest ratio of substituted fatty acids to lignin phenols as indicated by CuO oxidation. Therefore, the organic matter of the Inceptisol sample, with a {sup 14}C age associated with 'passive' pools of carbon (680 years), had the largest proportion of easily metabolizable organic molecules with low thermodynamic stability, whereas the organic matter of the much younger Oxisol sample (107 years) had the highest proportion of supposedly stable organic structures considered more difficult to metabolize. Our results demonstrate that C age is not necessarily related to molecular structure or thermodynamic stability, and we suggest that soil carbon models would benefit from viewing turnover rate as codetermined by the interaction between substrates, microbial actors, and abiotic driving variables. Furthermore, assuming that old carbon is composed of complex or 'recalcitrant' compounds will erroneously attribute a greater temperature sensitivity to those materials than they may actually possess.« less

Oxidation and Reduction Reactions in Organic Chemistry

ERIC Educational Resources Information Center

Shibley, Ivan A., Jr.; Amaral, Katie E.; Aurentz, David J.; McCaully, Ronald J.

2010-01-01

A variety of approaches to the concept of oxidation and reduction appear in organic textbooks. The method proposed here is different than most published approaches. The oxidation state is calculated by totaling the number of heterogeneous atoms, [pi]-bonds, and rings. A comparison of the oxidation states of reactant and product determine what type…

Cloud droplet activation through oxidation of organic aerosol influenced by temperature and particle phase state: CLOUD ACTIVATION BY AGED ORGANIC AEROSOL

DOE PAGES

Slade, Jonathan H.; Shiraiwa, Manabu; Arangio, Andrea; ...

2017-02-04

Chemical aging of organic aerosol (OA) through multiphase oxidation reactions can alter their cloud condensation nuclei (CCN) activity and hygroscopicity. However, the oxidation kinetics and OA reactivity depend strongly on the particle phase state, potentially influencing the hydrophobic-to-hydrophilic conversion rate of carbonaceous aerosol. Here, amorphous Suwannee River fulvic acid (SRFA) aerosol particles, a surrogate humic-like substance (HULIS) that contributes substantially to global OA mass, are oxidized by OH radicals at different temperatures and phase states. When oxidized at low temperature in a glassy solid state, the hygroscopicity of SRFA particles increased by almost a factor of two, whereas oxidation ofmore » liquid-like SRFA particles at higher temperatures did not affect CCN activity. Low-temperature oxidation appears to promote the formation of highly-oxygenated particle-bound fragmentation products with lower molar mass and greater CCN activity, underscoring the importance of chemical aging in the free troposphere and its influence on the CCN activity of OA.« less

Appearance of the minority dz2 surface state and disappearance of the image-potential state: Criteria for clean Fe(001)

NASA Astrophysics Data System (ADS)

Eibl, Christian; Schmidt, Anke B.; Donath, Markus

2012-10-01

The unoccupied surface electronic structure of clean and oxidized Fe(001) was studied with spin-resolved inverse photoemission and target current spectroscopy. For the clean surface, we detected a dz2 surface state with minority spin character just above the Fermi level, while the image-potential surface state disappears. The opposite is observed for the ordered p(1×1)O/Fe(001) surface: the dz2-type surface state is quenched, while the image-potential state shows up as a pronounced feature. This behavior indicates enhanced surface reflectivity at the oxidized surface. The appearance and disappearance of specific unoccupied surface states prove to be decisive criteria for a clean Fe(001) surface. In addition, enhanced spin asymmetry in the unoccupied states is observed for the oxidized surface. Our results have implications for the use of clean and oxidized Fe(001) films as spin-polarization detectors.

Using ToxCast data to reconstruct dynamic cell state ...

EPA Pesticide Factsheets

AbstractBackground. High-throughput in vitro screening is an important tool for evaluating the potential biological activity of the thousands of existing chemicals in commerce and the hundreds more introduced each year. Among the assay technologies available, high-content imaging (HCI) allows multiplexed measurements of cellular phenotypic changes induced by chemical exposures. For a large chemical inventory having limited concentration-time series data, the deconvolution of cellular response profiles into transitive or irrevocable state trajectories is an important consideration. Objectives. Our goal was to analyze temporal and concentration-related cellular changes measured using HCI to identify the “tipping point” at which the cells did not show recovery towards a normal phenotypic state. Methods. The effects of 976 chemicals (ToxCast Phase I and II) were evaluated using HCI as a function of concentration and time in HepG2 cells over a 72-hr exposure period to concentrations ranging from 0.4- to 200 µM. The cellular endpoints included nuclear p53 accumulation, JNK, markers of oxidative stress, cytoskeletal changes, mitochondrial energization and density, cell viability and cell cycle progression. A novel computational model was developed to interpret dynamic multidimensional system responses as cell-state trajectories. Results. Analysis of cell-state trajectories showed that HepG2 cells were resilient to the effects of 178 chemicals up to the highest co

Tin Oxide Nanowires: The Influence of Trap States on Ultrafast Carrier Relaxation

PubMed Central

2009-01-01

We have studied the optical properties and carrier dynamics in SnO2nanowires (NWs) with an average radius of 50 nm that were grown via the vapor–liquid solid method. Transient differential absorption measurements have been employed to investigate the ultrafast relaxation dynamics of photogenerated carriers in the SnO2NWs. Steady state transmission measurements revealed that the band gap of these NWs is 3.77 eV and contains two broad absorption bands. The first is located below the band edge (shallow traps) and the second near the center of the band gap (deep traps). Both of these absorption bands seem to play a crucial role in the relaxation of the photogenerated carriers. Time resolved measurements suggest that the photogenerated carriers take a few picoseconds to move into the shallow trap states whereas they take ~70 ps to move from the shallow to the deep trap states. Furthermore the recombination process of electrons in these trap states with holes in the valence band takes ~2 ns. Auger recombination appears to be important at the highest fluence used in this study (500 μJ/cm2); however, it has negligible effect for fluences below 50 μJ/cm2. The Auger coefficient for the SnO2NWs was estimated to be 7.5 ± 2.5 × 10−31 cm6/s. PMID:20596473

Does pharmaconutrition with L-arginine and/or alpha-tocopherol improve the gut barrier in bile duct ligated rats?

PubMed

Tuncyurek, P; Sari, M; Firat, O; Mutaf, I; Gulter, C; Tunger, A; Yuce, G; Yilmaz, M; Makay, O; Dayangac, M; Ersin, S

2006-01-01

Nitric oxide supplementation and antioxidant therapy modulate gut barrier function, but the relationships between enhanced nitric oxide production, antioxidant administration, and biliary obstruction remain unclear. We evaluated the role of nitric oxide and alpha-tocopherol supplementation in bile duct ligated rats. Fifty male Wistar albino rats underwent sham operation (group I; control animals) or bile duct ligation (groups II, III, IV, and V). The ligation groups received the following regimens: standard pellet diet (group II), pellet diet plus intramuscularly administered alpha-tocopherol (group III), and L-arginine-enriched pellet diet without (group IV) or with (group V) alpha-tocopherol. Nitric oxide, malondialdehyde, and alpha-tocopherol concentrations were assessed at the end of 3 weeks. Liver and intestinal samples were scored histologically. Mesenteric lymph node and liver cultures were assessed for bacterial translocation. The liver malondialdehyde concentration was highest in group III. The nitric oxide content in the liver was higher in groups III and V, as were the blood alpha-tocopherol levels. Bacterial translocation was evident following bile duct ligation, but did not differ among the treatment groups. Intestinal histology revealed that group III had the lowest villus height, that group V had the least villus count, and that group II had the highest mucous cell count. The fibrosis scores were higher in groups IV and V. An obvious effect of alpha-tocopherol (with or without L-arginine) on the gut barrier could not be demonstrated. Moreover, the L-arginine-enriched diet promoted fibrosis in the liver. Thus, while biliary duct obstruction triggers bacterial translocation, nitric oxide and/or alpha-tocopherol supplementation did not seem to improve the gut barrier in our model. Copyright 2006 S. Karger AG, Basel.

Ti4O7/g-C3N4 Visible Light Photocatalytic Performance on Hypophosphite Oxidation: Effect of Annealing Temperature

PubMed Central

Guan, Wei; Sun, Gaoge; Yin, Lei; Zhang, Zhenghua; Tian, Shichao

2018-01-01

The oxidation of hypophosphite to phosphate is the key to recover the phosphorus resource from the hypophosphite wastewater. In the present work, Ti4O7/g-C3N4 composites were synthesized at two different temperatures (100 and 160°C) and their performance on photocatalytic oxidation of hypophosphite under visible light irradiation and the corresponding mechanism were evaluated. A hydrolysis method using g-C3N4 and Ti4O7 was applied to synthesize the Ti4O7/g-C3N4 composites with their hybrid structure and morphology confirmed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectra (XPS). The annealing temperature significantly affected the photocatalytic performance of Ti4O7/g-C3N4 that the 160-Ti4O7/g-C3N4 composite (fabricated at 160°C) showed the highest oxidation efficiency of hypophosphite of 81% and the highest photocatalytic oxidation rate of 0.467 h−1 comparing with the 100-Ti4O7/g-C3N4 composite (fabricated at 100°C) and pure g-C3N4. The enhanced photocatalytic performance of 160-Ti4O7/g-C3N4 could be ascribed to the effective charge separation and enhanced photoabsorption efficiency. Additionally, electron spin resonance (ESR) results showed that hydroxyl radicals and superoxide anion radicals were mainly responsible to the oxidation of hypophosphite with superoxide anion radicals accounting for a more significant contribution. Moreover, Ti4O7/g-C3N4 photocatalysts showed the remarkable stability in the repetitive experiments. PMID:29546041

Ti4O7/g-C3N4 visible light photocatalytic performance on hypophosphite oxidation: Effect of annealing temperature

NASA Astrophysics Data System (ADS)

Guan, Wei; Sun, Gaoge; Yin, Lei; Zhang, Zhenghua; Tian, Shichao

2018-03-01

The oxidation of hypophosphite to phosphate is the key to recover the phosphorus resource from the hypophosphite wastewater. In the present work, Ti4O7/g-C3N4 composites were synthesized at two different temperatures (100 and 160 °C) and their performance on photocatalytic oxidation of hypophosphite under visible light irradiation and the corresponding mechanism were evaluated. A hydrolysis method using g-C3N4 and Ti4O7 was applied to synthesize the Ti4O7/g-C3N4 composites with their hybrid structure and morphology confirmed by XRD, SEM and XPS. The annealing temperature significantly affected the photocatalytic performance of Ti4O7/g-C3N4 that the 160-Ti4O7/g-C3N4 composite (fabricated at 160 °C) showed the highest oxidation efficiency of hypophosphite of 81% and the highest photocatalytic oxidation rate of 0.467 h-1 comparing with the 100-Ti4O7/g-C3N4 composite (fabricated at 100 °C) and pure g-C3N4. The enhanced photocatalytic performance of 160-Ti4O7/g-C3N4 could be ascribed to the effective charge separation and enhanced photoabsorption efficiency. Additionally, electron spin resonance (ESR) results showed that hydroxyl radicals and superoxide anion radicals were mainly responsible to the oxidation of hypophosphite with superoxide anion radicals accounting for a more significant contribution. Moreover, Ti4O7/g-C3N4 photocatalysts showed the remarkable stability in the repetitive experiments.

Ti4O7/g-C3N4 Visible Light Photocatalytic Performance on Hypophosphite Oxidation: Effect of Annealing Temperature.

PubMed

Guan, Wei; Sun, Gaoge; Yin, Lei; Zhang, Zhenghua; Tian, Shichao

2018-01-01

The oxidation of hypophosphite to phosphate is the key to recover the phosphorus resource from the hypophosphite wastewater. In the present work, Ti 4 O 7 /g-C 3 N 4 composites were synthesized at two different temperatures (100 and 160°C) and their performance on photocatalytic oxidation of hypophosphite under visible light irradiation and the corresponding mechanism were evaluated. A hydrolysis method using g-C 3 N 4 and Ti 4 O 7 was applied to synthesize the Ti 4 O 7 /g-C 3 N 4 composites with their hybrid structure and morphology confirmed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectra (XPS). The annealing temperature significantly affected the photocatalytic performance of Ti 4 O 7 /g-C 3 N 4 that the 160-Ti 4 O 7 /g-C 3 N 4 composite (fabricated at 160°C) showed the highest oxidation efficiency of hypophosphite of 81% and the highest photocatalytic oxidation rate of 0.467 h -1 comparing with the 100-Ti 4 O 7 /g-C 3 N 4 composite (fabricated at 100°C) and pure g-C 3 N 4 . The enhanced photocatalytic performance of 160-Ti 4 O 7 /g-C 3 N 4 could be ascribed to the effective charge separation and enhanced photoabsorption efficiency. Additionally, electron spin resonance (ESR) results showed that hydroxyl radicals and superoxide anion radicals were mainly responsible to the oxidation of hypophosphite with superoxide anion radicals accounting for a more significant contribution. Moreover, Ti 4 O 7 /g-C 3 N 4 photocatalysts showed the remarkable stability in the repetitive experiments.

Atmospheric nitrous oxide uptake in boreal spruce forest soil

NASA Astrophysics Data System (ADS)

Siljanen, Henri; Welti, Nina; Heikkinen, Juha; Biasi, Christina; Martikainen, Pertti

2017-04-01

Nitrous oxide (N2O) uptake from the atmosphere has been found in forest soils but environmental factors controlling the uptake and its atmospheric impact are poorly known. We measured N2O fluxes over growing season in a boreal spruce forest having control plots and plots with long nitrogen fertilization history. Also methane (CH4) fluxes were measured to compare the atmospheric impact of N2O and CH4fluxes. Soil chemical and physical characteristics and climatic conditions were measured as background data. Nitrous oxide consumption and uptake mechanisms were measured in complementary laboratory incubation experiments using stable isotope approaches. Gene transcript numbers of nitrous oxide reductase (nosZ) I and II genes were quantified along the incubation with elevated N2O atmosphere. The spruce forests without fertilization history showed highest N2O uptake rates whereas pine forest had low emissions. Nitrous oxide uptake correlated positively with soil moisture, high soil silt content, and low temperature. Nitrous oxide uptake varied seasonally, being highest in spring and autumn when temperature was low and water content was high. The spruce forest was sink for CH4.Methane fluxes were decoupled from the N2O fluxes (i.e. when the N2O uptake was high the CH4 uptake was low). By using GWP approach, the cooling effect of N2O uptake was on average 30% of the cooling effect of CH4 uptake in spruce forest without fertilization. Anoxic conditions promoted higher N2O consumption rates in all soils. Gene transcription of nosZ-I genes were activated at beginning of the incubation. However, atypical/clade-II nosZ was not detected. These results suggests, that also N2O uptake rates have to be considered when accounting for the GHG budget of spruce forests.

Catalyst for Oxidation of Volatile Organic Compounds

NASA Technical Reports Server (NTRS)

Wood, George M. (Inventor); Upchurch, Billy T. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); Schyryer, Jacqueline L. (Inventor); DAmbrosia, Christine M. (Inventor)

2000-01-01

Disclosed is a process for oxidizing volatile organic compounds to carbon dioxide and water with the minimal addition of energy. A mixture of the volatile organic compound and an oxidizing agent (e.g. ambient air containing the volatile organic compound) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.

Correlation of the oxidation state of cerium in sol-gel glasses as a function of thermal treatment via optical spectroscopy and XANES studies.

PubMed

Assefa, Zerihun; Haire, R G; Caulder, D L; Shuh, D K

2004-07-01

Sol-gel glass matrices containing lanthanides have numerous technological applications and their formation involves several chemical facets. In the case of cerium, its ability to exist in two different oxidation states or in mixed valence state provides additional complexities for the sol-gel process. The oxidation state of cerium present during different facets of preparation of sol-gel glasses, and also as a function of the starting oxidation state of cerium added, were studied both by optical spectroscopy and X-ray absorption near-edge structures (XANES). The findings acquired by each approach were compared. The primary focus was on the redox chemistries associated with sample preparation, gelation, and thermal treatment. When Ce3+ is introduced into the starting sols, the trivalent state normally prevails in the wet and room temperature-dried gels. Heating in air at >100 degrees C can generate a light yellow coloration with partial oxidation to the tetravalent state. Above 200 degrees C and up to approximately 1000 degrees C, cerium is oxidized to its tetravalent state. In contrast, when tetravalent cerium is introduced into the sol, both the wet and room temperature-dried gels lose the yellow-brown color of the initial ceric ammonium nitrate solution. When the sol-gel is heated to 110 degrees C it turns yellowish as the cerium tends to be re-oxidized. The yellow color is believed to represent the effect of oxidation and oligomerization of the cerium-silanol units in the matrix. The luminescence properties are also affected by these changes, the details of which are reported herein.

Vanadium(V) Complexes with Substituted 1,5-bis(2-hydroxybenzaldehyde)carbohydrazones and Their Use As Catalyst Precursors in Oxidation of Cyclohexane.

PubMed

Dragancea, Diana; Talmaci, Natalia; Shova, Sergiu; Novitchi, Ghenadie; Darvasiová, Denisa; Rapta, Peter; Breza, Martin; Galanski, Markus; Kožı́šek, Jozef; Martins, Nuno M R; Martins, Luísa M D R S; Pombeiro, Armando J L; Arion, Vladimir B

2016-09-19

Six dinuclear vanadium(V) complexes have been synthesized: NH4[(VO2)2((H)LH)] (NH4[1]), NH4[(VO2)2((t-Bu)LH)] (NH4[2]), NH4[(VO2)2((Cl)LH)] (NH4[3]), [(VO2)(VO)((H)LH)(CH3O)] (4), [(VO2)(VO)((t-Bu)LH)(C2H5O)] (5), and [(VO2)(VO)((Cl)LH)(CH3O)(CH3OH/H2O)] (6) (where (H)LH4 = 1,5-bis(2-hydroxybenzaldehyde)carbohydrazone, (t-Bu)LH4 = 1,5-bis(3,5-di-tert-butyl-2-hydroxybenzaldehyde)carbohydrazone, and (Cl)LH4 = 1,5-bis(3,5-dichloro-2-hydroxybenzaldehyde)carbohydrazone). The structures of NH4[1] and 4-6 have been determined by X-ray diffraction (XRD) analysis. In all complexes, the triply deprotonated ligand accommodates two V ions, using two different binding sites ONN and ONO separated by a diazine unit -N-N-. In two pockets of NH4[1], two identical VO2(+) entities are present, whereas, in those of 4-6, two different VO2(+) and VO(3+) are bound. The highest oxidation state of V ions was corroborated by X-ray data, indicating the presence of alkoxido ligand bound to VO(3+) in 4-6, charge density measurements on 4, magnetic susceptibility, NMR spectroscopy, spectroelectrochemistry, and density functional theory (DFT) calculations. All four complexes characterized by XRD form dimeric associates in the solid state, which, however, do not remain intact in solution. Compounds NH4[1], NH4[2], and 4-6 were applied as alternative selective homogeneous catalysts for the industrially significant oxidation of cyclohexane to cyclohexanol and cyclohexanone. The peroxidative (with tert-butyl hydroperoxide, TBHP) oxidation of cyclohexane was performed under solvent-free and additive-free conditions and under low-power microwave (MW) irradiation. Cyclohexanol and cyclohexanone were the only products obtained (high selectivity), after 1.5 h of MW irradiation. Theoretical calculations suggest a key mechanistic role played by the carbohydrazone ligand, which can undergo reduction, instead of the metal itself, to form an active reduced form of the catalyst.

Screening of postharvest agricultural wastes as alternative sources of peroxidases: characterization and kinetics of a novel peroxidase from lentil ( Lens culinaris L.) stubble.

PubMed

Hidalgo-Cuadrado, Nazaret; Pérez-Galende, Patricia; Manzano, Teresa; De Maria, Cándido Garcia; Shnyrov, Valery L; Roig, Manuel G

2012-05-16

Aqueous crude extracts of a series of plant wastes (agricultural, wild plants, residues from sports activities (grass), ornamental residues (gardens)) from 17 different plant species representative of the typical biodiversity of the Iberian peninsula were investigated as new sources of peroxidases (EC 1.11.1.7). Of these, lentil (Lens culinaris L.) stubble crude extract was seen to provide one of the highest specific peroxidase activities, catalyzing the oxidation of guaiacol in the presence of hydrogen peroxide to tetraguaiacol, and was used for further studies. For the optimum extraction conditions found, the peroxidase activity in this crude extract (110 U mL(-1)) did not vary for at least 15 months when stored at 4 °C (k(inact) = 0.146 year(-1), t(1/2 inact) = 4.75 year), whereas, for comparative purposes, the peroxidase activity (60 U mL(-1)) of horseradish (Armoracia rusticana L.) root crude extract, obtained and stored under the same conditions, showed much faster inactivation kinetics (k(inact) = 2.2 × 10(-3) day(-1), t(1/2 inact) = 315 days). Using guaiacol as an H donor and a universal buffer (see above), all crude extract samples exhibited the highest peroxidase activity in the pH range between 4 and 7. Once semipurified by passing the crude extract through hydrophobic chromatography on phenyl-Sepharose CL-4B, the novel peroxidase (LSP) was characterized as having a purity number (RZ) of 2.5 and three SDS-PAGE electrophoretic bands corresponding to molecular masses of 52, 35, and 18 kDa. The steady-state kinetic study carried out on the H(2)O(2)-mediated oxidation of guaiacol by the catalytic action of this partially purified peroxidase pointed to apparent Michaelian kinetic behavior (K(m)(appH(2)O(2)) = 1.87 mM; V(max)(appH(2)O(2)) = 6.4 mM min(-1); K(m)(app guaicol) = 32 mM; V(max)(app guaicol) = 9.1 mM min(-1)), compatible with the two-substrate ping-pong mechanism generally accepted for peroxidases. Finally, after the effectiveness of the crude extracts of LSP in oxidizing and removing from solution a series of last-generation dyes present in effluents from textile industries (1) had been checked, a steady-state kinetic study of the H(2)O(2)-mediated oxidation and decolorization of Green Domalan BL by the catalytic action of the lentil stubble extract was carried out, with the observation of the same apparent Michaelian kinetic behavior (K(m)(appGD) = 471 μM; V(max)(appGD)= 23 μM min(-1)). Further studies are currently under way to address the application of this LSP crude extract for the clinical and biochemical analysis of biomarkers.

Comparison of coal reactivityduring conversion into different oxidizing medium

NASA Astrophysics Data System (ADS)

Korotkikh, A. G.; Slyusarskiy, K. V.; Larionov, K. B.; Osipov, V. I.

2016-10-01

Acoal conversion process of different coal samples into three different types of oxidizing medium (argon, air and steam) were studied by means of thermogravimetry. Two coal types with different metamorphism degree (lignite and bituminous coal) were used. The experimental procedure was carried out in non-isothermal conditions in temperature range from 373 K to 1273 K with 20 K/min heating rate. Purge gas consisted of argon and oxidizer with volumetric ratio 1:24 and had 250 ml/min flow rate.The ignition and burnout indexes were calculated to evaluate sample reactivity at different oxidizing mediums. The highest reactivity coefficient values in same atmosphere were obtained for lignite. It was caused by higher particle special surface area and volatile matter content.

Dual passivation of intrinsic defects at the compound semiconductor/oxide interface using an oxidant and a reductant.

PubMed

Kent, Tyler; Chagarov, Evgeniy; Edmonds, Mary; Droopad, Ravi; Kummel, Andrew C

2015-05-26

Studies have shown that metal oxide semiconductor field-effect transistors fabricated utilizing compound semiconductors as the channel are limited in their electrical performance. This is attributed to imperfections at the semiconductor/oxide interface which cause electronic trap states, resulting in inefficient modulation of the Fermi level. The physical origin of these states is still debated mainly because of the difficulty in assigning a particular electronic state to a specific physical defect. To gain insight into the exact source of the electronic trap states, density functional theory was employed to model the intrinsic physical defects on the InGaAs (2 × 4) surface and to model the effective passivation of these defects by utilizing both an oxidant and a reductant to eliminate metallic bonds and dangling-bond-induced strain at the interface. Scanning tunneling microscopy and spectroscopy were employed to experimentally determine the physical and electronic defects and to verify the effectiveness of dual passivation with an oxidant and a reductant. While subsurface chemisorption of oxidants on compound semiconductor substrates can be detrimental, it has been shown theoretically and experimentally that oxidants are critical to removing metallic defects at oxide/compound semiconductor interfaces present in nanoscale channels, oxides, and other nanostructures.

1D and 2D oxidized carbon nanomaterials on epoxy matrix: performance of composites over the same processing conditions

NASA Astrophysics Data System (ADS)

Ramos-Galicia, Lourdes; Martinez-Hernandez, Ana Laura; Fuentes-Ramirez, Rosalba; Velasco-Santos, Carlos

2017-11-01

Oxidized multi-walled carbon nanotubes and graphene oxide were evaluated as reinforcements of an epoxy resin. The composites were synthesized at concentrations of 0.1, 0.5, and 1.0 wt% under the same processing conditions. Nanocomposites with graphene oxide at 0.5 wt% present the highest mechanical properties, reaching up to ~180%, and ~760% of improvement in tensile strength and tensile toughness with respect to neat epoxy. Nevertheless, composites with oxidized nanotubes exhibit a tendency to improve mechanical properties as load increases. Storage moduli diminish due to cross-linking density reduction in all nanocomposites. Difference in thermal degradation are not observed in composites in comparison with matrix. Dimension play an important role in mechanical properties, because each nanoreinforcement has different performance with the concentration.

Hawkmoths use nectar sugar to reduce oxidative damage from flight.

PubMed

Levin, E; Lopez-Martinez, G; Fane, B; Davidowitz, G

2017-02-17

Nectar-feeding animals have among the highest recorded metabolic rates. High aerobic performance is linked to oxidative damage in muscles. Antioxidants in nectar are scarce to nonexistent. We propose that nectarivores use nectar sugar to mitigate the oxidative damage caused by the muscular demands of flight. We found that sugar-fed moths had lower oxidative damage to their flight muscle membranes than unfed moths. Using respirometry coupled with δ 13 C analyses, we showed that moths generate antioxidant potential by shunting nectar glucose to the pentose phosphate pathway (PPP), resulting in a reduction in oxidative damage to the flight muscles. We suggest that nectar feeding, the use of PPP, and intense exercise are causally linked and have allowed the evolution of powerful fliers that feed on nectar. Copyright © 2017, American Association for the Advancement of Science.

Degradation of chloramphenicol by potassium ferrate (VI) oxidation: kinetics and products.

PubMed

Zhou, Jia-Heng; Chen, Kai-Bo; Hong, Qian-Kun; Zeng, Fan-Cheng; Wang, Hong-Yu

2017-04-01

The oxidation of chloramphenicol (CAP) by potassium ferrate (VI) in test solution was studied in this paper. A series of jar tests were performed at bench scale with pH of 5-9 and molar ratio [VI/CAP] of 16.3:1-81.6:1. Results showed that raising VI dose could improve the treatment performance and the influence of solution pH was significant. VI is more reactive in neutral conditions, presenting the highest removal efficiency of CAP. The rate law for the oxidation of CAP by VI was first order with respect to each reactant, yielding an overall second-order reaction. Furthermore, five oxidation products were observed during CAP oxidation by VI. Results revealed that VI attacked the amide group of CAP, leading to the cleavage of the group, while benzene ring remained intact.

Dietary fat oxidation as a function of body fat.

PubMed

Westerterp, Klaas R; Smeets, Astrid; Lejeune, Manuela P; Wouters-Adriaens, Mirjam P E; Westerterp-Plantenga, Margriet S

2008-01-01

It is hypothesized that low dietary fat oxidation makes subjects prone to weight gain. The aim of the study was to determine dietary fat oxidation in normal, overweight, and obese subjects. The subjects were 38 women and 18 men with a mean (+/-SD) age of 30+/-12 y and a body mass index (in kg/m2) of 25+/-4 (range: 18-39). Dietary fat oxidation was measured with deuterated palmitic acid, given simultaneously with breakfast, while the subjects were fed under controlled conditions in a respiration chamber. Body composition was measured by hydrodensitometry and deuterium dilution. Dietary fat oxidation, measured over 12 h after breakfast, ranged from 4% to 28% with a mean (+/-SD) of 16+/-6%. Dietary fat oxidation was negatively related to percentage body fat, and lean subjects had the highest and obese subjects the lowest values (r=-0.65, P<0.001). The observed reduction in dietary fat oxidation in subjects with a higher percentage body fat may play a role in human obesity.

Real-time electrical detection of nitric oxide in biological systems with sub-nanomolar sensitivity

NASA Astrophysics Data System (ADS)

Jiang, Shan; Cheng, Rui; Wang, Xiang; Xue, Teng; Liu, Yuan; Nel, Andre; Huang, Yu; Duan, Xiangfeng

2013-07-01

Real-time monitoring of nitric oxide concentrations is of central importance for probing the diverse roles of nitric oxide in neurotransmission, cardiovascular systems and immune responses. Here we report a new design of nitric oxide sensors based on hemin-functionalized graphene field-effect transistors. With its single atom thickness and the highest carrier mobility among all materials, graphene holds the promise for unprecedented sensitivity for molecular sensing. The non-covalent functionalization through π-π stacking interaction allows reliable immobilization of hemin molecules on graphene without damaging the graphene lattice to ensure the highly sensitive and specific detection of nitric oxide. Our studies demonstrate that the graphene-hemin sensors can respond rapidly to nitric oxide in physiological environments with a sub-nanomolar sensitivity. Furthermore, in vitro studies show that the graphene-hemin sensors can be used for the detection of nitric oxide released from macrophage cells and endothelial cells, demonstrating their practical functionality in complex biological systems.

Tribological Properties of Ti-Based Alloys in a Simulated Bone-Implant Interface with Ringer's Solution at Fretting Contacts

PubMed Central

Ramos-Saenz, C.R.; Sundaram, P.A.; Diffoot-Carlo, N.

2010-01-01

The wear properties of oxidized and non-oxidized gamma-TiAl (a potential biomaterial) as well as Ti-6Al-4V and CP-Ti disks were studied and characterized by means of standard wear tests using a custom made bone pin arrangement. The Ti-base disks were oxidized in air at 500°C and 800°C for one hour. The tribological properties of the oxides formed over the disks were studied using a linear reciprocating wear testing machine under both dry and simulated biological conditions using Ringer's solution. Loss of metal oxide and coefficient of friction values were determined from the wear testing. From the results, abrasion and adhesion were the primary wear mechanisms in each of the three alloy-bone pairs. Specifically, the oxide formed on gamma-TiAl possessed the highest COF and wear resistance of the three materials which were studied. Also, as expected, bone wears down faster than the Ti-base metal oxide. PMID:20826360

Insight into the structure and mechanism of nickel-containing superoxide dismutase derived from peptide-based mimics.

PubMed

Shearer, Jason

2014-08-19

Nickel superoxide dismutase (NiSOD) is a nickel-containing metalloenzyme that catalyzes the disproportionation of superoxide through a ping-pong mechanism that relies on accessing reduced Ni(II) and oxidized Ni(III) oxidation states. NiSOD is the most recently discovered SOD. Unlike the other known SODs (MnSOD, FeSOD, and (CuZn)SOD), which utilize "typical" biological nitrogen and oxygen donors, NiSOD utilizes a rather unexpected ligand set. In the reduced Ni(II) oxidation state, NiSOD utilizes nitrogen ligands derived from the N-terminal amine and an amidate along with two cysteinates sulfur donors. These are unusual biological ligands, especially for an SOD: amine and amidate donors are underrepresented as biological ligands, whereas cysteinates are highly susceptible to oxidative damage. An axial histidine imidazole binds to nickel upon oxidation to Ni(III). This bond is long (2.3-2.6 Å) owing to a tight hydrogen-bonding network. All of the ligating residues to Ni(II) and Ni(III) are found within the first 6 residues from the NiSOD N-terminus. Thus, small nickel-containing metallopeptides derived from the first 6-12 residues of the NiSOD sequence can reproduce many of the properties of NiSOD itself. Using these nickel-containing metallopeptide-based NiSOD mimics, we have shown that the minimal sequence needed for nickel binding and reproduction of the structural, spectroscopic, and functional properties of NiSOD is H2N-HCXXPC. Insight into how NiSOD avoids oxidative damage has also been gained. Using small NiN2S2 complexes and metallopeptide-based mimics, it was shown that the unusual nitrogen donor atoms protect the cysteinates from oxidative damage (both one-electron oxidation and oxygen atom insertion reactions) by fine-tuning the electronic structure of the nickel center. Changing the nitrogen donor set to a bis-amidate or bis-amine nitrogen donor led to catalytically nonviable species owing to nickel-cysteinate bond oxidative damage. Only the amine/amidate nitrogen donor atoms within the NiSOD ligand set produce a catalytically viable species. These metallopeptide-based mimics have also hinted at the detailed mechanism of SOD catalysis by NiSOD. One such aspect is that the axial imidazole likely remains ligated to the Ni center under rapid catalytic conditions (i.e., high superoxide loads). This reduces the degree of structural rearrangement about the nickel center, leading to higher catalytic rates. Metallopeptide-based mimics have also shown that, although an axial ligand to Ni(III) is required for catalysis, the rates are highest when this is a weak interaction, suggesting a reason for the long axial His-Ni(III) bond found in NiSOD. These mimics have also suggested a surprising mechanistic insight: O2(-) reduction via a "H(•)" tunneling event from a R-S(H(+))-Ni(II) moiety to O2(-) is possible. The importance of this mechanism in NiSOD has not been verified.

Oxide films state analysis by IR spectroscopy based on the simple oscillator approximation

NASA Astrophysics Data System (ADS)

Volkov, N. V.; Yakutkina, T. V.; Karpova, V. V.

2017-05-01

Stabilization of structure-phase state in a wide temperature range is one of the most important problems of improving properties of oxide compounds. As such, the search of new effective methods for obtaining metal oxides with desired physic-chemical, electro-physical and thermal properties and their control is important and relevant. The aim of this work is identification features state of the oxide films of some metals Be, Al, Fe, Cu, Zr on the metal surface of the polycrystalline samples by infrared spectroscopy. To identify the resonance emission bands the algorithm of IR-spectra processing was developed and realized on the basis of table processor EXCEL-2010, which allow revealing characteristic resonance bands successfully and identification of inorganic chemical compounds. In the frame of simple oscillator model, resonance frequencies of normal vibrations of water and some inorganic compounds: metal oxides - Be, Al, Fe, Cu, Zr were calculated and characteristic frequencies for different states (aggregate, deformation, phase) were specified. By means of IR-spectroscopy fundamental possibility of revealing oxides films on metal substrate features state is shown, that allow development and optimization of the technology for production of the oxide films with desired properties.

Ferric Iron Production in Magma Oceans and Evolution of Mantle Oxidation State

NASA Astrophysics Data System (ADS)

Schaefer, L.; Elkins-Tanton, L. T.; Pahlevan, K.

2018-05-01

Self-oxidation of the magma ocean by ferric iron production at high pressure may explain the mantle oxidation state of the Earth. Partitioning during fractional crystallization can further increase the mantle oxygen fugacity during solidification.

Enhancement of Catalytic Activity of Reduced Graphene Oxide Via Transition Metal Doping Strategy

NASA Astrophysics Data System (ADS)

Lee, Hangil; Hong, Jung A.

2017-06-01

To compare the catalytic oxidation activities of reduced graphene oxide (rGO) and rGO samples doped with five different transition metals (TM-rGO), we determine their effects on the oxidation of L-cysteine (Cys) in aqueous solution by performing electrochemistry (EC) measurements and on the photocatalytic oxidation of Cys by using high-resolution photoemission spectroscopy (HRPES) under UV illumination. Our results show that Cr-, Fe-, and Co-doped rGO with 3+ charge states (stable oxide forms: Cr3+, Fe3+, and Co3+) exhibit enhanced catalytic activities that are due to the charge states of the doped metal ions as we compare them with Cr-, Fe-, and Co-doped rGO with 2+ charge states.

Bond-length distributions for ions bonded to oxygen: results for the non-metals and discussion of lone-pair stereoactivity and the polymerization of PO4

PubMed Central

Gagné, Olivier Charles

2018-01-01

Bond-length distributions are examined for three configurations of the H+ ion, 16 configurations of the group 14–16 non-metal ions and seven configurations of the group 17 ions bonded to oxygen, for 223 coordination polyhedra and 452 bond distances for the H+ ion, 5957 coordination polyhedra and 22 784 bond distances for the group 14–16 non-metal ions, and 248 coordination polyhedra and 1394 bond distances for the group 17 non-metal ions. H⋯O and O—H + H⋯O distances correlate with O⋯O distance (R 2 = 0.94 and 0.96): H⋯O = 1.273 × O⋯O – 1.717 Å; O—H + H⋯O = 1.068 × O⋯O – 0.170 Å. These equations may be used to locate the hydrogen atom more accurately in a structure refined by X-ray diffraction. For non-metal elements that occur with lone-pair electrons, the most observed state between the n versus n+2 oxidation state is that of highest oxidation state for period 3 cations, and lowest oxidation state for period 4 and 5 cations when bonded to O2−. Observed O—X—O bond angles indicate that the period 3 non-metal ions P3+, S4+, Cl3+ and Cl5+ are lone-pair seteroactive when bonded to O2−, even though they do not form secondary bonds. There is no strong correlation between the degree of lone-pair stereoactivity and coordination number when including secondary bonds. There is no correlation between lone-pair stereoactivity and bond-valence sum at the central cation. In synthetic compounds, PO4 polymerizes via one or two bridging oxygen atoms, but not by three. Partitioning our PO4 dataset shows that multi-modality in the distribution of bond lengths is caused by the different bond-valence constraints that arise for Obr = 0, 1 and 2. For strongly bonded cations, i.e. oxyanions, the most probable cause of mean bond length variation is the effect of structure type, i.e. stress induced by the inability of a structure to follow its a priori bond lengths. For ions with stereoactive lone-pair electrons, the most probable cause of variation is bond-length distortion.

Computational investigation of the photochemical deoxygenation of thiophene-S-oxide and selenophene-Se-oxide.

PubMed

Stoffregen, Stacey A; Lee, Stephanie Y; Dickerson, Pearl; Jenks, William S

2014-02-01

CASSCF and multireference MP2 calculations were carried out on thiophene-S-oxide (TO) and selenophene-Se-oxide (SeO), comparing the energies of the ground state to the first two electronically excited singlet and triplet states, using constrained optimizations and multiple fixed S-O or Se-O distances. For both molecules, one of the two triplet states smoothly dissociates to yield O((3)P) with little or no barrier. Single point calculations are consistent with the same phenomenon occurring for dibenzothiophene-S-oxide (DBTO). This provides an explanation for the inefficient unimolecular photochemical dissociation of O((3)P) from DBTO despite a phosphorescence energy below that of S-O dissociation, i.e., that S-O scission probably occurs from a spectroscopically unobserved triplet (T2) state.

Oxidation and Volatilization of Silica-Formers in Water Vapor

NASA Technical Reports Server (NTRS)

Opila, E. J.; Gray, Hugh R. (Technical Monitor)

2002-01-01

At high temperatures SiC and Si3N4 react with water vapor to form a silica scale. Silica scales also react with water vapor to form a volatile Si(OH)4 species. These simultaneous reactions, one forming silica and the other removing silica, are described by paralinear kinetics. A steady state, in which these reactions occur at the same rate, is eventually achieved, After steady state is achieved, the oxide found on the surface is a constant thickness and recession of the underlying material occurs at a linear rate. The steady state oxide thickness, the time to achieve steady state, and the steady state recession rate can all be described in terms of the rate constants for the oxidation and volatilization reactions. In addition, the oxide thickness, the time to achieve steady state, and the recession rate can also be determined from parameters that describe a water vapor-containing environment. Accordingly, maps have been developed to show these steady state conditions as a function of reaction rate constants, pressure, and gas velocity. These maps can be used to predict the behavior of silica formers in water-vapor containing environments such as combustion environments. Finally, these maps are used to explore the limits of the paralinear oxidation model for SiC and Si3N4

Colossal super saturation of oxygen at the iron-aluminum interfaces fabricated using solid state welding

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

Sridharan, Niyanth; Isheim, D.; Seidman, David N.

Solid state joining is achieved in three steps, (i) interface asperity deformation, (ii) oxide dispersion, followed by (iii) atomic contact and bonding. Atomically clean metallic surfaces without an oxide layer bond spontaneously. Despite its importance the oxide dispersion mechanism is not well studied. In this work the first ever atom probe study of iron-aluminum solid state welds show that the oxygen concentration at the interface is 20 at.%. This is significantly lower than any equilibrium oxide concentration. Here, we therefore propose that the high-strain rate deformation at the interfaces renders the oxide unstable resulting in the observed concentration of oxygen.

Colossal super saturation of oxygen at the iron-aluminum interfaces fabricated using solid state welding

DOE PAGES

Sridharan, Niyanth; Isheim, D.; Seidman, David N.; ...

2016-12-14

Solid state joining is achieved in three steps, (i) interface asperity deformation, (ii) oxide dispersion, followed by (iii) atomic contact and bonding. Atomically clean metallic surfaces without an oxide layer bond spontaneously. Despite its importance the oxide dispersion mechanism is not well studied. In this work the first ever atom probe study of iron-aluminum solid state welds show that the oxygen concentration at the interface is 20 at.%. This is significantly lower than any equilibrium oxide concentration. Here, we therefore propose that the high-strain rate deformation at the interfaces renders the oxide unstable resulting in the observed concentration of oxygen.

Comparative assessment of synthetic strategies toward active platinum-rhodium-tin electrocatalysts for efficient ethanol electro-oxidation

NASA Astrophysics Data System (ADS)

Erini, Nina; Krause, Paul; Gliech, Manuel; Yang, Ruizhi; Huang, Yunhui; Strasser, Peter

2015-10-01

The present work explores the effect of autoclave-based autogenous-pressure vs. ambient pressure conditions on the synthesis and properties of carbon-supported Pt-Rh-Sn nanoparticle electrocatalysts. The Pt-Rh-Sn nanoparticles were characterized by X-ray spectroscopy, electron microscopy and mass spectroscopy and deployed as catalysts for the electrocatalytic ethanol oxidation reaction. Pt-Rh-Sn catalysts precipitated with carbon already present showed narrow particle size distribution around 7 nm, while catalysts supported on carbon after particle formation showed broader size distribution ranging from 8 to 16 nm, similar metal loadings between 40 and 48 wt.% and similar atomic ratios of Pt:Rh:Sn of 30:10:60. The highest ethanol oxidation activity at low overpotentials associated with exceptionally early ethanol oxidation onset potential was observed for ambient-pressure catalysts with the active ternary alloy phase formed in presence of the carbon supports. In contrast, catalysts prepared under ambient pressure in a two-step approach, involving alloy particle formation followed by particle separation and subsequent deposition on the carbon support, yielded the highest overall mass activities. Based on the observed synthesis-activity correlations, a comparative assessment is provided of the synthetic techniques at high vs. low pressures, and in presence and absence of carbon support. Plausible hypotheses in terms of particle dispersion and interparticle distance accounting for these observed differences are discussed.

Evaluation of the effect of brominated flame retardants on hemoglobin oxidation and hemolysis in human erythrocytes.

PubMed

Jarosiewicz, Monika; Duchnowicz, Piotr; Włuka, Anna; Bukowska, Bożena

2017-11-01

Brominated flame retardants (BFRs) are widely used in many everyday products. Numerous studies have shown that BFRs can be released into the environment. Environmental pollution with these compounds raises concerns about their potentially adverse health effects. The aim of this study was to evaluate the effect of tetrabromobisphenol A (TBBPA), tetrabromobisphenol S (TBBPS), 2,4-dibromophenol (2,4-DBP), 2,4,6- tribromophenol (2,4,6-TBP) and pentabromophenol (PBP) on hemolysis induction and hemoglobin oxidation in human erythrocytes. The erythrocytes were incubated with selected BFRs in a wide concentrations ranging from 0.01 to 100 μg/ml for 24 h, 48 h and 72 h. All compounds studied, exhibited hemolytic potential and induced methemoglobin formation. Hemolytic and oxidative potential of BFRs increased along with the increasing concentrations of the compounds studied and elongation of the incubation time. Our study showed that both the number of aromatic rings and the number of bromine atoms in the molecule of the compounds examined influence hemoglobin oxidation and damage to the cellular membrane. Furthermore, we may conclude that 2,4-DBP is potentially most toxic compound because it causes statistically significant changes at the lowest concentration, while the highest toxicity at the highest concentrations was noted for TBBPA. Copyright © 2017 Elsevier Ltd. All rights reserved.

Study of the antioxidant capacity in gills of the Pacific oyster Crassostrea gigas in link with its reproductive investment.

PubMed

Béguel, Jean-Philippe; Huvet, Arnaud; Quillien, Virgile; Lambert, Christophe; Fabioux, Caroline

2013-01-01

Energy allocation principle is a core element of life-history theory in which "the cost of reproduction" corresponds to an acceleration of senescence caused by an increase in reproductive investment. In the "theory of aging", senescence is mainly due to the degradation of lipids, proteins and DNA by reactive oxygen species (ROS), by-products of oxidative metabolism. Some studies have shown that oxidative stress susceptibility could be a cost of reproduction. The present study investigates the effect of reproductive investment on antioxidant capacity in the gills of a species with a very high reproductive investment, the Pacific oyster Crassostrea gigas. We used RNA interference targeting the oyster vasa-like gene (Oyvlg) to produce oysters with contrasted reproductive investment. Antioxidant capacity was studied by measuring the mRNA levels of genes encoding major antioxidant enzymes, and the activity of these enzymes. The highest reproductive investment was associated with the highest transcript levels for glutathione peroxidase and extra-cellular and mitochondrial superoxide dismutase. In contrast, lipid peroxidation did not show any sign of oxidative damage whatever the reproductive investment. Up-regulation of certain genes encoding enzymes involved in the first step of ROS detoxification could therefore be a part of the organism's strategy for managing the pro-oxidant species produced by heavy reproductive investment. Copyright © 2012 Elsevier Inc. All rights reserved.

2,4-Dichlorophenoxyacetic acid (2,4-D) degradation promoted by nanoparticulate zerovalent iron (nZVI) in aerobic suspensions.

PubMed

Correia de Velosa, Adriana; Pupo Nogueira, Raquel F

2013-05-30

Reactive species generated by Fe(0) oxidation promoted by O2 (catalyzed or not by ligands) are able to degrade contaminant compounds like the herbicide 2,4-dichlorophenoxyacetic acid. The degradation of 2,4-D was influenced by the concentrations of zero valent iron (ZVI) and different ligands, as well as by pH. In the absence of ligands, the highest 2,4-D degradation rate was obtained at pH 3, while the highest percentage degradation (50%) was achieved at pH 5 after 120 min of reaction. Among the ligands studied (DTPA, EDTA, glycine, oxalate, and citrate), only ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) significantly enhanced oxidation of 2,4-D. This increase in oxidation was observed at all pH values tested (including neutral to alkaline conditions), indicating the feasibility of the technique for treatment of contaminated water. In the presence of EDTA, the oxidation rate was greater at pH 3 than at pH 5 or 7. Increasing the EDTA concentration increased the rate and percentage of 2,4-D degradation, however increasing the Fe(0) concentration resulted in the opposite behavior. It was found that degradation of EDTA and 2,4-D occurred simultaneously, and that the new methodology avoided any 2,4-D removal by adsorption/coprecipitation. Copyright © 2013 Elsevier Ltd. All rights reserved.

SOMO–HOMO Level Inversion in Biologically Important Radicals

PubMed Central

2017-01-01

Conventionally, the singly occupied molecular orbital (SOMO) of a radical species is considered to be the highest occupied molecular orbital (HOMO), but this is not the case always. In this study, we considered a number of radicals from smallest diatomic anion radicals such as superoxide anion radical to one-electron oxidized DNA related base radicals that show the SOMO is energetically lower than one or more doubly occupied molecular orbitals (MOs) (SOMO–HOMO level inversion). The electronic configurations are calculated employing the B3LYP/6-31++G** method, with the inclusion of aqueous phase via the integral equation formalism of the polarized continuum model solvation model. From the extensive study of the electronic configurations of radicals produced by one-electron oxidation or reduction of natural-DNA bases, bromine-, sulfur-, selenium-, and aza-substituted DNA bases, as well as 20 diatomic molecules, we highlight the following important findings: (i) SOMO–HOMO level inversion is a common phenomenon in radical species. (ii) The more localized spin density in σ-orbital on a single atom (carbon, nitrogen, oxygen, sulfur, or selenium), the greater the gap between HOMO and SOMO. (iii) In species with SOMO–HOMO level inversion, one-electron oxidation takes place from HOMO not from the SOMO, which produces a molecule in its triplet ground state. Oxidation of aqueous superoxide anion producing triplet molecular oxygen is one example of many. (iv) These results are for conventional radicals and in contrast with those reported for distonic radical anions in which SOMO–HOMO gaps are smaller for more localized radicals and the orbital inversions vanish in water. Our findings yield new insights into the properties of free radical systems. PMID:29240424

Relationship between bicarbonate retention and bone characteristics in broiler chickens.

PubMed

Leslie, M A; Coleman, R A; Moehn, S; Ball, R O; Korver, D R

2006-11-01

Determination of the bicarbonate retention factor (BRF) is an important step during development of the indicator amino acid oxidation technique for use in a new model. A series of 4-h oxidation experiments were performed to determine the BRF of broilers aged 7, 14, 21, 28, 35, and 42 d using 4 birds per age group. A priming dose of 1.2 microCi of NaH(14)CO(3), followed by eight half-hourly doses of 1 microCi of NaH(14)CO(3) were given orally to each of 4 birds per age. The percentage of (14)C dose expired by the bird at a steady state was measured. These birds, as well as 12 additional birds matched for age and BW, were killed, and femur bone mineral density was measured by quantitative computed tomography to determine the relationship between bone development and bicarbonate retention at each age. There was a correlation (r = 0.50; P < 0.05) between total cross-sectional femur bone mineral density and bicarbonate retention at each age. A prediction equation (Y = 6.95 x 10(-2)X - 3.51 x 10(-5)X(2) + 27.58; P < 0.0001, R(2) = 0.79) where Y = bicarbonate retention and X = BW was generated to predict Y as a function of X. Bicarbonate retention values peaked at 28 d, during the stage of the most rapid bone deposition and the highest growth rate. A constant BRF was found from 1,900 to 2,700 g of BW of 35.15 +/- 1.095% (mean +/- SEM). This retention factor will allow the accurate correction of oxidation of (14)C-labeled substrates in broilers of different ages and BW in future indicator amino acid oxidation studies.

The Periplasmic Nitrate Reductase Nap Is Required for Anaerobic Growth and Involved in Redox Control of Magnetite Biomineralization in Magnetospirillum gryphiswaldense

PubMed Central

Li, Yingjie; Katzmann, Emanuel; Borg, Sarah

2012-01-01

The magnetosomes of many magnetotactic bacteria consist of membrane-enveloped magnetite crystals, whose synthesis is favored by a low redox potential. However, the cellular redox processes governing the biomineralization of the mixed-valence iron oxide have remained unknown. Here, we show that in the alphaproteobacterium Magnetospirillum gryphiswaldense, magnetite biomineralization is linked to dissimilatory nitrate reduction. A complete denitrification pathway, including gene functions for nitrate (nap), nitrite (nir), nitric oxide (nor), and nitrous oxide reduction (nos), was identified. Transcriptional gusA fusions as reporters revealed that except for nap, the highest expression of the denitrification genes coincided with conditions permitting maximum magnetite synthesis. Whereas microaerobic denitrification overlapped with oxygen respiration, nitrate was the only electron acceptor supporting growth in the entire absence of oxygen, and only the deletion of nap genes, encoding a periplasmic nitrate reductase, and not deletion of nor or nos genes, abolished anaerobic growth and also delayed aerobic growth in both nitrate and ammonium media. While loss of nosZ or norCB had no or relatively weak effects on magnetosome synthesis, deletion of nap severely impaired magnetite biomineralization and resulted in fewer, smaller, and irregular crystals during denitrification and also microaerobic respiration, probably by disturbing the proper redox balance required for magnetite synthesis. In contrast to the case for the wild type, biomineralization in Δnap cells was independent of the oxidation state of carbon substrates. Altogether, our data demonstrate that in addition to its essential role in anaerobic respiration, the periplasmic nitrate reductase Nap has a further key function by participating in redox reactions required for magnetite biomineralization. PMID:22730130

Inside HOLMES experiment: 163Ho metallic target production for the micro-calorimeter absorber

NASA Astrophysics Data System (ADS)

Pizzigoni, G.; Alpert, B.; Balata, M.; Bennett, D.; Biasotti, M.; Boragno, C.; Brofferio, C.; De Gerone, M.; Dressler, R.; Faverazani, M.; Ferri, E.; Folwer, J.; Gatti, F.; Giachero, A.; Heinitz, S.; Hilton, G.; Köster, U.; Lusignoli, M.; Maino, M.; Mates, J.; Nisi, S.; Nizzolo, R.; Nucciotti, A.; Pessina, G.; Puiu, A.; Ragazzi, S.; Reintsema, C.; Ribeiro Gomes, M.; Shmidt, D.; Schumann, D.; Sisti, M.; Swetz, D.; Terranova, F.; Ullom, J.; Day, P. K.

2016-07-01

The main goal in the HOLMES experiment is the neutrino mass measurement using an array of 1000 micro-calorimeters with standard metallic absorber. A good isotope for such measurement is the 163Ho, those isotopes embedded in the metallic absorber will be 1011-1013. Since 163Ho is not available in nature, a dedicated process must be set up to produce the amount needed for this neutrino mass experiment. The process with the highest born-up cross-section is the neutron irradiation of Er2O3 enriched in 162Er: 162Er(n,γ)163Er →163Ho+νe, where the decay is an EC with half-life of about 75 min and the (n,γ) is about 20 barns for thermal neutron. After the neutron irradiation in the oxide powder there are several radioactive isotopes which are potentially disturbing because of the background that they cause below 5 keV. The chemical separation of holmium from the irradiation enriched Er2O3 powder is therefore mandatory and will be performed by means of ion exchange chromatography. On the end of those processes the oxide powder enriched in 162Er will have the 163Ho isotope number required. The holmium chemical state influences the end point of the EC spectrum, in order to avoid such effect it is necessary to embed in the absorber only the metallic isotope. Reduction and distillation technique allowed us to obtain a pure metallic holmium, starting from natural oxide holmium. This technique will be applied on the irradiated oxide powder to obtain the metallic 163Ho, ready to be embedded in the micro-calorimeter absorber.

Origin and enhancement of spin polarized current in diluted magnetic oxides by oxygen vacancies

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

Chou, Hsiung, E-mail: hchou@mail.nsysu.edu.tw; Yang, Kung-Shang; Tsao, Yao-Chung

Spin polarized current (SPC) is a crucial characteristic of diluted magnetic oxides due to the potential application of oxides in spintronic devices. However, most research has been focused on ferromagnetic properties rather than polarization of electric current, because direct measurements are difficult and the origin of SPC has yet to be fully understood. The method to increase the SPC percentage is beyond practical consideration at present. To address this problem, we focus on the role of oxygen vacancies (V{sub O}) on SPC, which are controlled by growing the Co-doped ZnO thin-films at room temperature in a reducing atmosphere [Ar + (1%–30%)H{sub 2}].more » We found that the conductivity increases with an increase of V{sub O} via two independent channels: the variable range hopping (VRH) within localized states and the itinerant transport in the conduction band. The point contact Andreev reflection measurements at 4.2 K, where the electric conduction is governed only by the VRH mechanism, prove that the current flowing in the VRH hopping channel is SPC. The percentage of SPC increases with the introduction of V{sub O} and increase in its concentration. The transport measurement shows that by manipulating V{sub O}, one can control the percentage of VRH hopping conduction such that it can even dominate room temperature conduction. The highest achieved SPC ratio at room temperature was 80%.« less

Impact of Metal Nanoform Colloidal Solution on the Adaptive Potential of Plants

NASA Astrophysics Data System (ADS)

Taran, Nataliya; Batsmanova, Ludmila; Kovalenko, Mariia; Okanenko, Alexander

2016-02-01

Nanoparticles are a known cause of oxidative stress and so induce antistress action. The latter property was the purpose of our study. The effect of two concentrations (120 and 240 mg/l) of nanoform biogenic metal (Ag, Cu, Fe, Zn, Mn) colloidal solution on antioxidant enzymes, superoxide dismutase and catalase; the level of the factor of the antioxidant state; and the content of thiobarbituric acid reactive substances (TBARSs) of soybean plant in terms of field experience were studied. It was found that the oxidative processes developed a metal nanoparticle pre-sowing seed treatment variant at a concentration of 120 mg/l, as evidenced by the increase in the content of TBARS in photosynthetic tissues by 12 %. Pre-sowing treatment in a double concentration (240 mg/l) resulted in a decrease in oxidative processes (19 %), and pre-sowing treatment combined with vegetative treatment also contributed to the reduction of TBARS (10 %). Increased activity of superoxide dismutase (SOD) was observed in a variant by increasing the content of TBARS; SOD activity was at the control level in two other variants. Catalase activity decreased in all variants. The factor of antioxidant activity was highest (0.3) in a variant with nanoparticle double treatment (pre-sowing and vegetative) at a concentration of 120 mg/l. Thus, the studied nanometal colloidal solution when used in small doses, in a certain time interval, can be considered as a low-level stress factor which according to hormesis principle promoted adaptive response reaction.

Molecular orbital study of some eight-coordinate sulfur chelate complexes of molybdenum

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

Perkins, P.G.; Schultz, F.A.

1983-03-30

A number of molybdenum complexes involving the formal oxidation states Mo(IV) and Mo(V) have been studied by a self-consistent-field molecular orbital technique. All the complexes were of dodecahedral geometry and had eight sulfurs chelated to the central metal atom. In all, a series of five tetrakis complexes was studied, including the ligands dithiocarbamate (dtc), thioxanthate (txn), 1,1-dicyano-2,2-ethylenedithiolate (i-mnt), 1-cyano-1-carbethoxy-2,2-ethylenedithiolate (ced), and 1,1-dicarbethoxy-2,2-ethylenedithiolate (ded). The 4d orbitals were included on molybdenum, and the empty 3d levels on all sulfur atoms. The results show that the highest occupied molecular orbital in each case has over 90% metal d/sub xy/ character. Further, themore » energy of this orbital is linearly related to the reversible half-wave potentials for Mo(IV) ..-->.. Mo(V) and Mo(V) ..-->.. Mo(VI) oxidations of the complexes. A further irreversible oxidation observed experimentally also is closely related to the calculated energy levels. Relationships between the calculated results and Mo 3d/sub 5///sub 2/ X-ray photoelectron binding energies, EPR parameters, and charge-transfer absorption energies are discussed. Electrochemical and spectroscopic properties of these MoS/sub 8/ complexes can be understood in terms of a manifold of orbital energies that retain approximately constant spacings between one another and that move up or down in absolute energy in response to the charge donated or withdrawn by the ligands.« less

The reactivity of sodium alanates with O[2], H[2]O, and CO[2] : an investigation of complex metal hydride contamination in the context of automotive systems.

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

Dedrick, Daniel E.; Bradshaw, Robert W.; Behrens, Richard, Jr.

2007-08-01

Safe and efficient hydrogen storage is a significant challenge inhibiting the use of hydrogen as a primary energy carrier. Although energy storage performance properties are critical to the success of solid-state hydrogen storage systems, operator and user safety is of highest importance when designing and implementing consumer products. As researchers are now integrating high energy density solid materials into hydrogen storage systems, quantification of the hazards associated with the operation and handling of these materials becomes imperative. The experimental effort presented in this paper focuses on identifying the hazards associated with producing, storing, and handling sodium alanates, and thus allowingmore » for the development and implementation of hazard mitigation procedures. The chemical changes of sodium alanates associated with exposure to oxygen and water vapor have been characterized by thermal decomposition analysis using simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) and X-ray diffraction methods. Partial oxidation of sodium alanates, an alkali metal complex hydride, results in destabilization of the remaining hydrogen-containing material. At temperatures below 70 C, reaction of sodium alanate with water generates potentially combustible mixtures of H{sub 2} and O{sub 2}. In addition to identifying the reaction hazards associated with the oxidation of alkali-metal containing complex hydrides, potential treatment methods are identified that chemically stabilize the oxidized material and reduce the hazard associated with handling the contaminated metal hydrides.« less

Self-Stacked Reduced Graphene Oxide Nanosheets Coated with Cobalt-Nickel Hydroxide by One-Step Electrochemical Deposition toward Flexible Electrochromic Supercapacitors.

PubMed

Grote, Fabian; Yu, Zi-You; Wang, Jin-Long; Yu, Shu-Hong; Lei, Yong

2015-09-01

The implementation of an optical function into supercapacitors is an innovative approach to make energy storage devices smarter and to meet the requirements of smart electronics. Here, it is reported for the first time that nickel-cobalt hydroxide on reduced graphene oxide can be utilized for flexible electrochromic supercapacitors. A new and straightforward one-step electrochemical deposition process is introduced that is capable of simultaneously reducing GO and depositing amorphous Co(1-x)Ni(x)(OH)2 on the rGO. It is shown that the rGO nanosheets are homogeneously coated with metal hydroxide and are vertically stacked. No high temperature processes are used so that flexible polymer-based substrates can be coated. The synthesized self-stacked rGO-Co(1-x)Ni(x)(OH)2 nanosheet material exhibits pseudocapacitive charge storage behavior with excellent rate capability, high Columbic efficiency, and nondiffusion limited behavior. It is shown that the electrochemical behavior of the Ni(OH)2 can be modulated, by simultaneously depositing nickel and cobalt hydroxide, into broad oxidization and reduction bands. Further, the material exhibits electrochromic property and can switch between a bleached and transparent state. Literature comparison reveals that the performance characteristics of the rGO-Co(1-x)Ni(x)(OH)2 nanosheet material, in terms of gravimetric capacitance, areal capacitance, and long-term cycling stability, are among the highest reported values of supercapacitors with electrochromic property. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The spatial distribution of two dimensional electron gas at the LaTiO3/KTaO3 interface

NASA Astrophysics Data System (ADS)

Song, Qi; Peng, Rui; Xu, Haichao; Feng, Donglai

2017-08-01

We report the photoemission spectroscopy studies on the newly discovered two dimensional electron gas (2DEG) system LaTiO3/KTaO3, whose interfacial carriers show much higher mobility than that in LaAlO3/SrTiO3 at room temperature, thus raising the application prospect of transition metal oxide-based 2DEG. By measuring the density of states at the Fermi energy (EF), we directly reveal the spatial distribution of the conducting electrons at the interface. The density of states near EF of the topmost LTO reaches the highest when LTO is 2-unit-cell thick, and diminishes at the 5th unit cell of LTO. We discussed the origin of such a spacial distribution of conducting electrons and its relation with 2DEG, and proposed two possible scenarios based on electrostatic relaxations and chemical reconstructions. These results offer experimental clues in understanding the characteristics and origin of the 2DEG, and also shed light on improving the performance of 2DEG.

The spatial distribution of two dimensional electron gas at the LaTiO3/KTaO3 interface.

PubMed

Song, Qi; Peng, Rui; Xu, Haichao; Feng, Donglai

2017-08-09

We report the photoemission spectroscopy studies on the newly discovered two dimensional electron gas (2DEG) system LaTiO 3 /KTaO 3 , whose interfacial carriers show much higher mobility than that in LaAlO 3 /SrTiO 3 at room temperature, thus raising the application prospect of transition metal oxide-based 2DEG. By measuring the density of states at the Fermi energy (E F ), we directly reveal the spatial distribution of the conducting electrons at the interface. The density of states near E F of the topmost LTO reaches the highest when LTO is 2-unit-cell thick, and diminishes at the 5th unit cell of LTO. We discussed the origin of such a spacial distribution of conducting electrons and its relation with 2DEG, and proposed two possible scenarios based on electrostatic relaxations and chemical reconstructions. These results offer experimental clues in understanding the characteristics and origin of the 2DEG, and also shed light on improving the performance of 2DEG.

Characteristics of greenhouse gas emission in three full-scale wastewater treatment processes.

PubMed

Yan, Xu; Li, Lin; Liu, Junxin

2014-02-01

Three full-scale wastewater treatment processes, Orbal oxidation ditch, anoxic/anaerobic/aerobic (reversed A2O) and anaerobic/anoxic/aerobic (A2O), were selected to investigate the emission characteristics of greenhouse gases (GHG), including carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O). Results showed that although the processes were different, the units presenting high GHG emission fluxes were remarkably similar, namely the highest CO2 and N2O emission fluxes occurred in the aerobic areas, and the highest CH4 emission fluxes occurred in the grit tanks. The GHG emission amount of each unit can be calculated from its area and GHG emission flux. The calculation results revealed that the maximum emission amounts of CO2, CH4 and N2O in the three wastewater treatment processes appeared in the aerobic areas in all cases. Theoretically, CH4 should be produced in anaerobic conditions, rather than aerobic conditions. However, results in this study showed that the CH4 emission fluxes in the forepart of the aerobic area were distinctly higher than in the anaerobic area. The situation for N2O was similar to that of CH4: the N2O emission flux in the aerobic area was also higher than that in the anoxic area. Through analysis of the GHG mass balance, it was found that the flow of dissolved GHG in the wastewater treatment processes and aerators may be the main reason for this phenomenon. Based on the monitoring and calculation results, GHG emission factors for the three wastewater treatment processes were determined. The A2O process had the highest CO2 emission factor of 319.3 g CO2/kg COD(removed), and the highest CH4 and N2O emission factors of 3.3 g CH4/kg COD(removed) and 3.6 g N2O/kg TN(removed) were observed in the Orbal oxidation ditch process.

Biquadratic coupling through nano-oxide layers in pinned layers of IrMn-based spin valves

NASA Astrophysics Data System (ADS)

Lai, Chih-Huang; Lu, K. H.

2003-05-01

We have investigated the coupling between top and bottom pinned layers through various nano-oxide layers (NOLs) in IrMn-based spin valves. The NOLs were formed by using oxygen-plasma oxidation or natural oxidation on 1 nm metallic layers. By inserting naturally oxidized Co-NOLs in the pinned layer, strong ferromagnetic coupling through NOLs and high specularity at the NOL interface were achieved. In contrast, when the plasma-oxidized Co-NOLs were inserted, ferromagnetic coupling through NOLs disappeared, plausibly due to the formation of nonferromagnetic oxides, which led to a low magnetoresistance (MR). Insertion of naturally oxidized Ni80Fe20-NOLs showed the same results as that of naturally oxidized Co-NOLs. On the other hand, biquadratic coupling between top and bottom pinned-Co90Fe10 layers was observed by inserting plasma-oxidized Ni80Fe20-NOLs. The highest MR was obtained when the field was applied along the direction perpendicular to the field-annealing direction. Similar biquadratic coupling was also found with naturally oxidized or plasma-oxidized Fe-NOLs. We suggest that the biquadratic coupling between pinned Co90Fe10 layers through NOLs results from the coupling between Fe (or Co90Fe10) and Fe+3 oxides

Crystallographic studies of [NiFe]-hydrogenase mutants: towards consensus structures for the elusive unready oxidized states.

PubMed

Volbeda, Anne; Martin, Lydie; Barbier, Elodie; Gutiérrez-Sanz, Oscar; De Lacey, Antonio L; Liebgott, Pierre-Pol; Dementin, Sébastien; Rousset, Marc; Fontecilla-Camps, Juan C

2015-01-01

Catalytically inactive oxidized O2-sensitive [NiFe]-hydrogenases are characterized by a mixture of the paramagnetic Ni-A and Ni-B states. Upon O2 exposure, enzymes in a partially reduced state preferentially form the unready Ni-A state. Because partial O2 reduction should generate a peroxide intermediate, this species was previously assigned to the elongated Ni-Fe bridging electron density observed for preparations of [NiFe]-hydrogenases known to contain the Ni-A state. However, this proposition has been challenged based on the stability of this state to UV light exposure and the possibility of generating it anaerobically under either chemical or electrochemical oxidizing conditions. Consequently, we have considered alternative structures for the Ni-A species including oxidation of thiolate ligands to either sulfenate or sulfenic acid. Here, we report both new and revised [NiFe]-hydrogenases structures and conclude, taking into account corresponding characterizations by Fourier transform infrared spectroscopy (FTIR), that the Ni-A species contains oxidized cysteine and bridging hydroxide ligands instead of the peroxide ligand we proposed earlier. Our analysis was rendered difficult by the typical formation of mixtures of unready oxidized states that, furthermore, can be reduced by X-ray induced photoelectrons. The present study could be carried out thanks to the use of Desulfovibrio fructosovorans [NiFe]-hydrogenase mutants with special properties. In addition to the Ni-A state, crystallographic results are also reported for two diamagnetic unready states, allowing the proposal of a revised oxidized inactive Ni-SU model and a new structure characterized by a persulfide ion that is assigned to an Ni-'Sox' species.

Effects of Activated Carbon Surface Property on Structure and Activity of Ru/AC Catalysts

NASA Astrophysics Data System (ADS)

Xu, S. K.; Li, L. M.; Guo, N. N.

2018-05-01

The activated carbon (AC) was modified by supercritical (SC) methanol, HNO3 oxidation, or HNO3 oxidation plus SC methanol, respectively. Then, the original and the modified AC were used as supports for Ru/AC catalysts prepared via the impregnation method. The results showed that the SC methanol modification decreased the content of surface acidic groups of AC. While HNO3 oxidation displayed the opposite behavior. Furthermore, the dispersion of ruthenium and the activity of catalysts were highly dependent on the content of surface acidic groups, and the SC methanol modified sample exhibited the highest activity for hydrogenation of glucose.

ReaxFF Study of the Oxidation of Softwood Lignin in View of Carbon Fiber Production

DOE PAGES

Beste, Ariana

2014-10-06

We investigate the oxidative, thermal conversion of softwood lignin by performing molecular dynamics simulations based on a reactive force field (ReaxFF). The lignin samples are constructed from coniferyl alcohol units, which are connected through linkages that are randomly selected from a natural distribution of linkages in softwood. The goal of this work is to simulate the oxidative stabilization step during carbon fiber production from lignin precursor. We find that at simulation conditions where stabilization reactions occur, the lignin fragments have already undergone extensive degradation. The 5-5 linkage shows the highest reactivity towards cyclization and dehydrogenation.

Electronic structure evolution in doping of fullerene (C{sub 60}) by ultra-thin layer molybdenum trioxide

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

Wang, Chenggong; Wang, Congcong; Kauppi, John

2015-08-28

Ultra-thin layer molybdenum oxide doping of fullerene has been investigated using ultraviolet photoemission spectroscopy (UPS) and X-ray photoemission spectroscopy (XPS). The highest occupied molecular orbital (HOMO) can be observed directly with UPS. It is observed that the Fermi level position in fullerene is modified by ultra-thin-layer molybdenum oxide doping, and the HOMO onset is shifted to less than 1.3 eV below the Fermi level. The XPS results indicate that charge transfer was observed from the C{sub 60} to MoO{sub x} and Mo{sup 6+} oxides is the basis as hole dopants.

Advanced TEM characterization of oxide nanoparticles in ODS Fe–12Cr–5Al alloys

DOE PAGES

Unocic, Kinga A; Hoelzer, David T; Pint, Bruce A

2016-01-01

For oxide nanoparticles present in three oxide-dispersion-strengthened (ODS) Fe–12Cr–5Al alloys containing additions of (1) Y 2O 3 (125Y), (2) Y 2O 3 + ZrO 2 (125YZ), and (3) Y 2O 3 + HfO 2 (125YH), were investigated using transmission and scanning transmission electron microscopy. Furthermore, in all three alloys nano-sized (<3.5 nm) oxide particles distributed uniformly throughout the microstructure were characterized using advanced electron microscopy techniques. In the 125Y alloy, mainly Al 2O 3 and yttrium–aluminum garnet (YAG) phases (Y 3Al 5O 12) were present, while in the 125YZ alloy, additional Zr(C,N) precipitates were identified. The 125YH alloy had themore » most complex precipitation sequence whereby in addition to the YAG and Al 2O 3 phases, Hf(C,N), Y 2Hf 2O 7, and HfO 2 precipitates were also found. The presence of HfO 2 was mainly due to the incomplete incorporation of HfO 2 powder during mechanical alloying of the 125YH alloy. The alloy having the highest total number density of the oxides, the smallest grain size, and the highest Vickers hardness was the 125YZ alloy indicating, that Y 2O 3 + ZrO 2 additions had the strongest effect on grain size and tensile properties. Finally, high-temperature mechanical testing will be addressed in the near future, while irradiation studies are underway to investigate the irradiation resistance of these new ODS FeCrAl alloys.« less

[Nitrous oxide emission, nitrification, denitrification and nitrogen mineralization during rice growing season in 2 soils from Uruguay].

PubMed

Illarze, Gabriela; Del Pino, Amabelia; Riccetto, Sara; Irisarri, Pilar

Microbial processes such as mineralization, nitrification and denitrification regulate nitrogen dynamics in the soil. The last two processes may produce nitrous oxide (N 2 O). In this work N 2 O fluxes were quantified at four moments of the rice cycle, sowing, tillering, panicle initiation and maturity, in two sites that differed mainly in their soil organic matter (OM) content, Salto (higher OM) and Treinta y Tres. Potential net N mineralization, ammonium oxidation and denitrification as well as the most probable numbers (MPN) of ammonia oxidizers and denitrifiers were determined. Potential N mineralization did not vary with the soil type and increased at rice maturity. Neither ammonia oxidation potential nor MPN were different among the soils. However, the soil with higher OM exhibited higher activity and MPN of denitrifiers, irrespective of the rice stage. In turn, at the latest phases of the crop, the MPN of denitrifiers increased coinciding with the highest mineralization potential and mineral N content of the soil. Significant differences in N 2 O flux were observed in Salto, where the highest emissions were detected at rice maturity, after the soil was drained (44.2 vs 20.8g N-N 2 O/ha d in Treinta y Tres). This work shows the importance of considering the soil type and end-of-season drainage of the rice field to elaborate GHGs (greenhouse gases) inventories. Copyright © 2017 Asociación Argentina de Microbiología. Publicado por Elsevier España, S.L.U. All rights reserved.

45 CFR 270.8 - How will we allocate the bonus award funds?

Code of Federal Regulations, 2011 CFR

2011-10-01

... absolute measure; (2) Award $6 million to the three States with the highest scores on the Medicaid/SCHIP absolute measure; (3) Award $14 million to the seven States with the highest scores on the Food Stamp...

Oxidation State of Nakhlites as inferred from Fe-Ti oxide Equilibria and Augite/Melt Europium Partitioning

NASA Technical Reports Server (NTRS)

Makishima, J.; McKay, G.; Le, L.; Miyamoto, M.; Mikouchi, T.

2007-01-01

Recent studies have shown that Martian magmas had wide range of oxygen fugacities (fO2) and that this variation is correlated with the variation of La/Yb ratio and isotopic characteristics of the Martian basalts, shergottite meteorites. The origin of this correlation must have important information about mantle sources and Martian evolution. In order to understand this correlation, it is necessary to know accurate value of oxidation state of other Martian meteorite groups. Nakhlites, cumulate clinopyroxenites, are another major group of Martian meteorites and have distinctly different trace element and isotopic characteristics from shergottites. Thus, estimates of oxidation state of nakhlites will give us important insight into the mantle source in general. Several workers have estimated oxidation state of nakhlites by using Fe-Ti oxide equilibrium. However, Fe-Ti oxides may not record the oxidation state of the parent melt of the nakhlite because it is a late-stage mineral. Furthermore, there is no comprehensive study which analyzed all nakhlite samples at the same time. Therefore, in this study (1) we reduced the uncertainty of the estimate using the same electron microprobe and the same standards under the same condition for Fe-Ti oxide in 6 nakhlites and (2) we also performed crystallization experiments to measure partition coefficients of Eu into pyroxene in the nakhlite system in order to estimate fO2 when the pyroxene core formed (i.e. Eu oxybarometer [e.g. 2,6]).

Effect of surface state on the oxidation behavior of welded 308L in simulated nominal primary water of PWR

NASA Astrophysics Data System (ADS)

Ming, Hongliang; Zhang, Zhiming; Wang, Jiazhen; Zhu, Ruolin; Ding, Jie; Wang, Jianqiu; Han, En-Hou; Ke, Wei

2015-05-01

The oxidation behavior of 308L weld metal (WM) with different surface state in the simulated nominal primary water of pressurized water reactor (PWR) was studied by scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) analyzer and X-ray photoelectron spectroscopy (XPS). After 480 h immersion, a duplex oxide film composed of a Fe-rich outer layer (Fe3O4, Fe2O3 and a small amount of NiFe2O4, Ni(OH)2, Cr(OH)3 and (Ni, Fe)Cr2O4) and a Cr-rich inner layer (FeCr2O4 and NiCr2O4) can be formed on the 308L WM samples with different surface state. The surface state has no influence on the phase composition of the oxide films but obviously affects the thickness of the oxide films and the morphology of the oxides (number & size). With increasing the density of dislocations and subgrain boundaries in the cold-worked superficial layer, the thickness of the oxide film, the number and size of the oxides decrease.

Active sulfur cycling by diverse mesophilic and thermophilic microorganisms in terrestrial mud volcanoes of Azerbaijan.

PubMed

Green-Saxena, A; Feyzullayev, A; Hubert, C R J; Kallmeyer, J; Krueger, M; Sauer, P; Schulz, H-M; Orphan, V J

2012-12-01

Terrestrial mud volcanoes (TMVs) represent geochemically diverse habitats with varying sulfur sources and yet sulfur cycling in these environments remains largely unexplored. Here we characterized the sulfur-metabolizing microorganisms and activity in four TMVs in Azerbaijan. A combination of geochemical analyses, biological rate measurements and molecular diversity surveys (targeting metabolic genes aprA and dsrA and SSU ribosomal RNA) supported the presence of active sulfur-oxidizing and sulfate-reducing guilds in all four TMVs across a range of physiochemical conditions, with diversity of these guilds being unique to each TMV. The TMVs varied in potential sulfate reduction rates (SRR) by up to four orders of magnitude with highest SRR observed in sediments where in situ sulfate concentrations were highest. Maximum temperatures at which SRR were measured was 60°C in two TMVs. Corresponding with these trends in SRR, members of the potentially thermophilic, spore-forming, Desulfotomaculum were detected in these TMVs by targeted 16S rRNA analysis. Additional sulfate-reducing bacterial lineages included members of the Desulfobacteraceae and Desulfobulbaceae detected by aprA and dsrA analyses and likely contributing to the mesophilic SRR measured. Phylotypes affiliated with sulfide-oxidizing Gamma- and Betaproteobacteria were abundant in aprA libraries from low sulfate TMVs, while the highest sulfate TMV harboured 16S rRNA phylotypes associated with sulfur-oxidizing Epsilonproteobacteria. Altogether, the biogeochemical and microbiological data indicate these unique terrestrial habitats support diverse active sulfur-cycling microorganisms reflecting the in situ geochemical environment. © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.

Proximate composition, phenolic content and in vitro antioxidant activity of aqueous extracts of the seaweeds Ascophyllum nodosum, Bifurcaria bifurcata and Fucus vesiculosus. Effect of addition of the extracts on the oxidative stability of canola oil under accelerated storage conditions.

PubMed

Agregán, Rubén; Munekata, Paulo E; Domínguez, Ruben; Carballo, Javier; Franco, Daniel; Lorenzo, José M

2017-09-01

Extracts from three macroalgae species (Ascophyllum nodosum (ANE), Bifurcaria bifurcata (BBE) and Fucus vesiculosus (FVE)) were tested for proximate composition (total solid, protein and total carbohydrate contents), total phenols content (TPC), and for their antioxidant activities in vitro in comparison to that of BHT compound by using four different assays (ABTS radical cation decolouration, DPPH free radical scavenging activity, ferric reducing antioxidant power (FRAP) and oxygen radical absorbance capacity (ORAC)). The inclusion of the extracts as oil stabilizers in canola oil in substitution of the synthetic antioxidant (BHT) was also evaluated by assessing lipid oxidation parameters (peroxide value (PV), p-anisidine value (AV), TBARS value, conjugated dienes (CD) and TOTOX index) under accelerated storage conditions (16days, 60°C). There was an inverse relationship between total solid content and total polyphenols content in the seaweed extracts. FVE showed an intermediate TPC (1.15g PGE/100g extract), but it presented the highest in vitro antioxidant activity when measured using the ABTS, DPPH and FRAP tests. BBE, that displayed the highest TPC (1.99g PGE/100g extract), only showed the highest in vitro antioxidant activity when measured using the ORAC test. ANE showed the lowest TPC and the lowest antioxidant activity in all the tests performed. The seaweed extracts added in a 500ppm concentration significantly reduced the oxidation during canola oil storage at 60°C, being this antioxidant effect significantly higher than that of BHT added at 50ppm. Results indicate that seaweed extracts can effectively inhibit the oxidation of canola oil and they can be a healthier alternative to the synthetic antioxidants in the oil industry. Copyright © 2016 Elsevier Ltd. All rights reserved.

The roles of phosphate and tungstate species in surface acidities of TiO2-ZrO2 binary oxides - A comparison study

NASA Astrophysics Data System (ADS)

Chaudhary, Manchal; Shen, Po-fan; Chang, Sue-min

2018-05-01

Porous tungstated and phosphated TiO2-ZrO2 (TZ) binary oxides with high and strong acidity were successfully prepared by means of sol-gel or impregnation approaches. In addition, the influences of the two types of modifiers on the microstructures and acidity were systematically examined, compared, and clarified. The TZ oxide derived from a surfactant-templating method exhibited a high surface area of 195 m2/g with a pore size of 6.3 nm. Moreover, it had a high acidity of 859 μmol/g with a density of 4.4 μmol/nm2 because of defective surface. Phosphation significantly increased the acidity to 1547 μmol/g and showed the highest acid density of 6.7 μmol/nm2 at a surface P density of 22.7P/nm2. On the other hand, tungstated compounds just showed the highest acidity of 972 μmol/g and the highest acid density of 4.8 μmol/nm2 at 4.7 W/nm2. Compared to tungstate species, phosphate anions are more capable of promoting the acidity because they are able to distort the host network and inhibit elemental rearrangement. While Lewis acidity prevailed in the tungstated compounds, Brønsted acidity was dominant in the phosphated oxides. The Wdbnd O and Psbnd OH groups were responsible for strong acidity in the modified compounds. Phosphated compounds formed strong Brønsted acid sites on the Psbnd OH groups with a particular strength, and tungstation produced Lewis acid sites with a continuous strength on the metal ions adjacent to the tungstate moieties. Cyclic NH3 adsorption-desorption processes revealed that the active sites for NH3 adsorption were stable in both the tungstate and phosphate modified compounds, revealing that these solid acids are promising as the adsorbents for removal of base gases.

Frugivory is associated with low measures of plasma oxidative stress and high antioxidant concentration in free-ranging bats

NASA Astrophysics Data System (ADS)

Schneeberger, Karin; Czirják, Gábor Á.; Voigt, Christian C.

2014-04-01

Oxidative stress—an imbalance between reactive pro- and neutralising antioxidants—damages cell structures and impairs fitness-relevant traits such as longevity and reproduction. Theory predicts that feeding on diets with high antioxidant content such as fruits should reduce oxidative stress; however, there is no support of this idea in free-ranging mammals. Bats cover a large variety of ecological niches, and therefore, we asked if measures of oxidative stress are lower in species with fruit diets. We measured reactive oxygen metabolites (ROM) representing total pro-oxidants produced and antioxidants in the plasma of 33 Neotropical bat species. Species with a fruit diet showed the lowest level of ROM and the highest concentration of antioxidants, followed by omnivorous and animalivorous species. Potentially, frugivorous species ingest more antioxidants with food and thus are able to neutralise more pro-oxidants than species not feeding on fruits, resulting in an overall lower level of oxidative stress. We therefore showed for the first time that measures of oxidative stress vary according to diets in free-ranging mammals.

Systems and methods for preparation and separation of products

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

Gilliam, Ryan J.; Boggs, Bryan; Self, Kyle

There are provided methods and systems for an electrochemical cell including an anode and a cathode where the anode is contacted with a metal ion that converts the metal ion from a lower oxidation state to a higher oxidation state. The metal ion in the higher oxidation state is reacted with hydrogen gas, an unsaturated hydrocarbon, and/or a saturated hydrocarbon to form products.

Assigning Oxidation States to Organic Compounds via Predictions from X-Ray Photoelectron Spectroscopy: A Discussion of Approaches and Recommended Improvements

ERIC Educational Resources Information Center

Gupta, Vipul; Ganegoda, Hasitha; Engelhard, Mark H.; Terry, Jeff; Linford, Matthew R.

2014-01-01

The traditional assignment of oxidation states to organic molecules is problematic. Accordingly, in 1999, Calzaferri proposed a simple and elegant solution that is based on the similar electronegativities of carbon and hydrogen: hydrogen would be assigned an oxidation state of zero when bonded to carbon. Here, we show that X-ray photoelectron…

Systems and methods for preparation and separation of products

DOEpatents

Gilliam, Ryan J.; Boggs, Bryan; Self, Kyle; Leclerc, Margarete K.; Gorer, Alexander; Weiss, Michael J.; Miller, John H.; Mohanta, Samaresh

2015-12-01

There are provided methods and systems for an electrochemical cell including an anode and a cathode where the anode is contacted with a metal ion that converts the metal ion from a lower oxidation state to a higher oxidation state. The metal ion in the higher oxidation state is reacted with hydrogen gas, an unsaturated hydrocarbon, and/or a saturated hydrocarbon to form products.

Partitioning Nitrification Between Specific Archaeal and Bacterial Clades in a Large, Nitrogen-Rich Estuary (San Francisco Bay, CA)

NASA Astrophysics Data System (ADS)

Damashek, J.; Casciotti, K. L.; Francis, C. A.

2014-12-01

Nitrification is the sole link between nitrogen inputs and losses in marine ecosystems, and understanding the microbial ecology and biogeochemistry of nitrification is therefore crucial for understanding how aquatic ecosystems process nitrogen. Recently-discovered ammonia-oxidizing archaea (AOA), rather than ammonia-oxidizing bacteria (AOB), appear to drive ammonia oxidation in many ecosystems, including much of the ocean. However, few studies have investigated these microbes in estuary waters, despite the fact nitrogen concentrations in estuaries are often far higher than the ocean, and can cause drastic ecological harm. We sought to determine the roles of AOA and AOB in driving pelagic nitrification throughout San Francisco Bay, by combining biogeochemical rate measurements with a suite of measurements of the abundance and diversity of AOA and AOB. It addition to traditional functional gene analyses and high-throughput 16S amplicon sequencing, we developed novel qPCR assays to selectively target the ammonia-oxidizing clades found in this estuary, which gave insights into clade-specific distributional patterns. Our biogeochemical data suggest a sizable fraction of ammonium in the bay is oxidized in the water column, likely by AOA, with nitrification in bottom waters also oxidizing a substantial portion of the ammonium exuded by sediments. Generally, Sacramento River waters and Suisun Bay bottom waters had the highest nitrification rates. AOA outnumbered AOB at most stations, and were present in high abundance at both the marine and freshwater ends of the estuary, while AOB abundance was highest in the low-salinity, brackish regions. Different archaeal clades were found at either end of the estuary, suggesting strong niche partitioning along the salinity gradient, with a third clade present largely in brackish waters. This work helps to assess the ability of ammonia-oxidizing microbes in estuaries to transform nitrogen prior to water discharge into the sea, and furthers our understanding of the roles of specific clades of these microbes in complex estuarine ecosystems.

HONO (nitrous acid) emissions from acidic northern soils

NASA Astrophysics Data System (ADS)

Maljanen, Marja; Yli-Pirilä, Pasi; Joutsensaari, Jorma; Sulassaari, Sirkka; Martikainen, Pertti J.

2014-05-01

The photolysis of HONO (nitrous acid) is an important source of OH radical, the key oxidizing agent in the atmosphere, contributing also to removal of atmospheric methane (CH4), the second most important greenhouse gas after carbon dioxide (CO2). There are missing sources of HONO when considering the chemical reactions in the atmosphere. Soil could be such a missing source. Emissions of HONO from soils studied in laboratory incubations have been recently reported. The soil-derived HONO has been connected to soil nitrite (NO2-) and a study with an ammonium oxidizing bacterium has shown that HONO could be produced in ammonium oxidation. Our hypothesis was that boreal acidic soils with high nitrification activity could be important sources of HONO. We selected a range of dominant northern acidic soils and showed in microcosm experiments that soils which have the highest nitrous oxide (N2O) and nitric oxide (NO) emissions (drained peatlands) also have the highest HONO production rates. The emissions of HONO are thus linked to nitrogen cycle processes. In contrast to drained peatlands, natural peatlands with high water table and boreal coniferous forests on mineral soils with low nitrification capacity had low HONO emissions. It is known that in natural peatlands with high water table and in boreal coniferous forest soils, low nitrification activity (microbial production of nitrite and nitrate) limits their N2O production. Low nitrification rate and low availability of nitrite in these soils are the likely reasons for their low HONO production rates. We studied the origin of HONO in one drained peat soil by inhibiting nitrification with acetylene. Acetylene blocked NO emissions but did not affect HONO or N2O emissions, thus ammonium oxidation is not the direct mechanism for the HONO emission in this soil. It is still an open question if HONO originates directly from some microbial process like ammonium oxidation or chemically from nitrite produced in microbial processes.

White light emission of dysprosium doped lanthanum calcium phosphate oxide and oxyfluoride glasses

NASA Astrophysics Data System (ADS)

Luewarasirikul, N.; Kim, H. J.; Meejitpaisan, P.; Kaewkhao, J.

2017-04-01

Lanthanum calcium phosphate oxide and oxyfluoride glasses doped with dysprosium oxide were prepared by melt-quenching technique with chemical composition 20La2O3:10CaO:69P2O5:1Dy2O3 and 20La2O3:10CaF2:69P2O5:1Dy2O3. The physical, optical and luminescence properties of the glass samples were studied to evaluate their potential to using as luminescence materials for solid-state lighting applications. The density, molar volume and refractive index of the glass samples were carried out. The optical and luminescence properties were studied by investigating absorption, excitation, and emission spectra of the glass samples. The absorption spectra were investigated in the UV-Vis-NIR region from 300 to 2000 nm. The excitation spectra observed under 574 nm emission wavelength showed the highest peak centered at 349 nm (6H15/2 → 6P7/2). The emission spectra, excited with 349 nm excitation wavelength showed two major peaks corresponding to 482 nm blue emission (4F9/2 → 6H15/2) and 574 nm yellow emission (4F9/2 → 6H13/2). The experimental lifetime were found to be 0.539 and 0.540 for oxide and oxyfluoride glass sample, respectively. The x,y color coordinates under 349 nm excitation wavelength were (0.38, 0.43) for both glass samples, that be plotted in white region of CIE 1931 chromaticity diagram. The CCT values obtained from the glass samples are 4204 K for oxide glass and 4228 K for oxyfluoride glass corresponding to the commercial cool white light (3100-4500 K). Judd-Ofelt theory had also been employed to obtain the J-O parameters (Ω2, Ω4 and Ω6), oscillator strength, radiative transition possibility, stimulated emission cross section and branching ratio. The Ω2 > Ω4 > Ω6 trend of J-O parameters of both glass samples may indicate the good quality of a glass host for using as optical device application. Temperature dependence of emission spectra was studied from 300 K to 10 K and found that the intensity of the emission peak was found to be increased with decreasing of the temperature. The results of the investigations in this work confirmed that the present Dy-doped lanthanum calcium phosphate oxide and oxyfluoride glasses perform high potential for using as efficient luminescence materials for solid-state lighting applications, especially for white LEDs. Furthermore, the oxyfluoride glass sample provides more luminescence potential than the oxide glass sample.

The influence of iridium chemical oxidation state on the performance and durability of oxygen evolution catalysts in PEM electrolysis

NASA Astrophysics Data System (ADS)

Siracusano, S.; Baglio, V.; Grigoriev, S. A.; Merlo, L.; Fateev, V. N.; Aricò, A. S.

2017-10-01

Nanosized Ir-black (3 nm) and Ir-oxide (5 nm) oxygen evolution electrocatalysts showing high performance in polymer electrolyte membrane (PEM) water electrolysis based on Aquivion® short-side chain ionomer membrane are investigated to understand the role of the Ir oxidation state on the electrocatalytic activity and stability. Despite the smaller mean crystallite size, the Ir-black electrocatalyst shows significantly lower initial performance than the Ir-oxide. During operation at high current density, the Ir-black shows a decrease of cell potential with time whereas the Ir-oxide catalyst shows increasing cell potential resulting in a degradation rate of about 10 μV/h, approaching 1000 h. The unusual behaviour of the Ir-black results from the oxidation of metallic Ir to IrOx. The Ir-oxide catalyst shows instead a hydrated structure on the surface and a negative shift of about 0.5 eV for the Ir 4f binding energy after 1000 h electrolysis operation. This corresponds to the formation of a sub-stoichiometric Ir-oxide on the surface. These results indicate that a hydrated IrO2 with high oxidation state on the surface is favourable in decreasing the oxygen evolution overpotential. Modifications of the Ir chemical oxidation state during operation can affect significantly the catalytic activity and durability of the electrolysis system.

Dechlorination of polychlorinated biphenyls by iron and its oxides.

PubMed

Sun, Yifei; Liu, Xiaoyuan; Kainuma, Masashi; Wang, Wei; Takaoka, Masaki; Takeda, Nobuo

2015-10-01

The decomposition efficiency of polychlorinated biphenyls (PCBs) was determined using elemental iron (Fe) and three iron (hydr)oxides, i.e., α-Fe2O3, Fe3O4, and α-FeOOH, as catalysts. The experiments were performed using four distinct PCB congeners (PCB-209, PCB-153, and the coplanar PCB-167 and PCB-77) at temperatures ranging from 180 °C to 380 °C and under an inert, oxidizing or reducing atmosphere composed of N2, N2+O2, or N2+H2. From these three options N2 showed to provide the best reaction atmosphere. Among the iron compounds tested, Fe3O4 showed the highest activity for decomposing PCBs. The decomposition efficiencies of PCB-209, PCB-167, PCB-153, and PCB-77 by Fe3O4 in an N2 atmosphere at 230 °C were 88.5%, 82.5%, 69.9%, and 66.4%, respectively. Other inorganic chlorine (Cl) products which were measured by the amount of inorganic Cl ions represented 82.5% and 76.1% of the reaction products, showing that ring cleavage of PCBs was the main elimination process. Moreover, the dechlorination did not require a particular hydrogen donor. We used X-ray photoelectron spectroscopy to analyze the elemental distribution at the catalyst's surface. The O/Fe ratio influenced upon the decomposition efficiency of PCBs: the lower this ratio, the higher the decomposition efficiency. X-ray absorption near edge structure spectra showed that α-Fe2O3 effectively worked as a catalyst, while Fe3O4 and α-FeOOH were consumed as reactants, as their final state is different from their initial state. Finally, a decomposition pathway was postulated in which the Cl atoms in ortho-positions were more difficult to eliminate than those in the para- or meta-positions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Benzene selectivity in competitive arene hydrogenation: effects of single-site catalyst···acidic oxide surface binding geometry.

PubMed

Gu, Weixing; Stalzer, Madelyn Marie; Nicholas, Christopher P; Bhattacharyya, Alak; Motta, Alessandro; Gallagher, James R; Zhang, Guanghui; Miller, Jeffrey T; Kobayashi, Takeshi; Pruski, Marek; Delferro, Massimiliano; Marks, Tobin J

2015-06-03

Organozirconium complexes are chemisorbed on Brønsted acidic sulfated ZrO2 (ZrS), sulfated Al2O3 (AlS), and ZrO2-WO3 (ZrW). Under mild conditions (25 °C, 1 atm H2), the supported Cp*ZrMe3, Cp*ZrBz3, and Cp*ZrPh3 catalysts are very active for benzene hydrogenation with activities declining with decreasing acidity, ZrS ≫ AlS ≈ ZrW, arguing that more Brønsted acidic oxides (those having weaker corresponding conjugate bases) yield stronger surface organometallic electrophiles and for this reason have higher benzene hydrogenation activity. Benzene selective hydrogenation, a potential approach for carcinogenic benzene removal from gasoline, is probed using benzene/toluene mixtures, and selectivities for benzene hydrogenation vary with catalyst as ZrBz3(+)/ZrS(-), 83% > Cp*ZrMe2(+)/ZrS(-), 80% > Cp*ZrBz2(+)/ZrS(-), 67% > Cp*ZrPh2(+)/ZrS(-), 57%. For Cp*ZrBz2(+)/ZrS(-), which displays the highest benzene hydrogenation activity with moderate selectivity in benzene/toluene mixtures. Other benzene/arene mixtures are examined, and benzene selectivities vary with arene as mesitylene, 99%, > ethylbenzene, 86% > toluene, 67%. Structural and computational studies by solid-state NMR spectroscopy, XAS, and periodic DFT methods applied to supported Cp*ZrMe3 and Cp*ZrBz3 indicate that larger Zr···surface distances are present in more sterically encumbered Cp*ZrBz2(+)/AlS(-) vs Cp*ZrMe2(+)/AlS(-). The combined XAS, solid state NMR, and DFT data argue that the bulky catalyst benzyl groups expand the "cationic" metal center-anionic sulfated oxide surface distances, and this separation/weakened ion-pairing enables the activation/insertion of more sterically encumbered arenes and influences hydrogenation rates and selectivity patterns.

Benzene selectivity in competitive arene hydrogenation: Effects of single-site catalyst···acidic oxide surface binding geometry

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

Gu, Weixing; Stalzer, Madelyn Marie; Nicholas, Christopher P.

Organozirconium complexes are chemisorbed on Brønsted acidic sulfated ZrO 2 (ZrS), sulfated Al 2O 3 (AlS), and ZrO 2–WO 3 (ZrW). Under mild conditions (25 °C, 1 atm H 2), the supported Cp*ZrMe 3, Cp*ZrBz 3, and Cp*ZrPh 3 catalysts are very active for benzene hydrogenation with activities declining with decreasing acidity, ZrS >> AlS ≈ ZrW, arguing that more Brønsted acidic oxides (those having weaker corresponding conjugate bases) yield stronger surface organometallic electrophiles and for this reason have higher benzene hydrogenation activity. Benzene selective hydrogenation, a potential approach for carcinogenic benzene removal from gasoline, is probed using benzene/toluene mixtures,more » and selectivities for benzene hydrogenation vary with catalyst as ZrBz 3 +/ZrS –, 83% > Cp*ZrMe 2 +/ZrS –, 80% > Cp*ZrBz 2 +/ZrS –, 67% > Cp*ZrPh 2 +/ZrS –, 57%. For Cp*ZrBz 2+/ZrS –, which displays the highest benzene hydrogenation activity with moderate selectivity in benzene/toluene mixtures. Other benzene/arene mixtures are examined, and benzene selectivities vary with arene as mesitylene, 99%, > ethylbenzene, 86% > toluene, 67%. Structural and computational studies by solid-state NMR spectroscopy, XAS, and periodic DFT methods applied to supported Cp*ZrMe 3 and Cp*ZrBz 3 indicate that larger Zr···surface distances are present in more sterically encumbered Cp*ZrBz 2 +/AlS – vs Cp*ZrMe 2 +/AlS –. Furthermore, the combined XAS, solid state NMR, and DFT data argue that the bulky catalyst benzyl groups expand the “cationic” metal center–anionic sulfated oxide surface distances, and this separation/weakened ion-pairing enables the activation/insertion of more sterically encumbered arenes and influences hydrogenation rates and selectivity patterns.« less

Benzene selectivity in competitive arene hydrogenation: Effects of single-site catalyst···acidic oxide surface binding geometry

DOE PAGES

Gu, Weixing; Stalzer, Madelyn Marie; Nicholas, Christopher P.; ...

2015-04-17

Organozirconium complexes are chemisorbed on Brønsted acidic sulfated ZrO 2 (ZrS), sulfated Al 2O 3 (AlS), and ZrO 2–WO 3 (ZrW). Under mild conditions (25 °C, 1 atm H 2), the supported Cp*ZrMe 3, Cp*ZrBz 3, and Cp*ZrPh 3 catalysts are very active for benzene hydrogenation with activities declining with decreasing acidity, ZrS >> AlS ≈ ZrW, arguing that more Brønsted acidic oxides (those having weaker corresponding conjugate bases) yield stronger surface organometallic electrophiles and for this reason have higher benzene hydrogenation activity. Benzene selective hydrogenation, a potential approach for carcinogenic benzene removal from gasoline, is probed using benzene/toluene mixtures,more » and selectivities for benzene hydrogenation vary with catalyst as ZrBz 3 +/ZrS –, 83% > Cp*ZrMe 2 +/ZrS –, 80% > Cp*ZrBz 2 +/ZrS –, 67% > Cp*ZrPh 2 +/ZrS –, 57%. For Cp*ZrBz 2+/ZrS –, which displays the highest benzene hydrogenation activity with moderate selectivity in benzene/toluene mixtures. Other benzene/arene mixtures are examined, and benzene selectivities vary with arene as mesitylene, 99%, > ethylbenzene, 86% > toluene, 67%. Structural and computational studies by solid-state NMR spectroscopy, XAS, and periodic DFT methods applied to supported Cp*ZrMe 3 and Cp*ZrBz 3 indicate that larger Zr···surface distances are present in more sterically encumbered Cp*ZrBz 2 +/AlS – vs Cp*ZrMe 2 +/AlS –. Furthermore, the combined XAS, solid state NMR, and DFT data argue that the bulky catalyst benzyl groups expand the “cationic” metal center–anionic sulfated oxide surface distances, and this separation/weakened ion-pairing enables the activation/insertion of more sterically encumbered arenes and influences hydrogenation rates and selectivity patterns.« less

Measuring the Thermodynamics of the Alloy/Scale Interface

NASA Technical Reports Server (NTRS)

Copland, Evan

2004-01-01

A method is proposed for the direct measurement of the thermodynamic properties of the alloy and oxide compound at the alloy/scale interface observed during steady-state oxidation. The thermodynamic properties of the alloy/scale interface define the driving force for solid-state transport in the alloy and oxide compound. Accurate knowledge of thermodynamic properties of the interface will advance our understanding of oxidation behavior. The method is based on the concept of local equilibrium and assumes that an alloy+scale equilibrium very closely approximates the alloy/scale interface observed during steady-state oxidation. The thermodynamics activities of this alloy+scale equilibrium are measured directly by Knudsen effusion-cell mass spectrometer (KEMS) using the vapor pressure technique. The theory and some practical considerations of this method are discussed in terms of beta-NiAl oxidation.

Cinetica de oxidacion de polimeros conductores: poli-3,4- etilendioxitiofeno

NASA Astrophysics Data System (ADS)

Caballero Romero, Maria

Films of poly-3,4-ethylenedioxythiophene (PEDOT) perchlorate used as electrodes in liquid electrolytes incorporate anions and solvent during oxidation for charge and osmotic balance: the film swells. During reduction the film shrinks, closes its structure trapping counterions getting then rising conformational packed states by expulsion of counterions and solvent. Here by potential step from the same reduced initial state to the same oxidized final state the rate coefficient, the activation energy and reaction orders related to the counterion concentration in solution and to the concentration of active centers in the polymer film, were attained following the usual methodology used for chemical and electrochemical kinetics. Now the full methodology was repeated using different reduced-shrunk or reduced-conformational compacted initial states every time. Those initial states were attained by reduction of the oxidized film at rising cathodic potentials for the same reduction time each. Rising reduced and conformational compacted states give slower subsequent oxidation rates by potential step to the same anodic potential every time. The activation energy, the reaction coefficient and reaction orders change for rising conformational compacted initial states. Decreasing rate constants and increasing activation energies are obtained for the PEDOT oxidation from increasing conformational compacted initial states. The experimental activation energy presents two linear ranges as a function of the initial reduced-compacted state. Using as initial states for the oxidation open structures attained by reduction at low cathodic potentials, activation energies attained were constant: namely the chemical activation energy. Using as initial states for the oxidation deeper reduced, closed and packed conformational structures, the activation energy includes two components: the constant chemical energy plus the conformational energy required to relax the conformational structure generating free volume which allows the entrance of the balancing counterions required for the reaction. The conformational energy increases linearly as a function of the reduction-compaction potential. The kinetic magnitudes include conformational and structural information. The Chemical Kinetics becomes Structural (or conformational) Chemical Kinetics.

The effect of processing conditions on the GaAs/plasma-grown insulator interface

NASA Technical Reports Server (NTRS)

Hshieh, F. I.; Borrego, J. M.; Ghandhi, S. K.

1986-01-01

The effect of processing conditions on the interface state density was evaluated from C-V measurements on metal-oxide-semiconductor capacitors. The optimum processing conditions for the minimum surface state density was found to be related to the postoxidation annealing temperature and time, and was independent of chemical treatments prior to oxidation. Annealing at the optimum condition (i.e., at 350 C for 1 h in either nitrogen or hydrogen gas, with or without an aluminum pattern on the oxide) reduces the fast surface state density by about one order of magnitude. By using a nitrogen/oxygen plasma, the static dielectric constant of the oxide decreased as the N/O ratio was increased, and nitrogen was incorporated into the oxide. In addition, the fast surface state density was reduced as a result of this nitridation process.

Characterization and mitigation of nitrous oxide (N2 O) emissions from partial and full-nitrification BNR processes based on post-anoxic aeration control.

PubMed

Brotto, Ariane Coelho; Li, Huosheng; Dumit, Muriel; Gabarró, Jordi; Colprim, Jesús; Murthy, Sudhir; Chandran, Kartik

2015-11-01

It has been reported that a directional change from anoxic to aerobic conditions is a common trigger for nitrous oxide (N2 O) production by ammonia oxidizing bacteria (AOB). By extension, during anoxic-aerobic cycling, post-anoxic dissolved oxygen (DO) concentrations might likely play a role in the magnitude of N2 O emissions observed. The overall goal of this study was to determine the impact of three select post-anoxic DO concentrations (0.8, 2.0, and 3.0 mg O2 /L) on N2 O emissions from partial-nitrification (PN) and full-nitrification (FN) reactors subjected to anoxic-aerobic cycling and, ultimately, to explore the development of strategies to minimize N2 O emissions from PN and FN based biological nitrogen removal (BNR) processes. Statistically similar N2 O emissions were observed during anoxia for both PN (0.62 ± 0.21% N load) and FN (0.61 ± 0.070% N load) processes. In contrast, N2 O emissions were statistically lower for PN (0.86 ± 0.25% N load) than for FN (4.6 ± 2.8% N load), during the post-anoxic aerobic phase, when compared together for all three post-anoxic DO concentrations. Further, for PN, the highest N2 O emissions were observed at the highest post-anoxic DO concentration of 3.0 mg O2 /L (1.2% N load), likely due to the highest corresponding AOB specific growth rate. In contrast, for FN, the highest N2 O emissions were at the lowest post-anoxic DO concentration of 0.8 mg O2 /L (8.5% N load). The higher emissions from FN process at low DO concentrations were associated with a lag in nitrite oxidizing bacteria activity upon recovery to aerobic conditions. This lag phase contributed to transient nitrite accumulation, and in turn correlated positively to the observed N2 O emissions. Based on our findings, a gradual ramp up in post-anoxic DO concentrations can minimize N2 O emissions during PN-based BNR, whereas a completely different strategy, entailing a rapid increase in post-anoxic DO concentrations can minimize emissions during FN-based BNR operations. © 2015 Wiley Periodicals, Inc.

Effect of meal fat quality on oxidation resistance of postprandial VLDL and LDL particles and plasma triacylglycerol level.

PubMed

Nielsen, N S; Marckmann, P; Høy, C

2000-12-01

This study was performed to examine the postprandial effects of meals containing dietary fats, with their natural fatty acid composition and tocopherol content, on the plasma triacylglycerols (TG) and tocopherols and on the resistance of VLDL and LDL to oxidation. On six separate days eighteen healthy male subjects were given low-fat meals (LF) or the LF meals enriched with sunflower oil (SO), rapeseed oil (RO), olive oil (OO), palm oil (PO), or butter (B) in a crossover design. The fat-rich meals all resulted in similar postprandial TG responses while the LF test meal did not increase plasma TG level. The postprandial plasma fatty acid profile changed to resemble the fatty acid composition of the ingested test fat. The alpha-tocopherol:gamma-tocopherol ratios in postprandial plasma and VLDL samples were greater than in the test fats. We found that the resistance of VLDL particles to oxidation in the postprandial state as assessed from lag time was increased after the PO-rich meal as compared with the SO-rich meal (p = 0.018), and the propagation rate was greater after the SO- and RO-rich meals compared with the others (p < 0.001). The resistance of LDL particles to oxidation was unaffected by the meals. In postprandial VLDL samples, the content of alpha-tocopherol was greater after the OO- and SO-rich meals compared with the meal rich in PO (P = 0.034 and 0.042 respectively). The gamma-tocopherol content of VLDL was highest after RO-meal as compared with all other test meals (P = 0.0019), and higher after SO as compared with B (P = 0.0148). Large individual differences were noted. In conclusion, meals enriched with different fats lead to the formation of VLDL particles with varying resistance to oxidation.

Study of the nitric oxide system in the rat cerebellum during aging.

PubMed

Blanco, Santos; Molina, Francisco J; Castro, Lourdes; Del Moral, Maria L; Hernandez, Raquel; Jimenez, Ana; Rus, Alma; Martinez-Lara, Esther; Siles, Eva; Peinado, Maria A

2010-06-24

The cerebellum is the neural structure with the highest levels of nitric oxide, a neurotransmitter that has been proposed to play a key role in the brain aging, although knowledge concerning its contribution to cerebellar senescence is still unclear, due mainly to absence of integrative studies that jointly evaluate the main factors involved in its cell production and function. Consequently, in the present study, we investigate the expression, location, and activity of nitric oxide synthase isoenzymes; the protein nitration; and the production of nitric oxide in the cerebellum of adult and old rats. Our results show no variation in the expression of nitric oxide synthase isoforms with aging, although, we have detected some changes in the cellular distribution pattern of the inducible isoform particularly in the cerebellar nuclei. There is also an increase in nitric oxide synthase activity, as well as greater protein-nitration levels, and maintenance of nitrogen oxides (NOx) levels in the senescent cerebellum. The nitric oxide/nitric oxide synthases system suffers from a number of changes, mainly in the inducible nitric oxide synthase distribution and in overall nitric oxide synthases activity in the senescent cerebellum, which result in an increase of the protein nitration. These changes might be related to the oxidative damage detected with aging in the cerebellum.

Direct Determination of the Intracellular Oxidation State of Plutonium

PubMed Central

Gorman-Lewis, Drew; Aryal, Baikuntha P.; Paunesku, Tatjana; Vogt, Stefan; Lai, Barry; Woloschak, Gayle E.; Jensen, Mark P.

2013-01-01

Microprobe X-ray absorption near edge structure (μ-XANES) measurements were used to determine directly, for the first time, the oxidation state of intracellular plutonium in individual 0.1 μm2 areas within single rat pheochromocytoma cells (PC12). The living cells were incubated in vitro for 3 hours in the presence of Pu added to the media in different oxidation states (Pu(III), Pu(IV), and Pu(VI)) and in different chemical forms. Regardless of the initial oxidation state or chemical form of Pu presented to the cells, the XANES spectra of the intracellular Pu deposits was always consistent with tetravalent Pu even though the intracellular milieu is generally reducing. PMID:21755934

45 CFR 270.8 - How will we allocate the bonus award funds?

Code of Federal Regulations, 2010 CFR

2010-10-01

... will allocate and award $140 million to the ten States with the highest scores for each work measure as... Work Force—$21 million; (b) In FY 2002 and beyond, we will allocate and award $20 million to the ten States with the highest scores on the Food Stamp measures and $20 million to the ten States with the...

Nitrous oxide emission by aquatic macrofauna

PubMed Central

Stief, Peter; Poulsen, Morten; Nielsen, Lars Peter; Brix, Hans; Schramm, Andreas

2009-01-01

A large variety of aquatic animals was found to emit the potent greenhouse gas nitrous oxide when nitrate was present in the environment. The emission was ascribed to denitrification by ingested bacteria in the anoxic animal gut, and the exceptionally high N2O-to-N2 production ratio suggested delayed induction of the last step of denitrification. Filter- and deposit-feeding animal species showed the highest rates of nitrous oxide emission and predators the lowest, probably reflecting the different amounts of denitrifying bacteria in the diet. We estimate that nitrous oxide emission by aquatic animals is quantitatively important in nitrate-rich aquatic environments like freshwater, coastal marine, and deep-sea ecosystems. The contribution of this source to overall nitrous oxide emission from aquatic environments might further increase because of the projected increase of nitrate availability in tropical regions and the numeric dominance of filter- and deposit-feeders in eutrophic ecosystems. PMID:19255427

Desulfurization of oxidized diesel using ionic liquids

NASA Astrophysics Data System (ADS)

Wilfred, Cecilia D.; Salleh, M. Zulhaziman M.; Mutalib, M. I. Abdul

2014-10-01

The extraction of oxidized sulfur compounds from diesel were carried out using ten types of ionic liquids consisting of different cation and anion i.e. 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazoium thiocyanate, 1-butyl-3-methylimidazoium dicyanamide, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazoliumhexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, trioctylmethylammonium chloride, 1-propionitrile-3-butylimidazolium thiocyanate, 1-propionitrile-3-butylimidazolium dicyanamide and 1-butyl-6-methylquinolinium dicyanamide. The oxidation of diesel was successfully done using phosphotungstic acid as the catalyst, hydrogen peroxide (H2O2) as the oxidant and trioctylmethylammonium chloride as the phase transfer agent. The oxidation of diesel changes the sulfur compounds into sulfone which increases its polarity and enhances the ionic liquid's extraction performance. Result showed that ionic liquid [C4mquin][N(CN)2] performed the highest sulfur removal (91% at 1:5 diesel:IL ratio) compared to the others.

Evaluation of the anti-oxidative effect (in vitro) of tea polyphenols.

PubMed

Hashimoto, Fumio; Ono, Masateru; Masuoka, Chikako; Ito, Yasuyuki; Sakata, Yusuke; Shimizu, Keiichi; Nonaka, Gen-ichiro; Nishioka, Itsuo; Nohara, Toshihiro

2003-02-01

Forty-three polyphenols from tea leaves were evaluated for their anti-oxidative effect against lipid peroxidation by the ferric thiocyanate method in vitro. Among these, 1,4,6-tri-O-galloyl-beta-D-glucose (hydrolyzable tannin) showed the highest anti-oxidative activity against lipid peroxidation, even stronger than that of 3-tert.-butyl-4-hydroxyanisole (BHA). The assay demonstrates that tea polyphenols, except for desgalloylated dimeric proanthocyanidins that possess a catechin structure in the upper unit and desgalloylated flavan-3-ols, and excepting theaflavin 3,3'-di-O-gallate, had more anti-oxidative activity than that of alpha-tocopherol. The chemical structure-activity relationship shows that the anti-oxidative action advanced with the condensation of two molecules of flavan-3-ols as well as with 3-O-acylation in the flavan skeleton such as that by galloyl, (3'-O-methyl)-galloyl, and p-coumaroyl groups.

Effects of dissolved oxygen and pH on nitrous oxide production rates in autotrophic partial nitrification granules.

PubMed

Rathnayake, Rathnayake M L D; Oshiki, Mamoru; Ishii, Satoshi; Segawa, Takahiro; Satoh, Hisashi; Okabe, Satoshi

2015-12-01

The effects of dissolved oxygen (DO) and pH on nitrous oxide (N2O) production rates and pathways in autotrophic partial nitrification (PN) granules were investigated at the granular level. N2O was primarily produced by betaproteobacterial ammonia-oxidizing bacteria, mainly Nitrosomonas europaea, in the oxic surface layer (<200μm) of the autotrophic PN granules. N2O production increased with increasing bulk DO concentration owing to activation of the ammonia (i.e., hydroxylamine) oxidation in this layer. The highest N2O emissions were observed at pH 7.5, although the ammonia oxidation rate was unchanged between pH 6.5 and 8.5. Overall, the results of this study suggest that in situ analyses of PN granules are essential to gaining insight into N2O emission mechanisms in a granule. Copyright © 2015 Elsevier Ltd. All rights reserved.

Investigation of the Genotoxicity of Aluminum Oxide, β-Tricalcium Phosphate, and Zinc Oxide Nanoparticles In Vitro.

PubMed

Akbaba, Giray Buğra; Türkez, Hasan

The aim of this study was to investigate the genotoxicity of aluminum oxide (Al 2 O 3 ), β-tricalcium phosphate (β-TCP) (Ca 3 (PO 4 ) 2 ), and zinc oxide (ZnO) nanoparticles (NPs) that were 4.175, 9.058, and 19.8 nm sized, respectively, on human peripheral blood lymphocytes using micronucleus (MN) and chromosome aberration (CA) techniques. Aluminum oxide and β-TCP NPs did not show genotoxic effects on human peripheral blood cultures in vitro, even at the highest concentrations; therefore, these materials may be suitable for use as biocompatible materials. It was observed that, even at a very low dose (≥12.5 ppm), ZnO NPs had led to genotoxicity. In addition, at high concentrations (500 ppm and above), ZnO NPs caused mortality of lymphocytes. For these reasons, it was concluded that ZnO NPs are not appropriate for using as a biocompatible biomaterial.

Oxidative damage increases with reproductive energy expenditure and is reduced by food-supplementation

PubMed Central

Fletcher, Quinn E.; Selman, Colin; Boutin, Stan; McAdam, Andrew G.; Woods, Sarah B.; Seo, Arnold Y.; Leeuwenburgh, Christiaan; Speakman, John R.; Humphries, Murray M.

2013-01-01

A central principle in life-history theory is that reproductive effort negatively affects survival. Costs of reproduction are thought to be physiologically-based, but the underlying mechanisms remain poorly understood. Using female North American red squirrels (Tamiasciurus hudsonicus), we test the hypothesis that energetic investment in reproduction overwhelms investment in antioxidant protection, leading to oxidative damage. In support of this hypothesis we found that the highest levels of plasma protein oxidative damage in squirrels occurred during the energetically-demanding period of lactation. Moreover, plasma protein oxidative damage was also elevated in squirrels that expended the most energy and had the lowest antioxidant protection. Finally, we found that squirrels that were food-supplemented during lactation and winter had increased antioxidant protection and reduced plasma protein oxidative damage providing the first experimental evidence in the wild that access to abundant resources can reduce this physiological cost. PMID:23617928

Fuzzy logic modeling of bioaccumulation pattern of metals in coastal biota of Ondo State, Nigeria.

PubMed

Agunbiade, Foluso O; Olu-Owolabi, Bamidele I; Adebowale, Kayode O

2012-01-01

The accumulation patterns of ten metals in tissues of plant, Eichornia crassipes, and fishes, Hydrocynus forskahlii and Oreochromis mossambicus, were modeled with simple fuzzy classification (SFC) to assess toxic effects of anthropogenic activities on the coastal biota. The plant sample was separated into root, stem, and leaves and the fishes into bones, internal tissues, and muscles. They were analyzed for As, Cd, Cr, Cu, Ni, Pb, V, Fe, Mn, and Zn after wet oxidation of their dried samples. The results were converted into membership functions of five accumulation classes and aggregated with SFC. The classification results showed that there was no metal accumulation in the plant parts while the fishes were classified into low accumulation category. The internal tissues of the fishes had higher metal accumulation than the other parts. Generally, Fe and Mn had highest concentrations in the biota but are natural to the area and may not constitute significant risk. Cr had the highest transfer and accumulation from the coastal water into the aquatic lives and may be indicative of risk prone system being a toxic metal. Metal contaminations in the zone had not significantly accumulated in the biota making them less prone to risk associated with metal accumulation.

Polaronic behavior in a weak-coupling superconductor.

PubMed

Swartz, Adrian G; Inoue, Hisashi; Merz, Tyler A; Hikita, Yasuyuki; Raghu, Srinivas; Devereaux, Thomas P; Johnston, Steven; Hwang, Harold Y

2018-02-13

The nature of superconductivity in the dilute semiconductor SrTiO 3 has remained an open question for more than 50 y. The extremely low carrier densities ([Formula: see text]-[Formula: see text] cm -3 ) at which superconductivity occurs suggest an unconventional origin of superconductivity outside of the adiabatic limit on which the Bardeen-Cooper-Schrieffer (BCS) and Migdal-Eliashberg (ME) theories are based. We take advantage of a newly developed method for engineering band alignments at oxide interfaces and access the electronic structure of Nb-doped SrTiO 3 , using high-resolution tunneling spectroscopy. We observe strong coupling to the highest-energy longitudinal optic (LO) phonon branch and estimate the doping evolution of the dimensionless electron-phonon interaction strength ([Formula: see text]). Upon cooling below the superconducting transition temperature ([Formula: see text]), we observe a single superconducting gap corresponding to the weak-coupling limit of BCS theory, indicating an order of magnitude smaller coupling ([Formula: see text]). These results suggest that despite the strong normal state interaction with electrons, the highest LO phonon does not provide a dominant contribution to pairing. They further demonstrate that SrTiO 3 is an ideal system to probe superconductivity over a wide range of carrier density, adiabatic parameter, and electron-phonon coupling strength.

Evaluation of Anticancer and Antioxidant Activity of a Commercially Available CO2 Supercritical Extract of Old Man's Beard (Usnea barbata).

PubMed

Zugic, Ana; Jeremic, Ivica; Isakovic, Aleksandra; Arsic, Ivana; Savic, Snezana; Tadic, Vanja

2016-01-01

There is a worldwide ongoing investigation for novel natural constituents with cytotoxic and antioxidant properties. The aim of this study was to investigate chemical profile and stated biological activities of the supercritical CO2 extract (SCE) of old man's beard compared to the extracts obtained using the conventional techniques (Soxhlet extracts and macerate). The most abundant compound identified was usnic acid, which content was inversely proportional to the polarity of the solvent used and was the highest in the SCE, which was the sample revealing the highest cytotoxic activity in tested tumor cell lines (B16 mouse melanoma and C6 rat glioma), with lower IC50 values compared to pure usnic acid. Further investigations suggested both SCE and usnic acid to induce apoptosis and/or autophagy in B16 and C6, indicating higher cytotoxicity of SCE to be related to the higher degree of ROS production. A good correlation of usnic acid content in the extracts and their antioxidant capacity was established, extricating SCE as the most active one. Presented results support further investigations of SCE of old man's beard as a prospective therapeutic agent with potential relevance in the treatment of cancer and/or in oxidative stress-mediated conditions.

Evaluation of Anticancer and Antioxidant Activity of a Commercially Available CO2 Supercritical Extract of Old Man’s Beard (Usnea barbata)

PubMed Central

Isakovic, Aleksandra; Arsic, Ivana; Savic, Snezana; Tadic, Vanja

2016-01-01

There is a worldwide ongoing investigation for novel natural constituents with cytotoxic and antioxidant properties. The aim of this study was to investigate chemical profile and stated biological activities of the supercritical CO2 extract (SCE) of old man’s beard compared to the extracts obtained using the conventional techniques (Soxhlet extracts and macerate). The most abundant compound identified was usnic acid, which content was inversely proportional to the polarity of the solvent used and was the highest in the SCE, which was the sample revealing the highest cytotoxic activity in tested tumor cell lines (B16 mouse melanoma and C6 rat glioma), with lower IC50 values compared to pure usnic acid. Further investigations suggested both SCE and usnic acid to induce apoptosis and/or autophagy in B16 and C6, indicating higher cytotoxicity of SCE to be related to the higher degree of ROS production. A good correlation of usnic acid content in the extracts and their antioxidant capacity was established, extricating SCE as the most active one. Presented results support further investigations of SCE of old man’s beard as a prospective therapeutic agent with potential relevance in the treatment of cancer and/or in oxidative stress-mediated conditions. PMID:26745885

Polaronic behavior in a weak-coupling superconductor

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

Swartz, Adrian G.; Inoue, Hisashi; Merz, Tyler A.

We report the nature of superconductivity in the dilute semiconductor SrTiO 3 has remained an open question for more than 50 y. The extremely low carrier densities (10 18–10 20 cm -3) at which superconductivity occurs suggest an unconventional origin of superconductivity outside of the adiabatic limit on which the Bardeen–Cooper–Schrieffer (BCS) and Migdal–Eliashberg (ME) theories are based. We take advantage of a newly developed method for engineering band alignments at oxide interfaces and access the electronic structure of Nb-doped SrTiO 3, using high-resolution tunneling spectroscopy. We observe strong coupling to the highest-energy longitudinal optic (LO) phonon branch and estimatemore » the doping evolution of the dimensionless electron–phonon interaction strength (λ). Upon cooling below the superconducting transition temperature (T c), we observe a single superconducting gap corresponding to the weak-coupling limit of BCS theory, indicating an order of magnitude smaller coupling (λ BCS≈0.1). These results suggest that despite the strong normal state interaction with electrons, the highest LO phonon does not provide a dominant contribution to pairing. Finally, they further demonstrate that SrTiO 3 is an ideal system to probe superconductivity over a wide range of carrier density, adiabatic parameter, and electron–phonon coupling strength.« less

Polaronic behavior in a weak-coupling superconductor

DOE PAGES

Swartz, Adrian G.; Inoue, Hisashi; Merz, Tyler A.; ...

2018-01-30

We report the nature of superconductivity in the dilute semiconductor SrTiO 3 has remained an open question for more than 50 y. The extremely low carrier densities (10 18–10 20 cm -3) at which superconductivity occurs suggest an unconventional origin of superconductivity outside of the adiabatic limit on which the Bardeen–Cooper–Schrieffer (BCS) and Migdal–Eliashberg (ME) theories are based. We take advantage of a newly developed method for engineering band alignments at oxide interfaces and access the electronic structure of Nb-doped SrTiO 3, using high-resolution tunneling spectroscopy. We observe strong coupling to the highest-energy longitudinal optic (LO) phonon branch and estimatemore » the doping evolution of the dimensionless electron–phonon interaction strength (λ). Upon cooling below the superconducting transition temperature (T c), we observe a single superconducting gap corresponding to the weak-coupling limit of BCS theory, indicating an order of magnitude smaller coupling (λ BCS≈0.1). These results suggest that despite the strong normal state interaction with electrons, the highest LO phonon does not provide a dominant contribution to pairing. Finally, they further demonstrate that SrTiO 3 is an ideal system to probe superconductivity over a wide range of carrier density, adiabatic parameter, and electron–phonon coupling strength.« less

The rat closely mimics oxidative stress and inflammation in humans after exercise but not after exercise combined with vitamin C administration.

PubMed

Veskoukis, Aristidis S; Goutianos, Georgios; Paschalis, Vassilis; Margaritelis, Nikos V; Tzioura, Aikaterini; Dipla, Konstantina; Zafeiridis, Andreas; Vrabas, Ioannis S; Kyparos, Antonios; Nikolaidis, Michalis G

2016-04-01

The purpose of the present study was to directly compare oxidative stress and inflammation responses between rats and humans. We contrasted rat and human oxidative stress and inflammatory responses to exercise (pro-oxidant stimulus) and/or vitamin C (anti-oxidant stimulus) administration. Vitamin C was administered orally in both species (16 mg kg(-1) of body weight). Twelve redox biomarkers and seven inflammatory biomarkers were determined in plasma and erythrocytes pre- and post-exercise or pre- and post-exercise combined with vitamin C administration. Exercise increased oxidative stress and induced an inflammatory state in rats and humans. There were only 1/19 significant species × exercise interactions (catalase), indicating similar responses to exercise between rats and humans in redox and inflammatory biomarkers. Vitamin C decreased oxidative stress and increased antioxidant capacity only in humans and did not affect the redox state of rats. In contrast, vitamin C induced an anti-inflammatory state only in rats and did not affect the inflammatory state of humans. There were 10/19 significant species × vitamin C interactions, indicating that rats poorly mimic human oxidative stress and inflammatory responses to vitamin C administration. Exercise after acute vitamin C administration altered redox state only in humans and did not affect the redox state of rats. On the contrary, inflammation biomarkers changed similarly after exercise combined with vitamin C in both rats and humans. The rat adequately mimics human responses to exercise in basic blood redox/inflammatory profile, yet this is not the case after exercise combined with vitamin C administration.

Influence of mineral oil and additives on microhardness and surface chemistry of magnesium oxide (001) surface

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Shigaki, H.; Buckley, D. H.

1982-01-01

X-ray photoelectron spectroscopy analyses and hardness experiments were conducted with cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved into specimens along the /001/ surface, and indentations were made on the cleaved surface in laboratory air, in nitrogen gas, or in degassed mineral oil with and without an additive while not exposing specimen surface to any other environment. The various additives examined contained sulfur, phosphorus, chlorine, or oleic acid. The sulfur-containing additive exhibited the highest hardness and smallest dislocation patterns evidencing plastic deformation; the chlorine-containing additive exhibited the lowest hardness and largest dislocation patterns evidencing plastic deformation. Hydrocarbon and chloride (MgCl2) films formed on the magnesium oxide surface. A chloride film was responsible for the lowest measured hardness.

Polyethylene glycol assisted growth of Sn-doped ZnO nanorod arrays prepared via sol-gel immersion method

NASA Astrophysics Data System (ADS)

Ismail, A. S.; Mamat, M. H.; Malek, M. F.; Saidi, S. A.; Yusoff, M. M.; Mohamed, R.; Sin, N. D. Md; Suriani, A. B.; Rusop, M.

2018-05-01

Tin-doped zinc oxide (SZO) nanorod films at different concentrations of polyethylene glycol (PEG) were successfully deposited on zinc oxide (ZnO) seeded layer catalyst using sol-gel immersion method. The morphology of the samples were characterized using field emission scanning electron microscopy (FESEM), optical properties using UV-Vis spectrophotometer and electrical properties using I-V measurement system. The current-voltage (I-V) characteristics displayed that 5 wt % sample produced the highest conductivity.

Model for determination of mid-gap states in amorphous metal oxides from thin film transistors

NASA Astrophysics Data System (ADS)

Bubel, S.; Chabinyc, M. L.

2013-06-01

The electronic density of states in metal oxide semiconductors like amorphous zinc oxide (a-ZnO) and its ternary and quaternary oxide alloys with indium, gallium, tin, or aluminum are different from amorphous silicon, or disordered materials such as pentacene, or P3HT. Many ZnO based semiconductors exhibit a steep decaying density of acceptor tail states (trap DOS) and a Fermi level (EF) close to the conduction band energy (EC). Considering thin film transistor (TFT) operation in accumulation mode, the quasi Fermi level for electrons (Eq) moves even closer to EC. Classic analytic TFT simulations use the simplification EC-EF> `several'kT and cannot reproduce exponential tail states with a characteristic energy smaller than 1/2 kT. We demonstrate an analytic model for tail and deep acceptor states, valid for all amorphous metal oxides and include the effect of trap assisted hopping instead of simpler percolation or mobility edge models, to account for the observed field dependent mobility.

Identification of ground-state spin ordering in antiferromagnetic transition metal oxides using the Ising model and a genetic algorithm

PubMed Central

Lee, Kyuhyun; Youn, Yong; Han, Seungwu

2017-01-01

Abstract We identify ground-state collinear spin ordering in various antiferromagnetic transition metal oxides by constructing the Ising model from first-principles results and applying a genetic algorithm to find its minimum energy state. The present method can correctly reproduce the ground state of well-known antiferromagnetic oxides such as NiO, Fe2O3, Cr2O3 and MnO2. Furthermore, we identify the ground-state spin ordering in more complicated materials such as Mn3O4 and CoCr2O4. PMID:28458746

A Pyridine Alkoxide Chelate Ligand That Promotes Both Unusually High Oxidation States and Water-Oxidation Catalysis

DOE PAGES

Michaelos, Thoe K.; Shopov, Dimitar Y.; Sinha, Shashi Bhushan; ...

2017-03-08

Here, water-oxidation catalysis is a critical bottleneck in the direct generation of solar fuels by artificial photosynthesis. Catalytic oxidation of difficult substrates such as water requires harsh conditions, so that the ligand must be designed both to stabilize high oxidation states of the metal center and to strenuously resist ligand degradation. Typical ligand choices either lack sufficient electron donor power or fail to stand up to the oxidizing conditions. This research on Ir-based water-oxidation catalysts (WOCs) has led us to identify a ligand, 2-(2'-pyridyl)-2-propanoate or “pyalk” that fulfills these requirements.

The relationship between skin aging and steady state ultraweak photon emission as an indicator of skin oxidative stress in vivo.

PubMed

Gabe, Y; Osanai, O; Takema, Y

2014-08-01

Ultraweak photon emission (UPE) is one potential method to evaluate the oxidative status of the skin in vivo. However, little is known about how the daily oxidative stress of the skin is related to skin aging-related alterations in vivo. We characterized the steady state UPE and performed a skin survey. We evaluated the skin oxidative status by UPE, skin elasticity, epidermal thickness and skin color on the inner upper arm, the outer forearm, and the buttock of 70 Japanese volunteers. The steady state UPE at the three skin sites increased with age. Correlation analysis revealed that the steady state UPE only from the buttock was related to skin elasticity, which showed age-dependent changes. Moreover, analysis by age group indicated that b* values of the inner upper arm of subjects in their 20s were inversely correlated with UPE as occurred in buttock skin. In contrast, photoaged skin did not show a clear relationship with steady state UPE because the accumulation of sun-exposure might influence the sensitivity to oxidative stress. These results suggest that steady state UPE reflects not only intrinsic skin aging and cutaneous color but also the current oxidative status independent of skin aging. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Quantitative Analysis of Major Phytochemicals in Orthodox tea (Camellia sinensis), Oxidized under Compressed Air Environment.

PubMed

Panda, Brajesh Kumar; Datta, Ashis Kumar

2016-04-01

This study describes major changes in phytochemical composition of orthodox tea (Camellia sinensis var. Assamica) oxidized under compressed air (CA). The experiments for oxidation were conducted under air pressure (101, 202, and 303 kPa) for 150 min. Relative change in the concentrations of caffeine, catechins, theaflavins (TF), and thearubigins (TR) were analyzed. Effect of CA pressure was found to be nonsignificant in regulating caffeine concentration during oxidation. But degradation in different catechins as well as formation of different TF was significantly affected by CA pressure. At high CA pressure, TF showed highest peak value. TR was found to have slower rate of formation during initial phase of oxidation than TF. Even though the rate of TR formation was significantly influenced by CA, a portion of catechins remained unoxidized at end of oxidation. Except caffeine, the percent change in rate of formation or degradation were more prominent at 202 kPa. © 2016 Institute of Food Technologists®

Protective Effects of Black Rice Extracts on Oxidative Stress Induced by tert-Butyl Hydroperoxide in HepG2 Cells

PubMed Central

Lee, Seon-Mi; Choi, Youngmin; Sung, Jeehye; Kim, Younghwa; Jeong, Heon-Sang; Lee, Junsoo

2014-01-01

Black rice contains many biologically active compounds. The aim of this study was to investigate the protective effects of black rice extracts (whole grain extract, WGE and rice bran extract, RBE) on tert-butyl hydroperoxide (TBHP)-induced oxidative injury in HepG2 cells. Cellular reactive oxygen species (ROS), antioxidant enzyme activities, malondialdehyde (MDA) and glutathione (GSH) concentrations were evaluated as biomarkers of cellular oxidative status. Cells pretreated with 50 and 100 μg/mL of WGE or RBE were more resistant to oxidative stress in a dose-dependent manner. The highest WGE and BRE concentrations enhanced GSH concentrations and modulated antioxidant enzyme activities (glutathione reductase, glutathione-S-transferase, catalase, and superoxide dismutase) compared to TBHP-treated cells. Cells treated with RBE showed higher protective effect compared to cells treated with WGE against oxidative insult. Black rice extracts attenuated oxidative insult by inhibiting cellular ROS and MDA increase and by modulating antioxidant enzyme activities in HepG2 cells. PMID:25580401

FeOx-TiO2 Film with Different Microstructures Leading to Femtosecond Transients with Different Properties: Biological Implications under Visible Light

PubMed Central

Rtimi, Sami; Pulgarin, Cesar; Nadtochenko, Victor A.; Gostev, Fedor E.; Shelaev, Ivan V.; Kiwi, John

2016-01-01

This study presents the first report addressing the effect of FeOx-TiO2 films microstructure on the transients detected by fast spectroscopy related to the long-range bacterial inactivation performance. The different fast kinetic femtosecond transient spectroscopy is reported for each FeOx+TiO2 microstructure. The lifetime of the short transient-species and the oxidative intermediate radicals generated under light were identified. Co-sputtered FeOx-TiO2 on polyethylene films presenting random distribution for both oxides were compared with sequentially sputtered FeOx/TiO2 films made up only by FeOx in the topmost layers. The ratio FeOx:TiO2 was optimized to attain the highest photo-conversion. By X-ray fluorescence, the Fe:Ti ration was found to be ~1.4 in the film bulk and by XPS-etching a ratio of 4:1 was found on the photocatalyst top-most layers. For co-sputtered FeOx-TiO2-PE films, the FeOx-TiO2 heterojunction led to electron injection from the FeOx to lower-lying TiO2 trapping states. The film optical properties, particle size, roughness, hydrophobic-hydrophilic shift and temporal evolution of the transient redox states were characterized in detail. Films with different microstructure led to different antibacterial activity. This suggests that the FeOx-TiO2-PE microstructure and not the position of the potential energy level of the semiconductors FeOx and TiO2 control the charge transfer under light irradiation. PMID:27443505

Understanding the influence of surface chemical states on the dielectric tunability of sputtered Ba0.5Sr0.5TiO3 thin films

NASA Astrophysics Data System (ADS)

Venkata Saravanan, K.; Raju, K. C. James

2014-03-01

The surface chemical states of RF-magnetron sputtered Ba0.5Sr0.5TiO3 (BST5) thin films deposited at different oxygen mixing percentage (OMP) was examined by x-ray photoelectron spectroscopy. The O1s XPS spectra indicate the existence of three kinds of oxygen species (dissociated oxygen ion O2 -, adsorbed oxide ion O- and lattice oxide ion O2-) on the films’ surface, which strongly depends on OMP. The presence of oxygen species other than lattice oxygen ion makes the films’ surface highly reactivity to atmospheric gases, resulting in the formation of undesired surface layers. The XPS results confirm the formation of surface nitrates for the films deposited under oxygen deficient atmosphere (OMP ≦̸ 25%), whereas the films deposited in oxygen rich atmosphere (OMP ≧̸ 75%) show the presence of metal-hydroxide. The influence of a surface dead layer on the tunable dielectric properties of BST5 films have been studied in detail and are reported. Furthermore, our observations indicate that an optimum ratio of Ar:O2 is essential for achieving desired material and dielectric properties in BST5 thin films. The films deposited at 50% OMP have the highest dielectric tunability of ~65% (@280 kV cm-1), with good ɛ r-E curve symmetry of 98% and low tan δ of 0.018. The figure of merit for these films is about 35, which is promising for frequency agile device applications.

On the superconducting state in Ba0.6K0.4BiO3 perovskite oxide

NASA Astrophysics Data System (ADS)

Szcześniak, D.; Kaczmarek, A. Z.; Drzazga, E. A.; Szewczyk, K. A.; Szcześniak, R.

2018-05-01

We report study on the superconducting state in Ba0.6K0.4BiO3 (BKBO) perovskite oxide, motivated by the inconclusive results on the pairing mechanism in this compound. Our investigations are conducted within the Migdal-Eliashberg formalism, to account for the phonon-mediated superconducting phase. The considered doping level of the discussed material corresponds to the highest critical temperature in this compound, and allows simultaneous analysis of the oxygen isotope effect, for the O16 and O18 isotopes, respectively. We found that such effect is particularly visible for the critical values of the Coulomb pseudopotential (μC⋆) , which equals to 0.18 for the O16 and 0.16 for the O18 isotope in BKBO. Moreover, we determine the size of the superconducting energy band gap (Δg) and note that obtained values (9.68 meV and 9.55 meV for the O16 and O18, respectively) are in good agreement with the experimental predictions which give Δg ∼ 8.68 meV . Finally, we calculate the characteristic dimensionless parameters, such as the zero-temperature energy gap to the critical temperature, the ratio for the specific heat, as well as the ratio associated with the zero-temperature thermodynamic critical field, which suggest occurrence of the strong-coupling and retardation effects within the phonon-mediated scenario in the analyzed material. Where possible the dimensionless ratios are compared to the experimental estimates, and agrees with these which account for the strong-coupling character of the BKBO superconductor.

Solid-State Kinetic Investigations of Nonisothermal Reduction of Iron Species Supported on SBA-15

PubMed Central

2017-01-01

Iron oxide catalysts supported on nanostructured silica SBA-15 were synthesized with various iron loadings using two different precursors. Structural characterization of the as-prepared FexOy/SBA-15 samples was performed by nitrogen physisorption, X-ray diffraction, DR-UV-Vis spectroscopy, and Mössbauer spectroscopy. An increasing size of the resulting iron species correlated with an increasing iron loading. Significantly smaller iron species were obtained from (Fe(III), NH4)-citrate precursors compared to Fe(III)-nitrate precursors. Moreover, smaller iron species resulted in a smoother surface of the support material. Temperature-programmed reduction (TPR) of the FexOy/SBA-15 samples with H2 revealed better reducibility of the samples originating from Fe(III)-nitrate precursors. Varying the iron loading led to a change in reduction mechanism. TPR traces were analyzed by model-independent Kissinger method, Ozawa, Flynn, and Wall (OFW) method, and model-dependent Coats-Redfern method. JMAK kinetic analysis afforded a one-dimensional reduction process for the FexOy/SBA-15 samples. The Kissinger method yielded the lowest apparent activation energy for the lowest loaded citrate sample (Ea ≈ 39 kJ/mol). Conversely, the lowest loaded nitrate sample possessed the highest apparent activation energy (Ea ≈ 88 kJ/mol). For samples obtained from Fe(III)-nitrate precursors, Ea decreased with increasing iron loading. Apparent activation energies from model-independent analysis methods agreed well with those from model-dependent methods. Nucleation as rate-determining step in the reduction of the iron oxide species was consistent with the Mampel solid-state reaction model. PMID:29230346

FeOx-TiO2 Film with Different Microstructures Leading to Femtosecond Transients with Different Properties: Biological Implications under Visible Light.

PubMed

Rtimi, Sami; Pulgarin, Cesar; Nadtochenko, Victor A; Gostev, Fedor E; Shelaev, Ivan V; Kiwi, John

2016-07-22

This study presents the first report addressing the effect of FeOx-TiO2 films microstructure on the transients detected by fast spectroscopy related to the long-range bacterial inactivation performance. The different fast kinetic femtosecond transient spectroscopy is reported for each FeOx+TiO2 microstructure. The lifetime of the short transient-species and the oxidative intermediate radicals generated under light were identified. Co-sputtered FeOx-TiO2 on polyethylene films presenting random distribution for both oxides were compared with sequentially sputtered FeOx/TiO2 films made up only by FeOx in the topmost layers. The ratio FeOx:TiO2 was optimized to attain the highest photo-conversion. By X-ray fluorescence, the Fe:Ti ration was found to be ~1.4 in the film bulk and by XPS-etching a ratio of 4:1 was found on the photocatalyst top-most layers. For co-sputtered FeOx-TiO2-PE films, the FeOx-TiO2 heterojunction led to electron injection from the FeOx to lower-lying TiO2 trapping states. The film optical properties, particle size, roughness, hydrophobic-hydrophilic shift and temporal evolution of the transient redox states were characterized in detail. Films with different microstructure led to different antibacterial activity. This suggests that the FeOx-TiO2-PE microstructure and not the position of the potential energy level of the semiconductors FeOx and TiO2 control the charge transfer under light irradiation.

FeOx-TiO2 Film with Different Microstructures Leading to Femtosecond Transients with Different Properties: Biological Implications under Visible Light

NASA Astrophysics Data System (ADS)

Rtimi, Sami; Pulgarin, Cesar; Nadtochenko, Victor A.; Gostev, Fedor E.; Shelaev, Ivan V.; Kiwi, John

2016-07-01

This study presents the first report addressing the effect of FeOx-TiO2 films microstructure on the transients detected by fast spectroscopy related to the long-range bacterial inactivation performance. The different fast kinetic femtosecond transient spectroscopy is reported for each FeOx+TiO2 microstructure. The lifetime of the short transient-species and the oxidative intermediate radicals generated under light were identified. Co-sputtered FeOx-TiO2 on polyethylene films presenting random distribution for both oxides were compared with sequentially sputtered FeOx/TiO2 films made up only by FeOx in the topmost layers. The ratio FeOx:TiO2 was optimized to attain the highest photo-conversion. By X-ray fluorescence, the Fe:Ti ration was found to be ~1.4 in the film bulk and by XPS-etching a ratio of 4:1 was found on the photocatalyst top-most layers. For co-sputtered FeOx-TiO2-PE films, the FeOx-TiO2 heterojunction led to electron injection from the FeOx to lower-lying TiO2 trapping states. The film optical properties, particle size, roughness, hydrophobic-hydrophilic shift and temporal evolution of the transient redox states were characterized in detail. Films with different microstructure led to different antibacterial activity. This suggests that the FeOx-TiO2-PE microstructure and not the position of the potential energy level of the semiconductors FeOx and TiO2 control the charge transfer under light irradiation.

Health spending by state of residence, 1991-2009.

PubMed

Cuckler, Gigi; Martin, Anne; Whittle, Lekha; Heffler, Stephen; Sisko, Andrea; Lassman, Dave; Benson, Joseph

2011-12-06

Provide a detailed discussion of baseline health spending by state of residence (per capita personal health care spending, per enrollee Medicare spending, and per enrollee Medicaid spending) in 2009, over the last decade (1998-2009), as well as the differential regional and state impacts of the recent recession. State Health Expenditures by State of Residence for 1991-2009, produced by the Centers for Medicare & Medicaid Services' Office of the Actuary. In 2009, the 10 states where per capita spending was highest ranged from 13 to 36 percent higher than the national average, and the 10 states where per capita spending was lowest ranged from 8 to 26 percent below the national average. States with the highest per capita spending tended to have older populations and the highest per capita incomes; states with the lowest per capita spending tended to have younger populations, lower per capita incomes, and higher rates of uninsured. Over the last decade, the New England and Mideast regions exhibited the highest per capita personal health care spending, while states in the Southwest and Rocky Mountain regions had the lowest per capita spending. Variation in per enrollee Medicaid spending, however, has consistently been greater than that of total per capita personal health care spending or per enrollee Medicare spending from 1998-2009. The Great Lakes, New England, and Far West regions experienced the largest slowdown in per person health spending growth during the recent recession, largely as a result of higher unemployment rates. Public Domain.

Reactive Gaseous Mercury Formation Over The North Pacific Ocean: Influence Of Environmental Parameters On Elemental Mercury Oxidation In The Marine Boundary Layer

NASA Astrophysics Data System (ADS)

Laurier, F. J.

2002-12-01

Global mercury models have identified wet and dry particle deposition and evasion of dissolved gaseous mercury from the ocean and from land as key controls over global mercury cycling (1,2). Recent ocean studies (3,4) however, have indicated that estimated mercury evasion rates from the ocean substantially exceed estimated deposition. Oxidized reactive gaseous mercury species (RGHg) are now known to play a major role in the global mercury cycle (2,5). RGHg species are water-soluble, exhibit a much shorter atmospheric lifetime than elemental mercury, and contribute to a large extent to atmospheric mercury deposition (2,3,6). Although recent global mercury models have accounted for the dry deposition of RGHg derived from point source emissions (6,7), the formation and deposition of RGHg in remote areas have not been incorporated. We suggest that the oxidation of elemental mercury over the ocean, by gas phase or heterogeneous reactions, is an important part the global mercury cycle. In agreement with previous studies (3,8,9) our recent data from atmospheric collections over the North Pacific Ocean support the notion of enhanced oxidation in the marine boundary layer. Our results show an inverse correlation between RGHg production and ozone, and a diurnal cycle with highest concentrations during periods of highest UV irradiation. In addition, the relationship between RGHg and other parameters measured during the cruise will be discussed. Our results clearly show that RGHg deposition to the ocean must be an important Hg source, and a crucial part of the global Hg cycle. (1) Mason R.P., Fitzgerald W.F., and Morel F.M.M. (1994), The biogeochemical cycling of elemental mercury: Anthropogenic influences, Geochim. Cosmochim. Acta, 58: 3191-3198 (2) Shia R.L., Seigneur C., Pai P., Ko M., and Sze N.-D. (1999), Global simulation of atmospheric mercury concentrations and deposition fluxes, J. Geophy. Res., 104(D19), 23, 747-23, 760 (3) Mason, R.P., Lawson N.M., and Sheu G.-R. (2001), Mercury in the Atlantic Ocean: factors controlling air-sea exchange of mercury and its distribution in the upper water, Deep-Sea Res. II, 2829-2853 (4) Lamborg, C.H., Rolfus K.R., and Fitzgerald W.F. (1999), The atmospheric cycling and air-sea exchange of mercury species in the south and equatorial Atlantic Ocean, Deep-Sea Res. II, 957-977 (5) Lindberg S.E., Brooks S., Lin C.-J., Scott K. J., Landis M. S., Stevens R.K., Goodsite M., and Richter A. (2002), Dynamic oxidation of gaseous mercury in the arctic troposphere at polar sunrise, Environ. Sci. Technol., 1245-1256 (6) Bullock O.R. (2000), Modeling assessment of transport and deposition patterns of anthropogenic mercury air emissions in the United States and Canada, Sci Total Environ., 259(1-3), 145-157 (7) Xu X., Yang X., Miller d.R., Helble J.J., and Carley R.J. (2000), a regional scale modelling study of atmospheric transport and formation of mercury. II. Simulation results for the northeast United states, Atmos. Environ., 34: 4945-4955 (8) Sheu G.-R. (2001), Speciation and distribution of atmospheric mercury: Significance of reactive gaseous mercury in the global mercury cycle. PhD. thesis, University of Maryland, College park, pp. 170 (9) Guentzel J.L., Landing W.M., Gill G.A., and Pollman C.D. (2001), Processes influencing rainfall deposition of mercury in Florida, Environ. Sci. Technol., 35: 863-873

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

PubMed Central

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

2015-01-01

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

On the behavior of Bronsted-Evans-Polanyi Relations for Transition Metal Oxides

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

Vojvodic, Aleksandra

2011-08-22

Versatile Broensted-Evans-Polanyi (BEP) relations are found from density functional theory for a wide range of transition metal oxides including rutiles and perovskites. For oxides, the relation depends on the type of oxide, the active site and the dissociating molecule. The slope of the BEP relation is strongly coupled to the adsorbate geometry in the transition state. If it is final state-like the dissociative chemisorption energy can be considered as a descriptor for the dissociation. If it is initial state-like, on the other hand, the dissociative chemisorption energy is not suitable as descriptor for the dissociation. Dissociation of molecules with strongmore » intramolecular bonds belong to the former and molecules with weak intramolecular bonds to the latter group. We show, for the prototype system La-perovskites, that there is a 'cyclic' behavior in the transition state characteristics upon change of the active transition metal of the oxide.« less

Spin State Control of the Perovskite Rh/Co Oxides

PubMed Central

Terasaki, Ichiro; Shibasaki, Soichiro; Yoshida, Shin; Kobayashi, Wataru

2010-01-01

We show why and how the spin state of transition-metal ions affects the thermoelectric properties of transition-metal oxides by investigating two perovskite-related oxides. In the A-site ordered cobalt oxide Sr3YCo4O10.5, partial substitution of Ca for Sr acts as chemical pressure, which compresses the unit cell volume to drive the spin state crossover, and concomitantly changes the magnetization and thermopower. In the perovskite rhodium oxide LaRhO3, partial substitution of Sr for La acts as hole-doping, and the resistivity and thermopower decrease systematically with the Sr concentration. The thermopower remains large values at high temperatures (>150 μV/K at 800 K), which makes a remarkable contrast to La1−xSrxCoO3. We associate this with the stability of the low spin state of the Rh3+ ions.

Assessment of anti-oxidant activity of plant extracts using microbial test systems.

PubMed

Oktyabrsky, O; Vysochina, G; Muzyka, N; Samoilova, Z; Kukushkina, T; Smirnova, G

2009-04-01

To evaluate the anti-oxidant properties of extracts from 20 medicinal herbs growing in western Siberia using microbial test systems and different in vitro methods. In vivo anti-oxidant activity of extracts was evaluated for their capacity to protect bacteria, Escherichia coli, against bacteriostatic and bactericidal effects of H(2)O(2) and menadione, and action on anti-oxidant gene expression. In vitro anti-oxidant activity has been examined by a number of methods including: the 1,1-diphenyl-2-picrylhydrazyl radical (DPPH(*))-scavenging assay, chelating activity and capacity to protect plasmid DNA against oxidative damage. In addition, total polyphenol content was determined. The extracts of Fragaria vesca, Rosa majalis, Pentaphylloides fruticosa, Alchemilla vulgaris and Pulmonaria mollis possessed the highest levels of anti-oxidant activity in vivo and in vitro. The protective properties were more closely related to the DPPH(*) radical-scavenging activity, tannin content and action on anti-oxidant gene expression than to other parameters. The extracts of medicinal plants may have anti-oxidant effects on bacteria simultaneously through several different pathways, including direct inhibition of reactive oxygen species, iron chelation and anti-oxidant genes induction. Using microbial test systems, we revealed herbs that may be used as potential sources of natural anti-oxidants.

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

PubMed

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

2012-08-28

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

Removal of ozone on clean, dusty and sooty supply air filters

NASA Astrophysics Data System (ADS)

Hyttinen, Marko; Pasanen, Pertti; Kalliokoski, Pentti

The removal of ozone (O 3) on supply air filters was studied. Especially, the effects of dust load, diesel soot, relative humidity (RH), and exposure time on the removal of O 3 were investigated. Some loss of O 3 was observed in all the filters, except in an unused G3 pre-filter made of polyester. Dust load and quality influenced the reduction of O 3; especially, diesel soot removed O 3 effectively. Increasing the RH resulted in a larger O 3 removal. The removal of O 3 was highest in the beginning of the test, but it declined within 2 h reaching almost a steady state as the exposure continued. However, the sooty filters continued to remove as much as 25-30% of O 3. Up to 11% of O 3 removed participated in the production of formaldehyde. Small amounts of other oxidation products were also detected.

Low voltage solid-state lateral coloration electrochromic device

DOEpatents

Tracy, C.E.; Benson, D.K.; Ruth, M.R.

1984-12-21

A solid-state transition metal oxide device comprising a plurality of layers having a predisposed orientation including an electrochromic oxide layer. Conductive material including anode and cathode contacts is secured to the device. Coloration is actuated within the electrochromic oxide layer after the application of a predetermined potential between the contacts. The coloration action is adapted to sweep or dynamically extend across the length of the electrochromic oxide layer.

Low voltage solid-state lateral coloration electrochromic device

DOEpatents

Tracy, C. Edwin; Benson, David K.; Ruth, Marta R.

1987-01-01

A solid-state transition metal oxide device comprising a plurality of lay having a predisposed orientation including an electrochromic oxide layer. Conductive material including anode and cathode contacts is secured to the device. Coloration is actuated within the electrochromic oxide layer after the application of a predetermined potential between the contacts. The coloration action is adapted to sweep or dynamically extend across the length of the electrochromic oxide layer.

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

Unuigbe, David M.; Harting, Margit; Jonah, Emmanuel O.

The presence of native oxide on the surface of silicon nanoparticles is known to inhibit charge transport on the surfaces. Scanning electron microscopy (SEM) studies reveal that the particles in the printed silicon network have a wide range of sizes and shapes. High-resolution transmission electron microscopy reveals that the particle surfaces have mainly the (111)- and (100)-oriented planes which stabilizes against further oxidation of the particles. X-ray absorption spectroscopy (XANES) and X-ray photoelectron spectroscopy (XPS) measurements at the O 1s-edge have been utilized to study the oxidation and local atomic structure of printed layers of silicon nanoparticles which were milledmore » for different times. XANES results reveal the presence of the +4 (SiO 2) oxidation state which tends towards the +2 (SiO) state for higher milling times. Si 2pXPS results indicate that the surfaces of the silicon nanoparticles in the printed layers are only partially oxidized and that all three sub-oxide, +1 (Si 2O), +2 (SiO) and +3 (Si 2O 3), states are present. The analysis of the change in the sub-oxide peaks of the silicon nanoparticles shows the dominance of the +4 state only for lower milling times.« less

Impact of the cation distribution homogeneity on the americium oxidation state in the U0.54Pu0.45Am0.01O2-x mixed oxide

NASA Astrophysics Data System (ADS)

Vauchy, Romain; Robisson, Anne-Charlotte; Martin, Philippe M.; Belin, Renaud C.; Aufore, Laurence; Scheinost, Andreas C.; Hodaj, Fiqiri

2015-01-01

The impact of the cation distribution homogeneity of the U0.54Pu0.45Am0.01O2-x mixed oxide on the americium oxidation state was studied by coupling X-ray diffraction (XRD), electron probe micro analysis (EPMA) and X-ray absorption spectroscopy (XAS). Oxygen-hypostoichiometric Am-bearing uranium-plutonium mixed oxide pellets were fabricated by two different co-milling based processes in order to obtain different cation distribution homogeneities. The americium was generated from β- decay of 241Pu. The XRD analysis of the obtained compounds did not reveal any structural difference between the samples. EPMA, however, revealed a high homogeneity in the cation distribution for one sample, and substantial heterogeneity of the U-Pu (so Am) distribution for the other. The difference in cation distribution was linked to a difference in Am chemistry as investigated by XAS, with Am being present at mixed +III/+IV oxidation state in the heterogeneous compound, whereas only Am(IV) was observed in the homogeneous compound. Previously reported discrepancies on Am oxidation states can hence be explained by cation distribution homogeneity effects.

Catalytic wet oxidation of ammonia solution: activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst.

PubMed

Hung, Chang-Mao

2009-04-15

Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H(2)PtCl(6), Pd(NO(3))(3) and Rh(NO(3))(3). Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes.

Variation in trace element content of magnetite crystallized from a fractionating sulfide liquid, Sudbury, Canada: Implications for provenance discrimination

NASA Astrophysics Data System (ADS)

Dare, Sarah A. S.; Barnes, Sarah-Jane; Beaudoin, Georges

2012-07-01

Laser ablation ICP-MS analysis has been applied to many accessory minerals in order to understand better the process by which the rock formed and for provenance discrimination. We have determined trace element concentrations of Fe-oxides in massive sulfides that form Ni-Cu-PGE deposits at the base of the Sudbury Igneous Complex in Canada. The samples represent the crystallization products of fractionating sulfide liquids and consist of early-forming Fe-rich monosulfide solution (MSS) cumulates and residual Cu-rich intermediate solid solution (ISS). This study shows that Fe-oxide geochemistry is a sensitive petrogenetic indicator for the degree of fractionation of the sulfide liquid and provides an insight into the partitioning of elements between sulfide and Fe-oxide phases. In addition, it is useful in determining the provenance of detrital Fe-oxide. In a sulfide melt, all lithophile elements (Cr, Ti, V, Al, Mn, Sc, Nb, Ga, Ge, Ta, Hf, W and Zr) are compatible into Fe-oxide. The concentrations of these elements are highest in the early-forming Fe-oxide (titanomagnetite) which crystallized with Fe-rich MSS. Upon the continual crystallization of Fe-oxide from the sulfide liquid, the lithophile elements gradually decrease so that late-forming Fe-oxide (magnetite), which crystallized from the residual Cu-rich liquid, is depleted in these elements. This behavior is in contrast with Fe-oxides that crystallized from a fractionating silicate melt, whereby the concentration of incompatible elements, such as Ti, increases rather than decreases. The behavior of the chalcophile elements in magnetite is largely controlled by the crystallization of the sulfide minerals with only Ni, Co, Zn, Mo, Sn and Pb present above detection limit in magnetite. Nickel, Mo and Co are compatible in Fe-rich MSS and thus the co-crystallizing Fe-oxide is depleted in these elements. In contrast, magnetite that crystallized later from the fractionated liquid with Cu-rich ISS is enriched in Ni, Mo and Co because Fe-rich MSS is absent. The concentrations of Sn and Pb, which are incompatible with Fe-rich MSS, are highest in magnetite that formed from the fractionated Cu-rich liquid. At subsolidus temperatures, ilmenite exsolved from titanomagnetite whereas Al-spinel exsolved from the cores of some magnetite, locally redistributing the trace elements. However, during laser ablation ICP-MS analysis of these Fe-oxides both the magnetite and its exsolution products are ablated so that the analysis represents the original magmatic composition of the Fe-oxide that crystallized from the sulfide melt.

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 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. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr05061d

Heterogeneous Oxidation of Atmospheric Organic Aerosol: Kinetics of Changes to the Amount and Oxidation State of Particle-Phase Organic Carbon.

PubMed

Kroll, Jesse H; Lim, Christopher Y; Kessler, Sean H; Wilson, Kevin R

2015-11-05

Atmospheric oxidation reactions are known to affect the chemical composition of organic aerosol (OA) particles over timescales of several days, but the details of such oxidative aging reactions are poorly understood. In this study we examine the rates and products of a key class of aging reaction, the heterogeneous oxidation of particle-phase organic species by the gas-phase hydroxyl radical (OH). We compile and reanalyze a number of previous studies from our laboratories involving the oxidation of single-component organic particles. All kinetic and product data are described on a common basis, enabling a straightforward comparison among different chemical systems and experimental conditions. Oxidation chemistry is described in terms of changes to key ensemble properties of the OA, rather than to its detailed molecular composition, focusing on two quantities in particular, the amount and the oxidation state of the particle-phase carbon. Heterogeneous oxidation increases the oxidation state of particulate carbon, with the rate of increase determined by the detailed chemical mechanism. At the same time, the amount of particle-phase carbon decreases with oxidation, due to fragmentation (C-C scission) reactions that form small, volatile products that escape to the gas phase. In contrast to the oxidation state increase, the rate of carbon loss is nearly uniform among most systems studied. Extrapolation of these results to atmospheric conditions indicates that heterogeneous oxidation can have a substantial effect on the amount and composition of atmospheric OA over timescales of several days, a prediction that is broadly in line with available measurements of OA evolution over such long timescales. In particular, 3-13% of particle-phase carbon is lost to the gas phase after one week of heterogeneous oxidation. Our results indicate that oxidative aging represents an important sink for particulate organic carbon, and more generally that fragmentation reactions play a major role in the lifecycle of atmospheric OA.

Passivating overcoat bilayer for multilayer reflective coatings for extreme ultraviolet lithography

DOEpatents

Montcalm, Claude; Stearns, Daniel G.; Vernon, Stephen P.

1999-01-01

A passivating overcoat bilayer is used for multilayer reflective coatings for extreme ultraviolet (EUV) or soft x-ray applications to prevent oxidation and corrosion of the multilayer coating, thereby improving the EUV optical performance. The overcoat bilayer comprises a layer of silicon or beryllium underneath at least one top layer of an elemental or a compound material that resists oxidation and corrosion. Materials for the top layer include carbon, palladium, carbides, borides, nitrides, and oxides. The thicknesses of the two layers that make up the overcoat bilayer are optimized to produce the highest reflectance at the wavelength range of operation. Protective overcoat systems comprising three or more layers are also possible.

Measurement of gaseous emissions from an afterburning turbojet engine at simulated altitude conditions

NASA Technical Reports Server (NTRS)

Diehl, L. A.

1973-01-01

Gaseous emissions from a J85-GE-13 turbojet engine were measured over a range of fuel-air ratios from idle to full afterburning and simulated altitudes from near sea-level to 12,800 meters (42,000 ft). Without afterburning, carbon monoxide and unburned hydrocarbon emissions were highest at idle and lowest at takeoff; oxides of nitrogen exhibited the reverse trend. With afterburning, carbon monoxide and unburned hydrocarbon emissions were greater than for military power. Carbon monoxide emissions were altitude dependent. Oxides of nitrogen emissions were less at minimum afterburning than at military power. For power levels above minimum afterburning, the oxides of nitrogen emissions were both power level and altitude dependent.

Population structure and abundance of arsenite-oxidizing bacteria along an arsenic pollution gradient in waters of the upper isle River Basin, France.

PubMed

Quéméneur, Marianne; Cébron, Aurélie; Billard, Patrick; Battaglia-Brunet, Fabienne; Garrido, Francis; Leyval, Corinne; Joulian, Catherine

2010-07-01

Denaturing gradient gel electrophoresis (DGGE) and quantitative real-time PCR (qPCR) were successfully developed to monitor functional aoxB genes as markers of aerobic arsenite oxidizers. DGGE profiles showed a shift in the structure of the aoxB-carrying bacterial population, composed of members of the Alpha-, Beta- and Gammaproteobacteria, depending on arsenic (As) and E(h) levels in Upper Isle River Basin waters. The highest aoxB gene densities were found in the most As-polluted oxic surface waters but without any significant correlation with environmental factors. Arsenite oxidizers seem to play a key role in As mobility in As-impacted waters.

The evidence basis for coenzyme Q therapy in oxidative phosphorylation disease.

PubMed

Haas, Richard H

2007-06-01

The evidence supporting a treatment benefit for coenzyme Q10 (CoQ10) in primary mitochondrial disease (mitochondrial disease) whilst positive is limited. Mitochondrial disease in this context is defined as genetic disease causing an impairment in mitochondrial oxidative phosphorylation (OXPHOS). There are no treatment trials achieving the highest Level I evidence designation. Reasons for this include the relative rarity of mitochondrial disease, the heterogeneity of mitochondrial disease, the natural cofactor status and easy 'over the counter availability' of CoQ10 all of which make funding for the necessary large blinded clinical trials unlikely. At this time the best evidence for efficacy comes from controlled trials in common cardiovascular and neurodegenerative diseases with mitochondrial and OXPHOS dysfunction the etiology of which is most likely multifactorial with environmental factors playing on a background of genetic predisposition. There remain questions about dosing, bioavailability, tissue penetration and intracellular distribution of orally administered CoQ10, a compound which is endogenously produced within the mitochondria of all cells. In some mitochondrial diseases and other commoner disorders such as cardiac disease and Parkinson's disease low mitochondrial or tissue levels of CoQ10 have been demonstrated providing an obvious rationale for supplementation. This paper discusses the current state of the evidence supporting the use of CoQ10 in mitochondrial disease.

Design of 3D Graphene-Oxide Spheres and Their Derived Hierarchical Porous Structures for High Performance Supercapacitors.

PubMed

Li, Zhuangnan; Gadipelli, Srinivas; Yang, Yuchen; Guo, Zhengxiao

2017-11-01

Graphene-oxide (GO) based porous structures are highly desirable for supercapacitors, as the charge storage and transfer can be enhanced by advancement in the synthesis. An effective route is presented of, first, synthesis of three-dimensional (3D) assembly of GO sheets in a spherical architecture (GOS) by flash-freezing of GO dispersion, and then development of hierarchical porous graphene (HPG) networks by facile thermal-shock reduction of GOS. This leads to a superior gravimetric specific capacitance of ≈306 F g -1 at 1.0 A g -1 , with a capacitance retention of 93% after 10 000 cycles. The values represent a significant capacitance enhancement by 30-50% compared with the GO powder equivalent, and are among the highest reported for GO-based structures from different chemical reduction routes. Furthermore, a solid-state flexible supercapacitor is fabricated by constructing the HPG with polymer gel electrolyte, exhibiting an excellent areal specific capacitance of ≈220 mF cm -2 at 1.0 mA cm -2 with exceptional cyclic stability. The work reveals a facile but efficient synthesis approach of GO-based materials to enhance the capacitive energy storage. © 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gaseous oxidized mercury dry deposition measurements in the southwestern USA: a comparison between Texas, eastern Oklahoma, and the Four Corners area.

PubMed

Sather, Mark E; Mukerjee, Shaibal; Allen, Kara L; Smith, Luther; Mathew, Johnson; Jackson, Clarence; Callison, Ryan; Scrapper, Larry; Hathcoat, April; Adam, Jacque; Keese, Danielle; Ketcher, Philip; Brunette, Robert; Karlstrom, Jason; Van der Jagt, Gerard

2014-01-01

Gaseous oxidized mercury (GOM) dry deposition measurements using aerodynamic surrogate surface passive samplers were collected in central and eastern Texas and eastern Oklahoma, from September 2011 to September 2012. The purpose of this study was to provide an initial characterization of the magnitude and spatial extent of ambient GOM dry deposition in central and eastern Texas for a 12-month period which contained statistically average annual results for precipitation totals, temperature, and wind speed. The research objective was to investigate GOM dry deposition in areas of Texas impacted by emissions from coal-fired utility boilers and compare it with GOM dry deposition measurements previously observed in eastern Oklahoma and the Four Corners area. Annual GOM dry deposition rate estimates were relatively low in Texas, ranging from 0.1 to 0.3 ng/m(2)h at the four Texas monitoring sites, similar to the 0.2 ng/m(2)h annual GOM dry deposition rate estimate recorded at the eastern Oklahoma monitoring site. The Texas and eastern Oklahoma annual GOM dry deposition rate estimates were at least four times lower than the highest annual GOM dry deposition rate estimate previously measured in the more arid bordering western states of New Mexico and Colorado in the Four Corners area.

Dose-Dependent Effects of CeO2 on Microstructure and Antibacterial Property of Plasma-Sprayed TiO2 Coatings for Orthopedic Application

NASA Astrophysics Data System (ADS)

Zhao, Xiaobing; Liu, Gaopeng; Zheng, Hai; Cao, Huiliang; Liu, Xuanyong

2015-02-01

Titanium and its alloys have been used extensively for orthopedic and dental implants. Although these devices have achieved high rates of success, two major complications may be encountered: the lack of osseointegration and the biomaterial-related infection. Accordingly, cerium oxide (CeO2)-doped titanium oxide (TiO2) materials were coated on titanium by an atmospheric plasma spraying (APS) technique. The phase structures, morphologies, and surface chemical states of the obtained coatings were characterized by x-ray diffraction, scanning electron microscopy, and x-ray photoelectron spectroscopy techniques. The in vitro antibacterial and cytocompatibility of the materials were studied with Staphylococcus aureus ( S. aureus, ATCC25923) and osteoblast precursor cell line MC3T3-E1. The results indicated that the addition of CeO2 shifts slightly the diffraction peaks of TiO2 matrix to low angles but does not change its rutile phase structure. In addition, the CeO2/TiO2 composite coatings possess dose-dependent corrosion resistance and antimicrobial properties. And doping of 10 wt.% CeO2 exhibits the highest activity against S. aureus, improved corrosion resistance, and competitive cytocompatibility, which argues a promising option for balancing the osteogenetic and antibacterial properties of titanium implants.

Optimization of synthesis of the nickel-cobalt oxide based anode electrocatalyst and of the related membrane-electrode assembly for alkaline water electrolysis

NASA Astrophysics Data System (ADS)

Chanda, Debabrata; Hnát, Jaromir; Bystron, Tomas; Paidar, Martin; Bouzek, Karel

2017-04-01

In this work, the Ni-Co spinel oxides are synthesized via different methods and using different calcination temperatures. Properties of the prepared materials are compared. The best route is selected and used to prepare a Ni1+xCo2-xO4 (-1 ≤ x ≤ 1) series of materials in order to investigate their catalytic activity towards the oxygen evolution reaction (OER). The results show that hydroxide preparation yields NiCo2O4 oxide with the highest activity. 325 °C is identified as the optimum calcination temperature. Subsequently, the catalysts are tested in an electrolysis cell. To prepare an anode catalyst layer based on NiCo2O4 catalyst on top of a nickel foam substrate for membrane electrode assembly (MEA) construction, following polymer binders are used: anion-selective quaternized polyphenylene oxide (qPPO), inert polytetrafluoroethylene (PTFE®), and cation-selective Nafion®. qPPO ionomer containing MEA exhibited highest OER activity. The current density obtained using a MEA containing qPPO binder attains a value of 135 mA cm-2 at a cell voltage of 1.85 V. After 7 h chronopotentiometric experiment at a constant current density of 225 mA cm-2, the MEA employing PTFE® binder shows higher stability than the other binders in alkaline water electrolysis at 50 °C. Under similar conditions, stability of the PTFE®-binding MEA is examined for 135 h.

Factors affecting the formation of iodo-trihalomethanes during oxidation with chlorine dioxide.

PubMed

Guo, Wanhong; Shan, Yingchun; Yang, Xin

2014-01-15

Effects of water characteristics, reaction time, temperature, bromide and iodide ion concentrations, oxidant doses, and pH on formation of iodinated trihalomethanes (I-THM) during oxidation of iodide-containing water with chlorine dioxide (ClO2) were investigated. Among the water samples collected from ten water sources, iodoform (CHI3) was the predominant I-THM and trace amount of chlorodiiodomethane (CHClI2) was occasionally found. CHI3 yields correlated moderately with specific UV absorbance (SUVA) (R(2)=0.79), indicating that hydrophobic aromatic content were important precursors. Longer reaction time led to continued formation of CHI3. I-THM containing bromide was also found in waters containing both bromide and iodide, but CHI3 was dominant. The formation of CHI3 was higher at 25°C than 5°C and 35°C. CHI3 formation showed an increase followed by a decrease trend with increasing ClO2 doses and iodide concentrations and the highest yields occurred at iodide to ClO2 molar ratios of 1-2. pH 8 resulted in the highest CHI3 formation. It should be noted that a high iodide concentration was spiked to waters before adding ClO2 and the results may not reflect the formation yields of iodinated THMs in real conditions, but they provide information about formation trend of I-THM during oxidation of ClO2. Copyright © 2013 Elsevier B.V. All rights reserved.

Application of as-synthesised MCM-41 and MCM-41 wrapped with reduced graphene oxide/graphene oxide in the remediation of acetaminophen and aspirin from aqueous system.

PubMed

Akpotu, Samson O; Moodley, Brenda

2018-03-01

In this study, ASM41 (as-synthesised MCM-41), MCM-41, MCM-41 encapsulated with graphene oxide (MCM-41-GO) and reduced graphene oxide (MCM-41-G) were fabricated and utilized in the remediation of acetaminophen and aspirin from water. A surfactant template (cetyltrimethylammonium bromide) was added to ASM41 to make it more hydrophobic and its effects on the remediation of acetaminophen and aspirin from wastewater was studied. To further improve the adsorption capacity of the adsorbent, MCM-41 was encapsulated with GO and G which also aided in easy separation of the adsorbent from the aqueous solution. Comparative studies of the adsorption of acetaminophen and aspirin on all four adsorbents were investigated. Batch adsorption studies of acetaminophen and aspirin were carried out to determine the effects of pH, initial concentration, time and adsorbent dose. Adsorption mechanism was through EDA, π-π interactions, and hydrophobic effects. Data from sorption kinetics showed ASM41 had the highest q m value for aspirin (909.1 mg/g) and MCM-41-G had the highest q m value for acetaminophen (555.6 mg/g). The significant adsorption by ASM41 can be attributed to increased hydrophobicity due to the retention of the surfactant template. Thermodynamic studies revealed the adsorption process as spontaneous and exothermic. Desorption studies revealed that adsorbents could be regenerated and reused for adsorption. Copyright © 2017 Elsevier Ltd. All rights reserved.

In-situ determination of the oxidation state of iron in Fe-bearing silicate melts

NASA Astrophysics Data System (ADS)

Courtial, P.; Wilke, M.; Potuzak, M.; Dingwell, D. B.

2005-12-01

Terrestrial lavas commonly contain up to 10 wt% of iron. Furthermore, rocks returned from the Moon indicate lunar lava containing up to 25 wt% of iron and planetary scientists estimated that the martian mantle has about 18 wt% of iron. An experimental challenge in dealing with Fe-bearing silicate melts is that the oxidation state, controlling the proportions of ferric and ferrous iron, is a function of composition, oxygen fugacity and temperature and may vary significantly. Further complications concerning iron originate from its potential to be either four-, six- or even five-fold coordinated in both valence states. Therefore, the oxidation state of iron was determined in air for various Fe-bearing silicate melts. Investigated samples were Na-disilicate (NS), one atmosphere anorthite-diopside eutectic (AD) and haplogranitic (HPG8) melts containing up to 20, 20 and 10 wt% of iron, respectively. XANES spectra at the Fe K-edge were collected for all the melts at beamline A1, HASYLAB, Hamburg, using a Si(111) 4-crystal monochromator. Spectra were collected for temperatures up to 1573 K using a Pt-Rh loop as heating device. The Fe oxidation state was determined from the centroid position of the pre-edge feature using the calibration of Wilke et al. (2004). XANES results suggest that oxidation state of iron does not change within error for NS melts with addition of Fe, while AD and HPG8 melts become more oxidised with increasing iron content. Furthermore, NS melts are well more oxidised than AD and HPG8 melts that exhibit relatively similar oxidation states for identical iron contents. The oxidation state of iron for NS melts appears to be slightly temperature-dependent within the temperature range investigated (1073-1573 K). However, this trend is stronger for AD and HPG8 melts. Assuming that glass reflects a picture of the homogeneous equilibria of the melt, the present in-situ Fe-oxidation states determined for these melts were compared to those obtained on quenched glasses from different temperatures, when possible, using wet-chemical analysis (i.e., K-dichromate potentiometry). Both datasets agree reasonably well (within 10 %). References: Wilke et al. (2004) Chemical Geology, 213, 71-87.

Nickel L-edge and K-edge X-ray absorption spectroscopy of non-innocent Ni[S₂C₂(CF₃)₂]₂(n) series (n = -2, -1, 0): direct probe of nickel fractional oxidation state changes.

PubMed

Gu, Weiwei; Wang, Hongxin; Wang, Kun

2014-05-07

A series of nickel dithiolene complexes Ni[S2C2(CF3)2]2(n) (n = -2, -1, 0) has been investigated using Ni L- and K-edge X-ray absorption spectroscopy (XAS). The L3 centroid shifts about 0.3 eV for a change of one unit in the formal oxidation state (or 0.3 eV per oxi), corresponding to ~33% of the shift for Ni oxides or fluorides (about 0.9 eV per oxi). The K-edge XAS edge position shifts about 0.7 eV per oxi, corresponding to ~38% of that for Ni oxides (1.85 eV per oxi). In addition, Ni L sum rule analysis found the Ni(3d) ionicity in the frontier orbitals being 50.5%, 44.0% and 38.5% respectively (for n = -2, -1, 0), in comparison with their formal oxidation states (of Ni(II), Ni(III), and Ni(IV)). For the first time, direct and quantitative measurement of the Ni fractional oxidation state changes becomes possible for Ni dithiolene complexes, illustrating the power of L-edge XAS and L sum rule analysis in such a study. The Ni L-edge and K-edge XAS can be used in a complementary manner to better assess the oxidation states for Ni.

BCL-2 inhibition targets oxidative phosphorylation and selectively eradicates quiescent human leukemia stem cells

PubMed Central

Lagadinou, Eleni D.; Sach, Alexander; Callahan, Kevin; Rossi, Randall M.; Neering, Sarah J.; Minhajuddin, Mohammad; Ashton, John M.; Pei, Shanshan; Grose, Valerie; O’Dwyer, Kristen M.; Liesveld, Jane L.; Brookes, Paul S.; Becker, Michael W.; Jordan, Craig T.

2013-01-01

Summary Most forms of chemotherapy employ mechanisms involving induction of oxidative stress, a strategy that can be effective due to the elevated oxidative state commonly observed in cancer cells. However, recent studies have shown that relative redox levels in primary tumors can be heterogeneous, suggesting that regimens dependent on differential oxidative state may not be uniformly effective. To investigate this issue in hematological malignancies, we evaluated mechanisms controlling oxidative state in primary specimens derived from acute myelogenous leukemia (AML) patients. Our studies demonstrate three striking findings. First, the majority of functionally-defined leukemia stem cells (LSCs) are characterized by relatively low levels of reactive oxygen species (termed “ROS-low”). Second, ROS-low LSCs aberrantly over-express BCL-2. Third, BCL-2 inhibition reduced oxidative phosphorylation and selectively eradicated quiescent LSCs. Based on these findings, we propose a model wherein the unique physiology of ROS-low LSCs provides an opportunity for selective targeting via disruption of BCL-2-dependent oxidative phosphorylation. PMID:23333149

Mechanistic Investigations of Water Oxidation by a Molecular Cobalt Oxide Analogue: Evidence for a Highly Oxidized Intermediate and Exclusive Terminal Oxo Participation.

PubMed

Nguyen, Andy I; Ziegler, Micah S; Oña-Burgos, Pascual; Sturzbecher-Hohne, Manuel; Kim, Wooyul; Bellone, Donatela E; Tilley, T Don

2015-10-14

Artificial photosynthesis (AP) promises to replace society's dependence on fossil energy resources via conversion of sunlight into sustainable, carbon-neutral fuels. However, large-scale AP implementation remains impeded by a dearth of cheap, efficient catalysts for the oxygen evolution reaction (OER). Cobalt oxide materials can catalyze the OER and are potentially scalable due to the abundance of cobalt in the Earth's crust; unfortunately, the activity of these materials is insufficient for practical AP implementation. Attempts to improve cobalt oxide's activity have been stymied by limited mechanistic understanding that stems from the inherent difficulty of characterizing structure and reactivity at surfaces of heterogeneous materials. While previous studies on cobalt oxide revealed the intermediacy of the unusual Co(IV) oxidation state, much remains unknown, including whether bridging or terminal oxo ligands form O2 and what the relevant oxidation states are. We have addressed these issues by employing a homogeneous model for cobalt oxide, the [Co(III)4] cubane (Co4O4(OAc)4py4, py = pyridine, OAc = acetate), that can be oxidized to the [Co(IV)Co(III)3] state. Upon addition of 1 equiv of sodium hydroxide, the [Co(III)4] cubane is regenerated with stoichiometric formation of O2. Oxygen isotopic labeling experiments demonstrate that the cubane core remains intact during this stoichiometric OER, implying that terminal oxo ligands are responsible for forming O2. The OER is also examined with stopped-flow UV-visible spectroscopy, and its kinetic behavior is modeled, to surprisingly reveal that O2 formation requires disproportionation of the [Co(IV)Co(III)3] state to generate an even higher oxidation state, formally [Co(V)Co(III)3] or [Co(IV)2Co(III)2]. The mechanistic understanding provided by these results should accelerate the development of OER catalysts leading to increasingly efficient AP systems.

Numerical analysis on effect of aspect ratio of planar solid oxide fuel cell fueled with decomposed ammonia

NASA Astrophysics Data System (ADS)

Tan, Wee Choon; Iwai, Hiroshi; Kishimoto, Masashi; Brus, Grzegorz; Szmyd, Janusz S.; Yoshida, Hideo

2018-04-01

Planar solid oxide fuel cells (SOFCs) with decomposed ammonia are numerically studied to investigate the effect of the cell aspect ratio. The ammonia decomposer is assumed to be located next to the SOFCs, and the heat required for the endothermic decomposition reaction is supplied by the thermal radiation from the SOFCs. Cells with aspect ratios (ratios of the streamwise length to the spanwise width) between 0.130 and 7.68 are provided with the reactants at a constant mass flow rate. A parametric study is conducted by varying the cell temperature and fuel utility factor to investigate their effects on the cell performance in terms of the voltage efficiency. The effect of the heat supply to the ammonia decomposer is also studied. The developed model shows good agreement, in terms of the current-voltage curve, with the experimental data obtained from a short stack without parameter tuning. The simulation study reveals that the cell with the highest aspect ratio achieves the highest performance under furnace operation. On the other hand, the 0.750 aspect ratio cell with the highest voltage efficiency of 0.67 is capable of thermally sustaining the ammonia decomposers at a fuel utility of 0.80 using the thermal radiation from both sidewalls.

Active three-way catalysis of rhodium particles with a low oxidation state maintained under an oxidative atmosphere on a La-containing ZrO2 support.

PubMed

Kawabata, Hisaya; Koda, Yuki; Sumida, Hirosuke; Shigetsu, Masahiko; Takami, Akihide; Inumaru, Kei

2013-05-11

Rhodium on a La-containing ZrO2 support effectively eliminated NOx from a synthetic auto exhaust gas under fluctuating oxygen conditions. Rhodium particles maintained a low oxidation state on the ZrO2-La2O3 mixed oxide even after treatment with 5% O2 at 773 K, highlighting the significant effect of the La addition.

Molecular beam epitaxy growth of niobium oxides by solid/liquid state oxygen source and lithium assisted metal-halide chemistry

NASA Astrophysics Data System (ADS)

Tellekamp, M. Brooks; Greenlee, Jordan D.; Shank, Joshua C.; Doolittle, W. Alan

2015-09-01

In order to consistently grow high quality niobium oxides and lithium niobium oxides, a novel solid/liquid state oxygen source, LiClO4, has been implemented in a molecular beam epitaxy (MBE) system. LiClO4 is shown to decompose into both molecular and atomic oxygen upon heating. This allows oxidation rates similar to that of molecular oxygen but at a reduced overall beam flux, quantified by in situ Auger analysis. LiClO4 operation is decomposition limited to less than 400 °C, and other material limitations are identified. The design of a custom near-ambient NbCl5 effusion cell is presented, which improves both short and long term stability. Films of Nb oxidation state +2, +3, and +5 are grown using these new tools, including the multi-functional sub-oxide LiNbO2.

Unified computational model of transport in metal-insulating oxide-metal systems

NASA Astrophysics Data System (ADS)

Tierney, B. D.; Hjalmarson, H. P.; Jacobs-Gedrim, R. B.; Agarwal, Sapan; James, C. D.; Marinella, M. J.

2018-04-01

A unified physics-based model of electron transport in metal-insulator-metal (MIM) systems is presented. In this model, transport through metal-oxide interfaces occurs by electron tunneling between the metal electrodes and oxide defect states. Transport in the oxide bulk is dominated by hopping, modeled as a series of tunneling events that alter the electron occupancy of defect states. Electron transport in the oxide conduction band is treated by the drift-diffusion formalism and defect chemistry reactions link all the various transport mechanisms. It is shown that the current-limiting effect of the interface band offsets is a function of the defect vacancy concentration. These results provide insight into the underlying physical mechanisms of leakage currents in oxide-based capacitors and steady-state electron transport in resistive random access memory (ReRAM) MIM devices. Finally, an explanation of ReRAM bipolar switching behavior based on these results is proposed.

Differentiation of Sclerotinia minor depends on thiol redox state and oxidative stress.

PubMed

Patsoukis, Nikolaos; Georgiou, Christos D

2008-01-01

Sclerotial differentiation in Sclerotinia minor is associated with oxidative stress and thiol redox state. The significance of oxidative stress to sclerotial differentiation was revealed by the higher oxidative stress of S. minor compared with a nonsclerotiogenic counterpart. The effect of thiol redox state on sclerotial differentiation was shown by the antioxidant action of the thiol (-SH) group of N-acetylcysteine and cysteine and by an unknown (not antioxidant) role of glutathione (GSH) on S. minor. The nonantioxidant role of GSH was indicated by the differentiation-inhibiting and differentiation-noninhibiting actions of the GSH biosynthesis inhibitor L-buthionine-S,R-sulfoximine and the GSH biosynthesis inducer L-2-oxo-thiazolidine-4-carboxylate, respectively, and by the increase of oxidative stress they caused during the transition from the undifferentiated to differentiated state of S. minor. Moreover, N-acetylcysteine can be used as a potent nontoxic fungicide against this phytopathogenic fungus by acting as a growth-inhibiting cytotoxic oxidant and by sustaining the fungus in the undifferentiated hyphal stage, which is vulnerable to degradation by soil microorganisms.

Formation and aging of secondary organic aerosol from toluene: Changes in chemical composition, volatility, and hygroscopicity

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

Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K. M.

Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NO x under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OS c), and mass yield. The OA oxidation state generallymore » increased during photo-oxidation, and the final OA OS c ranged from –0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. In conclusion, there was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less

Formation and aging of secondary organic aerosol from toluene: Changes in chemical composition, volatility, and hygroscopicity

DOE PAGES

Hildebrandt Ruiz, L.; Paciga, A. L.; Cerully, K. M.; ...

2015-07-24

Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NO x under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OS c), and mass yield. The OA oxidation state generallymore » increased during photo-oxidation, and the final OA OS c ranged from –0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. In conclusion, there was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less

Iridium Oxide pH Sensor Based on Stainless Steel Wire for pH Mapping on Metal Surface

NASA Astrophysics Data System (ADS)

Shahrestani, S.; Ismail, M. C.; Kakooei, S.; Beheshti, M.; Zabihiazadboni, M.; Zavareh, M. A.

2018-03-01

A simple technique to fabricate the iridium oxide pH sensor is useful in several applications such as medical, food processing and engineering material where it is able to detect the changes of pH. Generally, the fabrication technique can be classified into three types: electro-deposition iridium oxide film (EIrOF), activated iridium oxide film (AIROF) and sputtering iridium oxide film (SIROF). This study focuses on fabricating electrode, calibration and test. Electro-deposition iridium oxide film is a simple and effective method of fabricating this kind of sensor via cyclic voltammetry process. The iridium oxide thick film was successfully electrodeposited on the surface of stainless steel wire with 500 cycles of sweep potential. A further analysis under FESEM shows detailed image of iridium oxide film which has cauliflower-liked microstructure. EDX analysis shows the highest element present are iridium and oxygen which concluded that the process is successful. The iridium oxide based pH sensor has shown a good performance in comparison to conventional glass pH sensor when it is being calibrated in buffer solutions with 2, 4, 7 and 9 pH values. The iridium oxide pH sensor is specifically designed to measure the pH on the surface of metal plate.

Transition state-finding strategies for use with the growing string method.

PubMed

Goodrow, Anthony; Bell, Alexis T; Head-Gordon, Martin

2009-06-28

Efficient identification of transition states is important for understanding reaction mechanisms. Most transition state search algorithms require long computational times and a good estimate of the transition state structure in order to converge, particularly for complex reaction systems. The growing string method (GSM) [B. Peters et al., J. Chem. Phys. 120, 7877 (2004)] does not require an initial guess of the transition state; however, the calculation is still computationally intensive due to repeated calls to the quantum mechanics code. Recent modifications to the GSM [A. Goodrow et al., J. Chem. Phys. 129, 174109 (2008)] have reduced the total computational time for converging to a transition state by a factor of 2 to 3. In this work, three transition state-finding strategies have been developed to complement the speedup of the modified-GSM: (1) a hybrid strategy, (2) an energy-weighted strategy, and (3) a substring strategy. The hybrid strategy initiates the string calculation at a low level of theory (HF/STO-3G), which is then refined at a higher level of theory (B3LYP/6-31G(*)). The energy-weighted strategy spaces points along the reaction pathway based on the energy at those points, leading to a higher density of points where the energy is highest and finer resolution of the transition state. The substring strategy is similar to the hybrid strategy, but only a portion of the low-level string is refined using a higher level of theory. These three strategies have been used with the modified-GSM and are compared in three reactions: alanine dipeptide isomerization, H-abstraction in methanol oxidation on VO(x)/SiO(2) catalysts, and C-H bond activation in the oxidative carbonylation of toluene to p-toluic acid on Rh(CO)(2)(TFA)(3) catalysts. In each of these examples, the substring strategy was proved most effective by obtaining a better estimate of the transition state structure and reducing the total computational time by a factor of 2 to 3 compared to the modified-GSM. The applicability of the substring strategy has been extended to three additional examples: cyclopropane rearrangement to propylene, isomerization of methylcyclopropane to four different stereoisomers, and the bimolecular Diels-Alder condensation of 1,3-butadiene and ethylene to cyclohexene. Thus, the substring strategy used in combination with the modified-GSM has been demonstrated to be an efficient transition state-finding strategy for a wide range of types of reactions.

Semiconducting large bandgap oxides as potential thermoelectric materials for high-temperature power generation?

NASA Astrophysics Data System (ADS)

Backhaus-Ricoult, M.; Rustad, J.; Moore, L.; Smith, C.; Brown, J.

2014-08-01

Semiconducting large bandgap oxides are considered as interesting candidates for high-temperature thermoelectric power generation (700-1,200 °C) due to their stability, lack of toxicity and low cost, but so far they have not reached sufficient performance for extended application. In this review, we summarize recent progress on thermoelectric oxides, analyze concepts for tuning semiconductor thermoelectric properties with view of their applicability to oxides and determine key drivers and limitations for electrical and thermal transport properties in oxides based on our own experimental work and literature results. For our experimental assessment, we have selected representative multicomponent oxides that range from materials with highly symmetric crystal structure (SrTiO3 perovskite) over oxides with large densities of planar crystallographic defects (Ti n O2 n-1 Magnéli phases with a single type of shear plane, NbO x block structures with intersecting shear planes and WO3- x with more defective block and channel structures) to layered superstructures (Ca3Co4O9 and double perovskites) and also include a wide range of their composites with a variety of second phases. Crystallographic or microstructural features of these oxides are in 0.3-2 nm size range, so that oxide phonons can efficiently interact with them. We explore in our experiments the effects of doping, grain size, crystallographic defects, superstructures, second phases, texturing and (to a limited extend) processing on electric conductivity, Seebeck coefficient, thermal conductivity and figure of merit. Jonker and lattice-versus-electrical conductivity plots are used to compare specific materials and material families and extract levers for future improvement of oxide thermoelectrics. We show in our work that oxygen vacancy doping (reduction) is a more powerful driver for improving the power factor for SrTiO3, TiO2 and NbO x than heterovalent doping. Based on our Seebeck-conductivity plots, we derived a set of highest achievable power factors. We met these best values in our own experiments for our titanium oxide- and niobium oxide-based materials. For strontium titanate-based materials, the estimated highest power factor was not reached; further material improvement is possible and can be reached for materials with higher carrier densities. Our results show that periodic crystallographic defects and superstructures are most efficient in reducing the lattice thermal conductivity in oxides, followed by hetero- and homovalent doping. Due to the small phonon mean free path in oxides, grain boundary scattering in nanoceramics or materials with nanodispersions is much less efficient. We investigated the impact of texturing in Ca3Co4O9 ceramics on thermoelectric performance; we did not find any improvement in the overall in-plane performance of a textured ceramic compared to the corresponding random ceramic.

Atomic solid state energy scale: Universality and periodic trends in oxidation state

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

Pelatt, Brian D.; Kokenyesi, Robert S.; Ravichandran, Ram

2015-11-15

The atomic solid state energy (SSE) scale originates from a plot of the electron affinity (EA) and ionization potential (IP) versus band gap (E{sub G}). SSE is estimated for a given atom by assessing an average EA (for a cation) or an average IP (for an anion) for binary inorganic compounds having that specific atom as a constituent. Physically, SSE is an experimentally-derived average frontier orbital energy referenced to the vacuum level. In its original formulation, 69 binary closed-shell inorganic semiconductors and insulators were employed as a database, providing SSE estimates for 40 elements. In this contribution, EA and IPmore » versus E{sub G} are plotted for an additional 92 compounds, thus yielding SSE estimates for a total of 64 elements from the s-, p-, d-, and f-blocks of the periodic table. Additionally, SSE is refined to account for its dependence on oxidation state. Although most cations within the SSE database are found to occur in a single oxidation state, data are available for nine d-block transition metals and one p-block main group metal in more than one oxidation state. SSE is deeper in energy for a higher cation oxidation state. Two p-block main group non-metals within the SSE database are found to exist in both positive and negative oxidation states so that they can function as a cation or anion. SSEs for most cations are positioned above −4.5 eV with respect to the vacuum level, and SSEs for all anions are positioned below. Hence, the energy −4.5 eV, equal to the hydrogen donor/acceptor ionization energy ε(+/−) or equivalently the standard hydrogen electrode energy, is considered to be an absolute energy reference for chemical bonding in the solid state. - Highlights: • Atomic solid-state energies are estimated for 64 elements from experimental data. • The relationship between atomic SSEs and oxidation state is assessed. • Cations are positioned above and absolute energy of −4.5 eV and anions below.« less

MnO2-Graphene Oxide-PEDOT:PSS Nanocomposite for an Electrochemical Supercapacitor

NASA Astrophysics Data System (ADS)

Patil, Dipali S.; Pawar, Sachin A.; Shin, Jae Cheol; Kim, Hyo Jin

2018-04-01

A ternary nanocomposite with poly (3,4 ethylene dioxythiophene:poly(styrene sulfonate) (PEDOT:PSS)-MnO2 nanowires-graphene oxide (PMn-GO) was synthesized by using simple chemical route. The formation of the nanocomposite was analyzed by using X-ray diffraction and X-ray photoelectron spectroscopy. Field-emission scanning microscopy (FESEM) revealed the formation of MnO2 nanowires and graphene oxide nanosheets. The highest specific capacitance (areal capacitance) of 841 Fg -1 (177 mFcm -2) at 10 mVs -1 and energy density of 0.593 kWhkg -1 at 0.5 mA were observed for PMn-GO, indicating a constructive synergistic effect of PEDOT:PSS, MnO2 nanowires and graphene oxide. The achieved promising electrochemical characteristics showed that this ternary nanocomposite is a good alternative as an electrode material for supercapacitor.

Incorporation of polydimethylsiloxane with reduced graphene oxide and zinc oxide for tensile and electrical properties

NASA Astrophysics Data System (ADS)

Danial, N. S.; Ramli, Muhammad. M.; Halin, D. S. C.; Hong, H. C.; Isa, S. Salwa M.; Abdullah, M. M. A. B.; Anhar, N. A. M.; Talip, L. F. A.; Mazlan, N. S.

2017-09-01

Polydimethylsiloxane (PDMS) is an organosilicon polymer that is commonly used to incorporate with other fillers. PDMS in high viscous liquid form is mechanically stirred with reduced graphene oxide (rGO) and mixed with zinc oxide (ZnO) with specific ratio, thus rendering into two types of samples. The mechanical and electrical properties of both samples are characterized. The result shows that PDMS sample with 50 mg rGO has the highest tensile strength with the value of 9.1 MPa. For electrical properties, sample with the lowest resistance is PDMS with 50 mg rGO and ZnO with the value of l.67×l05 Ω. This experiment shows the significant role of conductive fillers like rGO and ZnO incorporated in polymeric material such as PDMS to improve its electrical properties.

Aqueous synthesis of polyhedral “brick-like” iron oxide nanoparticles for hyperthermia and T2 MRI contrast enhancement†

PubMed Central

Worden, Matthew; Bruckman, Michael A.; Kim, Min-Ho; Steinmetz, Nicole F.; Kikkawa, James M.; LaSpina, Catherine

2015-01-01

A low temperature, aqueous synthesis of polyhedral iron oxide nanoparticles (IONPs) is presented. The modification of the co-precipitation hydrolysis method with Triton X surfactants results in the formation of crystalline polyhedral particles. The particles are herein termed iron oxide “nanobricks” (IONBs) as the variety of particles made are all variations on a simple “brick-like” rhombohedral shape as evaluated by TEM. These IONBs can be easily coated with hydrophilic silane ligands, allowing them to be dispersed in aqueous media. The dispersed particles are investigated for potential applications as hyperthermia and T2 MRI contrast agents. The results demonstrate that the IONBs perform better than comparable spherical IONPs in both applications, and show r2 values amongst the highest for iron oxide based materials reported in the literature. PMID:26693011

New Aptes Cross-linked Polymers from Poly(ethylene oxide)s and Cyanuric Chloride for Lithium Batteries

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Meador, Mary Ann B.; Kinder, James D.; Bennett, William R.

2005-01-01

A new series of polymer electrolytes for use as membranes for lithium batteries are described. Electrolytes were made by polymerization between cyanuric chloride and diamino-terminated poly(ethylene oxide)s, followed by cross-linking via a sol-gel process. Thermal analysis and lithium conductivity of freestanding polymer films were studied. The effects of several variables on conductivity were investigated, such as length of backbone PEO chain, length of branching PEO chain, extent of branching, extent of cross-linking, salt content, and salt counterion. Polymer films with the highest percentage of PEO were found to be the most conductive, with a maximum lithium conductivity of 3.9 x 10(exp -5) S/cm at 25 C. Addition of plasticizer to the dry polymers increased conductivity by an order of magnitude.

Stable Isotope and Isotopomeric Constraints on Nitrous Oxide Production in a Wastewater Treatment Plant

NASA Astrophysics Data System (ADS)

Bellucci, F.; Gonzalez-Meler, M. A.; Sturchio, N. C.; Bohlke, J. K.; Ostrom, N. E.; Kozak, J. A.

2011-12-01

Estimates of US anthropogenic greenhouse gas emissions by USEPA (Inventory of U.S. Greenhouse Gas Emissions and Sinks: 1990-2009; 2011) indicate that wastewater treatment plants are the 7th highest contributor to atmospheric nitrous oxide. This unregulated gas has an estimated global warming potential (GWP) 310 times that of carbon dioxide on a per mol basis. There is general agreement that, within wastewater treatment plants, the vast majority of the nitrous oxide emissions occur in the aerobic zones for biological ammonia oxidation and/or downstream from anoxic zones used in biological nitrogen removal. However, the exact mechanism of production is not well understood, as both incomplete nitrification and denitrification might contribute to the overall nitrous oxide emissions. Determining the dominant biological pathways responsible for these emissions is important for the development of improved treatment systems that can reduce nitrous oxide greenhouse gas emissions to the atmosphere. In this study, we determined the total nitrous oxide flux from a single tank of one of the aeration basins from a large metropolitan wastewater treatment plant in Stickney, Illinois. Furthermore, we analyzed the changes in nitrogen and oxigen stable isotopic composition for ammonium, nitrate, and nitrous oxide, as well as the intramolecular site preference (SP) for δ15N within the linear N-N-O molecule, along the 520 meter wastewater flow path within the tank. Assuming the measured tank was representative of the 32 tanks constituting the 4 aeration basins of the plant, we estimate the combined annual nitrous oxide flux from this source to be approximately 230 metric ton/y. The δ15N values for ammonium ranged between +19.9% and +6.4%, those for nitrate ranged between +20.4% and +5.3%, and those for nitrous oxide ranged between -34.4% and 0.4%. The nitrous oxide SP ranged between +11.7% and -4.5%. The concentrations and δ15N values of ammonium and nitrate showed trends along the flow path of the tank that appear to be largely consistent with nitrification. The nitrous oxide SP values averaged near 0% in most samples, with the exception of the area near the inlet, where slightly positive values were measured. These data indicate that nitrification controlled the major features of ammonium and nitrate dynamics and isotopic compositions in the aeration tank, whereas incomplete denitrification may have been the main pathway responsible for nitrous oxide flux emission. Nitrification could have played a minor role in nitrous oxide production in the anoxic area at the reactor inlet. Nitrous oxide emissions were highest in the portion of the tank where dissolved oxygen concentrations were 0.2-2.0 mg/L. Inhibition of the nitrous oxide reductase enzyme by observed levels of dissolved oxygen might contribute to emissions of nitrous oxide from denitrification.

The mitochondrial oxidoreductase CHCHD4 is present in a semi-oxidized state in vivo.

PubMed

Erdogan, Alican J; Ali, Muna; Habich, Markus; Salscheider, Silja L; Schu, Laura; Petrungaro, Carmelina; Thomas, Luke W; Ashcroft, Margaret; Leichert, Lars I; Roma, Leticia Prates; Riemer, Jan

2018-07-01

Disulfide formation in the mitochondrial intermembrane space is an essential process catalyzed by a disulfide relay machinery. In mammalian cells, the key enzyme in this machinery is the oxidoreductase CHCHD4/Mia40. Here, we determined the in vivo CHCHD4 redox state, which is the major determinant of its cellular activity. We found that under basal conditions, endogenous CHCHD4 redox state in cultured cells and mouse tissues was predominantly oxidized, however, degrees of oxidation in different tissues varied from 70% to 90% oxidized. To test whether differences in the ratio between CHCHD4 and ALR might explain tissue-specific differences in the CHCHD4 redox state, we determined the molar ratio of both proteins in different mouse tissues. Surprisingly, ALR is superstoichiometric over CHCHD4 in most tissues. However, the levels of CHCHD4 and the ratio of ALR over CHCHD4 appear to correlate only weakly with the redox state, and although ALR is present in superstoichiometric amounts, it does not lead to fully oxidized CHCHD4. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

Revealing the role of oxidation state in interaction between nitro/amino-derived particulate matter and blood proteins

PubMed Central

Liu, Zhen; Li, Ping; Bian, Weiwei; Yu, Jingkai; Zhan, Jinhua

2016-01-01

Surface oxidation states of ultrafine particulate matter can influence the proinflammatory responses and reactive oxygen species levels in tissue. Surface active species of vehicle-emission soot can serve as electron transfer-mediators in mitochondrion. Revealing the role of surface oxidation state in particles-proteins interaction will promote the understanding on metabolism and toxicity. Here, the surface oxidation state was modeled by nitro/amino ligands on nanoparticles, the interaction with blood proteins were evaluated by capillary electrophoresis quantitatively. The nitro shown larger affinity than amino. On the other hand, the affinity to hemoglobin is 103 times larger than that to BSA. Further, molecular docking indicated the difference of binding intensity were mainly determined by hydrophobic forces and hydrogen bonds. These will deepen the quantitative understanding of protein-nanoparticles interaction from the perspective of surface chemical state. PMID:27181651

Theoretical study of the diatomic alkali and alkaline-earth oxides

NASA Technical Reports Server (NTRS)

Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.

1986-01-01

Theoretical dissociation energies for the ground states of the alkali and alkaline earth oxides are presented that are believed to be accurate to 0.1 eV. The 2 Pi - 2 Sigma + separations for the alkali oxides are found to be more sensitive to basis set than to electron correlation. Predicted 2 Pi ground states for LiO and NaO and 2 Sigma + ground states for RbO and CsO are found to be in agreement with previous theoretical and experimental work. For KO, a 2 Sigma + state is found at both the numerical Hartree-Fock (NHF) level and at the singles plus doubles configuration interaction level using a Slater basis set that is within 0.02 eV of the NHF limit. It is found that an accurate balanced treatment of the two states requires correlating the electrons on both the metal and oxide ion.

The creep properties of dispersion-strengthened silver-gallium oxide alloys.

NASA Technical Reports Server (NTRS)

Lenel, F. V.; Ansell, G. S.; Nazmy, M. Y.

1971-01-01

Steady-state creep rates were measured for two preparations of a dispersion-strengthened alloy of silver with 1 mol % gallium oxide. One preparation, an internally-oxidized type, had a grain size 40 times that of the other preparation, which was a consolidated-powder type of alloy. The temperature and stress dependence of the steady-state creep rate differs widely for the two alloys and must be attributed to the difference in grain size. The activation energy for steady-state creep of the internally-oxidized coarse grained material is near that for self-diffusion of silver, which strongly indicates a creep process controlled by dislocation climb.

Lithium metal oxide electrodes for lithium cells and batteries

DOEpatents

Thackeray, Michael M [Naperville, IL; Johnson, Christopher S [Naperville, IL; Amine, Khalil [Oakbrook, IL

2008-12-23

A lithium metal oxide positive electrode for a non-aqueous lithium cell is disclosed. The cell is prepared in its initial discharged state and has a general formula xLiMO.sub.2.(1-x)Li.sub.2M'O.sub.3 in which 0

Lithium Metal Oxide Electrodes For Lithium Cells And Batteries

DOEpatents

Thackeray, Michael M.; Johnson, Christopher S.; Amine, Khalil; Kim, Jaekook

2004-01-20

A lithium metal oxide positive electrode for a non-aqueous lithium cell is disclosed. The cell is prepared in its initial discharged state and has a general formula xLiMO.sub.2.(1-x)Li.sub.2 M'O.sub.3 in which 0

Lithium metal oxide electrodes for lithium cells and batteries

DOEpatents

Thackeray, Michael M.; Johnson, Christopher S.; Amine, Khalil; Kim, Jaekook

2006-11-14

A lithium metal oxide positive electrode for a non-aqueous lithium cell is disclosed. The cell is prepared in its initial discharged state and has a general formula xLiMO.sub.2.(1-x)Li.sub.2M'O.sub.3 in which 0

Binding of higher alcohols onto Mn(12) single-molecule magnets (SMMs): access to the highest barrier Mn(12) SMM.

PubMed

Lampropoulos, Christos; Redler, Gage; Data, Saiti; Abboud, Khalil A; Hill, Stephen; Christou, George

2010-02-15

Two new members of the Mn(12) family of single-molecule magnets (SMMs), [Mn(12)O(12)(O(2)CCH(2)Bu(t))(16)(Bu(t)OH)(H(2)O)(3)].2Bu(t)OH (3.2Bu(t)OH) and [Mn(12)O(12)(O(2)CCH(2)Bu(t))(16)(C(5)H(11)OH)(4)] (4) (C(5)H(11)OH is 1-pentanol), are reported. They were synthesized from [Mn(12)O(12)(O(2)CMe)(16)(H(2)O)(4)].2MeCO(2)H.4H(2)O (1) by carboxylate substitution and crystallization from the appropriate alcohol-containing solvent. Complexes 3 and 4 are new members of the recently established [Mn(12)O(12)(O(2)CCH(2)Bu(t))(16)(solv)(4)] (solv = H(2)O, alcohols) family of SMMs. Only one bulky Bu(t)OH can be accommodated into 3, and even this causes significant distortion of the [Mn(12)O(12)] core. Variable-temperature, solid-state alternating current (AC) magnetization studies were carried out on complexes 3 and 4, and they established that both possess an S = 10 ground state spin and are SMMs. However, the magnetic behavior of the two compounds was found to be significantly different, with 4 showing out-of-phase AC peaks at higher temperatures than 3. High-frequency electron paramagnetic resonance (HFEPR) studies were carried out on single crystals of 3.2Bu(t)OH and 4, and these revealed that the axial zero-field splitting constant, D, is very different for the two compounds. Furthermore, it was established that 4 is the Mn(12) SMM with the highest kinetic barrier (U(eff)) to date. The results reveal alcohol substitution as an additional and convenient means to affect the magnetization relaxation barrier of the Mn(12) SMMs without major change to the ligation or oxidation state.

Thermochemistry of rare earth doped uranium oxides LnxU1-xO2-0.5x+y (Ln = La, Y, Nd)

NASA Astrophysics Data System (ADS)

Zhang, Lei; Navrotsky, Alexandra

2015-10-01

Lanthanum, yttrium, and neodymium doped uranium dioxide samples in the fluorite structure have been synthesized, characterized in terms of metal ratio and oxygen content, and their enthalpies of formation measured by high temperature oxide melt solution calorimetry. For oxides doped with 10-50 mol % rare earth (Ln) cations, the formation enthalpies from constituent oxides (LnO1.5, UO2 and UO3 in a reaction not involving oxidation or reduction) become increasingly exothermic with increasing rare earth content, while showing no significant dependence on the varying uranium oxidation state. The oxidation enthalpy of LnxU1-xO2-0.5x+y is similar to that of UO2 to UO3 for all three rare earth doped systems. Though this may suggest that the oxidized uranium in these systems is energetically similar to that in the hexavalent state, thermochemical data alone can not constrain whether the uranium is present as U5+, U6+, or a mixture of oxidation states. The formation enthalpies from elements calculated from the calorimetric data are generally consistent with those from free energy measurements.

Characterization of copper oxides, iron oxides, and zinc copper ferrite desulfurization sorbents by X-ray photoelectron spectroscopy and scanning electron microscopy

NASA Astrophysics Data System (ADS)

Siriwardane, Ranjani V.; Poston, James A.

1993-05-01

Characterization of copper oxides, iron oxides, and zinc copper ferrite desulfurization sorbents was performed by X-ray photoelectron spectroscopy and scanning electron microscopy/energy-dispersive spectroscopy at temperatures of 298 to 823 K. Analysis of copper oxides indicated that the satellite structure of the Cu22p region was absent in the Cu(I) state but was present in the Cu(II) state. Reduction of CuO at room temperature was observed when the ion gauge was placed close to the sample. The satellite structure was absent in all the copper oxides at 823 K in vacuum. Differentiation of the oxidation state of copper utilizing both Cu(L 3M 4,5M 4,5) X-ray-induced Auger lines and Cu2p satellite structure, indicated that the copper in zinc copper ferrite was in the + 1 oxidation state at 823 K. This + 1 state of copper was not significantly changed after exposure to H 2, CO, and H 2O. There was an increase in Cu/Zn ratio and a decrease in Fe/Zn ratio on the surface of zinc copper ferrite at 823 K compared to that at room temperature. These conditions of copper offered the best sulfidation equilibrium for the zinc copper ferrite desulfurization sorbent. Analysis of iron oxides indicated that there was some reduction of both Fe 2O 3 and FeO at 823K. The iron in zinc copper ferrite was similar to that of Fe 2O 3 at room temperature but there was some reduction of this Fe(III) state to Fe(II) at 823 K. This reduction was more enhanced in the presence of H 2 and CO. Reduction to Fe(II) may not be desirable for the lifetime of the sorbent.

The role of lager beer yeast in oxidative stability of model beer.

PubMed

Berner, T S; Arneborg, N

2012-03-01

In this study, we investigated the relationship between the ability of lager brewing yeast strains to tolerate oxidative stress and their ability to produce oxidative stable model beer. Screening of 21 lager brewing yeast strains against diamide and paraquat showed that the oxidative stress resistance was strain dependent. Fermentation of model wort in European Brewing Convention tubes using three yeast strains with varying oxidative stress resistances resulted in three model beers with different rates of radical formation as measured by electron spin resonance in forced ageing experiments. Interestingly, the strain with the lowest oxidative stress resistance and lowest secretion of thioredoxin, as measured by Western blotting, resulted in the highest uptake of iron, as measured by inductively coupled plasma-mass spectrometry, and the slowest formation of radicals in the model beers. A more oxidative stable beer is not obtained by a more-oxidative-stress-tolerant lager brewing yeast strain, exhibiting a higher secretion of thioredoxin, but rather by a less-oxidative-stress-tolerant strain, exhibiting a higher iron uptake. To obtain lager beers with enhanced oxidative stability, yeast strains should be screened for their low oxidative stress tolerance and/or high ability to take up iron rather than for their high oxidative stress tolerance and/or high ability to secrete thioredoxin. © 2011 The Authors. Letters in Applied Microbiology © 2011 The Society for Applied Microbiology.

Fatty Acid Composition as a Predictor for the Oxidation Stability of Korean Vegetable Oils with or without Induced Oxidative Stress

PubMed Central

Yun, Jung-Mi; Surh, Jeonghee

2012-01-01

This study was designed to investigate whether the fatty acid composition could make a significant contribution to the oxidation stability of vegetable oils marketed in Korea. Ten kinds, 97 items of vegetable oils that were produced in either an industrialized or a traditional way were collected and analyzed for their fatty acid compositions and lipid oxidation products, in the absence or presence of oxidative stress. Peroxidability index (PI) calculations based on the fatty acid composition ranged from 7.10 to 111.87 with the lowest value found in olive oils and the highest in perilla oils. In the absence of induced oxidative stress, malondialdehyde (MDA), the secondary lipid oxidation product, was generated more in the oils with higher PI (r=0.890), while the tendency was not observed when the oils were subjected to an oxidation-accelerating system. In the presence of the oxidative stress, the perilla oils produced in an industrialized manner generated appreciably higher amounts of MDA than those produced in a traditional way, although both types of oils presented similar PIs. The results implicate that the fatty acid compositions could be a predictor for the oxidation stability of the vegetable oils at the early stage of oil oxidation, but not for those at a later stage of oxidation. PMID:24471078

Mn K-Edge XANES and Kβ XES Studies of Two Mn–Oxo Binuclear Complexes: Investigation of Three Different Oxidation States Relevant to the Oxygen-Evolving Complex of Photosystem II

PubMed Central

Visser, Hendrik; Anxolabéhère-Mallart, Elodie; Bergmann, Uwe; Glatzel, Pieter; Robblee, John H.; Cramer, Stephen P.; Girerd, Jean-Jacques; Sauer, Kenneth; Klein, Melvin P.; Yachandra, Vittal K.

2014-01-01

Two structurally homologous Mn compounds in different oxidation states were studied to investigate the relative influence of oxidation state and ligand environment on Mn K-edge X-ray absorption near-edge structure (XANES) and Mn Kβ X-ray emission spectroscopy (Kβ XES). The two manganese compounds are the di-μ-oxo compound [L′2MnIIIO2MnIVL′2](ClO4)3, where L′ is 1,10-phenanthroline (Cooper, S. R.; Calvin, M. J. Am. Chem. Soc. 1977, 99, 6623–6630) and the linear mono-μ-oxo compound [LMnIIIOMnIIIL](ClO4)2, where L− is the monoanionic N,N-bis(2-pyridylmethyl)-N′-salicylidene-1,2-diaminoethane ligand (Horner, O.; Anxolabéhère-Mallart, E.; Charlot, M. F.; Tchertanov, L.; Guilhem, J.; Mattioli, T. A.; Boussac, A.; Girerd, J.-J. Inorg. Chem. 1999, 38, 1222–1232). Preparative bulk electrolysis in acetonitrile was used to obtain higher oxidation states of the compounds: the MnIVMnIV species for the di-μ-oxo compound and the MnIIIMnIV and MnIVMnIV species for the mono-μ-oxo compound. IR, UV/vis, EPR, and EXAFS spectra were used to determine the purity and integrity of the various sample solutions. The Mn K-edge XANES spectra shift to higher energy upon oxidation when the ligand environment remains similar. However, shifts in energy are also observed when only the ligand environment is altered. This is achieved by comparing the di-μ-oxo and linear mono-μ-oxo Mn–Mn moieties in equivalent oxidation states, which represent major structural changes. The magnitude of an energy shift due to major changes in ligand environment can be as large as that of an oxidation-state change. Therefore, care must be exercised when correlating the Mn K-edge energies to manganese oxidation states without taking into account the nature of the ligand environment and the overall structure of the compound. In contrast to Mn K-edge XANES, Kβ XES spectra show less dependence on ligand environment. The Kβ1,3 peak energies are comparable for the di-μ-oxo and mono-μ-oxo compounds in equivalent oxidation states. The energy shifts observed due to oxidation are also similar for the two different compounds. The study of the different behavior of the XANES pre-edge and main-edge features in conjunction with Kβ XES provides significant information about the oxidation state and character of the ligand environment of manganese atoms. PMID:11459481

Rare earth element partitioning between hydrous ferric oxides and acid mine water during iron oxidation

USGS Publications Warehouse

Verplanck, P.L.; Nordstrom, D. Kirk; Taylor, Howard E.; Kimball, B.A.

2004-01-01

Ferrous iron rapidly oxidizes to Fe (III) and precipitates as hydrous Fe (III) oxides in acid mine waters. This study examines the effect of Fe precipitation on the rare earth element (REE) geochemistry of acid mine waters to determine the pH range over which REEs behave conservatively and the range over which attenuation and fractionation occur. Two field studies were designed to investigate REE attenuation during Fe oxidation in acidic, alpine surface waters. To complement these field studies, a suite of six acid mine waters with a pH range from 1.6 to 6.1 were collected and allowed to oxidize in the laboratory at ambient conditions to determine the partitioning of REEs during Fe oxidation and precipitation. Results from field experiments document that even with substantial Fe oxidation, the REEs remain dissolved in acid, sulfate waters with pH below 5.1. Between pH 5.1 and 6.6 the REEs partitioned to the solid phases in the water column, and heavy REEs were preferentially removed compared to light REEs. Laboratory experiments corroborated field data with the most solid-phase partitioning occurring in the waters with the highest pH. ?? 2004 Elsevier Ltd. All rights reserved.

Effect of support size on the catalytic activity of metal-oxide-doped silica particles in the glycolysis of polyethylene terephthalate.

PubMed

Wi, Rinbok; Imran, Muhammad; Lee, Kyoung G; Yoon, Sun Hong; Cho, Bong Gyoo; Kim, Do Hyun

2011-07-01

Zinc oxide (ZnO) and cerium oxide (CeO2) nanoparticles were deposited on the surface of preformed silica spheres with diameters ranging from 60 to 750 nm. Ultrasonic irradiation was employed to promote the deposition of the metal oxide nanoparticles on the surface of silica. Silica-supported zinc oxide or cerium oxide was used as a catalyst in the glycolysis of polyethylene terephthalate, one of the key processes in the depolymerization of polyethylene terephthalate. The effect of the support size on the catalytic activity was studied in terms of monomer yield, and the monomer concentration was analyzed via high-performance liquid chromatography (HPLC). The morphologies and surface properties of the catalysts were characterized using a scanning electron microscope, a transmission electron microscope, and a BET surface area analyzer, while the monomer was characterized via HPLC and nuclear-magnetic-resonance spectroscopy. Both the zinc oxide and cerium oxide deposited on a smaller support showed better distribution and less aggregation. The high specific surface area of the smaller support catalysts provided a large number of active sites. The highest monomer yield was obtained with a catalyst of 60-nm silica support.

Health Spending by State of Residence, 1991–2009

PubMed Central

Cuckler, Gigi; Martin, Anne; Whittle, Lekha; Heffler, Stephen; Sisko, Andrea; Lassman, Dave; Benson, Joseph

2011-01-01

Objective Provide a detailed discussion of baseline health spending by state of residence (per capita personal health care spending, per enrollee Medicare spending, and per enrollee Medicaid spending) in 2009, over the last decade (1998–2009), as well as the differential regional and state impacts of the recent recession. Data Source State Health Expenditures by State of Residence for 1991–2009, produced by the Centers for Medicare & Medicaid Services' Office of the Actuary. Principal Findings In 2009, the 10 states where per capita spending was highest ranged from 13 to 36 percent higher than the national average, and the 10 states where per capita spending was lowest ranged from 8 to 26 percent below the national average. States with the highest per capita spending tended to have older populations and the highest per capita incomes; states with the lowest per capita spending tended to have younger populations, lower per capita incomes, and higher rates of uninsured. Over the last decade, the New England and Mideast regions exhibited the highest per capita personal health care spending, while states in the Southwest and Rocky Mountain regions had the lowest per capita spending. Variation in per enrollee Medicaid spending, however, has consistently been greater than that of total per capita personal health care spending or per enrollee Medicare spending from 1998–2009. The Great Lakes, New England, and Far West regions experienced the largest slowdown in per person health spending growth during the recent recession, largely as a result of higher unemployment rates. PMID:22340779

Investigating the effects of nitrous oxide sedation on frontal-parietal interactions.

PubMed

Ryu, Ji-Ho; Kim, Pil-Jong; Kim, Hong-Gee; Koo, Yong-Seo; Shin, Teo Jeon

2017-06-09

Although functional connectivity has received considerable attention in the study of consciousness, few studies have investigated functional connectivity limited to the sedated state where consciousness is maintained but impaired. The aim of the present study was to investigate changes in functional connectivity of the parietal-frontal network resulting from nitrous oxide-induced sedation, and to determine the neural correlates of cognitive impairment during consciousness transition states. Electroencephalography was acquired from healthy adult patients who underwent nitrous oxide inhalation to induce cognitive impairment, and was analyzed using Granger causality (GC). Periods of awake, sedation and recovery for GC between frontal and parietal areas in the delta, theta, alpha, beta, gamma and total frequency bands were obtained. The Friedman test with post-hoc analysis was conducted for GC values of each period for comparison. As a sedated state was induced by nitrous oxide inhalation, power in the low frequency band showed increased activity in frontal regions that was reversed with discontinuation of nitrous oxide. Feedback and feedforward connections analyzed in spectral GC were changed differently in accordance with EEG frequency bands in the sedated state by nitrous oxide administration. Calculated spectral GC of the theta, alpha, and beta frequency regions in the parietal-to-frontal direction was significantly decreased in the sedated state while spectral GC in the reverse direction did not show significant change. Frontal-parietal functional connectivity is significantly affected by nitrous oxide inhalation. Significantly decreased parietal-to-frontal interaction may induce a sedated state. Copyright © 2017 Elsevier B.V. All rights reserved.

Forcing Cesium into Higher Oxidation States Using Useful hard x-ray Induced Chemistry under High Pressure

NASA Astrophysics Data System (ADS)

Sneed, D.; Pravica, M.; Kim, E.; Chen, N.; Park, C.; White, M.

2017-10-01

This paper discusses our attempt to synthesize higher oxidation forms of cesium fluoride by pressurizing cesium fluoride in a fluorine-rich environment created via the x-ray decomposition of potassium tetrafluoroborate. This was done in order to confirm recent theoretical predictions of higher oxidation forms of CsFn. We discuss the development of a technique to produce molecular fluorine in situ via useful hard x-ray photochemistry, and the attempt to utilize this technique to form higher oxidation states of cesium fluoride. In order to verify the formation of the novel stoichiometric species of CsFn. X-ray Absorption Near Edge Spectroscopy (XANES) centered on the cesium K-edge was performed to probe the oxidation state of cesium as well as the local molecular coordination around Cs.

BISON Fuel Performance Analysis of FeCrAl cladding with updated properties

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

Sweet, Ryan; George, Nathan M.; Terrani, Kurt A.

2016-08-30

In order to improve the accident tolerance of light water reactor (LWR) fuel, alternative cladding materials have been proposed to replace zirconium (Zr)-based alloys. Of these materials, there is a particular focus on iron-chromium-aluminum (FeCrAl) alloys due to much slower oxidation kinetics in high-temperature steam than Zr-alloys. This should decrease the energy release due to oxidation and allow the cladding to remain integral longer in the presence of high temperature steam, making accident mitigation more likely. As a continuation of the development for these alloys, suitability for normal operation must also be demonstrated. This research is focused on modeling themore » integral thermo-mechanical performance of FeCrAl-cladded fuel during normal reactor operation. Preliminary analysis has been performed to assess FeCrAl alloys (namely Alkrothal 720 and APMT) as a suitable fuel cladding replacement for Zr-alloys, using the MOOSE-based, finite-element fuel performance code BISON and the best available thermal-mechanical and irradiation-induced constitutive properties. These simulations identify the effects of the mechanical-stress and irradiation response of FeCrAl, and provide a comparison with Zr-alloys. In comparing these clad materials, fuel rods have been simulated for normal reactor operation and simple steady-state operation. Normal reactor operating conditions target the cladding performance over the rod lifetime (~4 cycles) for the highest-power rod in the highest-power fuel assembly under reactor power maneuvering. The power histories and axial temperature profiles input into BISON were generated from a neutronics study on full-core reactivity equivalence for FeCrAl using the 3D full core simulator NESTLE. Evolution of the FeCrAl cladding behavior over time is evaluated by using steady-state operating conditions such as a simple axial power profile, a constant cladding surface temperature, and a constant fuel power history. The fuel rod designs and operating conditions used are based off the Peach Bottom BWR and design consideration was given to minimize the neutronic penalty of the FeCrAl cladding by changing fuel enrichment and cladding thickness. As this study progressed, systematic parametric analysis of the fuel and cladding creep responses were also performed.« less

Solid-State Reaction Between Fe-Al-Ca Alloy and Al2O3-CaO-FeO Oxide During Heat Treatment at 1473 K (1200 °C)

NASA Astrophysics Data System (ADS)

Liu, Chengsong; Yang, Shufeng; Li, Jingshe; Ni, Hongwei; Zhang, Xueliang

2017-04-01

The aim of this study was to control the physicochemical characteristics of inclusions in steel through appropriate heat treatment. Using a confocal scanning laser microscope (CSLM) and pipe furnace, the solid-state reactions between Fe-Al-Ca alloy and Al2O3-CaO-FeO oxide during heat treatment at 1473 K (1200 °C) and the influence of these reactions on the compositions of and phases in the alloy and oxide were investigated by the diffusion couple method. Suitable pretreatment of the oxide using a CSLM and production of the diffusion couple of Fe-Al-Ca alloy and Al2O3-CaO-FeO oxide gave good contact between the alloy and oxide. The diffusion couple was then sealed in a quartz tube with a piece of Ti foil to lower oxygen partial pressure and a block of Fe-Al-Ca alloy was introduced to conduct heat treatment experiments. Solid-state reactions between the alloy and oxide during heat treatment at 1473 K (1200 °C) were analyzed and discussed. A dynamic model to calculate the width of the particle precipitation zone based on the Wagner model of internal oxidation of metal was proposed. This model was helpful to understand the solid-state reaction mechanism between Fe-Al-Ca alloy and Al2O3-CaO-FeO oxide.

Oxidation of extracellular cysteine/cystine redox state in bleomycin-induced lung fibrosis

PubMed Central

Iyer, Smita S.; Ramirez, Allan M.; Ritzenthaler, Jeffrey D.; Torres-Gonzalez, Edilson; Roser-Page, Susanne; Mora, Ana L.; Brigham, Kenneth L.; Jones, Dean P.; Roman, Jesse; Rojas, Mauricio

2009-01-01

Several lines of evidence indicate that depletion of glutathione (GSH), a critical thiol antioxidant, is associated with the pathogenesis of idiopathic pulmonary fibrosis (IPF). However, GSH synthesis depends on the amino acid cysteine (Cys), and relatively little is known about the regulation of Cys in fibrosis. Cys and its disulfide, cystine (CySS), constitute the most abundant low-molecular weight thiol/disulfide redox couple in the plasma, and the Cys/CySS redox state (Eh Cys/CySS) is oxidized in association with age and smoking, known risk factors for IPF. Furthermore, oxidized Eh Cys/CySS in the culture media of lung fibroblasts stimulates proliferation and expression of transitional matrix components. The present study was undertaken to determine whether bleomycin-induced lung fibrosis is associated with a decrease in Cys and/or an oxidation of the Cys/CySS redox state and to determine whether these changes were associated with changes in Eh GSH/glutathione disulfide (GSSG). We observed distinct effects on plasma GSH and Cys redox systems during the progression of bleomycin-induced lung injury. Plasma Eh GSH/GSSG was selectively oxidized during the proinflammatory phase, whereas oxidation of Eh Cys/CySS occurred at the fibrotic phase. In the epithelial lining fluid, oxidation of Eh Cys/CySS was due to decreased food intake. Thus the data show that decreased precursor availability and enhanced oxidation of Cys each contribute to the oxidation of extracellular Cys/CySS redox state in bleomycin-induced lung fibrosis. PMID:18931052

The effects of heavy metals and their interactions with polycyclic aromatic hydrocarbons on the oxidative stress among coke-oven workers

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

Wang, Tian; Feng, Wei; Kuang, Dan

Heavy metals and polycyclic aromatic hydrocarbons (PAHs) are predominate toxic constituents of particulate air pollution that may be related to the increased risk of cardiopulmonary events. We aim to investigate the effects of the toxic heavy metals (arsenic, As; cadmium, Cd; chromium, Cr; nickel, Ni; and lead, Pb), and their interactions with PAHs on oxidative stress among coke-oven workers. A total of 1333 male workers were recruited in this study. We determined their urinary levels of As, Cd, Cr, Ni, Pb, twelve PAH metabolites, 8-hydroxydeoxyguanosine (8-OHdG), and 8-iso-prostaglandin-F2α (8-iso-PGF2α). Multivariate linear regression models were used to analyze the effects ofmore » these metals and their interactions with PAHs on 8-OHdG and 8-iso-PGF2α levels. It was found that only urinary As and Ni showed marginal or significant positive linear dose-dependent effects on 8-OHdG in this study population, especially among smokers (β=0.103, P=0.073 and β=0.110, P=0.002, respectively). After stratifying all participants by the quartiles of ΣOH-PAH, all five metals showed linear association with 8-OHdG in the highest quartile subgroup (Q4) of ΣOH-PAHs. However, these five urinary metals showed significantly consistent linear associations with 8-iso-PGF2α in all subjects and each stratum. Urinary ΣOH-PAHs can significant modify the effects of heavy metals on oxidative stress, while co-exposure to both high levels of ΣOH-PAHs and heavy metals render the workers with highest 8-OHdG and 8-iso-PGF2α (all P{sub interaction}≤0.005). This study showed evidence on the interaction effects of heavy metals and PAHs on increasing the oxidative stress, and these results warrant further investigation in more longitudinal studies. - Highlights: • Heavy metals and PAHs are predominate toxic constituents of particulate matters. • Urinary As and Ni showed linear dose-dependent effects on 8-OHdG and 8-iso-PGF2α. • PAHs significant interact with toxic metal in increasing 8-OHdG and 8-iso-PGF2α. • Co-exposure to high PAHs and toxic metals contribute to highest oxidative stress.« less

Effects of water temperature and diets containing palm oil on fatty acid desaturation and oxidation in hepatocytes and intestinal enterocytes of rainbow trout (Oncorhynchus mykiss).

PubMed

Tocher, Douglas R; Fonseca-Madrigal, Jorge; Dick, James R; Ng, Wing-Keong; Bell, J Gordon; Campbell, Patrick J

2004-01-01

Food grade fisheries have reached their sustainable limits while aquaculture production has increased to meet consumer demands. However, for growth in aquaculture to continue and utilise sustainable, feeding ingredients, alternatives to fish oil (FO), the predominant lipid component of fish diets, must be developed. Therefore, there is currently considerable interest in the regulation of fatty acid metabolism in fish in order to determine strategies for the best use of plant oils in diets for commercially important cultured fish species. Plant oils are characteristically rich in C18 polyunsaturated fatty acids (PUFA) but devoid of C20 and C22 highly unsaturated fatty acids (HUFA) found in FO. The fatty acyl desaturase enzyme activities involved in the biosynthesis of HUFA from PUFA are known to be under nutritional regulation and can be increased in fish fed diets rich in plant oils. However, fatty acid desaturase activity is also known to be modulated by water temperature in fish. The present study aimed to investigate the interaction between water temperature and diet in the regulation of fatty acid metabolism in rainbow trout. Trout, acclimatized to 7, 11 or 15 degrees C, were fed for 4 weeks on diets in which the FO was replaced in a graded manner by palm oil. At the end of the trial, fatty acyl desaturation/elongation and beta-oxidation activities were determined in isolated hepatocytes and intestinal enterocytes using [1-14C]18:3n-3 as substrate, and samples of liver were collected for analysis of lipid and fatty acid composition. The most obvious effect of temperature was that fatty acid desaturation/elongation and beta-oxidation were reduced in both hepatocytes and intestinal enterocytes from fish maintained at the highest water temperature (15 degrees C). There were differences between the two tissues with the highest desaturation/elongation and beta-oxidation activities tending to be in fish held at 11 degrees C in the case of hepatocytes, but 7 degrees C in enterocytes. Correlations between fatty acid metabolism and dietary palm oil were most clearly observed in desaturation/elongation activities in both hepatocytes and enterocytes at 11 degrees C. The highest beta-oxidation activities were generally observed in fish fed FO alone in both hepatocytes and enterocytes with palm oil having differential effects in the two cell types.

Comparative study of energy-transducing properties of cytoplasmic membranes from mesophilic and thermophilic Bacillus species.

PubMed Central

De Vrij, W; Bulthuis, R A; Konings, W N

1988-01-01

The properties of enzymes involved in energy transduction from a mesophilic (Bacillus subtilis) and a thermophilic (B. stearothermophilus) bacterium were compared. Membrane preparations of the two organisms contained dehydrogenases for NADH, succinate, L-alpha-glycerophosphate, and L-lactate. Maximum NADH and cytochrome c oxidation rates were obtained at the respective growth temperatures of the two bacteria. The enzymes involved in the oxidation reactions in membranes of the thermophilic species were more thermostable than those of the mesophilic species. The apparent microviscosities of the two membrane preparations were studied at different temperatures. At the respective optimal growth temperatures, the apparent microviscosities of the membranes of the two organisms were remarkably similar. The transition from the gel to the liquid-crystalline state occurred at different temperatures in the two species. In the two species, the oxidation of physiological (NADH) and nonphysiological (N,N,N',N'-tetramethyl-p-phenylenediamine or phenazine methosulfate) electron donors led to generation of a proton motive force which varied strongly with temperature. At increasing temperatures, the efficiency of energy transduction declined because of increasing H+ permeability. At the growth temperature, the efficiency of energy transduction was lower in B. stearothermophilus than in the mesophilic species. Extremely high respiratory activities enabled B. stearothermophilus to maintain a high proton motive force at elevated temperatures. The pH dependence of proton motive force generation appeared to be similar in the two membrane preparations. The highest proton motive forces were generated at low external pH, mainly because of a high pH gradient. At increasing external pH, the proton motive force declined. PMID:2834342