Structural insight into the substrate- and dioxygen-binding manner in the catalytic cycle of rieske nonheme iron oxygenase system, carbazole 1,9a-dioxygenase.

PubMed

Ashikawa, Yuji; Fujimoto, Zui; Usami, Yusuke; Inoue, Kengo; Noguchi, Haruko; Yamane, Hisakazu; Nojiri, Hideaki

2012-06-24

Dihydroxylation of tandemly linked aromatic carbons in a cis-configuration, catalyzed by multicomponent oxygenase systems known as Rieske nonheme iron oxygenase systems (ROs), often constitute the initial step of aerobic degradation pathways for various aromatic compounds. Because such RO reactions inherently govern whether downstream degradation processes occur, novel oxygenation mechanisms involving oxygenase components of ROs (RO-Os) is of great interest. Despite substantial progress in structural and physicochemical analyses, no consensus exists on the chemical steps in the catalytic cycles of ROs. Thus, determining whether conformational changes at the active site of RO-O occur by substrate and/or oxygen binding is important. Carbazole 1,9a-dioxygenase (CARDO), a RO member consists of catalytic terminal oxygenase (CARDO-O), ferredoxin (CARDO-F), and ferredoxin reductase. We have succeeded in determining the crystal structures of oxidized CARDO-O, oxidized CARDO-F, and both oxidized and reduced forms of the CARDO-O: CARDO-F binary complex. In the present study, we determined the crystal structures of the reduced carbazole (CAR)-bound, dioxygen-bound, and both CAR- and dioxygen-bound CARDO-O: CARDO-F binary complex structures at 1.95, 1.85, and 2.00 Å resolution. These structures revealed the conformational changes that occur in the catalytic cycle. Structural comparison between complex structures in each step of the catalytic mechanism provides several implications, such as the order of substrate and dioxygen bindings, the iron-dioxygen species likely being Fe(III)-(hydro)peroxo, and the creation of room for dioxygen binding and the promotion of dioxygen binding in desirable fashion by preceding substrate binding. The RO catalytic mechanism is proposed as follows: When the Rieske cluster is reduced, substrate binding induces several conformational changes (e.g., movements of the nonheme iron and the ligand residue) that create room for oxygen binding. Dioxygen bound in a side-on fashion onto nonheme iron is activated by reduction to the peroxo state [Fe(III)-(hydro)peroxo]. This state may react directly with the bound substrate, or O-O bond cleavage may occur to generate Fe(V)-oxo-hydroxo species prior to the reaction. After producing a cis-dihydrodiol, the product is released by reducing the nonheme iron. This proposed scheme describes the catalytic cycle of ROs and provides important information for a better understanding of the mechanism.

Molecular simulations reveal a new entry site in quercetin 2,3-dioxygenase. A pathway for dioxygen?

PubMed

Fiorucci, Sébastien; Golebiowski, Jérôme; Cabrol-Bass, Daniel; Antonczak, Serge

2006-09-01

Molecular dynamics simulations performed on quercetin 2,3-dioxygenase have shown the existence of a channel linking the bulk solvent and the cavity of the enzyme. Although much is known about the the oxygenolysis reaction catalyzed by this enzyme, the way dioxygen enters the active site has not been firmly established. The size, orientation and hydrophobic character of this channel suggests that it could provide an entrance for molecular dioxygen into the cavity. Free energy calculations show that such a process is likely to occur. (c) 2006 Wiley-Liss, Inc.

Redox inactive metal ion triggered N-dealkylation by an iron catalyst with dioxygen activation: a lesson from lipoxygenases.

PubMed

Zhang, Jisheng; Wang, Yujuan; Luo, Nengchao; Chen, Zhuqi; Wu, Kangbing; Yin, Guochuan

2015-06-07

Utilization of dioxygen as the terminal oxidant at ambient temperature is always a challenge in redox chemistry, because it is hard to oxidize a stable redox metal ion like iron(III) to its high oxidation state to initialize the catalytic cycle. Inspired by the dioxygenation and co-oxidase activity of lipoxygenases, herein, we introduce an alternative protocol to activate the sluggish iron(III) species with non-redox metal ions, which can promote its oxidizing power to facilitate substrate oxidation with dioxygen, thus initializing the catalytic cycle. In oxidations of N,N-dimethylaniline and its analogues, adding Zn(OTf)2 to the [Fe(TPA)Cl2]Cl catalyst can trigger the amine oxidation with dioxygen, whereas [Fe(TPA)Cl2]Cl alone is very sluggish. In stoichiometric oxidations, it has also been confirmed that the presence of Zn(OTf)2 can apparently improve the electron transfer capability of the [Fe(TPA)Cl2]Cl complex. Experiments using different types of substrates as trapping reagents disclosed that the iron(IV) species does not occur in the catalytic cycle, suggesting that oxidation of amines is initialized by electron transfer rather than hydrogen abstraction. Combined experiments from UV-Vis, high resolution mass spectrometry, electrochemistry, EPR and oxidation kinetics support that the improved electron transfer ability of iron(III) species originates from its interaction with added Lewis acids like Zn(2+) through a plausible chloride or OTf(-) bridge, which has promoted the redox potential of iron(III) species. The amine oxidation mechanism was also discussed based on the available data, which resembles the co-oxidase activity of lipoxygenases in oxidative dealkylation of xenobiotic metabolisms where an external electron donor is not essential for dioxygen activation.

REDUCTIVE ACTIVATION OF DIOXYGEN FOR DEGRADATION OF METHYL TERT-BUTYL ETHER BY BIFUNCTION

EPA Science Inventory

Bifunctional aluminum is prepared by sulfating aluminum metal with sulfuric acid. The use of bifunctional aluminum to degrade methyl tert-butyl ether (MTBE) in the presence of dioxygen has been examined using batch systems. Primary degradation products were tert-butyl alcohol, ...

A personal perspective on the discovery of dioxygen adducts of copper and iron by Nobumasa Kitajima.

PubMed

Fujisawa, Kiyoshi

2017-04-01

Transition metal-dioxygen complexes have fascinated bioinorganic and inorganic chemists for over half a century. The late Nobumasa Kitajima was one of the very successful researchers in this field. Despite his short career (40 years old), he made many important contributions. This Commentary highlights his important accomplishments and how they have impacted subsequent work in this area.

Modeling dioxygen reduction at multicopper oxidase cathodes.

PubMed

Agbo, Peter; Heath, James R; Gray, Harry B

2014-10-01

We report a general kinetics model for catalytic dioxygen reduction on multicopper oxidase (MCO) cathodes. Our rate equation combines Butler-Volmer (BV) electrode kinetics and the Michaelis-Menten (MM) formalism for enzymatic catalysis, with the BV model accounting for interfacial electron transfer (ET) between the electrode surface and the MCO type 1 copper site. Extending the principles of MM kinetics to this system produced an analytical expression incorporating the effects of subsequent intramolecular ET and dioxygen binding to the trinuclear copper cluster into the cumulative model. We employed experimental electrochemical data on Thermus thermophilus laccase as benchmarks to validate our model, which we suggest will aid in the design of more efficient MCO cathodes. In addition, we demonstrate the model's utility in determining estimates for both the electronic coupling and average distance between the laccase type-1 active site and the cathode substrate.

Neutron and Atomic Resolution X-ray Structures of a Lytic Polysaccharide Monooxygenase Reveal Copper-Mediated Dioxygen Binding and Evidence for N-Terminal Deprotonation

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

Bacik, John-Paul; Mekasha, Sophanit; Forsberg, Zarah

A 1.1 Å resolution, room-temperature X-ray structure and a 2.1 Å resolution neutron structure of a chitin-degrading lytic polysaccharide monooxygenase domain from the bacterium Jonesia denitrificans (JdLPMO10A) show a putative dioxygen species equatorially bound to the active site copper. We found that both structures show an elongated density for the dioxygen, most consistent with a Cu(II)-bound peroxide. The coordination environment is consistent with Cu(II). Furthermore, in the neutron and X-ray structures, difference maps reveal the N-terminal amino group, involved in copper coordination, is present as a mixed ND 2 and ND –, suggesting a role for the copper ion inmore » shifting the pK a of the amino terminus.« less

Neutron and Atomic Resolution X-ray Structures of a Lytic Polysaccharide Monooxygenase Reveal Copper-Mediated Dioxygen Binding and Evidence for N-Terminal Deprotonation

DOE PAGES

Bacik, John-Paul; Mekasha, Sophanit; Forsberg, Zarah; ...

2017-05-08

A 1.1 Å resolution, room-temperature X-ray structure and a 2.1 Å resolution neutron structure of a chitin-degrading lytic polysaccharide monooxygenase domain from the bacterium Jonesia denitrificans (JdLPMO10A) show a putative dioxygen species equatorially bound to the active site copper. We found that both structures show an elongated density for the dioxygen, most consistent with a Cu(II)-bound peroxide. The coordination environment is consistent with Cu(II). Furthermore, in the neutron and X-ray structures, difference maps reveal the N-terminal amino group, involved in copper coordination, is present as a mixed ND 2 and ND –, suggesting a role for the copper ion inmore » shifting the pK a of the amino terminus.« less

Selective identification of specialized pro-resolving lipid mediators from their biosynthetic double di-oxygenation isomers.

PubMed

Hansen, Trond V; Dalli, Jesmond; Serhan, Charles N

The n-3 polyunsaturated fatty acids are substrates for lipoxygenases and cyclooxygenases. During inflammatory processes, these enzymes form several distinct families of oxygenated polyunsaturated fatty acids coined specialized pro-resolving lipid mediators. Structural elucidation of these natural products using LC-MS/MS based metabololipidomics with the pico- to nanogram amounts of biosynthetic material available have been performed. The specialized pro-resolving lipid mediators display stereospecific and potent anti-inflammatory and pro-resolving actions. Most often the different families among these mediators are chemically characterized by two or three chiral, secondary alcohols, separated by either an E,E,Z -triene or an E,Z,E,E -tetraenemoiety. The lipoxygenases also form other oxygenated polyunsaturated natural products, coined double di-oxygenation products, that are constitutional isomers of the protectin and maresin families of specialized pro-resolving lipid mediators. Very often these products exhibit similar chromatographic properties and mass spectrometrical fragment ions as the pro-resolving mediators. In addition, the double di-oxygenation products are sometimes formed in larger amounts than the specialized pro-resolving lipid mediators. Thus, it is not always possible to distinguish between the specialized pro-resolving mediators and their double di-oxygenation isomers in biological systems, using LC/MS-based techniques. Herein, a convenient and easy-to-use protocol to meet this challenge is presented.

Issues for storing plant-based alternative fuels in marine environments.

PubMed

Lee, Jason S; Ray, Richard I; Little, Brenda J; Duncan, Kathleen E; Aktas, Deniz F; Oldham, Athenia L; Davidova, Irene A; Suflita, Joseph M

2014-06-01

Two coastal seawaters (Key West, FL, USA and the Persian Gulf, Bahrain, representing oligotrophic and eutrophic environments, respectively) were used to evaluate potential biodegradation and corrosion problems during exposure to alternative and conventional fuels. Uncoated carbon steel was exposed at the fuel/seawater interface and polarization resistance was monitored. Under typical marine storage conditions, dioxygen in natural seawater exposed to fuel and carbon steel was reduced to <0.1parts-per-million within 2d due to consumption by corrosion reactions and aerobic microbial respiration. Sulfides, produced by anaerobic sulfate-reducing bacteria, and chlorides were co-located in corrosion products. Transient dioxygen influenced both metabolic degradation pathways and resulting metabolites. Catechols, indicative of aerobic biodegradation, persisted after 90d exposures. Detection of catechols suggested that initial exposure to dioxygen resulted in the formation of aerobic metabolites that exacerbated subsequent corrosion processes. Published by Elsevier B.V.

Oxygen Activation at Mononuclear Nonheme Iron Centers: A Superoxo Perspective

PubMed Central

Mukherjee, Anusree; Cranswick, Matthew A.; Chakraborti, Mrinmoy; Paine, Tapan K.; Fujisawa, Kiyoshi; Münck, Eckard; Que, Lawrence

2010-01-01

Dioxygen activation by iron enzymes is responsible for many metabolically important transformations in biology. Often a high-valent iron-oxo oxidant is proposed to form upon dioxygen activation at a mononuclear nonheme iron center, presumably via intervening iron-superoxo and iron-peroxo species. While iron(IV)-oxo intermediates have been trapped and characterized in enzymes and models, less is known of the putative iron(III)-superoxo species. Utilizing a synthetic model for the 2-oxoglutarate-dependent monoiron enzymes, [(TpiPr2)FeII(O2CC(O)CH3)], we have obtained indirect evidence for the formation of the putative iron(III)-superoxo species, which can undergo one-electron reduction, hydrogen-atom transfer, or conversion to an iron(IV)-oxo species, depending on the reaction conditions. These results demonstrate the various roles the iron(III)-superoxo species can play in the course of dioxygen activation at a nonheme iron center. PMID:20380464

Ozone-Activated Nanoporous Gold: A Stable and Storable Material for Catalytic Oxidation

DOE PAGES

Personick, Michelle L.; Zugic, Branko; Biener, Monika M.; ...

2015-05-28

We report a new method for facile and reproducible activation of nanoporous gold (npAu) materials of different forms for the catalytic selective partial oxidation of alcohols under ambient pressure, steady flow conditions. This method, based on the surface cleaning of npAu ingots with ozone to remove carbon documented in ultrahigh vacuum conditions, produces active npAu catalysts from ingots, foils, and shells by flowing an ozone/dioxygen mixture over the catalyst at 150 °C, followed by a temperature ramp from 50 to 150 °C in a flowing stream of 10% methanol and 20% oxygen. With this treatment, all three materials (ingots, foils,more » and shells) can be reproducibly activated, despite potential carbonaceous poisons resulting from their synthesis, and are highly active for the selective oxidation of primary alcohols over prolonged periods of time. The npAu materials activated in this manner exhibit catalytic behavior substantially different from those activated under different conditions previously reported. Once activated in this manner, they can be stored and easily reactivated by flow of reactant gases at 150 °C for a few hours. They possess improved selectivity for the coupling of higher alcohols, such as 1-butanol, and are not active for carbon monoxide oxidation. As a result, this ozone-treated npAu is a functionally new catalytic material.« less

UV Lamp as a Facile Ozone Source for Structural Analysis of Unsaturated Lipids Via Electrospray Ionization-Mass Spectrometry

NASA Astrophysics Data System (ADS)

Stinson, Craig A.; Zhang, Wenpeng; Xia, Yu

2017-12-01

Ozonolysis of alkene functional groups is a type of highly specific and effective chemical reaction, which has found increasing applications in structural analysis of unsaturated lipids via coupling with mass spectrometry (MS). In this work, we utilized a low-pressure mercury lamp (6 W) to initiate ozonolysis inside electrospray ionization (ESI) sources. By placing the lamp near a nanoESI emitter that partially transmits 185 nm ultraviolet (UV) emission from the lamp, dissolved dioxygen in the spray solution was converted into ozone, which subsequently cleaved the double bonds within fatty acyls of lipids. Solvent conditions, such as presence of water and acid solution pH, were found to be critical in optimizing ozonolysis yields. Fast (on seconds time scale) and efficient (50%-100% yield) ozonolysis was achieved for model unsaturated phospholipids and fatty acids with UV lamp-induced ozonolysis incorporated on a static and an infusion nanoESI source. The method was able to differentiate double bond location isomers and identify the geometry of the double bond based on yield. The analytical utility of UV lamp-induced ozonolysis was further demonstrated by implementation on a liquid chromatography (LC)-MS platform. Ozonolysis was effected in a flow microreactor that was made from ozone permeable tubing, so that ambient ozone produced by the lamp irradiation could diffuse into the reactor and induce online ozonolysis post-LC separation and before ESI-MS.

Ozone-Activated Nanoporous Gold: A Stable and Storable Material for Catalytic Oxidation

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

Personick, Michelle L.; Zugic, Branko; Biener, Monika M.

We report a new method for facile and reproducible activation of nanoporous gold (npAu) materials of different forms for the catalytic selective partial oxidation of alcohols under ambient pressure, steady flow conditions. This method, based on the surface cleaning of npAu ingots with ozone to remove carbon documented in ultrahigh vacuum conditions, produces active npAu catalysts from ingots, foils, and shells by flowing an ozone/dioxygen mixture over the catalyst at 150 °C, followed by a temperature ramp from 50 to 150 °C in a flowing stream of 10% methanol and 20% oxygen. With this treatment, all three materials (ingots, foils,more » and shells) can be reproducibly activated, despite potential carbonaceous poisons resulting from their synthesis, and are highly active for the selective oxidation of primary alcohols over prolonged periods of time. The npAu materials activated in this manner exhibit catalytic behavior substantially different from those activated under different conditions previously reported. Once activated in this manner, they can be stored and easily reactivated by flow of reactant gases at 150 °C for a few hours. They possess improved selectivity for the coupling of higher alcohols, such as 1-butanol, and are not active for carbon monoxide oxidation. As a result, this ozone-treated npAu is a functionally new catalytic material.« less

Oxidation of Naphthenoaromatic and Methyl-Substituted Aromatic Compounds by Naphthalene 1,2-Dioxygenase

PubMed Central

Selifonov, S. A.; Grifoll, M.; Eaton, R. W.; Chapman, P. J.

1996-01-01

Oxidation of acenaphthene, acenaphthylene, and fluorene was examined with recombinant strain Pseudomonas aeruginosa PAO1(pRE695) expressing naphthalene dioxygenase genes cloned from plasmid NAH7. Acenaphthene underwent monooxygenation to 1-acenaphthenol with subsequent conversion to 1-acenaphthenone and cis- and trans-acenaphthene-1,2-diols, while acenaphthylene was dioxygenated to give cis-acenaphthene-1,2-diol. Nonspecific dehydrogenase activities present in the host strain led to the conversion of both of the acenaphthene-1,2-diols to 1,2-acenaphthoquinone. The latter was oxidized spontaneously to naphthalene-1,8-dicarboxylic acid. No aromatic ring dioxygenation products were detected from acenaphthene and acenaphthylene. Mixed monooxygenase and dioxygenase actions of naphthalene dioxygenase on fluorene yielded products of benzylic 9-monooxygenation, aromatic ring dioxygenation, or both. The action of naphthalene dioxygenase on a variety of methyl-substituted aromatic compounds, including 1,2,4-trimethylbenzene and isomers of dimethylnaphthalene, resulted in the formation of benzylic alcohols, i.e., methyl group monooxygenation products, which were subsequently converted to the corresponding carboxylic acids by dehydrogenase(s) in the host strain. Benzylic monooxygenation of methyl groups was strongly predominant over aromatic ring dioxygenation and essentially nonspecific with respect to the substitution pattern of the aromatic substrates. In addition to monooxygenating benzylic methyl and methylene groups, naphthalene dioxygenase behaved as a sulfoxygenase, catalyzing monooxygenation of the sulfur heteroatom of 3-methylbenzothiophene. PMID:16535238

Effect of Dioxygen on Copper(II) Binding to α-Synuclein

PubMed Central

Lucas, Heather R.; Lee, Jennifer C.

2010-01-01

Using the fluorescent amino acid tryptophan (Trp), we have characterized the copper(II) binding of F4W α-synuclein in the presence and absence of dioxygen at neutral pH. Variations in Trp fluorescence indicate that copper(II) binding is enhanced by the presence of dioxygen, with the apparent dissociation constant (Kd(app)) changing from 100 nM (anaerobic) to 10 nM (aerobic). To investigate the possible role of methionine oxidation, complementary work focused on synthetic peptide models of the N-terminal Cu(II)-α-syn site, MDV(F/W) and M*DV(F/W), where M*= methionine sulfoxide. Furthermore, we employed circular dichroism (CD) spectroscopy to demonstrate that the phenyl-to-indole (F→W) substitution does not alter copper(II) binding properties and to confirm the 1:1 metal-peptide binding stoichiometry. CD comparisons also revealed that Met1 oxidation does not affect the copper-peptide conformation and further suggested the possible existence of a CuII-Trp/Phe (cation-π) interaction. PMID:20064662

Carbon and nitrogen isotope effects associated with the dioxygenation of aniline and diphenylamine.

PubMed

Pati, Sarah G; Shin, Kwanghee; Skarpeli-Liati, Marita; Bolotin, Jakov; Eustis, Soren N; Spain, Jim C; Hofstetter, Thomas B

2012-11-06

Dioxygenation of aromatic rings is frequently the initial step of biodegradation of organic subsurface pollutants. This process can be tracked by compound-specific isotope analysis to assess the extent of contaminant transformation, but the corresponding isotope effects, especially for dioxygenation of N-substituted, aromatic contaminants, are not well understood. We investigated the C and N isotope fractionation associated with the biodegradation of aniline and diphenylamine using pure cultures of Burkholderia sp. strain JS667, which can biodegrade both compounds, each by a distinct dioxygenase enzyme. For diphenylamine, the C and N isotope enrichment was normal with ε(C)- and ε(N)-values of -0.6 ± 0.1‰ and -1.0 ± 0.1‰, respectively. In contrast, N isotopes of aniline were subject to substantial inverse fractionation (ε(N) of +13 ± 0.5‰), whereas the ε(C)-value was identical to that of diphenylamine. A comparison of the apparent kinetic isotope effects for aniline and diphenylamine dioxygenation with those from abiotic oxidation by manganese oxide (MnO(2)) suggest that the oxidation of a diarylamine system leads to distinct C-N bonding changes compared to aniline regardless of reaction mechanism and oxidant involved. Combined evaluation of the C and N isotope signatures of the contaminants reveals characteristic Δδ(15)N/Δδ(13)C-trends for the identification of diphenylamine and aniline oxidation in contaminated subsurfaces and for the distinction of aniline oxidation from its formation by microbial and/or abiotic reduction of nitrobenzene.

Apparatus and method for the preparation of dioxygen difluoride

DOEpatents

Beattie, W.H.

1985-01-30

Dioxygen difluoride, O/sub 2/F/sub 2/, is prepared in high yield by microwave discharge of a flowing gas mixture of F/sub 2/ with or without a carrier gas such as argon or helium with the subsequent reaction of the discharge products with molecular gaseous oxygen downstream from and outside of the region of discharge. The O/sub 2/F/sub 2/ product is collected by cryogenic trapping, and is free of oxygen difluoride impurity and ozone since the oxygen molecules are not dissociated before they react with the microwave discharge products.

Four-electron Reduction of Dioxygen by a Multicopper Oxidase, CueO, and Roles of Asp112 and Glu506 Located Adjacent to the Trinuclear Copper Center*S⃞

PubMed Central

Kataoka, Kunishige; Sugiyama, Ryosuke; Hirota, Shun; Inoue, Megumi; Urata, Kanae; Minagawa, Yoichi; Seo, Daisuke; Sakurai, Takeshi

2009-01-01

The mechanism of the four-electron reduction of dioxygen by a multicopper oxidase, CueO, was studied based on reactions of single and double mutants with Cys500, a type I copper ligand, and the noncoordinating Asp112 and Glu506, which form hydrogen bonds with the trinuclear copper center directly and indirectly via a water molecule. The reaction of C500S containing a vacant type I copper center produced intermediate I in an EPR-silent peroxide-bound form. The formation of intermediate I from C500S/D112N was restricted due to a reduction in the affinity of the trinuclear copper center for dioxygen. The state of intermediate I was realized to be the resting form of C500S/E506Q and C500S of the truncated mutant Δα5–7CueO, in which the 50 amino acids covering the substrate-binding site were removed. Reactions of the recombinant CueO and E506Q afforded intermediate II, a fully oxidized form different from the resting one, with a very broad EPR signal, g < 2, detectable only at cryogenic temperatures and unsaturated with high power microwaves. The lifetime of intermediate II was prolonged by the mutation at Glu506 involved in the donation of protons. The structure of intermediates I and II and the mechanism of the four-electron reduction of dioxygen driven by Asp112 and Glu506 are discussed. PMID:19297322

Iron complexes of dendrimer-appended carboxylates for activating dioxygen and oxidizing hydrocarbons.

PubMed

Zhao, Min; Helms, Brett; Slonkina, Elena; Friedle, Simone; Lee, Dongwhan; Dubois, Jennifer; Hedman, Britt; Hodgson, Keith O; Fréchet, Jean M J; Lippard, Stephen J

2008-04-02

The active sites of metalloenzymes are often deeply buried inside a hydrophobic protein sheath, which protects them from undesirable hydrolysis and polymerization reactions, allowing them to achieve their normal functions. In order to mimic the hydrophobic environment of the active sites in bacterial monooxygenases, diiron(II) compounds of the general formula [Fe2([G-3]COO)4(4-RPy)2] were prepared, where [G-3]COO- is a third-generation dendrimer-appended terphenyl carboxylate ligand and 4-RPy is a pyridine derivative. The dendrimer environment provides excellent protection for the diiron center, reducing its reactivity toward dioxygen by about 300-fold compared with analogous complexes of terphenyl carboxylate ([G-1]COO-) ligands. An FeIIFeIII intermediate was characterized by electronic, electron paramagnetic resonance, Mössbauer, and X-ray absorption spectroscopic analyses following the oxygenation of [Fe2([G-3]COO)4(4-PPy)2], where 4-PPy is 4-pyrrolidinopyridine. The results are consistent with the formation of a superoxo species. This diiron compound, in the presence of dioxygen, can oxidize external substrates.

Iron Complexes of Dendrimer-Appended Carboxylates for Activating Dioxygen and Oxidizing Hydrocarbons

PubMed Central

Zhao, Min; Helms, Brett; Slonkina, Elena; Friedle, Simone; Lee, Dongwhan; DuBois, Jennifer; Hedman, Britt; Hodgson, Keith O.; Fréchet, Jean M. J.; Lippard, Stephen J.

2008-01-01

The active sites of metalloenzymes are often deeply buried inside a hydrophobic protein sheath, which protects them from undesirable hydrolysis and polymerization reactions, allowing them to achieve their normal functions. In order to mimic the hydrophobic environment of the active sites in bacterial monooxygenases, diiron(II) compounds of the general formula [Fe2([G-3]COO)4(4-RPy)2] were prepared, where [G-3]COO− is a third-generation dendrimer-appended terphenyl carboxylate ligand and 4-RPy is a pyridine derivative. The dendrimer environment provides excellent protection for the diiron center, reducing its reactivity toward dioxygen by about 300-fold compared with analogous complexes of terphenyl carboxylate ([G-1]COO−) ligands. An FeIIFeIII intermediate was characterized by electronic, electron paramagnetic resonance, Mössbauer, and X-ray absorption spectroscopic analyses following the oxygenation of [Fe2−([G-3]COO)4(4-PPy)2], where 4-PPy is 4-pyrrolidinopyridine. The results are consistent with the formation of a superoxo species. This diiron compound, in the presence of dioxygen, can oxidize external substrates. PMID:18331028

UV Lamp as a Facile Ozone Source for Structural Analysis of Unsaturated Lipids Via Electrospray Ionization-Mass Spectrometry.

PubMed

Stinson, Craig A; Zhang, Wenpeng; Xia, Yu

2018-03-01

Ozonolysis of alkene functional groups is a type of highly specific and effective chemical reaction, which has found increasing applications in structural analysis of unsaturated lipids via coupling with mass spectrometry (MS). In this work, we utilized a low-pressure mercury lamp (6 W) to initiate ozonolysis inside electrospray ionization (ESI) sources. By placing the lamp near a nanoESI emitter that partially transmits 185 nm ultraviolet (UV) emission from the lamp, dissolved dioxygen in the spray solution was converted into ozone, which subsequently cleaved the double bonds within fatty acyls of lipids. Solvent conditions, such as presence of water and acid solution pH, were found to be critical in optimizing ozonolysis yields. Fast (on seconds time scale) and efficient (50%-100% yield) ozonolysis was achieved for model unsaturated phospholipids and fatty acids with UV lamp-induced ozonolysis incorporated on a static and an infusion nanoESI source. The method was able to differentiate double bond location isomers and identify the geometry of the double bond based on yield. The analytical utility of UV lamp-induced ozonolysis was further demonstrated by implementation on a liquid chromatography (LC)-MS platform. Ozonolysis was effected in a flow microreactor that was made from ozone permeable tubing, so that ambient ozone produced by the lamp irradiation could diffuse into the reactor and induce online ozonolysis post-LC separation and before ESI-MS. Graphical Abstract ᅟ.

UV Lamp as a Facile Ozone Source for Structural Analysis of Unsaturated Lipids Via Electrospray Ionization-Mass Spectrometry

NASA Astrophysics Data System (ADS)

Stinson, Craig A.; Zhang, Wenpeng; Xia, Yu

2018-03-01

Ozonolysis of alkene functional groups is a type of highly specific and effective chemical reaction, which has found increasing applications in structural analysis of unsaturated lipids via coupling with mass spectrometry (MS). In this work, we utilized a low-pressure mercury lamp (6 W) to initiate ozonolysis inside electrospray ionization (ESI) sources. By placing the lamp near a nanoESI emitter that partially transmits 185 nm ultraviolet (UV) emission from the lamp, dissolved dioxygen in the spray solution was converted into ozone, which subsequently cleaved the double bonds within fatty acyls of lipids. Solvent conditions, such as presence of water and acid solution pH, were found to be critical in optimizing ozonolysis yields. Fast (on seconds time scale) and efficient (50%-100% yield) ozonolysis was achieved for model unsaturated phospholipids and fatty acids with UV lamp-induced ozonolysis incorporated on a static and an infusion nanoESI source. The method was able to differentiate double bond location isomers and identify the geometry of the double bond based on yield. The analytical utility of UV lamp-induced ozonolysis was further demonstrated by implementation on a liquid chromatography (LC)-MS platform. Ozonolysis was effected in a flow microreactor that was made from ozone permeable tubing, so that ambient ozone produced by the lamp irradiation could diffuse into the reactor and induce online ozonolysis post-LC separation and before ESI-MS. [Figure not available: see fulltext.

Probing the mechanism of proton coupled electron transfer to dioxygen: the oxidative half-reaction of bovine serum amine oxidase.

PubMed

Su, Q; Klinman, J P

1998-09-08

Bovine serum amine oxidase (BSAO) catalyzes the oxidative deamination of primary amines, concomitant with the reduction of molecular oxygen to hydrogen peroxide via a ping-pong mechanism. A protocol has been developed for an analysis of chemical and kinetic mechanisms in the conversion of dioxygen to hydrogen peroxide. Steady-state kinetics show that two groups need to be deprotonated to facilitate the oxidative half-reaction. The pH dependence of Vmax/Km(O2) reveals pKa's of 6.2 +/- 0.3 and 7.0 +/- 0.2, respectively. A pKa of 7.2 +/- 0.1 has been obtained from a titration of anaerobically reduced BSAO using UV-vis spectrophotometry. The near identity of the pKa obtained from the reduced enzyme titration with the second pKa from steady-state kinetics suggests that this second pKa arises from the reduced cofactor. The assignment of pKa is supported by the observed pH dependence for formation of the cofactor semiquinone signal, detected by EPR spectroscopy under anaerobic conditions. To address the nature of rate-limiting steps in the oxidative half-reaction, the solvent isotope effect, viscosity effect, and O-18 isotope effect on Vmax/Km(O2) have been determined. The solvent isotope effect is indistinguishable from unity, ruling out a proton transfer as a rate-determining step. Use of glucose as a solvent viscosogen shows no viscosity effect, indicating that binding of oxygen is not in the rate-determining step. The O-18 kinetic isotope effect is independent of pH with an average value of 18(V/K) = 1.0097 +/- 0. 0010. This has been compared to calculated equilibrium O-18 isotope effects for various dioxygen intermediate species [Tian and Klinman (1993) J. Am. Chem. Soc. 115, 8891], leading to the conclusion that either the first electron transfer to dioxygen or the desorption of product peroxide from a Cu(II)-OOH complex could be the rate-limiting step. The distribution of steady-state enzyme species was, therefore, analyzed through a combination of stopped-flow experiments and analysis of DV and D(V/K) for benzylamine oxidation. We conclude that the major species accumulating in the steady state are the oxidized cofactor-substrate Schiff base complex and the reduced, aminoquinol form of cofactor. These data rule out a slow release of product hydroperoxide from the aminoquinone form of enzyme, leading to the conclusion that the first electron transfer from substrate-reduced cofactor to dioxygen is the rate-determining step in the oxidative half-reaction. This step is also estimated to be 40% rate-limiting in kcat. An important mechanistic conclusion from this study is that dioxygen binding is a separate step from the rate-limiting electron-transfer step to form superoxide. On the basis of a recently determined X-ray structure for the active form of a yeast amine oxidase from Hansenula polymorpha [Li et al. (1998) Structure 6, 293], a hydrophobic space has been identified near the O-2 position of reduced cofactor as the putative dioxygen binding site. Movement of superoxide from this site onto the Cu(II) at the active site may occur prior to further electron transfer from cofactor to superoxide.

Reversible uptake of molecular oxygen by heteroligand Co(II)-L-α-amino acid-imidazole systems: equilibrium models at full mass balance.

PubMed

Pająk, Marek; Woźniczka, Magdalena; Vogt, Andrzej; Kufelnicki, Aleksander

2017-09-19

The paper examines Co(II)-amino acid-imidazole systems (where amino acid = L-α-amino acid: alanine, asparagine, histidine) which, when in aqueous solutions, activate and reversibly take up dioxygen, while maintaining the structural scheme of the heme group (imidazole as axial ligand and O 2 uptake at the sixth, trans position) thus imitating natural respiratory pigments such as myoglobin and hemoglobin. The oxygenated reaction shows higher reversibility than for Co(II)-amac systems with analogous amino acids without imidazole. Unlike previous investigations of the heteroligand Co(II)-amino acid-imidazole systems, the present study accurately calculates all equilibrium forms present in solution and determines the [Formula: see text]equilibrium constants without using any simplified approximations. The equilibrium concentrations of Co(II), amino acid, imidazole and the formed complex species were calculated using constant data obtained for analogous systems under oxygen-free conditions. Pehametric and volumetric (oxygenation) studies allowed the stoichiometry of O 2 uptake reaction and coordination mode of the central ion in the forming oxygen adduct to be determined. The values of dioxygen uptake equilibrium constants [Formula: see text] were evaluated by applying the full mass balance equations. Investigations of oxygenation of the Co(II)-amino acid-imidazole systems indicated that dioxygen uptake proceeds along with a rise in pH to 9-10. The percentage of reversibility noted after acidification of the solution to the initial pH ranged within ca 30-60% for alanine, 40-70% for asparagine and 50-90% for histidine, with a rising tendency along with the increasing share of amino acid in the Co(II): amino acid: imidazole ratio. Calculations of the share of the free Co(II) ion as well as of the particular complex species existing in solution beside the oxygen adduct (regarding dioxygen bound both reversibly and irreversibly) indicated quite significant values for the systems with alanine and asparagine-in those cases the of oxygenation reaction is right shifted to a relatively lower extent. The experimental results indicate that the "active" complex, able to take up dioxygen, is a heteroligand CoL 2 L'complex, where L = amac (an amino acid with a non-protonated amine group) while L' = Himid, with the N1 nitrogen protonated within the entire pH range under study. Moreover, the corresponding log  [Formula: see text] value at various initial total Co(II), amino acid and imidazole concentrations was found to be constant within the limits of error, which confirms those results. The highest log [Formula: see text] value, 14.9, occurs for the histidine system; in comparison, asparagine is 7.8 and alanine is 9.7. This high value is most likely due to the participation of the additional effective N3 donor of the imidazole side group of histidine. The Co(II)-amac-Himid systems formed by using a [Co(imid) 2 ] n polymer as starting material demonstrate that the reversible uptake of molecular oxygen occurs by forming dimeric μ-peroxy adducts. The essential impact on the electron structure of the dioxygen bridge, and therefore, on the reversibility of O 2 uptake, is due to the imidazole group at axial position (trans towards O 2 ). However, the results of reversibility measurements of O 2 uptake, unequivocally indicate a much higher effectiveness of dioxygenation than in systems in which the oxygen adducts are formed in equilibrium mixtures during titration of solutions containing Co(II) ions, the amino acid and imidazole, separately.

Density functional theory studies of oxygen and carbonate binding to a dicopper patellamide complex.

PubMed

Latifi, Reza; Bagherzadeh, Mojtaba; Milne, Bruce F; Jaspars, Marcel; de Visser, Sam P

2008-12-01

In this work we present results of density functional theory (DFT) calculations on dicopper patellamides and their affinity for molecular oxygen and carbonate. Patellamides are cyclic octapeptides that are produced by a cyanobacterium, and may show promise as therapeutics. Thus, carbonate binding to a dicopper patellamide center gives a stable cyclic octapeptide with a twist of almost 90 degrees . The system exists in close-lying open-shell singlet and triplet spin states with two unpaired electrons in orthogonal sigma* orbitals on each metal center. Subsequently, we replaced carbonate with dioxygen and found a stable Cu2(mu-O)2 diamond shaped patellamide core. In this structure the original dioxygen bond is significantly weakened to essentially a single bond, which should enable the system to transfer these oxygen atoms to substrates. We predicted the IR and Raman spectra of the Cu2(mu-O)2 diamond shaped patellamide structure using density functional theory and found a considerable isotope effect on the O-O stretch vibration for 16O2 versus 18O2 bound structures. Our studies reveal that carbonate forms an extremely stable complex with dicopper patellamide, but that additional molecular oxygen to this system does not give a potential oxidant. Therefore, it is more likely that carbonate prepares the system for dioxygen binding by folding it into the correct configuration followed in the proposed catalytic cycle by a protonation event preceding dioxygen binding to enable the system to reorganize to form a stable Cu2(mu-O)2-patellamide cluster. Alternatively, carbonate may act as an inhibitor that blocks the catalytic activity of the system. It is anticipated that the Cu2(mu-O)2-patellamide structure is a potential active oxidant of the dicopper patellamide complex.

Synthesis, structure and catechol-oxidase activity of copper(II) complexes of 17-hydroxy-16-(N-3-oxo-prop-1-enyl)amino steroids.

PubMed

Wegner, Rainer; Dubs, Manuela; Görls, Helmar; Robl, Christian; Schönecker, Bruno; Jäger, Ernst-G

2002-09-01

Copper is next to iron the most important element in the biological transport, storage and in redox reactions of dioxygen. A bioanalogous activation of dioxygen with copper complexes is used for catalytical epoxidation, allylic hydroxylation and oxidative coupling of aromatic substrates, for example. With stereochemical information in form of chiral ligands, enantioselective reactions may be possible. Another aspect of interest on copper catalyzed reactions with dioxygen is that the exact mechanism and biological function of some enzymes (especially catechol oxidase) is yet not fully clear. For studies mimicking the copper-containing catechol oxidase appropriate chiral steroid ligands with defined stereochemistry and conformation have been synthesized. The four diastereomeric 16,17-aminoalcohols of the 3-methoxy-estra-1,3,5(10)-triene series have been condensed with salicylic aldehyde and different beta-ketoenols to the chiral ligand types 1-5. These compounds with different steric and electronic properties and different arrangements of the neighboring hydroxy and nitrogen functions were reacted with copper(II) acetate to copper complexes. The structure of these complexes will be discussed. The bioanalogous oxidation of 3,5-di-tbutyl-catechol (dtbc) to the corresponding quinone was catalyzed by most of the complexes, indicating their ability to activate dioxygen. The trans configurations c and d showed an activity one magnitude higher than the cis configurations a and b. Comparing compounds with the same diastereomeric configuration, the main influence was that of the peripheral R(1-3) substituents at the beta-ketoenaminic group which are useful for the fine-tuning of the properties of the copper atoms like redox potential and Lewis acidity.

Experimental and theoretical investigation of topological and energetic characteristics of Sb complexes reversibly binding molecular oxygen.

PubMed

Fukin, Georgy K; Baranov, Evgenii V; Jelsch, Christian; Guillot, Benoît; Poddel'sky, Andrey I; Cherkasov, Vladimir K; Abakumov, Gleb A

2011-07-28

The experimental distribution of electron density in Ph(3)(4,5-OMe-3,6-Bu(t)-Cat)Sb·MeCN (1*) and Ph(3)(4,5-N(2)C(4)H(6)-3,6-Bu(t)-Cat)Sb·MeOH (2*) complexes was studied. According to atoms in molecules theory, the Sb-C(Ph), Sb-O(catecholate), and Sb···N(O) bonds are intermediate, whereas the O-C and C-C bonds are covalent, respectively. The energy of the Sb···N(MeCN) and Sb···O(MeOH) bonds are 7.0 and 11.3 kcal/mol according to the Espinosa equation. Density functional theory and Hartree-Fock calculations were carried out for a series of catecholate and amidophenolate complexes of antimony(V). It was shown that such calculations reliably reproduce geometrical and topological parameters and therefore can be used for a criterion search of dioxygen reversible binding by the catecholate and amidophenolate complexes of antimony(V). It was found that the "critical" value of the HOMO energy vary in the range from -5.197 to -5.061 eV for reversible binding of dioxygen complexes. This can serve as a thermodynamic criterion to predict the possibility of the dioxygen reversible binding by the catecholate and amidophenolate complexes of Sb(V). The HOMO energies correlate with the conversion of the catecholate and amidophenolate complexes in corresponding spiroendoperoxide derivatives as well. The contribution of the atom orbitals of the carbon atoms in the five-membered metallocycle to HOMO in complexes with different substitutes in the 4- and 5-positions of the catecholate ligand allows predicting the place of dioxygen addition. © 2011 American Chemical Society

On the Dynamical Behavior of the Cysteine Dioxygenase-l-Cysteine Complex in the Presence of Free Dioxygen and l-Cysteine.

PubMed

Pietra, Francesco

2017-11-01

In this work, viable models of cysteine dioxygenase (CDO) and its complex with l-cysteine dianion were built for the first time, under strict adherence to the crystal structure from X-ray diffraction studies, for all atom molecular dynamics (MD). Based on the CHARMM36 FF, the active site, featuring an octahedral dummy Fe(II) model, allowed us observing water exchange, which would have escaped attention with the more popular bonded models. Free dioxygen (O 2 ) and l-cysteine, added at the active site, could be observed being expelled toward the solvating medium under Random Accelerated Molecular Dynamics (RAMD) along major and minor pathways. Correspondingly, free dioxygen (O 2 ), added to the solvating medium, could be observed to follow the same above pathways in getting to the active site under unbiased MD. For the bulky l-cysteine, 600 ns of trajectory were insufficient for protein penetration, and the molecule was stuck at the protein borders. These models pave the way to free energy studies of ligand associations, devised to better clarify how this cardinal enzyme behaves in human metabolism. © 2017 Wiley-VHCA AG, Zurich, Switzerland.

The Effects of Non-Redox Active Metal Ions on the Activation of Dioxygen: Isolation and Characterization of a Heterobimetallic Complex Containing a MnIII–(μ-OH)–CaII core

PubMed Central

Park, Young Jun; Ziller, Joseph W.; Borovik, A. S.

2011-01-01

Rate enhancements for the reduction of dioxygen by a MnII complex were observed in the presence of redox inactive Group 2 metal ions. The rate changes correlated with an increase in the Lewis acidity of the Group 2 metal ions. These studies led to the isolation of heterobimetallic complexes that contain MnIII-(μ-OH)-MII cores (MII = CaII, BaII), in which the hydroxo oxygen atom is derived from O2. This type of core structure has relevance to the oxygen evolving complexes within photosystem II. PMID:21595481

Visible-Light-Driven Oxidation of Organic Substrates with Dioxygen Mediated by a [Ru(bpy)3 ](2+) /Laccase System.

PubMed

Schneider, Ludovic; Mekmouche, Yasmina; Rousselot-Pailley, Pierre; Simaan, A Jalila; Robert, Viviane; Réglier, Marius; Aukauloo, Ally; Tron, Thierry

2015-09-21

Oxidation reactions are highly important chemical transformations that still require harsh reaction conditions and stoichiometric amounts of chemical oxidants that are often toxic. To circumvent these issues, olefins oxidation is achieved in mild conditions upon irradiation of an aqueous solution of the complex [Ru(bpy)3 ](2+) and the enzyme laccase. Epoxide formation is coupled to the light-driven reduction of O2 by [Ru(bpy)3 ](2+) /laccase system. The reactivity can be explained by dioxygen acting both as an oxidative agent and as renewable electron acceptor, avoiding the use of a sacrificial electron acceptor. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Further Study of the Products of Sc and Dioxygen Reactions

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Zhou, Mingfei; Andrews, Lester; Johnson, J. R. Tobias; Panas, Itai; Snis, Anders; Roos, Bjoern O.; Arnold, James O. (Technical Monitor)

1999-01-01

The products of the reaction of Sc and dioxygen have been reinvestigated. By adding the electron-trapping molecule CC14, additional information about the IR spectra has been obtained, as well as the observation of new bands. New ab initio calculations are also performed on possible products of the Sc plus O2 reaction. The previously observed band at 722.5 per cm is assigned as the b2 mode of ScO2(-). Bands arising from ScO(+), Sc(O2)(+), and(O2)ScO are also assigned. We are still unable to assign any bands to OScO. The problems associated with the computational study of ScO2 are discussed.

Molecular dynamics simulation of dioxygen pathways through mini singlet oxygen generator (miniSOG), a genetically encoded marker and killer protein.

PubMed

Pietra, Francesco

2014-12-01

In this work, molecular dynamics (MD) simulations of the permeation of proteins by small gases of biological significance have been extended from gas carrier, sensor, and enzymatic proteins to genetically encoded tags and killer proteins. To this end, miniSOG was taken as an example of current high interest, using a biased form of MD, called random-acceleration MD. Various egress gates and binding pockets for dioxygen, as an indistinguishable mimic of singlet dioxygen, were found on both above and below the isoalloxazine plane of the flavin mononucleotide cofactor in miniSOG. Of such gates and binding pockets, those lying within two opposite cones, coaxial with a line normal to the isoalloxazine plane, and with the vertex at the center of such a plane are those most visited by the escaping gas molecule. Out of residues most capable of quenching (1) O2 , Y30, lying near the base of one such a cone, and H85, near the base of the opposite cone, are held to be most responsible for the reduced quantum yield of (1) O2 with folded miniSOG with respect to free flavin mononucleotide in solution. Copyright © 2014 Verlag Helvetica Chimica Acta AG, Zürich.

[Effect of calcium cations on acid-base properties and free radical oxidation of dopamine and pyrocatechol].

PubMed

Lebedev, A V; Ivanova, M V; Timoshin, A A; Ruuge, E K

2008-01-01

Ca2+-induced increase in the rate of pyrocatechol and dopamine oxidation by dioxygen and Ca2+-dependent acid-base properties of the catechols were studied by potentiometric titration, UV/Vis-spectrophotometry, EPR-spectroscopy, and by measurement of oxygen consumption. The effect of Ca2+ on the chain reactions of oxidation can be explained by additional deprotonation (decrease in pKai) of the catechols that accelerates one electron transport to dioxygen and formation of calcium semiquinonate, undergoing further oxidation. The described Ca2+-dependent redox-conversion of ortho-phenols proposes that an additional function of calcium in the cell can be its involvement in free radical oxidoreductive reactions at pH > pKai.

Where Water Is Oxidized to Dioxygen: Structure of the Photosynthetic Mn4Ca Cluster

PubMed Central

Yano, Junko; Kern, Jan; Sauer, Kenneth; Latimer, Matthew J.; Pushkar, Yulia; Biesiadka, Jacek; Loll, Bernhard; Saenger, Wolfram; Messinger, Johannes; Zouni, Athina; Yachandra, Vittal K.

2014-01-01

The oxidation of water to dioxygen is catalyzed within photosystem II (PSII) by a Mn4Ca cluster, the structure of which remains elusive. Polarized extended x-ray absorption fine structure (EXAFS) measurements on PSII single crystals constrain the Mn4Ca cluster geometry to a set of three similar high-resolution structures. Combining polarized EXAFS and x-ray diffraction data, the cluster was placed within PSII, taking into account the overall trend of the electron density of the metal site and the putative ligands. The structure of the cluster from the present study is unlike either the 3.0 or 3.5 angstrom–resolution x-ray structures or other previously proposed models. PMID:17082458

Visible light-driven O2 reduction by a porphyrin-laccase system.

PubMed

Lazarides, Theodore; Sazanovich, Igor V; Simaan, A Jalila; Kafentzi, Maria Chrisanthi; Delor, Milan; Mekmouche, Yasmina; Faure, Bruno; Réglier, Marius; Weinstein, Julia A; Coutsolelos, Athanassios G; Tron, Thierry

2013-02-27

Several recent studies have shown that the combination of photosensitizers with metalloenzymes can support a light-driven multielectron reduction of molecules such as CO(2) or HCN. Here we show that the association of the zinc tetramethylpyridinium porphyrin (ZnTMPyP(4+)) photosensitizer with the multicopper oxidase (MCO) laccase allows to link the oxidation of an organic molecule to the four electrons reduction of dioxygen into water. The enzyme is photoreduced within minutes with porphyrin/enzyme ratio as low as 1:40. With a 1:1 ratio, the dioxygen consumption rate is 1.7 μmol L(-1) s(-1). Flash photolysis experiments support the formation of the triplet excited state of ZnTMPyP(4+) which reduces the enzyme to form a radical cation of the porphyrin with a k(ET) ≈ 10(7) s(-1) M(-1). The long-lived triplet excited state of the ZnTMPyP(4+) (τ(0) = 0.72 ms) accounts for a substantial electron-transfer quantum yield, φ(ET) = 0.35. Consequently, the enzyme-dependent photo-oxidation of the electron donor occurs with a turnover of 8 min(-1) for the one-electron oxidation process, thereby supporting the suitability of such enzyme/sensitizer hybrid systems for aerobic photodriven transformations on substrates. This study is the first example of a phorphyrin-sensitized four-electron reduction of an enzyme of the MCO family, leading to photoreduction of dioxygen into water.

Activation of Dioxygen by Iron and Manganese Complexes: A Heme and Nonheme Perspective

PubMed Central

Sahu, Sumit; Goldberg, David P.

2016-01-01

The rational design of well-defined, first-row transition metal complexes that can activate dioxygen has been a challenging goal for the synthetic inorganic chemist. The activation of O2 is important in part because of its central role in the functioning of metalloenzymes, which utilize O2 to perform a number of challenging reactions including the highly selective oxidation of various substrates. There is also great interest in utilizing O2, an abundant and environmentally benign oxidant, in synthetic catalytic oxidation systems. This Perspective brings together recent examples of biomimetic Fe and Mn complexes that can activate O2 in heme or nonheme-type ligand environments. The use of oxidants such as hypervalent iodine (e.g., ArIO), peracids (e.g., m-CPBA), peroxides (e.g., H2O2) or even superoxide is a popular choice for accessing well-characterized metal–superoxo, metal–peroxo, or metal–oxo species, but the instances of biomimetic Fe/Mn complexes that react with dioxygen to yield such observable metal–oxygen species are surprisingly few. This Perspective focuses on mononuclear Fe and Mn complexes that exhibit reactivity with O2 and lead to spectroscopically observable metal–oxygen species, and/or oxidize biologically relevant substrates. Analysis of these examples reveals that solvent, spin state, redox potential, external co-reductants, and ligand architecture can all play important roles in the O2 activation process. PMID:27576170

Transformation of Chlorinated Benzenes and Toluenes by Ralstonia sp. Strain PS12 tecA (Tetrachlorobenzene Dioxygenase) and tecB (Chlorobenzene Dihydrodiol Dehydrogenase) Gene Products

PubMed Central

Pollmann, Katrin; Beil, Stefan; Pieper, Dietmar H.

2001-01-01

The tecB gene, located downstream of tecA and encoding tetrachlorobenzene dioxygenase, in Ralstonia sp. strain PS12 was cloned into Escherichia coli DH5α together with the tecA gene. The identity of the tecB gene product as a chlorobenzene dihydrodiol dehydrogenase was verified by transformation into the respective catechols of chlorobenzene, the three isomeric dichlorobenzenes, as well as 1,2,3- and 1,2,4-trichlorobenzenes, all of which are transformed by TecA into the respective dihydrodihydroxy derivatives. Di- and trichlorotoluenes were either subject to TecA-mediated dioxygenation (the major or sole reaction observed for the 1,2,4-substituted 2,4-, 2,5-, and 3,4-dichlorotoluenes), resulting in the formation of the dihydrodihydroxy derivatives, or to monooxygenation of the methyl substituent (the major or sole reaction observed for 2,3-, 2,6-, and 3,5-dichloro- and 2,4,5-trichlorotoluenes), resulting in formation of the respective benzyl alcohols. All of the chlorotoluenes subject to dioxygenation by TecA were transformed, without intermediate accumulation of dihydrodihydroxy derivatives, into the respective catechols by TecAB, indicating that dehydrogenation is no bottleneck for chlorobenzene or chlorotoluene degradation. However, only those chlorotoluenes subject to a predominant dioxygenation were growth substrates for PS12, confirming that monooxygenation is an unproductive pathway in PS12. PMID:11526005

The Relationship between Environmental Dioxygen and Iron-Sulfur Proteins Explored at the Genome Level

PubMed Central

Andreini, Claudia; Rosato, Antonio; Banci, Lucia

2017-01-01

About 2 billion years ago, the atmosphere of the Earth experienced a great change due to the buildup of dioxygen produced by photosynthetic organisms. This transition caused a reduction of iron bioavailability and at the same time exposed living organisms to the threat of oxidative stress. Iron-sulfur (Fe-S) clusters require iron ions for their biosynthesis and are labile if exposed to reactive oxygen species. To assess how the above transition influenced the usage of Fe-S clusters by organisms, we compared the distribution of the Fe-S proteins encoded by the genomes of more than 400 prokaryotic organisms as a function of their dioxygen requirements. Aerobic organisms use less Fe-S proteins than the majority of anaerobic organisms with a similar genome size. Furthermore, aerobes have evolved specific Fe-S proteins that bind the less iron-demanding and more chemically stable Fe2S2 clusters while reducing the number of Fe4S4-binding proteins in their genomes. However, there is a shared core of Fe-S protein families composed mainly by Fe4S4-binding proteins. Members of these families are present also in humans. The distribution of human Fe-S proteins within cell compartments shows that mitochondrial proteins are inherited from prokaryotic proteins of aerobes, whereas nuclear and cytoplasmic Fe-S proteins are inherited from anaerobic organisms. PMID:28135316

Hydrogen Peroxide as a Sustainable Energy Carrier: Electrocatalytic Production of Hydrogen Peroxide and the Fuel Cell.

PubMed

Fukuzumi, Shunichi; Yamada, Yusuke; Karlin, Kenneth D

2012-11-01

This review describes homogeneous and heterogeneous catalytic reduction of dioxygen with metal complexes focusing on the catalytic two-electron reduction of dioxygen to produce hydrogen peroxide. Whether two-electron reduction of dioxygen to produce hydrogen peroxide or four-electron O 2 -reduction to produce water occurs depends on the types of metals and ligands that are utilized. Those factors controlling the two processes are discussed in terms of metal-oxygen intermediates involved in the catalysis. Metal complexes acting as catalysts for selective two-electron reduction of oxygen can be utilized as metal complex-modified electrodes in the electrocatalytic reduction to produce hydrogen peroxide. Hydrogen peroxide thus produced can be used as a fuel in a hydrogen peroxide fuel cell. A hydrogen peroxide fuel cell can be operated with a one-compartment structure without a membrane, which is certainly more promising for the development of low-cost fuel cells as compared with two compartment hydrogen fuel cells that require membranes. Hydrogen peroxide is regarded as an environmentally benign energy carrier because it can be produced by the electrocatalytic two-electron reduction of O 2 , which is abundant in air, using solar cells; the hydrogen peroxide thus produced could then be readily stored and then used as needed to generate electricity through the use of hydrogen peroxide fuel cells.

Hydroquinone-Mediated Redox Cycling of Iron and Concomitant Oxidation of Hydroquinone in Oxic Waters under Acidic Conditions: Comparison with Iron-Natural Organic Matter Interactions.

PubMed

Jiang, Chao; Garg, Shikha; Waite, T David

2015-12-15

Interactions of 1,4-hydroquinone with soluble iron species over a pH range of 3-5 in the air-saturated and partially deoxygenated solution are examined here. Our results show that 1,4-hydroquinone reduces Fe(III) in acidic conditions, generating semiquinone radicals (Q(•-)) that can oxidize Fe(II) back to Fe(III). The oxidation rate of Fe(II) by Q(•-)increases with increase in pH due to the speciation change of Q(•-) with its deprotonated form (Q(•-)) oxidizing Fe(II) more rapidly than the protonated form (HQ(•)). Although the oxygenation of Fe(II) is negligible at pH < 5, O2 still plays an important role in iron redox transformation by rapidly oxidizing Q(•-) to form benzoquinone (Q). A kinetic model is developed to describe the transformation of quinone and iron under all experimental conditions. The results obtained here are compared with those obtained in our previous studies of iron-Suwannee River fulvic acid (SRFA) interactions in acidic solutions and support the hypothesis that hydroquinone moieties can reduce Fe(III) in natural waters. However, the semiquinone radicals generated in pure hydroquinone solution are rapidly oxidized by dioxygen, while the semiquinone radicals generated in SRFA solution are resistant to oxidation by dioxygen, with the result that steady-state semiquinone concentrations in SRFA solutions are 2-3 orders of magnitude greater than in solutions of 1,4-hydroquinone. As a result, semiquinone moieties in SRFA play a much more important role in iron redox transformations than is the case in solutions of simple quinones such as 1,4-hydroquinone. This difference in the steady-state concentration of semiquinone species has a dramatic effect on the cycling of iron between the +II and +III oxidation states, with iron turnover frequencies in solutions containing SRFA being 10-20 times higher than those observed in solutions of 1,4-hydroquinone.

Thin film devices used as oxygen partial pressure sensors

NASA Technical Reports Server (NTRS)

Canady, K. S.; Wortman, J. J.

1970-01-01

Electrical conductivity of zinc oxide films to be used in an oxygen partial pressure sensor is measured as a function of temperature, oxygen partial pressure, and other atmospheric constituents. Time response following partial pressure changes is studied as a function of temperature and environmental changes.

Conformational States of the Rapana thomasiana Hemocyanin and Its Substructures Studied by Dynamic Light Scattering and Time-Resolved Fluorescence Spectroscopy

PubMed Central

Georgieva, Dessislava; Schwark, Daniel; Nikolov, Peter; Idakieva, Krassimira; Parvanova, Katja; Dierks, Karsten; Genov, Nicolay; Betzel, Christian

2005-01-01

Hemocyanins are dioxygen-transporting proteins freely dissolved in the hemolymph of mollusks and arthropods. Dynamic light scattering and time-resolved fluorescence measurements show that the oxygenated and apo-forms of the Rapana thomasiana hemocyanin, its structural subunits RtH1 and RtH2, and those of the functional unit RtH2e, exist in different conformations. The oxygenated respiratory proteins are less compact and more asymmetric than the respective apo-forms. Different conformational states were also observed for the R. thomasiana hemocyanin in the absence and presence of an allosteric regulator. The results are in agreement with a molecular mechanism for cooperative dioxygen binding in molluscan hemocyanins including transfer of conformational changes from one functional unit to another. PMID:15533921

Factors associated with blood oxygen partial pressure and carbon dioxide partial pressure regulation during respiratory extracorporeal membrane oxygenation support: data from a swine model.

PubMed

Park, Marcelo; Mendes, Pedro Vitale; Costa, Eduardo Leite Vieira; Barbosa, Edzangela Vasconcelos Santos; Hirota, Adriana Sayuri; Azevedo, Luciano Cesar Pontes

2016-01-01

The aim of this study was to explore the factors associated with blood oxygen partial pressure and carbon dioxide partial pressure. The factors associated with oxygen - and carbon dioxide regulation were investigated in an apneic pig model under veno-venous extracorporeal membrane oxygenation support. A predefined sequence of blood and sweep flows was tested. Oxygenation was mainly associated with extracorporeal membrane oxygenation blood flow (beta coefficient = 0.036mmHg/mL/min), cardiac output (beta coefficient = -11.970mmHg/L/min) and pulmonary shunting (beta coefficient = -0.232mmHg/%). Furthermore, the initial oxygen partial pressure and carbon dioxide partial pressure measurements were also associated with oxygenation, with beta coefficients of 0.160 and 0.442mmHg/mmHg, respectively. Carbon dioxide partial pressure was associated with cardiac output (beta coefficient = 3.578mmHg/L/min), sweep gas flow (beta coefficient = -2.635mmHg/L/min), temperature (beta coefficient = 4.514mmHg/ºC), initial pH (beta coefficient = -66.065mmHg/0.01 unit) and hemoglobin (beta coefficient = 6.635mmHg/g/dL). In conclusion, elevations in blood and sweep gas flows in an apneic veno-venous extracorporeal membrane oxygenation model resulted in an increase in oxygen partial pressure and a reduction in carbon dioxide partial pressure 2, respectively. Furthermore, without the possibility of causal inference, oxygen partial pressure was negatively associated with pulmonary shunting and cardiac output, and carbon dioxide partial pressure was positively associated with cardiac output, core temperature and initial hemoglobin.

The reduction of nitric oxide by ammonia over polycrystalline platinum model catalysts in the presence of oxygen

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

Katona, T.; Guczi, L.; Somorjai, G.A.

1992-06-01

The reaction system of nitric oxide, ammonia, and oxygen was studied using batch-mode measurements in partial pressure ranges of 65-1000 Pa (0.5-7.6 Torr) on polycrystalline Pt foils over the temperature range 423-598 K. Under these conditions the oxidation of nitric oxide was not detectable. The ammonia oxidation reaction, using dioxygen, occurred in the temperature range 423-493 K, producing nitrogen and water as the only products. The activation energy of the nitrogen formation was found to be 86 kJ/mol. Above this temperature range, flow-mode measurements showed the formation of both nitrous oxide and nitric oxide. The reaction rate between ammonia andmore » oxygen was greatly decreased (about a factor of 10) by nitric oxide, while the reaction rate between nitric oxide and ammonia was accelerated (about 10-fold) due to the presence of oxygen. Nitric oxide reduction by ammonia in the presence of oxygen occurred in the temperature range 423-598 K. The products of the reaction were nitrogen, oxygen nitrous oxide, and water. The Arrhenius plot of the reaction showed a break near 523 K. Below this temperature the activation energy of the reaction was 13 kJ/mol, and in the higher-temperature range it was 62 kJ/mol. At 473 K, the N[sub 2]/N[sub 2]O ratio was about 0.6 and O[sub 2] formation was also monitored. At 573 K, the N[sub 2]N[sub 2]O ratio was approximately 2 and oxygen was consumed in the course of the reaction as well.« less

Reactivity of molecular dioxygen towards a series of isostructural dichloroiron(III) complexes with tripodal tetraamine ligands: general access to mu-oxodiiron(III) complexes and effect of alpha-fluorination on the reaction kinetics.

PubMed

Thallaj, Nasser K; Rotthaus, Olaf; Benhamou, Leila; Humbert, Nicolas; Elhabiri, Mourad; Lachkar, Mohammed; Welter, Richard; Albrecht-Gary, Anne-Marie; Mandon, Dominique

2008-01-01

We have synthesized the mono, di-, and tri-alpha-fluoro ligands in the tris(2-pyridylmethyl)amine (TPA) series, namely, FTPA, F(2)TPA and F(3)TPA, respectively. Fluorination at the alpha-position of these nitrogen-containing tripods shifts the oxidation potential of the ligand by 45-70 mV per added fluorine atom. The crystal structures of the dichloroiron(II) complexes with FTPA and F(2)TPA reveal that the iron center lies in a distorted octahedral geometry comparable to that already found in TPAFeCl(2). All spectroscopic data indicate that the geometry is retained in solution. These three isostructural complexes all react with molecular dioxygen to yield stable mu-oxodiiron(III) complexes. Crystal structure analyses are reported for each of these three mu-oxo compounds. With TPA, a symmetrical structure is obtained for a dicationic compound with the tripod coordinated in the kappa(4)N coordination mode. With FTPA, the compound is a neutral mu-oxodiiron(III) complex with a kappa(3)N coordination mode of the ligand. Oxygenation of the F(2)TPA complex gave a neutral unsymmetrical compound, the structure of which is reminiscent of that already found with the trifluorinated ligand. On reduction, all mu-oxodiiron(III) complexes revert to the starting iron(II) species. The oxygenation reaction parallels the well-known formation of mu-oxo derivatives from dioxygen in the chemistry of porphyrins reported almost three decades ago. The striking feature of the series of iron(II) precursors is the effect of the ligand on the kinetics of oxygenation of the complexes. Whereas the parent complex undergoes 90 % conversion over 40 h, the monofluorinated ligand provides a complex that has fully reacted after 30 h, whereas the reaction time for the complex with the difluorinated ligand is only 10 h. Analysis of the spectroscopic data reveals that formation of the mu-oxo complexes proceeds in two distinct reversible kinetic steps with k(1) approximately 10 k(2). For TPAFeCl(2) and FTPAFeCl(2) only small variations in the k(1) and k(2) values are observed. By contrast, F(2)TPAFeCl(2) exhibits k(1) and k(2) values that are ten times higher. These differences in kinetics are interpreted in the light of structural and electronic effects, especially the Lewis acidity at the metal center. Our results suggest coordination of dioxygen as an initial step in the process leading to formation of mu-oxodiiron(III) compounds, by contrast with an unlikely outer-sphere reduction of dioxygen, which generally occurs at negative potentials.

21 CFR 868.1150 - Indwelling blood carbon dioxide partial pressure (PCO2) analyzer.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Indwelling blood carbon dioxide partial pressure....1150 Indwelling blood carbon dioxide partial pressure (PCO2) analyzer. (a) Identification. An indwelling blood carbon dioxide partial pressure PCO2 analyzer is a device that consists of a catheter-tip...

21 CFR 868.1150 - Indwelling blood carbon dioxide partial pressure (PCO2) analyzer.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Indwelling blood carbon dioxide partial pressure....1150 Indwelling blood carbon dioxide partial pressure (PCO2) analyzer. (a) Identification. An indwelling blood carbon dioxide partial pressure PCO2 analyzer is a device that consists of a catheter-tip...

21 CFR 868.1150 - Indwelling blood carbon dioxide partial pressure (PCO2) analyzer.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Indwelling blood carbon dioxide partial pressure....1150 Indwelling blood carbon dioxide partial pressure (PCO2) analyzer. (a) Identification. An indwelling blood carbon dioxide partial pressure PCO2 analyzer is a device that consists of a catheter-tip...

21 CFR 868.1150 - Indwelling blood carbon dioxide partial pressure (PCO2) analyzer.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Indwelling blood carbon dioxide partial pressure....1150 Indwelling blood carbon dioxide partial pressure (PCO2) analyzer. (a) Identification. An indwelling blood carbon dioxide partial pressure PCO2 analyzer is a device that consists of a catheter-tip...

Factors associated with blood oxygen partial pressure and carbon dioxide partial pressure regulation during respiratory extracorporeal membrane oxygenation support: data from a swine model

PubMed Central

Park, Marcelo; Mendes, Pedro Vitale; Costa, Eduardo Leite Vieira; Barbosa, Edzangela Vasconcelos Santos; Hirota, Adriana Sayuri; Azevedo, Luciano Cesar Pontes

2016-01-01

Objective The aim of this study was to explore the factors associated with blood oxygen partial pressure and carbon dioxide partial pressure. Methods The factors associated with oxygen - and carbon dioxide regulation were investigated in an apneic pig model under veno-venous extracorporeal membrane oxygenation support. A predefined sequence of blood and sweep flows was tested. Results Oxygenation was mainly associated with extracorporeal membrane oxygenation blood flow (beta coefficient = 0.036mmHg/mL/min), cardiac output (beta coefficient = -11.970mmHg/L/min) and pulmonary shunting (beta coefficient = -0.232mmHg/%). Furthermore, the initial oxygen partial pressure and carbon dioxide partial pressure measurements were also associated with oxygenation, with beta coefficients of 0.160 and 0.442mmHg/mmHg, respectively. Carbon dioxide partial pressure was associated with cardiac output (beta coefficient = 3.578mmHg/L/min), sweep gas flow (beta coefficient = -2.635mmHg/L/min), temperature (beta coefficient = 4.514mmHg/ºC), initial pH (beta coefficient = -66.065mmHg/0.01 unit) and hemoglobin (beta coefficient = 6.635mmHg/g/dL). Conclusion In conclusion, elevations in blood and sweep gas flows in an apneic veno-venous extracorporeal membrane oxygenation model resulted in an increase in oxygen partial pressure and a reduction in carbon dioxide partial pressure 2, respectively. Furthermore, without the possibility of causal inference, oxygen partial pressure was negatively associated with pulmonary shunting and cardiac output, and carbon dioxide partial pressure was positively associated with cardiac output, core temperature and initial hemoglobin. PMID:27096671

21 CFR 868.1200 - Indwelling blood oxygen partial pressure (PO2) analyzer.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Indwelling blood oxygen partial pressure (PO2... Indwelling blood oxygen partial pressure (PO2) analyzer. (a) Identification. An indwelling blood oxygen... electrode) and that is used to measure, in vivo, the partial pressure of oxygen in blood to aid in...

21 CFR 868.1200 - Indwelling blood oxygen partial pressure (PO2) analyzer.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Indwelling blood oxygen partial pressure (PO2... Indwelling blood oxygen partial pressure (PO2) analyzer. (a) Identification. An indwelling blood oxygen... electrode) and that is used to measure, in vivo, the partial pressure of oxygen in blood to aid in...

21 CFR 868.1200 - Indwelling blood oxygen partial pressure (PO2) analyzer.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Indwelling blood oxygen partial pressure (PO2... Indwelling blood oxygen partial pressure (PO2) analyzer. (a) Identification. An indwelling blood oxygen... electrode) and that is used to measure, in vivo, the partial pressure of oxygen in blood to aid in...

21 CFR 868.1200 - Indwelling blood oxygen partial pressure (PO2) analyzer.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Indwelling blood oxygen partial pressure (PO2... Indwelling blood oxygen partial pressure (PO2) analyzer. (a) Identification. An indwelling blood oxygen... electrode) and that is used to measure, in vivo, the partial pressure of oxygen in blood to aid in...

21 CFR 868.1200 - Indwelling blood oxygen partial pressure (PO2) analyzer.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Indwelling blood oxygen partial pressure (PO2... Indwelling blood oxygen partial pressure (PO2) analyzer. (a) Identification. An indwelling blood oxygen... electrode) and that is used to measure, in vivo, the partial pressure of oxygen in blood to aid in...

Controlling the Chiral Inversion Reaction of the Metallopeptide Ni-Asparagine-Cysteine-Cysteine with Dioxygen

PubMed Central

Glass, Amanda M.; Krause, Mary E.; Laurence, Jennifer S.; Jackson, Timothy A.

2014-01-01

Synthetically generated metallopeptides have the potential to serve a variety of roles in biotechnology applications, but the use of such systems is often hampered by the inability to control secondary reactions. We have previously reported that the NiII complex of the tripeptide LLL-asparagine-cysteine-cysteine, LLL-NiII-NCC, undergoes metal-facilitated chiral inversion to DLD-NiII-NCC, which increases the observed superoxide scavenging activity. However, the mechanism for this process remained unexplored. Electronic absorption and circular dichroism studies of the chiral inversion reaction of NiII-NCC reveal a unique dependence on dioxygen. Specifically, in the absence of dioxygen, the chiral inversion is not observed, even at elevated pH, whereas the addition of O2 initiates this reactivity and concomitantly generates superoxide. Scavenging experiments using acetaldehyde are indicative of the formation of carbanion intermediates, demonstrating that inversion takes place by deprotonation of the alpha carbons of Asn1 and Cys3. Together, these data are consistent with the chiral inversion being dependent on the formation of a NiIII-NCC intermediate from NiII-NCC and O2. The data further suggest that the anionic thiolate and amide ligands in NiII-NCC inhibit Cα–H deprotonation for the NiII oxidation state, leading to a stable complex in the absence of O2. Together, these results offer insights into the factors controlling reactivity in synthetic metallopeptides. PMID:22928993

Partial Pressures of Te2 and Thermodynamic Properties of Ga-Te System

NASA Technical Reports Server (NTRS)

Su, Ching-Hua; Curreri, Peter A. (Technical Monitor)

2001-01-01

The partial pressures of Te2 in equilibrium with Ga(1-x)Te(x) samples were measured by optical absorption technique from 450 to 1100 C for compositions, x, between 0.333 and 0.612. To establish the relationship between the partial pressure of Te, and the measured optical absorbance, the calibration runs of a pure Te sample were also conducted to determine the Beer's Law constants. The partial pressures of Te2 in equilibrium with the GaTe(s) and Ga2Te3(s)compounds, or the so-called three-phase curves, were established. These partial pressure data imply the existence of the Ga3Te4(s) compound. From the partial pressures of Te2 over the Ga-Te melts, partial molar enthalpy and entropy of mixing for Te were derived and they agree reasonable well with the published data. The activities of Te in the Ga-Te melts were also derived from the measured partial pressures of Te2. These data agree well with most of the previous results. The possible reason for the high activity of Te measured for x less than 0.60 is discussed.

Relationships between nitric oxide, nitroxyl ion, nitrosonium cation and peroxynitrite.

PubMed

Hughes, M N

1999-05-05

This review is concerned mainly with the three redox-related, but chemically distinct, species NO-, NO. and NO+, with greatest emphasis being placed on the chemistry and biology of the nitroxyl ion. Biochemical routes for the formation of nitroxyl ion and methods for showing the intermediacy of this species are discussed, together with chemical methods for generating nitroxyl ion in solution. Reactions of nitroxyl ion with NO., thiols, iron centres in haem and with dioxygen are reviewed The significance of the reaction between NO- and dioxygen as a source of peroxynitrite is assessed, and attention drawn to the possible significance of the spin state of the nitroxyl ion in this context. The biological significance of nitrosation and the importance of S-nitrosothiols and certain metal nitrosyl complexes as carriers of NO+ at physiological pH is stressed. Some features in the chemistry of peroxynitrite are noted.

Aliphatic C-C Bond Cleavage in α-Hydroxy Ketones by a Dioxygen-Derived Nucleophilic Iron-Oxygen Oxidant.

PubMed

Bhattacharya, Shrabanti; Rahaman, Rubina; Chatterjee, Sayanti; Paine, Tapan K

2017-03-17

A nucleophilic iron-oxygen oxidant, formed in situ in the reaction between an iron(II)-benzilate complex and O 2 , oxidatively cleaves the aliphatic C-C bonds of α-hydroxy ketones. In the cleavage reaction, α-hydroxy ketones without any α-C-H bond afford a 1:1 mixture of carboxylic acid and ketone. Isotope labeling studies established that one of the oxygen atoms from dioxygen is incorporated into the carboxylic acid product. Furthermore, the iron(II) complex cleaves an aliphatic C-C bond of 17-α-hydroxyprogesterone affording androstenedione and acetic acid. The O 2 -dependent aliphatic C-C bond cleavage of α-hydroxy ketones containing no α-C-H bond bears similarity to the lyase activity of the heme enzyme, cytochrome P450 17A1 (CYP17A1). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygen Partial Pressure and Oxygen Concentration Flammability: Can They Be Correlated?

NASA Technical Reports Server (NTRS)

Harper, Susana A.; Juarez, Alfredo; Perez, Horacio, III; Hirsch, David B.; Beeson, Harold D.

2016-01-01

NASA possesses a large quantity of flammability data performed in ISS airlock (30% Oxygen 526mmHg) and ISS cabin (24.1% Oxygen 760 mmHg) conditions. As new programs develop, other oxygen and pressure conditions emerge. In an effort to apply existing data, the question arises: Do equivalent oxygen partial pressures perform similarly with respect to flammability? This paper evaluates how material flammability performance is impacted from both the Maximum Oxygen Concentration (MOC) and Maximum Total Pressures (MTP) perspectives. From these studies, oxygen partial pressures can be compared for both the MOC and MTP methods to determine the role of partial pressure in material flammability. This evaluation also assesses the influence of other variables on flammability performance. The findings presented in this paper suggest flammability is more dependent on oxygen concentration than equivalent partial pressure.

Pressure (Or No Royal Road)

ERIC Educational Resources Information Center

Bradley, J.

1973-01-01

Discusses how difficult the various problems of pressure, partial pressure, gas laws, and vapor pressure are for students. Outlines the evolution of the concept of pressure, the gas equation for a perfect gas, partial pressures, saturated vapor pressure, Avogadro's hypothesis, Raoult's law, and the vapor pressure of ideal solutions. (JR)

Characterization and dioxygen reactivity of a new series of coordinatively unsaturated thiolate-ligated manganese(II) complexes.

PubMed

Coggins, Michael K; Toledo, Santiago; Shaffer, Erika; Kaminsky, Werner; Shearer, Jason; Kovacs, Julie A

2012-06-18

The synthesis, structural, and spectroscopic characterization of four new coordinatively unsaturated mononuclear thiolate-ligated manganese(II) complexes ([Mn(II)(S(Me2)N(4)(6-Me-DPEN))](BF(4)) (1), [Mn(II)(S(Me2)N(4)(6-Me-DPPN))](BPh(4))·MeCN (3), [Mn(II)(S(Me2)N(4)(2-QuinoPN))](PF(6))·MeCN·Et(2)O (4), and [Mn(II)(S(Me2)N(4)(6-H-DPEN)(MeOH)](BPh(4)) (5)) is described, along with their magnetic, redox, and reactivity properties. These complexes are structurally related to recently reported [Mn(II)(S(Me2)N(4)(2-QuinoEN))](PF(6)) (2) (Coggins, M. K.; Kovacs, J. A. J. Am. Chem. Soc.2011, 133, 12470). Dioxygen addition to complexes 1-5 is shown to result in the formation of five new rare examples of Mn(III) dimers containing a single, unsupported oxo bridge: [Mn(III)(S(Me2)N(4)(6-Me-DPEN)](2)-(μ-O)(BF(4))(2)·2MeOH (6), [Mn(III)(S(Me2)N(4)(QuinoEN)](2)-(μ-O)(PF(6))(2)·Et(2)O (7), [Mn(III)(S(Me2)N(4)(6-Me-DPPN)](2)-(μ-O)(BPh(4))(2) (8), [Mn(III)(S(Me2)N(4)(QuinoPN)](2)-(μ-O)(BPh(4))(2) (9), and [Mn(III)(S(Me2)N(4)(6-H-DPEN)](2)-(μ-O)(PF(6))(2)·2MeCN (10). Labeling studies show that the oxo atom is derived from (18)O(2). Ligand modifications, involving either the insertion of a methylene into the backbone or the placement of an ortho substituent on the N-heterocyclic amine, are shown to noticeably modulate the magnetic and reactivity properties. Fits to solid-state magnetic susceptibility data show that the Mn(III) ions of μ-oxo dimers 6-10 are moderately antiferromagnetically coupled, with coupling constants (2J) that fall within the expected range. Metastable intermediates, which ultimately convert to μ-oxo bridged 6 and 7, are observed in low-temperature reactions between 1 and 2 and dioxygen. Complexes 3-5, on the other hand, do not form observable intermediates, thus illustrating the effect that relatively minor ligand modifications have upon the stability of metastable dioxygen-derived species.

Pressures of Partial Crystallization of Magmas Along Transforms: Implications for Crustal Accretion

NASA Astrophysics Data System (ADS)

Scott, J. L.; Zerda, C.; Brown, D.; Ciaramitaro, S. C.; Barton, M.

2016-12-01

Plate spreading at mid-ocean ridges is responsible for the creation of most of the crust on earth. The ridge system is very complex and many questions remain unresolved. Among these is the nature of magma plumbing systems beneath transform faults. Pervious workers have suggested that increased conductive cooling along transforms promotes higher pressures of partial crystallization, and that this explains the higher partial pressures of crystallization inferred for magmas erupted along slow spreading ridges compared to magmas erupted along faster spreading ridges. To test this hypothesis, we undertook a detailed analysis of pressures of partial crystallization for magmas erupted at 3 transforms along the fast to intermediate spreading East Pacific Rise(Blanco, Clipperton, and Siqueiros) and 3 transforms along the slow spreading Mid Atlantic Ridge(Famous Transform B, Kane, and 15°20'N). Pressures of partial crystallization were calculated from the compositions of glasses (quenched liquids) lying along the P (and T) dependent olivine, plagioclase, and augite cotectic using the method described by Kelley and Barton (2008). Published analyses of mid-ocean ridge basalt glasses sampled from these transforms and surrounding ridge segments were used as input data. Samples with anomalous chemical compositions and samples that yielded pressures associated with unrealistically large uncertainties were filtered out of the database. The pressures of partial crystallization for the remaining 916 samples ranged from 0 to 520 MPa with the great majority ( 95%) of sample returning pressures of less than 300 MPa. Pressures of < 300 MPa are within error of the pressure range associated with partial crystallization within oceanic crust with a thickness of 7 km. Higher (sub-crustal) pressures (>300 MPa) are associated with a small number of samples from the Pacific segments. Except for the Blanco, pressures of partial crystallization do not increase as transforms are approached. These observations contrast with those of previous workers, who reported anomalously high pressures (up to 1000 MPa) for a large number of samples erupted near both Atlantic and Pacific Transforms. We conclude that higher rates of cooling along transform does not have a major effect on the onset of partial crystallization along the mid-ocean ridges

Influence of N2 partial pressure on structural and microhardness properties of TiN/ZrN multilayers deposited by Ar/N2 vacuum arc discharge

NASA Astrophysics Data System (ADS)

Naddaf, M.; Abdallah, B.; Ahmad, M.; A-Kharroub, M.

2016-08-01

The influence of N2 partial pressure on structural, mechanical and wetting properties of multilayered TiN/ZrN thin films deposited on silicon substrates by vacuum arc discharge of (N2 + Ar) gas mixtures is investigated. X-ray diffraction (XRD) results show that the average texturing coefficient of (1 1 1) orientation and the grain size of both TiN and ZrN individual layers increase with increasing the N2 partial pressure. The Rutherford back scattering (RBS) measurements and analysis reveal that incorporation of the nitrogen in the film increases with increasing the N2 partial pressure and both TiN and ZrN individual layers have a nitrogen over-stoichiometry for N2 partial pressure ⩾50%. The change in the film micro-hardness is correlated to the changes in crystallographic texture, grain size, stoichiometry and the residual stress in the film as a function of the N2 partial pressure. In particular, stoichiometry of ZrN and TiN individual is found to play the vital role in determining the multilayer hardness. The multilayer film deposited at N2 partial pressure of 25% has the best stoichiometric ratio of both TiN and ZrN layers and the highest micro-hardness of about 32 GPa. In addition, water contact angle (WCA) measurements and analysis show a decrease in the work of adhesion on increasing the N2 partial pressure.

Nitrite reductase activity of rat and human xanthine oxidase, xanthine dehydrogenase, and aldehyde oxidase: evaluation of their contribution to NO formation in vivo.

PubMed

Maia, Luisa B; Pereira, Vânia; Mira, Lurdes; Moura, José J G

2015-01-27

Nitrite is presently considered a NO "storage form" that can be made available, through its one-electron reduction, to maintain NO formation under hypoxia/anoxia. The molybdoenzymes xanthine oxidase/dehydrogenase (XO/XD) and aldehyde oxidase (AO) are two of the most promising mammalian nitrite reductases, and in this work, we characterized NO formation by rat and human XO/XD and AO. This is the first characterization of human enzymes, and our results support the employment of rat liver enzymes as suitable models of the human counterparts. A comprehensive kinetic characterization of the effect of pH on XO and AO-catalyzed nitrite reduction showed that the enzyme's specificity constant for nitrite increase 8-fold, while the Km(NO2(-)) decrease 6-fold, when the pH decreases from 7.4 to 6.3. These results demonstrate that the ability of XO/AO to trigger NO formation would be greatly enhanced under the acidic conditions characteristic of ischemia. The dioxygen inhibition was quantified, and the Ki(O2) values found (24.3-48.8 μM) suggest that in vivo NO formation would be fine-tuned by dioxygen availability. The potential in vivo relative physiological relevance of XO/XD/AO-dependent pathways of NO formation was evaluated using HepG2 and HMEC cell lines subjected to hypoxia. NO formation by the cells was found to be pH-, nitrite-, and dioxygen-dependent, and the relative contribution of XO/XD plus AO was found to be as high as 50%. Collectively, our results supported the possibility that XO/XD and AO can contribute to NO generation under hypoxia inside a living human cell. Furthermore, the molecular mechanism of XO/AO-catalyzed nitrite reduction was revised.

Dopamine, 6-hydroxydopamine, iron, and dioxygen--their mutual interactions and possible implication in the development of Parkinson's disease.

PubMed

Linert, W; Herlinger, E; Jameson, R F; Kienzl, E; Jellinger, K; Youdim, M B

1996-08-23

The reactions of dopamine (1-amino-2-(3,4-dihydroxyphenyl)-ethane, DA), 5-hydroxydopamine (5-OHDA), and 6-hydroxydopamine (6-OHDA), with molecular oxygen-with and without the addition of catalytic amounts of iron(III) and other metal ions-have been studied and the implication of these results with respect to the chemistry involved in the progress of Parkinson's disease is discussed. In the presence of O2 DA reacts spontaneously without the necessity of metal-ion catalysis under the production of stoichiometric amounts of H2O2, to form initially pink dopaminochrome, which is not stable and reacts further (without the consumption of dioxygen) to form the insoluble polymeric material known as 'melanine'. DA reacts with iron(III) yielding an intermediate 1:1 complex, which decomposes releasing Fe(II) and the semiquinone, which reacts further under involvement of both Fe(III) and dioxygen. 6-OHDA reacts without showing the necessity of such an intermediate, and it is shown to be able to release iron as Fe(II) from ferritine. On the other hand, it is shown (in vitro) that Fe(II) reacts in a Fenton type reaction with DA and the present H2O2 producing 5-OHDA and especially 6-OHDA. Based on these mutual interacting reactions a mechanism for the initiation and progress of Parkinson's disease is suggested. The catalytic effects of some other transition-metal ions are presented and an explanation for the peculiarly toxic effects of manganese(II) is put forward. Finally, a possible reason for the effect that nicotine has in the mitigation of Parkinson's disease is discussed.

Redox Control of the Human Iron-Sulfur Repair Protein MitoNEET Activity via Its Iron-Sulfur Cluster*

PubMed Central

Golinelli-Cohen, Marie-Pierre; Lescop, Ewen; Mons, Cécile; Gonçalves, Sergio; Clémancey, Martin; Santolini, Jérôme; Guittet, Eric; Blondin, Geneviève; Latour, Jean-Marc; Bouton, Cécile

2016-01-01

Human mitoNEET (mNT) is the first identified Fe-S protein of the mammalian outer mitochondrial membrane. Recently, mNT has been implicated in cytosolic Fe-S repair of a key regulator of cellular iron homeostasis. Here, we aimed to decipher the mechanism by which mNT triggers its Fe-S repair capacity. By using tightly controlled reactions combined with complementary spectroscopic approaches, we have determined the differential roles played by both the redox state of the mNT cluster and dioxygen in cluster transfer and protein stability. We unambiguously demonstrated that only the oxidized state of the mNT cluster triggers cluster transfer to a generic acceptor protein and that dioxygen is neither required for the cluster transfer reaction nor does it affect the transfer rate. In the absence of apo-acceptors, a large fraction of the oxidized holo-mNT form is converted back to reduced holo-mNT under low oxygen tension. Reduced holo-mNT, which holds a [2Fe-2S]+ with a global protein fold similar to that of the oxidized form is, by contrast, resistant in losing its cluster or in transferring it. Our findings thus demonstrate that mNT uses an iron-based redox switch mechanism to regulate the transfer of its cluster. The oxidized state is the “active state,” which reacts promptly to initiate Fe-S transfer independently of dioxygen, whereas the reduced state is a “dormant form.” Finally, we propose that the redox-sensing function of mNT is a key component of the cellular adaptive response to help stress-sensitive Fe-S proteins recover from oxidative injury. PMID:26887944

Effects of Chamber Pressure and Partial Pressure of Water Vapor on Secondary Drying in Lyophilization.

PubMed

Searles, James A; Aravapalli, Sridhar; Hodge, Cody

2017-10-01

Secondary drying is the final step of lyophilization before stoppering, during which water is desorbed from the product to yield the final moisture content. We studied how chamber pressure and partial pressure of water vapor during this step affected the time course of water content of aqueous solutions of polyvinylpyrrolidone (PVP) in glass vials. The total chamber pressure had no effect when the partial pressure of water vapor was very low. However, when the vapor phase contained a substantial fraction of water vapor, the PVP moisture content was much higher. We carried out dynamic vapor sorption experiments (DVS) to demonstrate that the higher PVP moisture content was a straightforward result of the higher water vapor content in the lyophilizer. The results highlight that the partial pressure of water vapor is extremely important during secondary drying in lyophilization, and that lower chamber pressure set points for secondary drying may sometimes be justified as a strategy for ensuring low partial pressure of water vapor, especially for lyophilizers that do not inject dry gas to control pressure. These findings have direct application for process transfers/scale ups from freeze-dryers that do not inject dry gas for pressure control to those that do, and vice versa.

Applying Chemical Potential and Partial Pressure Concepts to Understand the Spontaneous Mixing of Helium and Air in a Helium-Inflated Balloon

ERIC Educational Resources Information Center

Jee-Yon Lee; Hee-Soo Yoo; Jong Sook Park; Kwang-Jin Hwang; Jin Seog Kim

2005-01-01

The spontaneous mixing of helium and air in a helium-inflated balloon is described in an experiment in which the partial pressure of the gases in the balloon are determined from the mole factions and the total pressure measured in the balloon. The results described provide a model for teaching concepts of partial pressure, chemical potential, and…

Combined hydraulic and regenerative braking system

DOEpatents

Venkataperumal, R.R.; Mericle, G.E.

1979-08-09

A combined hydraulic and regenerative braking system and method for an electric vehicle is disclosed. The braking system is responsive to the applied hydraulic pressure in a brake line to control the braking of the vehicle to be completely hydraulic up to a first level of brake line pressure, to be partially hydraulic at a constant braking force and partially regenerative at a linearly increasing braking force from the first level of applied brake line pressure to a higher second level of brake line pressure, to be partially hydraulic at a linearly increasing braking force and partially regenerative at a linearly decreasing braking force from the second level of applied line pressure to a third and higher level of applied line pressure, and to be completely hydraulic at a linearly increasing braking force from the third level to all higher applied levels of line pressure.

Combined hydraulic and regenerative braking system

DOEpatents

Venkataperumal, Rama R.; Mericle, Gerald E.

1981-06-02

A combined hydraulic and regenerative braking system and method for an electric vehicle, with the braking system being responsive to the applied hydraulic pressure in a brake line to control the braking of the vehicle to be completely hydraulic up to a first level of brake line pressure, to be partially hydraulic at a constant braking force and partially regenerative at a linearly increasing braking force from the first level of applied brake line pressure to a higher second level of brake line pressure, to be partially hydraulic at a linearly increasing braking force and partially regenerative at a linearly decreasing braking force from the second level of applied line pressure to a third and higher level of applied line pressure, and to be completely hydraulic at a linearly increasing braking force from the third level to all higher applied levels of line pressure.

Identification of 4-oxo-13-cis-retinoic acid as the major metabolite of 13-cis-retinoic acid in human blood.

PubMed

Vane, F M; Buggé, C J

1981-01-01

The metabolites of 13-cis-retinoic acid (Accutane) were investigated in blood samples from human volunteers on chronic treatment for dermatological disorders. The major metabolite was isolated by reverse-phase high-pressure liquid chromatography and identified as 4-oxo-13-cis-retinoic acid by comparison of its mass and NMR spectra to the spectra of the reference compound. 4-Oxo-all-trans-retinoic acid was also identified, but the extent to which this compound was a metabolite of 13-cis-retinoic acid or an artifactual isomerization product of the major metabolite is unknown. Chromatographic data suggested that small amounts of 13-cis-retinoic acid, 4-hydroxy-13-cis-retinoic acid, and dioxygenated metabolites of 13-cis-retinoic acid may also be present in the blood. This study indicates that a major metabolic pathway of 13-cis-retinoic acid in humans is oxidation at C4 of the cyclohexenyl group.

Production of Dioxygen in the Dark: Dismutases of Oxyanions

PubMed Central

Ojha, Sunil

2016-01-01

O2 generating reactions are exceedingly rare in biology and difficult to mimic synthetically. Perchlorate-respiring bacteria enzymatically detoxify chlorite (ClO2−), the end product of the perchlorate (ClO4−) respiratory pathway, by rapidly converting it to dioxygen (O2) and chloride (Cl−). This reaction is catalyzed by a heme-containing protein, called chlorite dismutase (Cld), which bears no structural or sequence relationships with known peroxidases or other heme proteins and is part of a large family of proteins with more than one biochemical function. The original assumptions from the 1990s that perchlorate is not a natural product and that perchlorate respiration might be confined to a taxonomically narrow group of species have been called into question, as have the roles of perchlorate respiration and Cld-mediated reactions in the global biogeochemical cycle of chlorine. In this chapter, the chemistry and biochemistry of Cld-mediated O2 generation, as well as the biological and geochemical context of this extraordinary reaction, are described. PMID:25707466

Enhanced dimethyl phthalate biodegradation by accelerating phthalic acid di-oxygenation.

PubMed

Tang, Yingxia; Zhang, Yongming; Jiang, Ling; Yang, Chao; Rittmann, Bruce E

2017-12-01

The aerobic biodegradation of dimethyl phthalate (DMP) is initiated with two hydrolysis reactions that generate an intermediate, phthalic acid (PA), that is further biodegraded through a two-step di-oxygenation reaction. DMP biodegradation is inhibited when PA accumulates, but DMP's biodegradation can be enhanced by adding an exogenous electron donor. We evaluated the effect of adding succinate, acetate, or formate as an exogenous electron donor. PA removal rates were increased by 15 and 30% for initial PA concentrations of 0.3 and 0.6 mM when 0.15 and 0.30 mM succinate, respectively, were added as exogenous electron donor. The same electron-equivalent additions of acetate and formate had the same acceleration impacts on PA removal. Consequently, the DMP-removal rate, even PA coexisting with DMP simultaneously, was accelerated by 37% by simultaneous addition of 0.3 mM succinate. Thus, lowering the accumulation of PA by addition of an electron increased the rate of DMP biodegradation.

THE WATER-WATER CYCLE IN CHLOROPLASTS: Scavenging of Active Oxygens and Dissipation of Excess Photons.

PubMed

Asada, Kozi

1999-06-01

Photoreduction of dioxygen in photosystem I (PSI) of chloroplasts generates superoxide radicals as the primary product. In intact chloroplasts, the superoxide and the hydrogen peroxide produced via the disproportionation of superoxide are so rapidly scavenged at the site of their generation that the active oxygens do not inactivate the PSI complex, the stromal enzymes, or the scavenging system itself. The overall reaction for scavenging of active oxygens is the photoreduction of dioxygen to water via superoxide and hydrogen peroxide in PSI by the electrons derived from water in PSII, and the water-water cycle is proposed for these sequences. An overview is given of the molecular mechanism of the water-water cycle and microcompartmentalization of the enzymes participating in it. Whenever the water-water cycle operates properly for scavenging of active oxygens in chloroplasts, it also effectively dissipates excess excitation energy under environmental stress. The dual functions of the water-water cycle for protection from photoinihibition are discussed.

Oxygenolysis of flavonoid compounds: DFT description of the mechanism for quercetin.

PubMed

Fiorucci, Sébastien; Golebiowski, Jerôme; Cabrol-Bass, Daniel; Antonczak, Serge

2004-11-12

Flavonoids are naturally occurring phenol derivatives present in substantial amounts in a large variety of plants, fruits and vegetables daily eaten by humans. Most of these compounds exhibit several interesting biological activities, such as antiradical and antioxidant actions. Indeed, by complexation with specific enzymes, flavonoids are notably liable to metabolize molecular dioxygen. On the basis of experimental results describing oxygenolysis of the flavonoid quercetin, activated by the enzyme quercetin 2,3-dioxygenase (2,3-QD),ur attention has focused on the role of metal center in the activation of the substrate quercetin. Thus, in the present study, by means of DFT calculations at the B3LYP/ 6-31(+)G* level on model molecular systems, we describe different mechanisms for dioxygen metabolization by quercetin. Stationary points are described, and energetic and structural analyses along the reaction paths are reported. Our calculations show that the copper cation must act as an oxidant towards the substrate and that the reaction proceeds through a 1,3-cycloaddition.

Structural, mechanical, electrical and wetting properties of ZrNx films deposited by Ar/N2 vacuum arc discharge: Effect of nitrogen partial pressure

NASA Astrophysics Data System (ADS)

Abdallah, B.; Naddaf, M.; A-Kharroub, M.

2013-03-01

Non-stiochiometric zirconium nitride (ZrNx) thin films have been deposited on silicon substrates by vacuum arc discharge of (N2 + Ar) gas mixtures at different N2 partial pressure ratio. The microstructure, mechanical, electrical and wetting properties of these films are studied by means of X-ray diffraction (XRD), micro-Raman spectroscopy, Rutherford back scattering (RBS) technique, conventional micro-hardness testing, electrical resistivity, atomic force microscopy (AFM) and contact angle (CA) measurements. RBS results and analysis show that the (N/Zr) ratio in the film increases with increasing the N2 partial pressure. A ZrNx film with (Zr/N) ratio in the vicinity of stoichiometric ZrN is obtained at N2 partial pressure of 10%. XRD and Raman results indicate that all deposited films have strained cubic crystal phase of ZrN, regardless of the N2 partial pressure. On increasing the N2 partial pressure, the relative intensity of (1 1 1) orientation with respect to (2 0 0) orientation is seen to decrease. The effect of N2 partial pressure on micro-hardness and the resistivity of the deposited film is revealed and correlated to the alteration of grain size, crystallographic texture, stoichiometry and residual stress developed in the film. In particular, it is found that residual stress and nitrogen incorporation in the film play crucial role in the alteration of micro-hardness and resistivity respectively. In addition, CA and AFM results demonstrate that as N2 partial pressure increases, both the surface hydrophobicity and roughness of the deposited film increase, leading to a significant decrease in the film surface free energy (SFE).

Effect of methane partial pressure on the performance of a membrane biofilm reactor coupling methane-dependent denitrification and anammox.

PubMed

Cai, Chen; Hu, Shihu; Chen, Xueming; Ni, Bing-Jie; Pu, Jiaoyang; Yuan, Zhiguo

2018-10-15

Complete nitrogen removal has recently been demonstrated by integrating anaerobic ammonium oxidation (anammox) and denitrifying anaerobic methane oxidation (DAMO) processes. In this work, the effect of methane partial pressure on the performance of a membrane biofilm reactor (MBfR) consisting of DAMO and anammox microorganisms was evaluated. The activities of DAMO archaea and DAMO bacteria in the biofilm increased significantly with increased methane partial pressure, from 367 ± 9 and 58 ± 22 mg-N L -1 d -1 to 580 ± 12 and 222 ± 22 mg-N L -1 d -1 , respectively, while the activity of anammox bacteria only increased slightly, when the methane partial pressure was elevated from 0.24 to 1.39 atm in the short-term batch tests. The results were supported by a long-term (seven weeks) continuous test, when the methane partial pressure was dropped from 1.39 to 0.78 atm. The methane utilization efficiency was always above 96% during both short-term and long-term tests. Taken together, nitrogen removal rate (especially the nitrate reduction rate by DAMO archaea) and methane utilization efficiency could be maintained at high levels in a broad range of methane partial pressure (0.24-1.39 atm in this study). In addition, a previously established DAMO/anammox biofilm model was used to analyze the experimental data. The observed impacts of methane partial pressure on biofilm activity were well explained by the modeling results. These results suggest that methane partial pressure can potentially be used as a manipulated variable to control reaction rates, ultimately to maintain high nitrogen removal efficiency, according to nitrogen loading rate. Copyright © 2018 Elsevier B.V. All rights reserved.

Hydro-isomerization of n-hexane on bi-functional catalyst: Effect of total and hydrogen partial pressures

NASA Astrophysics Data System (ADS)

Thoa, Dao Thi Kim; Loc, Luu Cam

2017-09-01

The effect of both total pressure and hydrogen partial pressure during n-hexane hydro-isomerization over platinum impregnated on HZSM-5 was studied. n-Hexane hydro-isomerization was conducted at atmospheric pressure and 0.7 MPa to observe the influence of total pressure. In order to see the effect of hydrogen partial pressure, the reaction was taken place at different partial pressure of hydrogen varied from 307 hPa to 718 hPa by dilution with nitrogen to keep the total pressure at 0.1 MPa. Physico-chemical characteristics of catalyst were determined by the methods of nitrogen physi-sorption BET, SEM, XRD, TEM, NH3-TPD, TPR, and Hydrogen Pulse Chemi-sorption. Activity of catalyst in the hydro-isomerization of n-hexane was studied in a micro-flow reactor in the temperature range of 225-325 °C; the molar ratio H2/ hydrocarbon: 5.92, concentration of n-hexane: 9.2 mol.%, GHSV 2698 h-1. The obtained catalyst expressed high acid density, good reducing property, high metal dispersion, and good balance between metallic and acidic sites. It is excellent contact for n-hexane hydro-isomerization. At 250 °C, n-hexane conversion and selectivity were as high as 59-76 % and 85-99 %, respectively. It was found that catalytic activity was promoted either by total pressure or hydrogen partial pressure. At total pressure of 0.7 MPa while hydrogen partial pressure of 718 hPa, catalyst produced 63 RON liquid product containing friendly environmental iso-paraffins which is superior blending stock for green gasoline. Hydrogen did not only preserve catalyst actives by depressing hydrocracking and removing coke precursors but also facilitated hydride transfer step in the bi-functional bi-molecular mechanism.

Sulfur control in ion-conducting membrane systems

DOEpatents

Stein, VanEric Edward; Richards, Robin Edward; Brengel, David Douglas; Carolan, Michael Francis

2003-08-05

A method for controlling the sulfur dioxide partial pressure in a pressurized, heated, oxygen-containing gas mixture which is contacted with an ion-conducting metallic oxide membrane which permeates oxygen ions. The sulfur dioxide partial pressure in the oxygen-depleted non-permeate gas from the membrane module is maintained below a critical sulfur dioxide partial pressure, p.sub.SO2 *, to protect the membrane material from reacting with sulfur dioxide and reducing the oxygen flux of the membrane. Each ion-conducting metallic oxide material has a characteristic critical sulfur dioxide partial pressure which is useful in determining the required level of sulfur removal from the feed gas and/or from the fuel gas used in a direct-fired feed gas heater.

Pressure Effects on Oxygen Concentration Flammability Thresholds of Materials for Aerospace Applications

NASA Technical Reports Server (NTRS)

Hirsch, David; Williams, Jim; Beeson, Harold

2006-01-01

Spacecraft materials selection is based on an upward flammability test conducted in a quiescent environment in the highest-expected oxygen-concentration environment. However, NASA s advanced space exploration program is anticipating using various habitable environments. Because limited data is available to support current program requirements, a different test logic is suggested to address these expanded atmospheric environments through the determination of materials self-extinguishment limits. This paper provides additional pressure effects data on oxygen concentration and partial pressure self-extinguishment limits under quiescent conditions. For the range of total pressures tested, the oxygen concentration and oxygen partial pressure flammability thresholds show a near linear function of total pressure. The oxygen concentration/oxygen partial pressure flammability thresholds depend on the total pressure and appear to increase with increasing oxygen concentration (and oxygen partial pressure). For the Constellation Program, the flammability threshold information will allow NASA to identify materials with increased flammability risk because of oxygen concentration and total pressure changes, minimize potential impacts, and allow for development of sound requirements for new spacecraft and extraterrestrial landers and habitats.

Method and apparatus for monitoring oxygen partial pressure in air masks

NASA Technical Reports Server (NTRS)

Kelly, Mark E. (Inventor); Pettit, Donald R. (Inventor)

2006-01-01

Method and apparatus are disclosed for monitoring an oxygen partial pressure in an air mask and providing a tactile warning to the user. The oxygen partial pressure in the air mask is detected using an electrochemical sensor, the output signal from which is provided to a comparator. The comparator compares the output signal with a preset reference value or range of values representing acceptable oxygen partial pressures. If the output signal is different than the reference value or outside the range of values, the air mask is vibrated by a vibrating motor to alert the user to a potentially hypoxic condition.

Effect of substrate temperature and oxygen partial pressure on RF sputtered NiO thin films

NASA Astrophysics Data System (ADS)

Cheemadan, Saheer; Santhosh Kumar, M. C.

2018-04-01

Nickel oxide (NiO) thin films were deposited by RF sputtering process and the physical properties were investigated for varying substrate temperatures and oxygen partial pressure. The variation of the crystallographic orientation and microstructure of the NiO thin films with an increase in substrate temperature were studied. It was observed that NiO thin films deposited at 350 °C shows relatively good crystalline characteristics with a preferential orientation along (111) plane. With the optimum substrate temperature of 350 °C, the NiO thin films were deposited under various oxygen partial pressures at the same experimental conditions. The structural, optical and electrical properties of NiO thin films under varying oxygen partial pressure of 10%–50% were investigated. From XRD it is clear that the films prepared in the pure argon atmosphere were amorphous while the films in oxygen partial pressure exhibited polycrystalline NiO phase. SEM and AFM investigations unveil that the higher substrate temperature improves the microstructure of the thin films. It is revealed that the NiO thin films deposited at oxygen partial pressure of 40% and a substrate temperature of 350 °C, showed higher electrical conductivity with p-type characteristics.

Oxygen partial pressure effects on the RF sputtered p-type NiO hydrogen gas sensors

NASA Astrophysics Data System (ADS)

Turgut, Erdal; Çoban, Ömer; Sarıtaş, Sevda; Tüzemen, Sebahattin; Yıldırım, Muhammet; Gür, Emre

2018-03-01

NiO thin films were grown by Radio Frequency (RF) Magnetron Sputtering method under different oxygen partial pressures, which are 0.6 mTorr, 1.3 mTorr and 2.0 mTorr. The effects of oxygen partial pressures on the thin films were analyzed through Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS) and Hall measurements. The change in the surface morphology of the thin films has been observed with the SEM and AFM measurements. While nano-pyramids have been obtained on the thin film grown at the lowest oxygen partial pressure, the spherical granules lower than 60 nm in size has been observed for the samples grown at higher oxygen partial pressures. The shift in the dominant XRD peak is realized to the lower two theta angle with increasing the oxygen partial pressures. XPS measurements showed that the Ni2p peak involves satellite peaks and two oxidation states of Ni, Ni2+ and Ni3+, have been existed together with the corresponding splitting in O1s spectrum. P-type conductivity of the grown NiO thin films are confirmed by the Hall measurements with concentrations on the order of 1013 holes/cm-3. Gas sensor measurements revealed minimum of 10% response to the 10 ppm H2 level. Enhanced responsivity of the gas sensor devices of NiO thin films is shown as the oxygen partial pressure increases.

Distribution of gases in the unsaturated zone at a low-level radioactive-waste disposal site near Sheffield, Illinois

USGS Publications Warehouse

Striegl, Robert G.

1988-01-01

The unsaturated zone is a medium that provides pneumatic communication for the movement of gases from wastes buried in landfills to the atmosphere, biota, and groundwater. Gases in unsaturated glacial and eolian deposits near a waste-disposal trench at the low-level radioactive-waste disposal site near Sheffield, Bureau County, Illinois, were identified, and the spatial and temporal distributions of the partial pressures of those gases were determined for the period January 1984 through January 1986. Methods for the collection and analyses of the gases are described, as are geologic and hydrologic characteristics of the unsaturated zone that affect gas transport. The identified gases, which are of natural and of waste origin, include nitrogen, oxygen, and argon, carbon dioxide, methane, propane, butane, tritiated water vapor, 14carbon dioxide, and 222 radon. Concentrations of methane and 14carbon dioxide originated at the waste, as shown by partial-pressure gradients of the gases; 14carbon dioxide partial pressures exceeded natural background partial pressures by factors greater than 1 million at some locations. Variations in partial pressures of oxygen and carbon dioxide were seasonal among piezometers because of increased root and soil-microbe respiration during summer. Variations in methane and 14carbon dioxide partial pressures were apparently related to discrete releases from waste sources at unpredictable intervals of time. No greater than background partial pressures for tritiated water vapor or 222 radon were measured. (USGS)

[Effects of gap junction blocking on the oxygen partial pressure in acupoints of the bladder meridian].

PubMed

Wang, Qi; Yu, Wei-Chang; Jiang, Hong-Zhi; Chen, Sheng-Li; Zhang, Ming-Min; Kong, E-Sheng; Huang, Guang-Ying

2010-12-01

To explore the relation between gap junction and meridian phenomenon. The oxygen partial pressure in acupoints [see text for formula] and in their corresponding non-acupoints of the Bladder Meridian was observed with the needle-type tissue oxygen tension sensor in the gap junction blocking goats by 1-Heptanol injection and the Connexin 43 (Cx43) gene knockout mice. (1) The oxygen partial pressure in acupoints of Bladder Meridian on goats was higher than that in non-acupoints after 1-Heptanol injection with significant differences between them (both P < 0.01). (2) The oxygen partial pressure in acupoints of Bladder Meridian on goats increased significantly after injecting 1-Heptanol as compare with that either injecting normal saline or injecting nothing with significant differences between them (all P < 0.01). (3) The oxygen partial pressure in acupoints of the Bladder Meridian was significantly higher than that in the non-acupoint controls in Cx43 wild type (WT) mice (all P < 0.01). In Cx43 heterozygote (HT) mice, the oxygen partial pressure between acupoints and non-acupoint controls showed no significant differences (all P > 0.05). (4) In acupoints, the oxygen partial pressure in Cx43 WT mice was significantly higher than that in Cx43 HT mice (all P < 0.05), while in the corresponding non-acupoints, this difference had no statistically significant (all P > 0.05). Gap junction maybe the essential factor in signal transduction of acupuncture.

Electron transfer from alpha-keggin anions to dioxygen

Treesearch

Yurii V. Geletii; Rajai H. Atalla; Craig L. Hill; Ira A. Weinstock

2004-01-01

Polyoxometalates (POMs), of which alpha-Keggin anions are representative, are a diverse and rapidly growing class of water-soluble cluster-anion structures with applications ranging from molecular catalysis to materials. [1] POMs are inexpensive, minimally or non-toxic, negatively charged clusters comprised of early transition-metals, usually in their do electronic...

The Synthetic Analogs of Oxygen-Binding Heme Proteins.

ERIC Educational Resources Information Center

Suslick, Kenneth S.; Reinert, Thomas J.

1985-01-01

Discusses model studies aimed at elucidating various ways in which molecular oxygen interacts with metalloproteins. The focus is on the chemistry of iron(II) porphyrins and their adducts with nitrogenous bases, carbon monoxide, and dioxygen, which are most relevant to the functional proteries of the heme proteins, hemoglobin, and myoglobin. (JN)

The effect of partial portal decompression on portal blood flow and effective hepatic blood flow in man: a prospective study.

PubMed

Rosemurgy, A S; McAllister, E W; Godellas, C V; Goode, S E; Albrink, M H; Fabri, P J

1995-12-01

With the advent of transjugular intrahepatic porta-systemic stent shunt and the wider application of the surgically placed small diameter prosthetic H-graft portacaval shunt (HGPCS), partial portal decompression in the treatment of portal hypertension has received increased attention. The clinical results supporting the use of partial portal decompression are its low incidence of variceal rehemorrhage due to decreased portal pressures and its low rate of hepatic failure, possibly due to maintenance of blood flow to the liver. Surprisingly, nothing is known about changes in portal hemodynamics and effective hepatic blood flow following partial portal decompression. To prospectively evaluate changes in portal hemodynamics and effective hepatic blood flow brought about by partial portal decompression, the following were determined in seven patients undergoing HGPCS: intraoperative pre- and postshunt portal vein pressures and portal vein-inferior vena cava pressure gradients, intraoperative pre- and postshunt portal vein flow, and pre- and postoperative effective hepatic blood flow. With HGPCS, portal vein pressures and portal vein-inferior vena cava pressure gradients decreased significantly, although portal pressures remained above normal. In contrast to the significant decreases in portal pressures, portal vein blood flow and effective hepatic blood flow do not decrease significantly. Changes in portal vein pressures and portal vein-inferior vena cava pressure gradients are great when compared to changes in portal vein flow and effective hepatic blood flow. Reduction of portal hypertension with concomitant maintenance of hepatic blood flow may explain why hepatic dysfunction is avoided following partial portal decompression.

The Effect of Oxygen Partial Pressure on Microstructure and Properties of Fe40Al Alloy Sintered under Vacuum

PubMed Central

Siemiaszko, Dariusz; Kowalska, Beata; Jóźwik, Paweł; Kwiatkowska, Monika

2015-01-01

This paper presents the results of studies on the influence of oxygen partial pressure (vacuum level in the chamber) on the properties of FeAl intermetallics. One of the problems in the application of classical methods of prepared Fe-Al intermetallic is the occurrence of oxides. Applying a vacuum during sintering should reduce this effect. In order to analyze the effect of oxygen partial pressure on sample properties, five samples were processed (by a pressure-assisted induction sintering—PAIS method) under the following pressures: 3, 8, 30, 80, and 300 mbar (corresponding to oxygen partial pressures of 0.63, 1.68, 6.3, 16.8, and 63 mbar, respectively). The chemical and phase composition, hardness, density, and microstructure observations indicate that applying a vacuum significantly impacts intermetallic samples. The compact sintered at pressure 3 mbar is characterized by the most homogeneous microstructure, the highest density, high hardness, and nearly homogeneous chemical composition. PMID:28788015

Dependence of magnetic anisotropy on MgO sputtering pressure in Co20Fe60B20/MgO stacks

NASA Astrophysics Data System (ADS)

Kaidatzis, A.; Serletis, C.; Niarchos, D.

2017-10-01

We investigated the dependence of magnetic anisotropy of Ta/Co20Fe60B20/MgO stacks on the Ar partial pressure during MgO deposition, in the range between 0.5 and 15 mTorr. The stacks are studied before and after annealing at 300°C and it is shown that magnetic anisotropy significantly depends on Ar partial pressure. High pressure results in stacks with very low perpendicular magnetic anisotropy even after annealing, while low pressure results in stacks with perpendicular anisotropy even at the as-deposited state. A monotonic increase of magnetic anisotropy energy is observed as Ar partial pressure is decreased.

Influence of oxygen partial pressure on the microstructural and magnetic properties of Er-doped ZnO thin films

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

Chen, Wei-Bin; Li, Fei; Chen, Hong-Ming

2015-06-15

Er-doped ZnO thin films have been prepared by using inductively coupled plasma enhanced physical vapor deposition at different O{sub 2}:Ar gas flow ratio (R = 0:30, 1:30, 1:15, 1:10 and 1:6). The influence of oxygen partial pressure on the structural, optical and magnetic properties was studied. It is found that an appropriate oxygen partial pressure (R=1:10) can produce the best crystalline quality with a maximum grain size. The internal strain, estimated by fitting the X-ray diffraction peaks, varied with oxygen partial pressure during growth. PL measurements show that plenty of defects, especially zinc vacancy, exist in Er-doped ZnO films. Allmore » the samples show room-temperature ferromagnetism. Importantly, the saturation magnetization exhibits similar dependency on oxygen partial pressure with the internal strain, which indicates that internal strain has an important effect on the magnetic properties of Er-doped ZnO thin films.« less

Effects of oxygen partial pressure on Li-air battery performance

NASA Astrophysics Data System (ADS)

Kwon, Hyuk Jae; Lee, Heung Chan; Ko, Jeongsik; Jung, In Sun; Lee, Hyun Chul; Lee, Hyunpyo; Kim, Mokwon; Lee, Dong Joon; Kim, Hyunjin; Kim, Tae Young; Im, Dongmin

2017-10-01

For application in electric vehicles (EVs), the Li-air battery system needs an air intake system to supply dry oxygen at controlled concentration and feeding rate as the cathode active material. To facilitate the design of such air intake systems, we have investigated the effects of oxygen partial pressure (≤1 atm) on the performance of the Li-air cell, which has not been systematically examined. The amounts of consumed O2 and evolved CO2 from the Li-air cell are measured with a custom in situ differential electrochemical gas chromatography-mass spectrometry (DEGC-MS). The amounts of consumed O2 suggest that the oxygen partial pressure does not affect the reaction mechanism during discharge, and the two-electron reaction occurs under all test conditions. On the other hand, the charging behavior varies by the oxygen partial pressure. The highest O2 evolution ratio is attained under 70% O2, along with the lowest CO2 evolution. The cell cycle life also peaks at 70% O2 condition. Overall, an oxygen partial pressure of about 0.5-0.7 atm maximizes the Li-air cell capacity and stability at 1 atm condition. The findings here indicate that the appropriate oxygen partial pressure can be a key factor when developing practical Li-air battery systems.

Effects of Oxygen Partial Pressure on the Surface Tension of Liquid Nickel

NASA Technical Reports Server (NTRS)

SanSoucie, Michael P.; Rogers, Jan R.; Gowda, Vijaya Kumar Malahalli Shankare; Rodriguez, Justin; Matson, Douglas M.

2015-01-01

The NASA Marshall Space Flight Center's electrostatic levitation (ESL) laboratory has been recently upgraded with an oxygen partial pressure controller. This system allows the oxygen partial pressure within the vacuum chamber to be measured and controlled, theoretically in the range from 10-36 to 100 bar. The oxygen control system installed in the ESL laboratory's main chamber consists of an oxygen sensor, oxygen pump, and a control unit. The sensor is a potentiometric device that determines the difference in oxygen activity in two gas compartments (inside the chamber and the air outside of the chamber) separated by an electrolyte, which is yttria-stabilized zirconia. The pump utilizes coulometric titration to either add or remove oxygen. The system is controlled by a desktop control unit, which can also be accessed via a computer. The controller performs temperature control for the sensor and pump, PID-based current loop, and a control algorithm. Oxygen partial pressure has been shown to play a significant role in the surface tension of liquid metals. Oxide films or dissolved oxygen may lead to significant changes in surface tension. The effects of oxygen partial pressure on the surface tension of undercooled liquid nickel will be analyzed, and the results will be presented. The surface tension will be measured at several different oxygen partial pressures while the sample is undercooled. Surface tension will be measured using the oscillating drop method. While undercooled, each sample will be oscillated several times consecutively to investigate how the surface tension behaves with time while at a particular oxygen partial pressure.

Sapwood development in Pinus radiata trees grown for three years at ambient and elevated carbon dioxide partial pressures.

PubMed

Atwell, B J; Henery, M L; Whitehead, D

2003-01-01

Clonal trees of Pinus radiata D. Don were grown in open-top chambers at a field site in New Zealand for 3 years at ambient (37 Pa) or elevated (65 Pa) carbon dioxide (CO2) partial pressure. Nitrogen (N) was supplied to half of the trees in each CO2 treatment, at 15 g N m-2 in the first year and 60 g N m-2 in the subsequent 2 years (high-N treatment). Trees in the low-N treatment were not supplied with N but received the same amount of other nutrients as trees in the high-N treatment. In the first year, stem basal area increased more in trees growing at elevated CO2 partial pressure and high-N supply than in control trees, suggesting a positive interaction between these resources. However, the relative rate of growth became the same across trees in all treatments after 450 days, resulting in trees growing at elevated CO2 partial pressure and high-N supply having larger basal areas than trees in the other treatments. Sapwood N content per unit dry mass was consistently about 0.09% in all treatments, indicating that N status was not suppressed by elevated CO2 partial pressure. Thus, during the first year of growth, an elevated CO2 partial pressure enhanced carbon (C) and N storage in woody stems, but there was no further stimulus to C and N deposition after the first year. The chemical composition of sapwood was unaffected by elevated CO2 partial pressure, indicating that no additional C was sequestered through lignification. However, independent of the treatments, early wood was 13% richer in lignin than late wood. Elevated CO2 partial pressure decreased the proportion of sapwood occupied by the lumina of tracheids by up to 12%, indicating increased sapwood density in response to CO2 enrichment. This effect was probably a result of thicker tracheid walls rather than narrower lumina.

Using Dalton's Law of Partial Pressures to Determine the Vapor Pressure of a Volatile Liquid

ERIC Educational Resources Information Center

Hilgeman, Fred R.; Bertrand, Gary; Wilson, Brent

2007-01-01

This experiment, designed for a general chemistry laboratory, illustrates the use of Dalton's law of partial pressures to determine the vapor pressure of a volatile liquid. A predetermined volume of air is injected into a calibrated tube filled with a liquid whose vapor pressure is to be measured. The volume of the liquid displaced is greater than…

Oxygen partial pressure sensor

DOEpatents

Dees, D.W.

1994-09-06

A method for detecting oxygen partial pressure and an oxygen partial pressure sensor are provided. The method for measuring oxygen partial pressure includes contacting oxygen to a solid oxide electrolyte and measuring the subsequent change in electrical conductivity of the solid oxide electrolyte. A solid oxide electrolyte is utilized that contacts both a porous electrode and a nonporous electrode. The electrical conductivity of the solid oxide electrolyte is affected when oxygen from an exhaust stream permeates through the porous electrode to establish an equilibrium of oxygen anions in the electrolyte, thereby displacing electrons throughout the electrolyte to form an electron gradient. By adapting the two electrodes to sense a voltage potential between them, the change in electrolyte conductivity due to oxygen presence can be measured. 1 fig.

Oxygen partial pressure sensor

DOEpatents

Dees, Dennis W.

1994-01-01

A method for detecting oxygen partial pressure and an oxygen partial pressure sensor are provided. The method for measuring oxygen partial pressure includes contacting oxygen to a solid oxide electrolyte and measuring the subsequent change in electrical conductivity of the solid oxide electrolyte. A solid oxide electrolyte is utilized that contacts both a porous electrode and a nonporous electrode. The electrical conductivity of the solid oxide electrolyte is affected when oxygen from an exhaust stream permeates through the porous electrode to establish an equilibrium of oxygen anions in the electrolyte, thereby displacing electrons throughout the electrolyte to form an electron gradient. By adapting the two electrodes to sense a voltage potential between them, the change in electrolyte conductivity due to oxygen presence can be measured.

Tibiofemoral contact pressures in radial tears of the meniscus treated with all-inside repair, inside-out repair and partial meniscectomy.

PubMed

Zhang, Alan L; Miller, Stephanie L; Coughlin, Dezba G; Lotz, Jeffrey C; Feeley, Brian T

2015-10-01

To test contact pressures in the knee after treatment of a radial meniscus tear with an all-inside meniscal repair technique and compare the results with inside-out repair and partial meniscectomy. Six non-paired cadaveric knees were analyzed with intra-compartment pressures measured at loads of 250 N, 500 N and 1000 N at 0°, eight degrees, 15°, and 30° of knee flexion. Compartmental contact pressures were measured for the intact medial meniscus, radial tear in the posterior horn, all-inside repair using the NovoStitch suture passer device (Ceterix Orthopaedics Inc., Menlo Park, CA), inside-out repair method, and partial meniscectomy. One-way ANOVA was used for statistical analysis. The greatest differences in peak pressures between treatments were observed under 1000 N load at 30° flexion (0.8± (SD) 0.1 MPa (intact meniscus), 0.8± (SD) 0.1 MPa (all-inside), 0.9± (SD) 0.1 MPa (inside-out) and 1.6± (SD) 0.2 MPa (partial meniscectomy)). Treatment with partial meniscectomy resulted in the highest peak pressures compared to all other states (p<0.0001 at each angle). Repair of the radial tear using the all-inside technique as well as the inside-out technique resulted in significantly decreased compartment pressures compared to partial meniscectomies (p<0.0001 at each angle). There were no significant differences between peak pressures in the intact state and after repair with the all-inside or inside-out techniques. An all-inside repair technique using the NovoStitch suture passer can decrease contact pressures for a radial meniscus tear similarly to the inside-out repair technique when compared to partial meniscectomy. This novel arthroscopic suture passer warrants further analysis in the clinical setting as it may be a reliable method for repair of radial meniscal tears through an arthroscopic all-inside technique. Copyright © 2015 Elsevier B.V. All rights reserved.

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

Theil, Elizabeth C.; Department of Nutritional Science and Toxicology, University of California, Berkeley, CA 94720

Ferritins are protein nanocages that use iron and oxygen chemistry to concentrate iron and trap dioxygen or hydrogen peroxide in biominerals of hydrated ferric oxides, 5-8 nm in diameter, inside the cages. The proteins are found in nature from archea to humans. Protein catalytic sites are embedded in the protein cage and initiate mineralization by oxido-reduction of ferrous ions and dioxygen or hydrogen peroxide to couple two iron ions through a peroxo bridge, followed by decay to diferric oxo/hydroxyl mineral precursors; ferritin protein subdomains that fold/unfold independently of the protein cage control recovery of ferrous ions from the mineral. Earlymore » EXAFS (1978) was extremely useful in defining the ferritin mineral. More recent use of rapid freeze quench (RFQ) EXAFS spectroscopies, coupled with RFQ Moessbauer, Resonance Raman and rapid mixing UV-vis spectroscopy, have identified and characterized unusual ferritin protein catalytic intermediates and mineral precursors. EXAFS spectroscopy can play an important role in the future understanding of protein catalysis in metalloproteins such as ferritin, ribonucleotide reductase and methane monooxygenases. Needed are instrumentation improvements that will provide rapid-scan fluorescence spectra with high signal/noise ratios.« less

Enhancement of C-H Oxidizing Ability in Co-O2  Complexes through an Isolated Heterobimetallic Oxo Intermediate.

PubMed

DeRosha, Daniel E; Mercado, Brandon Q; Lukat-Rodgers, Gudrun; Rodgers, Kenton R; Holland, Patrick L

2017-03-13

The characterization of intermediates formed through the reaction of transition-metal complexes with dioxygen (O 2 ) is important for understanding oxidation in biological and synthetic processes. Here, the reaction of the diketiminate-supported cobalt(I) complex L tBu Co with O 2 gives a rare example of a side-on dioxygen complex of cobalt. Structural, spectroscopic, and computational data are most consistent with its assignment as a cobalt(III)-peroxo complex. Treatment of L tBu Co(O 2 ) with low-valent Fe and Co diketiminate complexes affords isolable oxo species with M 2 O 2 "diamond" cores, including the first example of a crystallographically characterized heterobimetallic bis(μ-oxo) complex of two transition metals. The bimetallic species are capable of cleaving C-H bonds in the supporting ligands, and kinetic studies show that the Fe/Co heterobimetallic species activates C-H bonds much more rapidly than the Co/Co homobimetallic analogue. Thus heterobimetallic oxo intermediates provide a promising route for enhancing the rates of oxidation reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reactivity of food phenols with iron and copper ions: binding, dioxygen activation and oxidation mechanisms.

PubMed

Nkhili, Ezzohra; Loonis, Michèle; Mihai, Simona; El Hajji, Hakima; Dangles, Olivier

2014-06-01

In this work, the affinity of common dietary phenols (gallic acid, caffeic acid, catechin, and rutin) for iron and copper ions was quantitatively investigated in neutral phosphate buffer as well as the reactivity of the complexes toward dioxygen. Contrasting behaviors were observed: because of the competing phosphate ions, Fe(III) binding is much slower than Fe(II) binding, which is rapidly followed by autoxidation of Fe(II) into Fe(III). With both ions, O2 consumption and H2O2 production are modest and the phenolic ligands are only slowly oxidized. By contrast, metal-phenol binding is fast with both Cu(I) and Cu(II). With Cu(I), O2 consumption and H2O2 production are very significant and the phenolic ligands are rapidly oxidized into a complex mixture of oligomers. The corresponding mechanism with Cu(II) is hampered by the preliminary rate-determining step of Cu(II) reduction by the phenols. The consequences of these findings for the stability and antioxidant activity of plant phenols are discussed.

Dinuclear PhotoCORMs: Dioxygen-Assisted Carbon Monoxide Uncaging from Long-Wavelength-Absorbing Metal-Metal-Bonded Carbonyl Complexes.

PubMed

Li, Zhi; Pierri, Agustin E; Huang, Po-Ju; Wu, Guang; Iretskii, Alexei V; Ford, Peter C

2017-06-05

We describe a new strategy for triggering the photochemical release of caged carbon monoxide (CO) in aerobic media using long-wavelength visible and near-infrared (NIR) light. The dinuclear rhenium-manganese carbonyl complexes (CO) 5 ReMn(CO) 3 (L), where L = phenanthroline (1), bipyridine (2), biquinoline (3), or phenanthrolinecarboxaldehyde (4), each show a strong metal-metal-bond-to-ligand (σ MM → π L *) charge-transfer absorption band at longer wavelengths. Photolysis with deep-red (1 and 2) or NIR (3 and 4) light leads to homolytic cleavage of the Re-Mn bonds to give mononuclear metal radicals. In the absence of trapping agents, these radicals primarily recombine to reform dinuclear complexes. In oxygenated media, however, the radicals react with dioxygen to form species much more labile toward CO release via secondary thermal and/or photochemical reactions. Conjugation of 4, with an amine-terminated poly(ethylene glycol) oligomer, gives a water-soluble derivative with similar photochemistry. In this context, we discuss the potential applications of these dinuclear complexes as visible/NIR-light-photoactivated CO-releasing moieties (photoCORMs).

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.

Redox-controlled dinitrosyl formation at the diiron-oxo center of NorA.

PubMed

Cramm, Rainer; Strube, Katja

2008-01-01

In the denitrifying bacterium Ralstonia eutropha H16, the NorA protein is coproduced with the respiratory nitric oxide (NO) reductase. NorA contains a diiron-oxo center, which can form stable adducts with dioxygen and NO. In contrast to other diiron proteins, the formation of NorA-NO requires both fully reduced protein and additional electrons. A minor fraction of in vitro NorA-NO represents a paramagnetic dinitrosyl iron complex (DNIC), while the major fraction is attributed to a DNIC of the structure {Fe(NO)(2)}, which shows no electron paramagnetic resonance. The NorA-DNIC may be formed either upon direct reaction of the protein with NO or upon incubation with nitrite due to an intrinsic nitrite reduction activity of NorA that liberates NO. NorA can be purified rapidly as a six histidine-tagged derivative from overproducing cells of Escherichia coli. This chapter describes procedures for the preparation of different redox forms of NorA for the formation of NorA adducts with NO, dioxygen, and azide, as well as for the quantification of NorA-bound NO.

The influence of participant characteristics on the relationship between cuff pressure and level of blood flow restriction.

PubMed

Hunt, Julie E A; Stodart, Clare; Ferguson, Richard A

2016-07-01

Previous investigations to establish factors influencing the blood flow restriction (BFR) stimulus have determined cuff pressures required for complete arterial occlusion, which does not reflect the partial restriction prescribed for this training technique. This study aimed to establish characteristics that should be accounted for when prescribing cuff pressures required for partial BFR. Fifty participants were subjected to incremental blood flow restriction of the upper and lower limbs by proximal pneumatic cuff inflation. Popliteal and brachial artery diameter, blood velocity and blood flow was assessed with Doppler ultrasound. Height, body mass, limb circumference, muscle-bone cross-sectional area, adipose thickness (AT) and arterial blood pressure were measured and used in different models of hierarchical linear regression to predict the pressure at which 60 % BFR (partial occlusion) occurred. Combined analysis revealed a difference in cuff pressures required to elicit 60 % BFR in the popliteal (111 ± 12 mmHg) and brachial arteries (101 ± 12 mmHg). MAP (r = 0.58) and AT (r = -0.45) were the largest independent determinants of lower and upper body partial occlusion pressures. However, greater variance was explained by upper and lower limb regression models composed of DBP and BMI (48 %), and arm AT and DBP (30 %), respectively. Limb circumference has limited impact on the cuff pressure required for partial blood flow restriction which is in contrast to its recognised relationship with complete arterial occlusion. The majority of the variance in partial occlusion pressure remains unexplained by the predictor variables assessed in the present study.

Alumina Volatility in Water Vapor at Elevated Temperatures: Application to Combustion Environments

NASA Technical Reports Server (NTRS)

Opila, Elizabeth J.; Myers, Dwight L.

2003-01-01

The volatility of alumina in high temperature water vapor was determined by measuring weight loss of sapphire coupons at temperatures between 1250 and 1500 C, water vapor partial pressures between 0.15 and 0.68 atm in oxygen, at one atmosphere total pressure, and a gas velocity of 4.4 centimeters per second. The variation of the volatility with water vapor partial pressure was consistent with Al(OH)3(g) formation. The enthalpy of reaction to form Al(OH)3(g) from alumina and water vapor was found to be 210 plus or minus 20 kJ/mol. Surface rearrangement of ground sapphire surfaces increased with water vapor partial pressure, temperature and volatility rate. Recession rates of alumina due to volatility were determined as a function of water vapor partial pressure and temperature to evaluate limits for use of alumina in long term applications in combustion environments.

Non-invasive multiwavelength photoplethysmography under low partial pressure of oxygen.

PubMed

Fang, Yung Chieh; Tai, Cheng-Chi

2016-08-01

A reduction in partial pressure of oxygen in the environment may be caused by a gain in altitude, which reduces the atmospheric pressure; it may also be caused by the carbon dioxide generated from breathing in an enclosed space. Does inhaling oxygen of lower partial pressure affect the oxygen-carrying function of haemoglobin in vivo? This study uses non-invasive multiwavelength photoplethysmography to measure the effects that inhaling this type of oxygen can have on the plethysmography of the appendages of the body (fingertips). The results indicate that under low partial pressure of oxygen, be it the result of a gain in carbon dioxide concentration or altitude, the change in visible light absorption is the biggest for short wavelengths (approximately 620 or 640 nm) near deoxyhaemoglobin, which has higher absorption coefficient. Moreover, increasing carbon dioxide concentration from 5000 to 10,000 ppm doubly reduces the absorption rate of these short wavelengths.

Report on ISS O2 Production, Gas Supply and Partial Pressure Management

NASA Technical Reports Server (NTRS)

Schaezler, Ryan N.; Cook, Anthony J.

2015-01-01

Oxygen is used on International Space Station (ISS) for metabolic support and denitrogenation procedures prior to Extra-Vehicular Activities. Nitrogen is used to maintain total pressure and account for losses associated with leakage and operational losses. Oxygen and nitrogen have been supplied by various visiting vehicles such as the Progress and Shuttle in addition to the on-orbit oxygen production capability. Starting in 2014, new high pressure oxygen/nitrogen tanks are available to launch on commercial cargo vehicles and will replace the high pressure gas source that Shuttle used to provide. To maintain a habitable atmosphere the oxygen and nitrogen partial pressures are controlled between upper and lower bounds. The full range of the allowable partial pressures along with the increased ISS cabin volume are utilized as a buffer allowing days to pass between oxygen production or direct addition of oxygen and nitrogen to the atmosphere from reserves. This paper summarizes the amount of gas supplied and produced from all of the sources and describes past experience of managing partial pressures along with the range of management options available to the ISS.

Isolation and Characterization of a Dihydroxo-Bridged Iron(III,III)(μ-OH)2 Diamond Core Derived from Dioxygen

PubMed Central

Coggins, Michael K.; Toledo, Santiago; Kovacs, Julie A.

2013-01-01

Dioxygen addition to coordinatively unsaturated [Fe(II)(OMe2N4(6-Me-DPEN))](PF6) (1) is shown to afford a complex containing a dihydroxo-bridged Fe(III)2(μ-OH)2 diamond core, [FeIII(OMe2N4(6-Me-DPEN))]2(μ-OH)2(PF6)2•(CH3CH2CN)2 (2). The diamond core of 2 resembles the oxidized methane monooxygenase (MMOox) resting state, as well as the active site product formed following H-atom abstraction from Tyr-OH by ribonucleotide reductase (RNR). The Fe-OH bond lengths of 2 are comparable with those of the MMOHox suggesting that MMOHox contains a Fe(III)2(μ-OH)2 as opposed to Fe(III)2(μ-OH)(μ-OH2) diamond core as had been suggested. Isotopic labeling experiments with 18O2 and CD3CN indicate that the oxygen and proton of the μ-OH bridges of 2 are derived from dioxygen and acetonitrile. Deuterium incorporation (from CD3CN) suggests that an unobserved intermediate capable of abstracting a H-atom from CH3CN forms en route to 2. Given the high C–H bond dissociation energy (BDE= 97 kcal/mol) of acetonitrile, this indicates that this intermediate is a potent oxidant, possibly a high-valent iron oxo. Consistent with this, iodosylbenzene (PhIO) also reacts with 1 in CD3CN to afford the deuterated Fe(III)2(μ-OD)2 derivative of 2. Intermediates are not spectroscopically observed in either reaction (O2 and PhIO) even at low-temperatures (−80 °C), indicating that this intermediate has a very short life-time, likely due to its highly reactive nature. Hydroxo-bridged 2 was found to stoichiometrically abstract hydrogen atoms from 9,10-dihydroanthracene (C-H BDE= 76 kcal/mol) at ambient temperatures. PMID:24229319

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

PubMed

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

2018-04-06

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

Thermal equation of state of TiC: A synchrotron x-ray diffraction study

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

Yu Xiaohui; National Lab for Condensed Matter Physics, Institute of Physics, CAS, Beijing 100080; Department of Physics, University of Science and Technology of China, Hefei 230026

2010-06-15

The pressure-volume-temperature measurements were carried out for titanium carbide (TiC) at pressures and temperatures up to 8.1 GPa and 1273 K using energy-dispersive synchrotron x-ray diffraction. Thermoelastic parameters were derived for TiC based on a modified high-temperature Birch-Murnaghan equation of state and a thermal pressure approach. With the pressure derivative of the bulk modulus, K{sub 0}{sup '}, fixed at 4.0, we obtain: the ambient bulk modulus K{sub 0}=268(6) GPa, which is comparable to previously reported value; temperature derivative of bulk modulus at constant pressure ({partial_derivative}K{sub T}/{partial_derivative}T){sub P}=-0.026(9) GPa K{sup -1}, volumetric thermal expansivity {alpha}{sub T}(K{sup -1})=a+bT with a=1.62(12)x10{sup -5} K{supmore » -1} and b=1.07(17)x10{sup -8} K{sup -2}, pressure derivative of thermal expansion ({partial_derivative}{alpha}/{partial_derivative}P){sub T}=(-3.62{+-}1.14)x10{sup -7} GPa{sup -1} K{sup -1}, and temperature derivative of bulk modulus at constant volume ({partial_derivative}K{sub T}/{partial_derivative}T){sub V}=-0.015(8) GPa K{sup -1}. These results provide fundamental thermophysical properties for TiC for the first time and are important to theoretical and computational modeling of transition metal carbides.« less

Thermal equation-of-state of TiC: a synchrotron x-ray diffraction study

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

Yu, Xiaohui; Lin, Zhijun; Zhang, Jianzhong

2009-01-01

The pressure (P)-volume (V)-temperature (T) measurements were carried out for titanium carbide at pressures and temperatures up to 8.1 GPa and 1273 K using energy-dispersive synchrotron x-ray diffraction. Thermoelastic parameters were derived for TiC based on a modified high-temperature Birch-Murnaghan equation of state and a thermal-pressure approach. With the pressure derivative of the bulk modulus, K'{sub 0}, fixed at 4.0, we obtain: the ambient bulk modulus K{sub 0} = 268(6) GPa, temperature derivative of bulk modulus at constant pressure ({partial_derivative}K{sub T}/{partial_derivative}T){sub p} = -0.026(9) GPa K{sup -1}, volumetric thermal expansivity a{sub T}(K{sup -1}) = a + bT with a =more » 1.62(12) x 10{sup -5} K{sup -1} and b = 1.07(17) x 10{sup -8} K{sup -2}, pressure derivative of thermal expansion ({partial_derivative}a/{partial_derivative}P){sub T} = (-3.62 {+-} 1.14) x 10{sup -7} GPa{sup -1} K{sup -1}, and temperature derivative of bulk modulus at constant volume ({partial_derivative}K{sub T}/{partial_derivative}T){sub v} = -0.015 (8) GPa K{sup -1}. These results provide fundamental thermo physical properties for TiC and are important to theoretical and computational modeling of transition metal carbides.« less

Effect of O 2 gas partial pressure on structures and dielectric characteristics of rf sputtered ZrO 2 thin films

NASA Astrophysics Data System (ADS)

Ma, C. Y.; Lapostolle, F.; Briois, P.; Zhang, Q. Y.

2007-08-01

Amorphous and polycrystalline zirconium oxide thin films have been deposited by reactive rf magnetron sputtering in a mixed argon/oxygen or pure oxygen atmosphere with no intentional heating of the substrate. The films were characterized by high-resolution transmission electron microscopy (HR-TEM), atomic force microscopy (AFM), spectroscopic ellipsometry (SE), and capacitance versus voltage ( C- V) measurements to investigate the variation of structure, surface morphology, thickness of SiO 2-like interfacial layer as well as dielectric characteristics with different oxygen partial pressures. The films deposited at low oxygen partial pressures (less than 15%) are amorphous and dense with a smooth surface. In contrast, the films prepared at an oxygen partial pressure higher than 73% are crystallized with the microstructure changing from the mixture of monoclinic and tetragonal phases to a single monoclinic structure. The film structural transition is believed to be consequences of decrease in the oxygen vacancy concentration in the film and of increase of the energetically neutral particles in the plasma due to an increased oxygen partial pressure. SE measurements showed that significant interfacial SiO 2 growth has taken place above approximately 51%. The best C- V results in terms of relative dielectric constant values are obtained for thin films prepared at an oxygen partial pressure of 15%.

Gas Exchange of Algae

PubMed Central

Ammann, Elizabeth C. B.; Lynch, Victoria H.

1966-01-01

Changes in the oxygen partial pressure of air over the range of 8 to 258 mm of Hg did not adversely affect the photosynthetic capacity of Chlorella pyrenoidosa. Gas exchange and growth measurements remained constant for 3-week periods and were similar to air controls (oxygen pressure of 160 mm of Hg). Oxygen partial pressures of 532 and 745 mm of Hg had an adverse effect on algal metabolism. Carbon dioxide consumption was 24% lower in the gas mixture containing oxygen at a pressure 532 mm of Hg than in the air control, and the growth rate was slightly reduced. Oxygen at a partial pressure of 745 mm of Hg decreased the photosynthetic rate 39% and the growth rate 37% over the corresponding rates in air. The lowered metabolic rates remained constant during 14 days of measurements, and the effect was reversible after this time. Substitution of helium or argon for the nitrogen in air had no effect on oxygen production, carbon dioxide consumption, or growth rate for 3-week periods. All measurements were made at a total pressure of 760 mm of Hg, and all gas mixtures were enriched with 2% carbon dioxide. Thus, the physiological functioning and reliability of a photosynthetic gas exchanger should not be adversely affected by: (i) oxygen partial pressures ranging from 8 to 258 mm of Hg; (ii) the use of pure oxygen at reduced total pressure (155 to 258 mm of Hg) unless pressure per se affects photosynthesis, or (iii) the inclusion of helium or argon in the gas environment (up to a partial pressure of 595 mm of Hg). PMID:5927028

Steady-State Plant Model to Predict Hydroden Levels in Power Plant Components

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

Glatzmaier, Greg C.; Cable, Robert; Newmarker, Marc

The National Renewable Energy Laboratory (NREL) and Acciona Energy North America developed a full-plant steady-state computational model that estimates levels of hydrogen in parabolic trough power plant components. The model estimated dissolved hydrogen concentrations in the circulating heat transfer fluid (HTF), and corresponding partial pressures within each component. Additionally for collector field receivers, the model estimated hydrogen pressure in the receiver annuli. The model was developed to estimate long-term equilibrium hydrogen levels in power plant components, and to predict the benefit of hydrogen mitigation strategies for commercial power plants. Specifically, the model predicted reductions in hydrogen levels within the circulatingmore » HTF that result from purging hydrogen from the power plant expansion tanks at a specified target rate. Our model predicted hydrogen partial pressures from 8.3 mbar to 9.6 mbar in the power plant components when no mitigation treatment was employed at the expansion tanks. Hydrogen pressures in the receiver annuli were 8.3 to 8.4 mbar. When hydrogen partial pressure was reduced to 0.001 mbar in the expansion tanks, hydrogen pressures in the receiver annuli fell to a range of 0.001 mbar to 0.02 mbar. When hydrogen partial pressure was reduced to 0.3 mbar in the expansion tanks, hydrogen pressures in the receiver annuli fell to a range of 0.25 mbar to 0.28 mbar. Our results show that controlling hydrogen partial pressure in the expansion tanks allows us to reduce and maintain hydrogen pressures in the receiver annuli to any practical level.« less

Oxygen partial pressure influenced structural and optical properties of DC magnetron sputtered ZrO{sub 2} films

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

Kondaiah, P.; Madhavi, V.; Uthanna, S.

2013-02-05

Thin films of zirconium oxide (ZrO{sub 2}) were deposited on (100) p-silicon and quartz substrates by sputtering of metallic zirconium target under different oxygen partial pressures in the range 8 Multiplication-Sign 10{sup -3}-6 Multiplication-Sign 10{sup -2}Pa. The effect of oxygen partial pressure on the structural and optical properties of the deposited films was systematically investigated. The deposition rate of the films decreased from 3.3 to 1.83 nm/min with the increase of oxygen partial pressure from 8 Multiplication-Sign 10{sup -3}-6 Multiplication-Sign 10{sup -2}Pa respectively. The X-ray diffraction profiles revealed that the films exhibit (111) refection of zirconium oxide in monoclinic phase.more » The optical band gap of the films increased from 5.62 to 5.80 eV and refractive index increased from 2.01 to 2.08 with the increase of oxygen partial pressure from 8 Multiplication-Sign 10{sup -3}-6 Multiplication-Sign 10{sup -2}Pa respectively.« less

Effects of hydrogen partial pressure on autotrophic growth and product formation of Acetobacterium woodii.

PubMed

Kantzow, Christina; Weuster-Botz, Dirk

2016-08-01

Low aqueous solubility of the gases for autotrophic fermentations (e.g., hydrogen gas) results in low productivities in bioreactors. A frequently suggested approach to overcome mass transfer limitation is to increase the solubility of the limiting gas in the reaction medium by increasing the partial pressure in the gas phase. An increased inlet hydrogen partial pressure of up to 2.1 bar (total pressure of 3.5 bar) was applied for the autotrophic conversion of hydrogen and carbon dioxide with Acetobacterium woodii in a batch-operated stirred-tank bioreactor with continuous gas supply. Compared to the autotrophic batch process with an inlet hydrogen partial pressure of 0.4 bar (total pressure of 1.0 bar) the final acetate concentration after 3.1 days was reduced to 50 % (29.2 g L(-1) compared to 59.3 g L(-1)), but the final formate concentration was increased by a factor of 18 (7.3 g L(-1) compared to 0.4 g L(-1)). Applying recombinant A. woodii strains overexpressing either genes for enzymes in the methyl branch of the Wood-Ljungdahl pathway or the genes phosphotransacetylase and acetate kinase at an inlet hydrogen partial pressure of 1.4 bar reduced the final formate concentration by up to 40 % and increased the final dry cell mass and acetate concentrations compared to the wild type strain. Solely the overexpression of the two genes for ATP regeneration at the end of the Wood-Ljungdahl pathway resulted in an initial switch off of formate production at increased hydrogen partial pressure until the maximum of the hydrogen uptake rate was reached.

Photosynthetic induction and its diffusional, carboxylation and electron transport processes as affected by CO2 partial pressure, temperature, air humidity and blue irradiance.

PubMed

Kaiser, Elias; Kromdijk, Johannes; Harbinson, Jeremy; Heuvelink, Ep; Marcelis, Leo F M

2017-01-01

Plants depend on photosynthesis for growth. In nature, factors such as temperature, humidity, CO 2 partial pressure, and spectrum and intensity of irradiance often fluctuate. Whereas irradiance intensity is most influential and has been studied in detail, understanding of interactions with other factors is lacking. We tested how photosynthetic induction after dark-light transitions was affected by CO 2 partial pressure (20, 40, 80 Pa), leaf temperatures (15·5, 22·8, 30·5 °C), leaf-to-air vapour pressure deficits (VPD leaf-air ; 0·5, 0·8, 1·6, 2·3 kPa) and blue irradiance (0-20 %) in tomato leaves (Solanum lycopersicum). Rates of photosynthetic induction strongly increased with CO 2 partial pressure, due to increased apparent Rubisco activation rates and reduced diffusional limitations. High leaf temperature produced slightly higher induction rates, and increased intrinsic water use efficiency and diffusional limitation. High VPD leaf-air slowed down induction rates and apparent Rubisco activation and (at 2·3 kPa) induced damped stomatal oscillations. Blue irradiance had no effect. Slower apparent Rubisco activation in elevated VPD leaf-air may be explained by low leaf internal CO 2 partial pressure at the beginning of induction. The environmental factors CO 2 partial pressure, temperature and VPD leaf-air had significant impacts on rates of photosynthetic induction, as well as on underlying diffusional, carboxylation and electron transport processes. Furthermore, maximizing Rubisco activation rates would increase photosynthesis by at most 6-8 % in ambient CO 2 partial pressure (across temperatures and humidities), while maximizing rates of stomatal opening would increase photosynthesis by at most 1-3 %. © The Author 2016. Published by Oxford University Press on behalf of the Annals of Botany Company. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Bulk YBa2Cu3O(x) superconductors through pressurized partial melt growth processing

NASA Technical Reports Server (NTRS)

Hu, S.; Hojaji, H.; Barkatt, A.; Boroomand, M.; Hung, M.; Buechele, A. C.; Thorpe, A. N.; Davis, D. D.; Alterescu, S.

1992-01-01

A novel pressurized partial melt growth process has been developed for producing large pieces of bulk Y-Ba-Cu-O superconductors. During long-time partial melt growth stage, an additional driving force for solidification is obtained by using pressurized oxygen gas. The microstructure and superconducting properties of the resulting samples were investigated. It was found that this new technique can eliminate porosity and inhomogeneity, promote large-scale grain-texturing, and improve interdomain coupling as well.

Growth responses of Neurospora crassa to increased partial pressures of the noble gases and nitrogen.

PubMed

Buchheit, R G; Schreiner, H R; Doebbler, G F

1966-02-01

Buchheit, R. G. (Union Carbide Corp., Tonawanda, N.Y.), H. R. Schreiner, and G. F. Doebbler. Growth responses of Neurospora crassa to increased partial pressures of the noble gases and nitrogen. J. Bacteriol. 91:622-627. 1966.-Growth rate of the fungus Neurospora crassa depends in part on the nature of metabolically "inert gas" present in its environment. At high partial pressures, the noble gas elements (helium, neon, argon, krypton, and xenon) inhibit growth in the order: Xe > Kr> Ar > Ne > He. Nitrogen (N(2)) closely resembles He in inhibitory effectiveness. Partial pressures required for 50% inhibition of growth were: Xe (0.8 atm), Kr (1.6 atm), Ar (3.8 atm), Ne (35 atm), and He ( approximately 300 atm). With respect to inhibition of growth, the noble gases and N(2) differ qualitatively and quantitatively from the order of effectiveness found with other biological effects, i.e., narcosis, inhibition of insect development, depression of O(2)-dependent radiation sensitivity, and effects on tissue-slice glycolysis and respiration. Partial pressures giving 50% inhibition of N. crassa growth parallel various physical properties (i.e., solubilities, solubility ratios, etc.) of the noble gases. Linear correlation of 50% inhibition pressures to the polarizability and of the logarithm of pressure to the first and second ionization potentials suggests the involvement of weak intermolecular interactions or charge-transfer in the biological activity of the noble gases.

Cu-catalyzed aerobic oxidative esterification of acetophenones with alcohols to α-ketoesters.

PubMed

Xu, Xuezhao; Ding, Wen; Lin, Yuanguang; Song, Qiuling

2015-02-06

Copper-catalyzed aerobic oxidative esterification of acetophenones with alcohols using molecular oxygen has been developed to form a broad range of α-ketoesters in good yields. In addition to reporting scope and limitations of our new method, mechanism studies are reported that reveal that the carbonyl oxygen in the ester mainly originated from dioxygen.

Copper-Zinc Superoxide Dismutase: A Unique Biological "Ligand" for Bioinorganic Studies.

ERIC Educational Resources Information Center

Valentine, Joan Selverstone; de Freitas, Duarte Mota

1985-01-01

Discusses superoxide dismutase (SOD) research and the properties of copper, zinc (Cu, Zn)-SOD. Emphasizes the controversy concerning the role of Cu,Zn-SOD and other SOD enzymes as protective agents in reactions involving dioxygen metabolism, and the properties of Cu, Zn-SOD that make it an interesting biological ligand for physical studies of…

A System for Incubations at High Gas Partial Pressure

PubMed Central

Sauer, Patrick; Glombitza, Clemens; Kallmeyer, Jens

2012-01-01

High-pressure is a key feature of deep subsurface environments. High partial pressure of dissolved gasses plays an important role in microbial metabolism, because thermodynamic feasibility of many reactions depends on the concentration of reactants. For gases, this is controlled by their partial pressure, which can exceed 1 MPa at in situ conditions. Therefore, high hydrostatic pressure alone is not sufficient to recreate true deep subsurface in situ conditions, but the partial pressure of dissolved gasses has to be controlled as well. We developed an incubation system that allows for incubations at hydrostatic pressure up to 60 MPa, temperatures up to 120°C, and at high gas partial pressure. The composition and partial pressure of gasses can be manipulated during the experiment. To keep costs low, the system is mainly made from off-the-shelf components with only very few custom-made parts. A flexible and inert PVDF (polyvinylidene fluoride) incubator sleeve, which is almost impermeable for gases, holds the sample and separates it from the pressure fluid. The flexibility of the incubator sleeve allows for sub-sampling of the medium without loss of pressure. Experiments can be run in both static and flow-through mode. The incubation system described here is usable for versatile purposes, not only the incubation of microorganisms and determination of growth rates, but also for chemical degradation or extraction experiments under high gas saturation, e.g., fluid–gas–rock-interactions in relation to carbon dioxide sequestration. As an application of the system we extracted organic compounds from sub-bituminous coal using H2O as well as a H2O–CO2 mixture at elevated temperature (90°C) and pressure (5 MPa). Subsamples were taken at different time points during the incubation and analyzed by ion chromatography. Furthermore we demonstrated the applicability of the system for studies of microbial activity, using samples from the Isis mud volcano. We could detect an increase in sulfate reduction rate upon the addition of methane to the sample. PMID:22347218

Thermal Equation of State of TiC: A Synchrotron X-ray Diffraction

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

Yu, X.; Lin, Z; Zhang, J

2010-01-01

The pressure-volume-temperature measurements were carried out for titanium carbide (TiC) at pressures and temperatures up to 8.1 GPa and 1273 K using energy-dispersive synchrotron x-ray diffraction. Thermoelastic parameters were derived for TiC based on a modified high-temperature Birch-Murnaghan equation of state and a thermal pressure approach. With the pressure derivative of the bulk modulus, K{prime}{sub 0}, fixed at 4.0, we obtain: the ambient bulk modulus K{sub 0} = 268(6) GPa, which is comparable to previously reported value; temperature derivative of bulk modulus at constant pressure ({partial_derivative}K{sub T}/{partial_derivative}T){sub P} = -0.026(9) GPa K{sup -1}, volumetric thermal expansivity {alpha}{sub T}(K{sup -1}) =more » a+b T with a = 1.62(12) x 10{sup -5} K{sup -1} and b = 1.07(17) x 10{sup -8}K{sup -2}, pressure derivative of thermal expansion ({partial_derivative}{sub {alpha}}/{partial_derivative}{sub P}){sub T} = (-3.62 {+-} 1.14) x 10{sup -7} GPa{sup -1} K{sup -1}, and temperature derivative of bulk modulus at constant volume ({partial_derivative}K{sub T}/{partial_derivative}T){sub V} = -0.015(8) GPa K{sup -1}. These results provide fundamental thermophysical properties for TiC for the first time and are important to theoretical and computational modeling of transition metal carbides.« less

Spatial Characteristics of F/A-18 Vertical Tail Buffet Pressures Measured in Flight

NASA Technical Reports Server (NTRS)

Moses, Robert W.; Shah, Gautam H.

1998-01-01

Buffeting is an aeroelastic phenomenon which plagues high performance aircraft, especially those with twin vertical tails, at high angles of attack. Previous wind-tunnel and flight tests were conducted to characterize the buffet loads on the vertical tails by measuring surface pressures, bending moments, and accelerations. Following these tests, buffeting estimates were computed using the measured buffet pressures and compared to the measured responses. The estimates did not match the measured data because the assumed spatial correlation of the buffet pressures was not correct. A better understanding of the partial (spatial) correlation of the differential buffet pressures on the tail was necessary to improve the buffeting estimates. Several wind-tunnel investigations were conducted for this purpose. When combined and compared, the results of these tests show that the partial correlation depends on and scales with flight conditions. One of the remaining questions is whether the windtunnel data is consistent with flight data. Presented herein, cross-spectra and coherence functions calculated from pressures that were measured on the high alpha research vehicle (HARV) indicate that the partial correlation of the buffet pressures in flight agrees with the partial correlation observed in the wind tunnel.

Correlation of Fin Buffet Pressures on an F/A-18 with Scaled Wind-Tunnel Measurements

NASA Technical Reports Server (NTRS)

Moses, Robert W.; Shah, Gautam H.

1999-01-01

Buffeting is an aeroelastic phenomenon occurring at high angles of attack that plagues high performance aircraft, especially those with twin vertical tails. Previous wind-tunnel and flight tests were conducted to characterize the buffet loads on the vertical tails by measuring surface pressures, bending moments, and accelerations. Following these tests, buffeting responses were computed using the measured buffet pressures and compared to the measured buffeting responses. The calculated results did not match the measured data because the assumed spatial correlation of the buffet pressures was not correct. A better understanding of the partial (spatial) correlation of the differential buffet pressures on the tail was necessary to improve the buffeting predictions. Several wind-tunnel investigations were conducted for this purpose. When compared, the results of these tests show that the partial correlation scales with flight conditions. One of the remaining questions is whether the wind-tunnel data is consistent with flight data. Presented herein, cross-spectra and coherence functions calculated from pressures that were measured on the High Alpha Research Vehicle indicate that the partial correlation of the buffet pressures in flight agrees with the partial correlation observed in the wind tunnel.

Effect of pressure on the Raman-active modes of zircon (ZrSiO4): a first-principles study

NASA Astrophysics Data System (ADS)

Sheremetyeva, Natalya; Cherniak, Daniele J.; Watson, E. Bruce; Meunier, Vincent

2018-02-01

Density-functional theory (DFT) was employed in a first-principles study of the effects of pressure on the Raman-active modes of zircon (ZrSiO4), using both the generalized gradient and local density approximations (GGA and LDA, respectively). Beginning with the equilibrium structure at zero pressure, we conducted a calibration of the effect of pressure in a manner procedurally similar to an experimental calibration. For pressures between 0 and 7 GPa, we find excellent qualitative agreement of frequency-pressure slopes partial ω /partial P calculated from GGA DFT with results of previous experimental studies. In addition, we were able to rationalize the ω vs. P behavior based on details of the vibrational modes and their atomic displacements. Most of the partial ω /partial P slopes are positive as expected, but the symmetry of the zircon lattice also results in two negative slopes for modes that involve slight shearing and rigid rotation of SiO4 tetrahedra. Overall, LDA yields absolute values of the frequencies of the Raman-active modes in good agreement with experimental values, while GGA reproduces the shift in frequency with pressure especially well.

High rate reactive sputtering of MoN(x) coatings

NASA Technical Reports Server (NTRS)

Rudnik, Paul J.; Graham, Michael E.; Sproul, William D.

1991-01-01

High rate reactive sputtering of MoN(x) films was performed using feedback control of the nitorgen partial pressure. Coatings were made at four different target powers: 2.5, 5.0, 7.5 and 10 kW. No hysteresis was observed in the nitrogen partial pressure vs. flow plot, as is typically seen for the Ti-N system. Four phases were determined by X-ray diffraction: molybdenum, Mo-N solid solution, Beta-Mo2N and gamma-Mo2N. The hardness of the coatings depended upon composition, substrate bias, and target power. The phases present in the hardest films differed depending upon deposition parameters. For example, the Beta-Mo2N phase was hardest (load 25 gf) at 5.0 kW with a value of 3200 kgf/sq mm, whereas the hardest coatings at 10 kW were the gamma-Mo2N phase (3000 kgf/sq mm). The deposition rate generally decreased with increasing nitrogen partial pressure, but there was a range of partial pressures where the rate was relatively constant. At a target power of 5.0 kW, for example, the deposition rates were 3300 A/min for a N2 partial pressure of 0.05 - 1.0 mTorr.

Growth of the microalgae Neochloris oleoabundans at high partial oxygen pressures and sub-saturating light intensity.

PubMed

Sousa, Cláudia; de Winter, Lenneke; Janssen, Marcel; Vermuë, Marian H; Wijffels, René H

2012-01-01

The effect of partial oxygen pressure on growth of Neochloris oleoabundans was studied at sub-saturating light intensity in a fully-controlled stirred tank photobioreactor. At the three partial oxygen pressures tested (P(O)₂= 0.24; 0.63; 0.84 bar), the specific growth rate was 1.38; 1.36 and 1.06 day(-1), respectively. An increase of the P(CO)₂from 0.007 to 0.02 bar at P(O₂) of 0.84 bar resulted in an increase in the growth rate from 1.06 to 1.36 day(-1). These results confirm that the reduction of algal growth at high oxygen concentrations at sub-saturating light conditions is mainly caused by competitive inhibition of Rubisco. This negative effect on growth can be overcome by restoring the O(2)/CO(2) ratio by an increase in the partial carbon dioxide pressure. In comparison to general practice (P(O(2)) = 0.42 bar), working at partial O(2) pressure of 0.84 bar could reduce the energy requirement for degassing by a factor of 3-4. Copyright © 2011 Elsevier Ltd. All rights reserved.

Decline in arterial partial pressure of oxygen after exercise: a surrogate marker of pulmonary vascular obstructive disease in patients with atrial septal defect and severe pulmonary hypertension.

PubMed

Laksmivenkateshiah, Srinivas; Singhi, Anil K; Vaidyanathan, Balu; Francis, Edwin; Karimassery, Sundaram R; Kumar, Raman K

2011-06-01

To examine the utility of decline in arterial partial pressure of oxygen after exercise as a marker of pulmonary vascular obstructive disease in patients with atrial septal defect and pulmonary hypertension. Treadmill exercise was performed in 18 patients with atrial septal defect and pulmonary hypertension. Arterial blood gas samples were obtained before and after peak exercise. A decline in the arterial pressure of oxygen of more than 10 millimetres of mercury after exercise was considered significant based on preliminary tests conducted on the controls. Cardiac catheterisation was performed in all patients and haemodynamic data sets were obtained on room air, oxygen, and a mixture of oxygen and nitric oxide (30-40 parts per million). There were 10 patients who had more than a 10 millimetres of mercury drop in arterial partial pressure of oxygen after exercise and who had a basal pulmonary vascular resistance index of more than 7 Wood units per square metre. Out of eight patients who had less than a 10 millimetres of mercury drop in arterial partial pressure of oxygen after exercise, seven had a basal pulmonary vascular resistance index of less than 7 Wood units per square metre, p equals 0.0001. A decline in arterial partial pressure of oxygen of more than 10 millimetres of mercury predicted a basal pulmonary vascular resistance index of more than 7 Wood units per square metre with a specificity of 100% and a sensitivity of 90%. A decline in arterial partial pressure of oxygen following exercise appears to predict a high pulmonary vascular resistance index in patients with atrial septal defect and pulmonary hypertension. This test is a useful non-invasive marker of pulmonary vascular obstructive disease in this subset.

Subatmospheric vapor pressures for fluoromethane (R41), 1,1-difluoroethane (R152a), and 1,1,1-trifluoroethane (R143a) evaluated from internal-energy measurements

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

Duarte-Garza, H.A.; Magee, J.W.

1999-09-01

Vapor pressures were evaluated from measured internal-energy changes {Delta}U{sup (2)} in the vapor + liquid two-phase region. The method employed a thermodynamic relationship between the derivative quantity ({partial_derivative}U{sup (2)}/{partial_derivative}V){sub T}, the vapor pressure p{sub {sigma}}, and its temperature derivative ({partial_derivative}p/{partial_derivative}T){sub {sigma}}. This method was applied at temperatures between the triple point and the normal boiling point of three substances: fluoromethane (R41), 1,1-difluoroethane (R152a), and 1,1,1-trifluoroethane (R143a). In the case of R41, vapor pressures up to 1 MPa were calculated to validate the technique at higher pressures. For R152a, the calculated vapor pressure at the triple-point temperature differed from a directmore » experimental measurement by less than the claimed uncertainty (5 Pa) of the measurement. The calculated vapor pressures for R41 helped to resolve discrepancies in several published vapor pressure sources. Agreement with experimentally measured vapor pressures for R152a and for R143a near the normal boiling point (101.325 kPa) was within the experimental uncertainty of approximately 0.04 kPa (0.04%) for the published measurements.« less

Effect of partial meniscectomy at the medial posterior horn on tibiofemoral contact mechanics and meniscal hoop strains in human knees.

PubMed

Seitz, Andreas Martin; Lubomierski, Anja; Friemert, Benedikt; Ignatius, Anita; Dürselen, Lutz

2012-06-01

We examined the influence of partial meniscectomy of 10 mm width on 10 human cadaveric knee joints, as it is performed during the treatment of radial tears in the posterior horn of the medial meniscus, on maximum contact pressure, contact area (CA), and meniscal hoop strain in the lateral and medial knee compartments. In case of 0° and 30° flexion angle, 20% and 50% partial meniscectomy did not influence maximum contact pressure and area. Only in case of 60° knee flexion, 50% partial resection increased medial maximum contact pressure and decreased the medial CA statistically significant. However, 100% partial resection increased maximum contact pressure and decreased CA significantly in the meniscectomized medial knee compartment in all tested knee positions. No significant differences were noted for meniscal hoop strain. From a biomechanical point of view, our in vitro study suggests that the medial joint compartment is not in danger of accelerated cartilage degeneration up to a resection limit of 20% meniscal depth and 10 mm width. Contact mechanics are likely to be more sensitive to partial meniscectomy at higher flexion angles, which has to be further investigated. Copyright © 2011 Orthopaedic Research Society.

Point Defect Structure of Cr203

DTIC Science & Technology

1987-10-01

Calculation of Electron Hole Mobility ........................ 104 6.2.3 Construction of the Defect Concentration vs. Oxygen Pressure Diagram...1000’ to 16000C ............ 123 7.7 Calculated diffusion coefficient vs. oxygen partial pressure diagram for pure Cr203 at 1100 0 C...127 7.10 Calculated parabolic rate constant vs. oxygen partial pressure diagram for pure Cr203 at

Growth Responses of Neurospora crassa to Increased Partial Pressures of the Noble Gases and Nitrogen

PubMed Central

Buchheit, R. G.; Schreiner, H. R.; Doebbler, G. F.

1966-01-01

Buchheit, R. G. (Union Carbide Corp., Tonawanda, N.Y.), H. R. Schreiner, and G. F. Doebbler. Growth responses of Neurospora crassa to increased partial pressures of the noble gases and nitrogen. J. Bacteriol. 91:622–627. 1966.—Growth rate of the fungus Neurospora crassa depends in part on the nature of metabolically “inert gas” present in its environment. At high partial pressures, the noble gas elements (helium, neon, argon, krypton, and xenon) inhibit growth in the order: Xe > Kr> Ar ≫ Ne ≫ He. Nitrogen (N2) closely resembles He in inhibitory effectiveness. Partial pressures required for 50% inhibition of growth were: Xe (0.8 atm), Kr (1.6 atm), Ar (3.8 atm), Ne (35 atm), and He (∼ 300 atm). With respect to inhibition of growth, the noble gases and N2 differ qualitatively and quantitatively from the order of effectiveness found with other biological effects, i.e., narcosis, inhibition of insect development, depression of O2-dependent radiation sensitivity, and effects on tissue-slice glycolysis and respiration. Partial pressures giving 50% inhibition of N. crassa growth parallel various physical properties (i.e., solubilities, solubility ratios, etc.) of the noble gases. Linear correlation of 50% inhibition pressures to the polarizability and of the logarithm of pressure to the first and second ionization potentials suggests the involvement of weak intermolecular interactions or charge-transfer in the biological activity of the noble gases. PMID:5883104

Report on ISS Oxygen Production, Resupply, and Partial Pressure Management

NASA Technical Reports Server (NTRS)

Schaezler, Ryan; Ghariani, Ahmed; Leonard, Daniel; Lehman, Daniel

2011-01-01

The majority of oxygen used on International Space Station (ISS) is for metabolic support and denitrogenation procedures prior to Extra-Vehicular Activities. Oxygen is supplied by various visiting vehicles such as the Progress and Shuttle in addition to oxygen production capability on both the United States On-Orbit Segment (USOS) and Russian Segment (RS). To maintain a habitable atmosphere the oxygen partial pressure is controlled between upper and lower bounds. The full range of the allowable oxygen partial pressure along with the increased ISS cabin volume is utilized as a buffer allowing days to pass between oxygen production or direct addition of oxygen to the atmosphere from reserves. This paper summarizes amount of oxygen supplied and produced from all of the sources and describes past experience of managing oxygen partial pressure along with the range of management options available to the ISS.

Thin film oxygen partial pressure sensor

NASA Technical Reports Server (NTRS)

Wortman, J. J.; Harrison, J. W.; Honbarrier, H. L.; Yen, J.

1972-01-01

The development is described of a laboratory model oxygen partial pressure sensor using a sputtered zinc oxide thin film. The film is operated at about 400 C through the use of a miniature silicon bar. Because of the unique resistance versus temperature relation of the silicon bar, control of the operational temperature is achieved by controlling the resistance. A circuit for accomplishing this is described. The response of sputtered zinc oxide films of various thicknesses to oxygen, nitrogen, argon, carbon dioxide, and water vapor caused a change in the film resistance. Over a large range, film conductance varied approximately as the square root of the oxygen partial pressure. The presence of water vapor in the gas stream caused a shift in the film conductance at a given oxygen partial pressure. A theoretical model is presented to explain the characteristic features of the zinc oxide response to oxygen.

Partial pressures of oxygen, phosphorus and fluorine in some lunar lavas

NASA Technical Reports Server (NTRS)

Nash, W. P.; Hausel, W. D.

1973-01-01

Lunar sample 14310 is a feldspar-rich basalt which shows no evidence of shock deformation or recrystallization. Pyroxenes include Mg-rich orthopyroxene, pigeonite and augite; pyroxferroite occurs in the interstitial residuum. Plagioclase feldspars are zoned from An(96) to An(67), and variations in feldspar compositions do not necessarily indicate loss of Na during eruption of the lava. Opaque phases include ilmenite, ulvospinel, metallic iron, troilite, and schreibersite. Both whitlockite and apatite are present, and the interstitial residua contain baddeleyite, tranquillityite and barium-rich sanidine. Theoretical calculations provide estimates of partial pressures of oxygen, phosphorus, and fluorine in lunar magmas. In general, partial pressures of oxygen are restricted by the limiting assemblages of iron-wuestite and ilmenite-iron-rutile; phosphorus partial pressures are higher in lunar magmas than in terrestrial lavas. The occurrence of whitlockite indicates significantly lower fugacities of fluorine in lunar magmas than in terrestrial magmas.

Diterpenoid alkaloids from the roots of Aconitum brachypodum Diels.

PubMed

Yang, Li-Guo; Zhang, Ying-Jie; Xie, Jia-Ying; Xia, Wei-Jun; Zhang, Hai-Yuan; Tang, Meng-Yun; Mei, Shuang-Xi; Cui, Tao; Wang, Jing-Kun; Zhu, Zhao-Yun

2016-09-01

A new diterpenoid alkaloid, named bullatine H (1), along with 10 known diterpenoid alkaloids were isolated from the roots of Aconitum brachypodum Diels (Ranunculaceae). The structure of 1 was elucidated by analysis of its spectroscopic data. It should be noted that compound 1 is the first example with 11, 13-dioxygenated denudatine-type diterpenoid alkaloid isolated from Aconitum brachypodum.

Formation kinetics and mechanism of metastable vacancy-dioxygen complex in neutron irradiated Czochralski silicon

NASA Astrophysics Data System (ADS)

Dong, Peng; Wang, Rong; Yu, Xuegong; Chen, Lin; Ma, Xiangyang; Yang, Deren

2017-07-01

We have quantitatively investigated the formation kinetics of metastable vacancy-dioxygen (VO2) complex in a structure of [VO + Oi], where a VO complex is trapped in a next-neighbor position to an interstitial oxygen atom (Oi). It is found that the VO annihilation is accompanied by the generation of metastable [VO + Oi] complex during annealing in the temperature range of 220-250 °C. The activation energy for [VO + Oi] generation appears at around 0.48 eV, which is much lower than the counterpart of stable VO2 complex. This indicates that the formation of [VO + Oi] complex originates from the reaction between VO and Oi. The ab initio calculations show that the formation energy of [VO + Oi] complex is larger than that of VO2 complex, which means that [VO + Oi] complex is thermodynamically unfavorable as compared to VO2 complex. However, the binding energy of [VO + Oi] complex is positive, indicating that [VO + Oi] complex is stable against decomposition of VO and Oi in silicon. It is believed that [VO + Oi] complex serves as the intermediate for VO to VO2 conversion.

Hole hopping through tyrosine/tryptophan chains protects proteins from oxidative damage

PubMed Central

Gray, Harry B.; Winkler, Jay R.

2015-01-01

Living organisms have adapted to atmospheric dioxygen by exploiting its oxidizing power while protecting themselves against toxic side effects. Reactive oxygen and nitrogen species formed during oxidative stress, as well as high-potential reactive intermediates formed during enzymatic catalysis, could rapidly and irreversibly damage polypeptides were protective mechanisms not available. Chains of redox-active tyrosine and tryptophan residues can transport potentially damaging oxidizing equivalents (holes) away from fragile active sites and toward protein surfaces where they can be scavenged by cellular reductants. Precise positioning of these chains is required to provide effective protection without inhibiting normal function. A search of the structural database reveals that about one third of all proteins contain Tyr/Trp chains composed of three or more residues. Although these chains are distributed among all enzyme classes, they appear with greatest frequency in the oxidoreductases and hydrolases. Consistent with a redox-protective role, approximately half of the dioxygen-using oxidoreductases have Tyr/Trp chain lengths ≥3 residues. Among the hydrolases, long Tyr/Trp chains appear almost exclusively in the glycoside hydrolases. These chains likely are important for substrate binding and positioning, but a secondary redox role also is a possibility. PMID:26195784

Locally enhanced sampling molecular dynamics study of the dioxygen transport in human cytoglobin.

PubMed

Orlowski, Slawomir; Nowak, Wieslaw

2007-07-01

Cytoglobin (Cyg)--a new member of the vertebrate heme globin family--is expressed in many tissues of the human body but its physiological role is still unclear. It may deliver oxygen under hypoxia, serve as a scavenger of reactive species or be involved in collagen synthesis. This protein is usually six-coordinated and binds oxygen by a displacement of the distal HisE7 imidazole. In this paper, the results of 60 ns molecular dynamics (MD) simulations of dioxygen diffusion inside Cyg matrix are discussed. In addition to a classical MD trajectory, an approximate Locally Enhanced Sampling (LES) method has been employed. Classical diffusion paths were carefully analyzed, five cavities in dynamical structures were determined and at least four distinct ligand exit paths were identified. The most probable exit/entry path is connected with a large tunnel present in Cyg. Several residues that are perhaps critical for kinetics of small gaseous diffusion were discovered. A comparison of gaseous ligand transport in Cyg and in the most studied heme protein myoglobin is presented. Implications of efficient oxygen transport found in Cyg to its possible physiological role are discussed.

Influence of oxygen partial pressure on the composition and orientation of strontium-doped lead zirconate titanate thin films.

PubMed

Sriram, S; Bhaskaran, M; du Plessis, J; Short, K T; Sivan, V P; Holland, A S

2009-01-01

The influence of oxygen partial pressure during the deposition of piezoelectric strontium-doped lead zirconate titanate thin films is reported. The thin films have been deposited by RF magnetron sputtering in an atmosphere of high purity argon and oxygen (in the ratio of 9:1), on platinum-coated silicon substrates (heated to 650 degrees C). The influence of oxygen partial pressure is studied to understand the manner in which the stoichiometry of the thin films is modified, and to understand the influence of stoichiometry on the perovskite orientation. This article reports on the results obtained from films deposited at oxygen partial pressures of 1-5 mTorr. The thin films have been studied using a combination of X-ray photoelectron spectroscopy (XPS), glancing angle X-ray diffraction (GA-XRD), and atomic force microscopy (AFM). XPS analysis highlights the marked influence of variations in oxygen pressure during sputtering, observed by variations in oxygen concentration in the thin films, and in some cases by the undesirable decrease in lead concentration in the thin films. GA-XRD is used to study the relative variations in perovskite peak intensities, and has been used to determine the deposition conditions to attain the optimal combination of stoichiometry and orientation. AFM scans show the marked influence of the oxygen partial pressure on the film morphology.

Measuring Ancient Air Pressure Using Fossilized Cyanobacteria

NASA Astrophysics Data System (ADS)

Silverman, S. N.; Som, S. M.; Gordon, R.; Bebout, B.

2016-12-01

The evolution of Earth's atmosphere has been governed by biological evolution. The dominant air component, nitrogen, has undergone substantial variation over geological time. Today, the partial pressure of nitrogen is 0.79 bar, but this value could have been much higher during early Earth1. The nitrogen partial pressure is postulated to have dropped to a maximum of 0.5 bar before the Great Oxidation Event 2.4 billion years ago, and subsequently recovered to the 0.8 bar value of our modern atmosphere over the next 330 million years2. We are placing constraints on the trajectory of this recovery by investigating how nitrogen partial pressure influences the morphology of a certain species of filamentous cyanobacteria that has been found fossilized in 2 billion year old rocks. These filamentous cyanobacteria convert nitrogen from its dissolved gaseous state (N2) to a biologically useful state (i.e. NH3) when the latter is present at growth-limiting concentrations in their aquatic environment. Such cyanobacteria develop heterocysts (specialized, visually distinct cells), which fix the nitrogen and laterally distribute it to neighboring cells along the one-dimensional filament. We suggest that the distance between heterocysts reflects the nitrogen partial pressure dissolved in water, which is related to atmospheric pN2 by Henry's law. In the laboratory, we are quantifying the relationship between heterocyst distance, variance and covariance to atmospheric pN2 by subjecting cyanobacteria (in media devoid of nitrate) to different partial pressures of N2 at a constant temperature and lighting for the representative species Anabaena variabilis. As far as we know, such experiments have not been previously conducted. This new geobarometer will complement existing methods of quantifying ancient nitrogen partial pressure. 1Goldblatt, Colin, et al. "Nitrogen-enhanced greenhouse warming on early Earth." Nature Geoscience 2 (2009): 891-896. 2Som, S., et al. "Earth's air pressure 2.7 billion years ago constrained to less than half of modern levels." Nature Geoscience 9 (2016): 448-451.

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

Karabourniotis, D.; Couris, S.; Damelincourt, J.J.

The partial pressure of thallium in high-pressure Hg-TlI discharges with different mercury, thallium, and electron pressures has been measured by using the optically thin line Tl 655 nm and the self-reversed line Tl 535 nm. The partial pressure of the arc axis has been measured from the line Tl 655nm. The effective partial pressure has been measured from the self-reversed line Tl 535 nm on the basis of the multiparameter method, and it has been calculated from the known axis pressure of thallium and the calculation of its radial variation by taking into account the chemical reactions. The experimental resultsmore » confirm the dispersion character of the blue wing of the line Tl 535 nm. The systematic difference obtained between the measured and calculated effective pressure, particularly at the moment of minimum electron density, may be interpreted by deviations from the local thermodynamic equilibrium (LTE) caused by overpopulation of the upper level of the line Tl 535 nm.« less

Methods and apparatus for reducing corrosion in refractory linings

DOEpatents

Poeppel, Roger B.; Greenberg, Sherman; Diercks, Dwight R.

1987-01-01

Methods and apparatus are provided for reducing corrosion in a refractory lining of a liquid-containing vessel used in direct steelmaking processes. The vessel operates at between about 1600.degree. C. and about 1800.degree. C. and an oxygen partial pressure of about 10.sup.-12 atmospheres, creating slag which is rich in FeO. The refractory lining includes a significant level of chromium oxide (Cr.sub.2 O.sub.3), and has small interconnected pores which may be filled with a gas mixture having a higher total pressure and oxygen partial pressure than the total pressure and oxygen partial pressure associted with the liquid against the lining of the vessel. The gas mixture is forced through the pores of the lining so that the pores are continuously filled with the mixture. In this manner, the gas mixture creates a blanket which increases the oxygen partial pressure at the lining enough to maintain the chromium in the lining in a selected valence state in which the chromium has decreased solubility in the FeO slag, thereby reducing corrosion by the FeO and increasing the useful life of the refractory lining.

Incidence and Determinants of Port Occlusions in Cancer Outpatients: A Prospective Cohort Study.

PubMed

Milani, Alessandra; Mazzocco, Ketti; Gandini, Sara; Pravettoni, Gabriella; Libutti, Livio; Zencovich, Claudia; Sbriglia, Ada; Pari, Chiara; Magon, Giorgio; Saiani, Luisa

Normal saline is considered a safe alternative for heparin as a locking solution in totally implantable venous access devices. The incidence rate of partial occlusion with the use of normal saline (easy injection, impossible aspiration) is estimated at 4%. The aim of this study was to investigate determinants of partial occlusions with the use of normal saline solution and the maintenance of positive pressure in the catheter. We enrolled 218 patients with different solid tumors who underwent pharmacologic treatment through the port with different frequencies: from once every week to at least once every month. The port was flushed with normal saline solution keeping a positive pressure in the catheter. We performed 4111 observations and documented normal port functioning in 99% of observations (n = 4057) and partial occlusions in 1% of observations (n = 54). Partial occlusions were significantly associated with frequency of port flushing (P < .05), chemotherapy (P < .001), and blood sample collection (P < .001). The use of positive pressure in addition to normal saline reduces the incidence rate of partial occlusions. The type of treatment, blood sample collection, and treatment schedule are important determinants of partial occlusions. Nurses play a key role in maintaining a functioning port using positive pressure during the flushing techniques. Certain risk factors must be monitored to prevent partial occlusions, and certain patients are more likely to present with port-related problems.

Effects of Shock-Breakout Pressure on Ejection of Micron-Scale Material from Shocked Tin Surfaces

NASA Astrophysics Data System (ADS)

Zellner, Michael; Hammerberg, James; Hixson, Robert; Morley, Kevin; Obst, Andrew; Olson, Russell; Payton, Jeremy; Rigg, Paulo; Buttler, William; Grover, Michael; Iverson, Adam; Macrum, Gregory; Stevens, Gerald; Turley, William; Veeser, Lynn; Routley, Nathan

2007-06-01

Los Alamos National Lab (LANL) is actively engaged in the development of a model to predict the formation of micron-scale fragments ejected (ejecta) from shocked metal surfaces. The LANL ejecta model considers that the amount of ejecta is mainly related to the material's phase on shock release at the free-surface. This effort investigates the relation between ejecta production and shock-breakout pressure for Sn shocked with high explosives to pressures near the solid-on-release/partial-liquid-on-release phase transition region. We found that the amount of ejecta produced for shock-breakout pressures that resulted in partial-liquid-on-release increased significantly compared to that which resulted in solid-on-release. Additionally, we found that the amount of ejecta remained relatively constant within the partial-liquid-on-release, regardless of shock-breakout pressure.

Pressure Effects on the Ejection of Material from Shocked Tin Surfaces

NASA Astrophysics Data System (ADS)

Zellner, M. B.; Grover, M.; Hammerberg, J. E.; Hixson, R. S.; Iverson, A. J.; Macrum, G. S.; Morley, K. B.; Obst, A. W.; Olson, R. T.; Payton, J. R.; Rigg, P. A.; Routley, N.; Stevens, G. D.; Turley, W. D.; Veeser, L.; Buttler, W. T.

2007-12-01

Los Alamos National Lab (LANL) is actively engaged in the development of a model to predict the formation of micron-scale fragments ejected (ejecta) from shocked metals that have surface defects. The LANL ejecta model considers that the amount of ejecta is mainly related to the material's phase on shock release at the free-surface. This effort investigates the relation between ejecta production and shock-breakout pressure for Sn shocked with high explosives to pressures near the solid-on-release/partial-liquid-on-release phase transition region. We found that the amount of ejecta produced for shock-breakout pressures that resulted in partial-liquid-on-release increased significantly compared to that which resulted in solid-on-release. Additionally, we found that the amount of ejecta remained relatively constant within the partial-liquid-on-release, regardless of shock-breakout pressure.

Equivalent air depth: fact or fiction.

PubMed

Berghage, T E; McCraken, T M

1979-12-01

In mixed-gas diving theory, the equivalent air depth (EAD) concept suggests that oxygen does not contribute to the total tissue gas tension and can therefore be disregarded in calculations of the decompression process. The validity of this assumption has been experimentally tested by exposing 365 rats to various partial pressures of oxygen for various lengths of time. If the EAD assumption is correct, under a constant exposure pressure each incremental change in the oxygen partial pressure would produce a corresponding incremental change in pressure reduction tolerance. Results of this study suggest that the EAD concept does not adequately describe the decompression advantages obtained from breathing elevated oxygen partial pressures. The authors suggest that the effects of breathing oxygen vary in a nonlinear fashion across the range from anoxia to oxygen toxicity, and that a simple inert gas replacement concept is no longer tenable.

Fuel cell serves as oxygen level detector

NASA Technical Reports Server (NTRS)

1965-01-01

Monitoring the oxygen level in the air is accomplished by a fuel cell detector whose voltage output is proportional to the partial pressure of oxygen in the sampled gas. The relationship between output voltage and partial pressure of oxygen can be calibrated.

Synthetic Heme/Copper Assemblies: Toward an Understanding of Cytochrome c Oxidase Interactions with Dioxygen and Nitrogen Oxides

PubMed Central

Hematian, Shabnam; Garcia-Bosch, Isaac; Karlin, Kenneth D.

2016-01-01

Conspectus Our long-time niche in synthetic biological inorganic chemistry has been to design ligands and generate coordination complexes of copper and/or iron ions, those reacting with dioxygen (O2) and/or nitrogen oxides (e.g., nitric oxide (NO(g)) and nitrite (NO2−)). As inspiration for this work, we turn to mitochondrial cytochrome c oxidase which is responsible for dioxygen consumption and is also the predominant target for NO(g) and nitrite within mitochondria. In this Account, we highlight recent advances in studying synthetic heme/Cu complexes in two respects. First, there is the design, synthesis and characterization of new O2-adducts whose further study will add insights into O2-reductive cleavage chemistry. Second, we describe how related heme/Cu constructs reduce nitrite ion to NO(g) or the reverse, oxidize NO(g) to nitrite. The reactions of nitrogen oxides occur as part of CcO’s function, which is intimately tied to cellular O2-balance. We had first discovered that reduced heme/Cu compounds react with O2 giving μ-oxo heme-FeIII-O-CuII(L) products; their properties are discussed. The O-atom is derived from dioxygen and interrogations of these systems led to the construction and characterization of three distinctive classes of heme-peroxo-complexes, two high-spin and one low-spin species. Recent investigations include a new approach to the synthesis of low-spin heme-peroxo-Cu complexes, employing a “naked” synthon, where the copper ligand denticity and geometric types can be varied. The result is a collection of such complexes; spectroscopic and structural features (by DFT calculations) are described. Some of these compounds are reactive toward reductants/protons effecting subsequent O-O cleavage. This points to how subtle improvements in ligand environment lead to a desired local structure and resulting optimized reactivity, as known to occur at enzyme active-sites. The other sector of research is focused on heme/Cu assemblies mediating the redox interplay between nitrite and NO(g). In the nitrite reductase chemistry, the cupric center serves as a Lewis acid while the heme is the redox active center providing the electron. The orientation of nitrite in approaching the ferrous heme center and N-atom binding are important. Also, detailed spectroscopic and kinetic studies of the NO(g) oxidase chemistry, in excellent agreement with theoretical calculations, reveal the intermediates and key mechanistic steps. Thus, we suggest that both chemical and biochemical heme/Cu mediated nitrite reductase and NO(g) oxidase chemistry require N-atom binding to a ferrous heme along with cupric ion O-atom coordination, proceeding via a three-membered O-Fe-N chelate ring transition state. These important mechanistic features of heme/Cu systems interconverting NO(g) and nitrite are discussed for the first time. PMID:26244814

Characterization of metastable intermediates formed in the reaction between a Mn(II) complex and dioxygen, including a crystallographic structure of a binuclear Mn(III)-peroxo species.

PubMed

Coggins, Michael K; Sun, Xianru; Kwak, Yeonju; Solomon, Edward I; Rybak-Akimova, Elena; Kovacs, Julie A

2013-04-17

Transition-metal peroxos have been implicated as key intermediates in a variety of critical biological processes involving O2. Because of their highly reactive nature, very few metal-peroxos have been characterized. The dioxygen chemistry of manganese remains largely unexplored despite the proposed involvement of a Mn-peroxo, either as a precursor to, or derived from, O2, in both photosynthetic H2O oxidation and DNA biosynthesis. These are arguably two of the most fundamental processes of life. Neither of these biological intermediates has been observed. Herein we describe the dioxygen chemistry of coordinatively unsaturated [Mn(II)(S(Me2)N4(6-Me-DPEN))] (+) (1), and the characterization of intermediates formed en route to a binuclear mono-oxo-bridged Mn(III) product {[Mn(III)(S(Me2)N4(6-Me-DPEN)]2(μ-O)}(2+) (2), the oxo atom of which is derived from (18)O2. At low-temperatures, a dioxygen intermediate, [Mn(S(Me2)N4(6-Me-DPEN))(O2)](+) (4), is observed (by stopped-flow) to rapidly and irreversibly form in this reaction (k1(-10 °C) = 3780 ± 180 M(-1) s(-1), ΔH1(++) = 26.4 ± 1.7 kJ mol(-1), ΔS1(++) = -75.6 ± 6.8 J mol(-1) K(-1)) and then convert more slowly (k2(-10 °C) = 417 ± 3.2 M(-1) s(-1), ΔH2(++) = 47.1 ± 1.4 kJ mol(-1), ΔS2(++) = -15.0 ± 5.7 J mol(-1) K(-1)) to a species 3 with isotopically sensitive stretches at νO-O(Δ(18)O) = 819(47) cm(-1), kO-O = 3.02 mdyn/Å, and νMn-O(Δ(18)O) = 611(25) cm(-1) consistent with a peroxo. Intermediate 3 releases approximately 0.5 equiv of H2O2 per Mn ion upon protonation, and the rate of conversion of 4 to 3 is dependent on [Mn(II)] concentration, consistent with a binuclear Mn(O2(2-)) Mn peroxo. This was verified by X-ray crystallography, where the peroxo of {[Mn(III)(S(Me2)N4(6-Me-DPEN)]2(trans-μ-1,2-O2)}(2+) (3) is shown to be bridging between two Mn(III) ions in an end-on trans-μ-1,2-fashion. This represents the first characterized example of a binuclear Mn(III)-peroxo, and a rare case in which more than one intermediate is observed en route to a binuclear μ-oxo-bridged product derived from O2. Vibrational and metrical parameters for binuclear Mn-peroxo 3 are compared with those of related binuclear Fe- and Cu-peroxo compounds.

Reductive Activation of O2 by Non-Heme Iron(II) Benzilate Complexes of N4 Ligands: Effect of Ligand Topology on the Reactivity of O2-Derived Oxidant.

PubMed

Chakraborty, Biswarup; Jana, Rahul Dev; Singh, Reena; Paria, Sayantan; Paine, Tapan Kanti

2017-01-03

A series of iron(II) benzilate complexes (1-7) with general formula [(L)Fe II (benzilate)] + have been isolated and characterized to study the effect of supporting ligand (L) on the reactivity of metal-based oxidant generated in the reaction with dioxygen. Five tripodal N 4 ligands (tris(2-pyridylmethyl)amine (TPA in 1), tris(6-methyl-2-pyridylmethyl)amine (6-Me 3 -TPA in 2), N 1 ,N 1 -dimethyl-N 2 ,N 2 -bis(2-pyridylmethyl)ethane-1,2-diamine (iso-BPMEN in 3), N 1 ,N 1 -dimethyl-N 2 ,N 2 -bis(6-methyl-2-pyridylmethyl)ethane-1,2-diamine (6-Me 2 -iso-BPMEN in 4), and tris(2-benzimidazolylmethyl)amine (TBimA in 7)) along with two linear tetradentate amine ligands (N 1 ,N 2 -dimethyl-N 1 ,N 2 -bis(2-pyridylmethyl)ethane-1,2-diamine (BPMEN in 5) and N 1 ,N 2 -dimethyl-N 1 ,N 2 -bis(6-methyl-2-pyridylmethyl)ethane-1,2-diamine (6-Me 2 -BPMEN in 6)) were employed in the study. Single-crystal X-ray structural studies reveal that each of the complex cations of 1-3 and 5 contains a mononuclear six-coordinate iron(II) center coordinated by a monoanionic benzilate, whereas complex 7 contains a mononuclear five-coordinate iron(II) center. Benzilate binds to the iron center in a monodentate fashion via one of the carboxylate oxygens in 1 and 7, but it coordinates in a bidentate chelating mode through carboxylate oxygen and neutral hydroxy oxygen in 2, 3, and 5. All of the iron(II) complexes react with dioxygen to exhibit quantitative decarboxylation of benzilic acid to benzophenone. In the decarboxylation pathway, dioxygen becomes reduced on the iron center and the resulting iron-oxygen oxidant shows versatile reactivity. The oxidants are nucleophilic in nature and oxidize sulfide to sulfoxide and sulfone. Furthermore, complexes 2 and 4-6 react with alkenes to produce cis-diols in moderate yields with the incorporation of both the oxygen atoms of dioxygen. The oxygen atoms of the nucleophilic oxidants do not exchange with water. On the basis of interception studies, nucleophilic iron(II) hydroperoxides are proposed to generate in situ in the reaction pathways. The difference in reactivity of the complexes toward external substrates could be attributed to the geometry of the O 2 -derived iron-oxygen oxidant. DFT calculations suggest that, among all possible geometries and spin states, high-spin side-on iron(II) hydroperoxides are energetically favorable for the complexes of 6-Me 3 -TPA, 6-Me 2 -iso-BPMEN, BPMEN, and 6-Me 2 -BPMEN ligands, while high spin end-on iron(II) hydroperoxides are favorable for the complexes of TPA, iso-BPMEN, and TBimA ligands.

Method of enhancing selective isotope desorption from metals

DOEpatents

Knize, Randall J.; Cecchi, Joseph L.

1984-01-01

A method of enhancing the thermal desorption of a first isotope of a diatomic gas from a metal comprises the steps of (a) establishing a partial pressure of a second isotope of the diatomic gas in vicinity of the metal; heating the metal to a temperature such that the first isotope is desorbed from the metal; and reducing the partial pressure of the desorbed first isotope while maintaining the partial pressure of the second isotope substantially constant. The method is especially useful for enhancing the desorption of tritium from the Zr-Al getter in a plasma confinement device.

Study on the intrinsic defects in ZnO by combing first-principle and thermodynamic calculations

NASA Astrophysics Data System (ADS)

Ma, Changmin; Liu, Tingyu; Chang, Qiuxiang

2015-11-01

In this paper, the intrinsic point defects in ZnO crystal have been studied by the approach that integrates first-principles, thermodynamic calculations and the contributions of vibrational entropy. With temperature increasing and oxygen partial pressure decreasing, the formation energies of oxygen vacancy (VO), zinc interstitial (Zni) and zinc anti-site (ZnO) are decreasing, while it increases for zinc vacancy (VZn), oxygen interstitial (Oi) and oxygen anti-site (OZn). They are more sensitive to temperature than oxygen partial pressure. There are two interesting phenomena. First, VO or VZn have the lowest formation energies for whole Fermi level at special environment condition (such as at T = 300K, about PO2 = 10-10atm or T = 1500K, about PO2 = 104atm) and intrinsic p-type doping of ZnO is possible by VZn at these special conditions. Second, VO as donors have lowest formation energy for all Fermi level at high temperature and low oxygen partial pressure (T = 1500K, PO2 = 10-10atm). According to our analysis, the VO could produce n-type doping in ZnO at these special conditions and change p-type ZnO to n-type ZnO at condition from low temperature and high oxygen partial pressure to high temperature and low oxygen partial pressure.

Oxygen Partial Pressure Is a Rate-Limiting Parameter for Cell Proliferation in 3D Spheroids Grown in Physioxic Culture Condition.

PubMed

Gomes, Aurélie; Guillaume, Ludivine; Grimes, David Robert; Fehrenbach, Jérôme; Lobjois, Valérie; Ducommun, Bernard

2016-01-01

The in situ oxygen partial pressure in normal and tumor tissues is in the range of a few percent. Therefore, when studying cell growth in 3D culture systems, it is essential to consider how the physiological oxygen concentration, rather than the one in the ambient air, influences the proliferation parameters. Here, we investigated the effect of reducing oxygen partial pressure from 21% to 5% on cell proliferation rate and regionalization in a 3D tumor spheroid model. We found that 5% oxygen concentration strongly inhibited spheroid growth, changed the proliferation gradient and reduced the 50% In Depth Proliferation index (IDP50), compared with culture at 21% oxygen. We then modeled the oxygen partial pressure profiles using the experimental data generated by culturing spheroids in physioxic and normoxic conditions. Although hypoxia occurred at similar depth in spheroids grown in the two conditions, oxygen partial pressure was a major rate-limiting factor with a critical effect on cell proliferation rate and regionalization only in spheroids grown in physioxic condition and not in spheroids grown at atmospheric normoxia. Our findings strengthen the need to consider conducting experiment in physioxic conditions (i.e., tissue normoxia) for proper understanding of cancer cell biology and the evaluation of anticancer drugs in 3D culture systems.

Conversion of chlorobiphenyls into phenylhexadienoates and benzoates by the enzymes of the upper pathway for polychlorobiphenyl degradation encoded by the bph locus of Pseudomonas sp. strain LB400.

PubMed Central

Seeger, M; Timmis, K N; Hofer, B

1995-01-01

Metabolism of 21 chlorobiphenyls by the enzymes of the upper biphenyl catabolic pathway encoded by the bph locus of Pseudomonas sp. strain LB400 was investigated by using recombinant strains harboring gene cassettes containing bphABC or bphABCD. The enzymes of the upper pathway were generally able to metabolize mono- and dichlorinated biphenyls but only partially transform most trichlorinated congeners investigated: 14 of 15 mono- and dichlorinated and 2 of 6 trichlorinated congeners were converted into benzoates. All mono- and at least 8 of 12 dichlorinated congeners were attacked by the bphA-encoded biphenyl dioxygenase virtually exclusively at ortho and meta carbons. This enzyme exhibited a high degree of selectivity for the aromatic ring to be attacked, with the order of ring preference being non- > ortho- > meta- > para-substituted for mono- and dichlorinated congeners. The influence of the chlorine substitution pattern of the metabolized ring on benzoate formation resembled its influence on the reactivity of initial dioxygenation, suggesting that the rate of benzoate formation may frequently be determined by the rate of initial attack. The absorption spectra of phenylhexadienoates formed correlated with the presence or absence of a chlorine substituent at an ortho position. PMID:7618878

Dioxygenase-like reactivity of an isolable superoxo-nickel(II) complex.

PubMed

Company, Anna; Yao, Shenglai; Ray, Kallol; Driess, Matthias

2010-08-16

Although O(2) activation by metals such as iron and copper has been a matter of intensive research in the last decades, this type of chemistry for nickel systems is still in its infancy. Moreover, studies regarding the oxidizing ability of the resulting "Ni(n)-O(2)" species towards exogenous substrates are scarce. In this work, we report on the reactivity of an isolable and thermally stable mononuclear superoxo-nickel compound [Ni(II)(beta-diketiminato)(O(2))] (1) towards different types of organic substrates. In addition, we have been able to prove that the beta-diketiminato ligand can undergo partial intramolecular oxidation due to close proximity between the isopropyl groups of the beta-diketiminato-aryl and the superoxo subunits. Compound 1 performs hydrogen-atom abstraction from O-H and N-H groups and most importantly it shows an unprecedented dioxygenase-like reactivity in the oxidation of 2,4,6-tri-tert-butylphenol. The latter reaction most likely occurs through the mediation of a putative [Ni(III)-oxo] intermediate, affording an unprecedented oxidation product of the phenol that incorporates two oxygen atoms from a single O(2) subunit. Results presented herein provide evidence of the striking oxidizing ability of dioxygen-nickel species and further support the viability to use such systems as oxidation catalysts analogous to its heavy metal congener, palladium.

New highlights on degradation process of verdigris from easel paintings

NASA Astrophysics Data System (ADS)

Santoro, Carlotta; Zarkout, Karim; Le Hô, Anne-Solenn; Mirambet, François; Gourier, Didier; Binet, Laurent; Pagès-Camagna, Sandrine; Reguer, Solenn; Mirabaud, Sigrid; Le Du, Yann; Griesmar, Pascal; Lubin-Germain, Nadège; Menu, Michel

2014-03-01

Verdigris is a green copper organometallic pigment, widely used in paintings during the fifteenth and sixteenth centuries. With ageing, chromatic modifications like browning or darkening can be observed on those green painted layers. An original but crucial approach has been developed based on the characterization of a reference neutral verdigris pigment—anhydrous copper acetate—and model samples, made of verdigris and linseed oil. Samples have undergone artificial ageing (temperature, light) to reproduce the color change effect. They were analysed before and after accelerated ageing tests by a complementary set of classical techniques: colorimetry, electron paramagnetic resonance, X-ray absorption spectroscopy, and UV-visible absorption. Our experiments revealed that the incorporation of the verdigris pigment in linseed oil induces a transformation of the copper acetate bimetallic structure, with the formation of monomeric species. These monomers, however, are not directly responsible for the darkening. The chromatic alteration seems instead linked to the transient formation of Cu(I) in the copper complexes of the pigment/oil system. This formation could be initiated by ambient light absorption through ligand-to-metal charge transfer, which favors the decarboxylation of the copper complexes leading to the reduction of Cu(II) into Cu(I). Moreover, dioxygen can react with partially decarboxylated dimers to form peroxy-Cu dimer complexes that can be responsible for the darkening.

Analysis of Substrate Access to Active Sites in Bacterial Multicomponent Monooxygenase Hydroxylases: X-ray Crystal Structure of Xenon-Pressurized Phenol Hydroxylase from Pseudomonas sp. OX1†,‡

PubMed Central

McCormick, Michael S.; Lippard, Stephen J.

2011-01-01

In all structurally characterized bacterial multicomponent monooxygenase (BMM) hydroxylase proteins, a series of hydrophobic cavities in the α-subunit trace a conserved path from the protein exterior to the carboxylate-bridged diiron active site. The present study examines these cavities as a potential route for dioxygen transport to the active site by crystallographic characterization of a xenon-pressurized sample of the hydroxylase component of phenol hydroxylase from Pseudomonas sp. OX1. Computational analyses of the hydrophobic cavities in the hydroxylase α-subunits of phenol hydroxylase (PHH), toluene/o-xylene monooxygenase (ToMOH), and soluble methane monooxygenase (sMMOH) are also presented. The results, together with previous findings from crystallographic studies of xenon-pressurized sMMO hydroxylase, clearly identify the propensity for these cavities to bind hydrophobic gas molecules in the protein interior. This proposed functional role is supported by recent stopped flow kinetic studies of ToMOH variants (Song, et al., 2011). In addition to information about the Xe sites, the structure determination revealed significantly reduced regulatory protein binding to the hydroxylase in comparison to the previously reported structure of PHH, as well as the presence of a newly identified metal binding site in the α-subunit that adopts a linear coordination environment consistent with Cu(I), and a glycerol molecule bound to Fe1 in a fashion that is unique among hydrocarbon-diiron site adducts reported to date in BMM hydroxylase structures. Finally, a comparative analysis of the α-subunit structures of MMOH, ToMOH, and PHH details proposed routes for the other three BMM substrates, the hydrocarbon, electrons, and protons, comprising cavities, channels, hydrogen-bonding networks, and pores in the structures of their α-subunits. PMID:22136180

Reversible effects of oxygen partial pressure on genes associated with placental angiogenesis and differentiation in primary-term cytotrophoblast cell culture.

PubMed

Debiève, F; Depoix, C; Gruson, D; Hubinont, C

2013-09-01

Timely regulated changes in oxygen partial pressure are important for placental formation. Disturbances could be responsible for pregnancy-related diseases like preeclampsia and intrauterine growth restriction. We aimed to (i) determine the effect of oxygen partial pressure on cytotrophoblast differentiation; (ii) measure mRNA expression and protein secretion from genes associated with placental angiogenesis; and (iii) determine the reversibility of these effects at different oxygen partial pressures. Term cytotrophoblasts were incubated at 21% and 2.5% O2 for 96 hr, or were switched between the two oxygen concentrations after 48 hr. Real-time PCR and enzyme-linked immunosorbent assays (ELISAs) were used to evaluate cell fusion and differentiation, measuring transcript levels for those genes involved in cell fusion and placental angiogenesis, including VEGF, PlGF, VEGFR1, sVEGFR1, sENG, INHA, and GCM1. Cytotrophoblasts underwent fusion and differentiation in 2.5% O2 . PlGF expression was inhibited while sVEGFR1 expression increased. VEGF and sENG mRNA expressions increased in 2.5% compared to 21% O2 , but no protein was detected in the cell supernatants. Finally, GCM1 mRNA expression increased during trophoblast differentiation at 21% O2 , but was inhibited at 2.5% O2 . These mRNA expression effects were reversed by returning the cells to 21% O2 . Thus, low-oxygen partial pressure does not inhibit term-cytotrophoblast cell fusion and differentiation in vitro. Lowering the oxygen partial pressure from 21% to 2.5% caused normal-term trophoblasts to reversibly modify their expression of genes associated with placental angiogenesis. This suggests that modifications observed in pregnancy diseases such as preeclampsia or growth retardation are probably due to an extrinsic effect on trophoblasts. Copyright © 2013 Wiley Periodicals, Inc.

Measurement of alveolar oxygen partial pressure in the rat lung using Carr-Purcell-Meiboom-Gill spin-spin relaxation times of hyperpolarized 3He and 129Xe at 74 mT.

PubMed

Kraayvanger, Ryan J; Bidinosti, Christopher P; Dominguez-Viqueira, William; Parra-Robles, Juan; Fox, Matthew; Lam, Wilfred W; Santyr, Giles E

2010-11-01

Regional measurement of alveolar oxygen partial pressure can be obtained from the relaxation rates of hyperpolarized noble gases, (3) He and (129) Xe, in the lungs. Recently, it has been demonstrated that measurements of alveolar oxygen partial pressure can be obtained using the spin-spin relaxation rate (R(2) ) of (3) He at low magnetic field strengths (<0.1 T) in vivo. R(2) measurements can be achieved efficiently using the Carr-Purcell-Meiboom-Gill pulse sequence. In this work, alveolar oxygen partial pressure measurements based on Carr-Purcell-Meiboom-Gill R(2) values of hyperpolarized (3) He and (129) Xe in vitro and in vivo in the rat lung at low magnetic field strength (74 mT) are presented. In vitro spin-spin relaxivity constants for (3) He and (129) Xe were determined to be (5.2 ± 0.6) × 10(-6) Pa(-1) sec(-1) and (7.3 ± 0.4) × 10(-6) Pa(-1) s(-1) compared with spin-lattice relaxivity constants of (4.0 ± 0.4) × 10(-6) Pa(-1) s(-1) and (4.3 ± 1.3) × 10(-6) Pa(-1) s(-1), respectively. In vivo experimental measurements of alveolar oxygen partial pressure using (3) He in whole rat lung show good agreement (r(2) = 0.973) with predictions based on lung volumes and ventilation parameters. For (129) Xe, multicomponent relaxation was observed with one component exhibiting an increase in R(2) with decreasing alveolar oxygen partial pressure. Copyright © 2010 Wiley-Liss, Inc.

Photoinduced water oxidation sensitized by a tetranuclear Ru(II) dendrimer.

PubMed

La Ganga, Giuseppina; Nastasi, Francesco; Campagna, Sebastiano; Puntoriero, Fausto

2009-12-07

A multimetallic ruthenium(II) dendrimer is used for the first time to photosensitize dioxygen production from water by IrO2 nanoparticles; the system is more efficient than an analogous system based on the more commonly used [Ru(bpy)3]2+-type photosensitizers, in particular for the ability of the dendrimer to take advantage of the red portion of the solar spectrum.

Photosynthetic dioxygen formation studied by time-resolved delayed fluorescence measurements--method, rationale, and results on the activation energy of dioxygen formation.

PubMed

Buchta, Joachim; Grabolle, Markus; Dau, Holger

2007-06-01

The analysis of the time-resolved delayed fluorescence (DF) measurements represents an important tool to study quantitatively light-induced electron transfer as well as associated processes, e.g. proton movements, at the donor side of photosystem II (PSII). This method can provide, inter alia, insights in the functionally important inner-protein proton movements, which are hardly detectable by conventional spectroscopic approaches. The underlying rationale and experimental details of the method are described. The delayed emission of chlorophyll fluorescence of highly active PSII membrane particles was measured in the time domain from 10 mus to 60 ms after each flash of a train of nanosecond laser pulses. Focusing on the oxygen-formation step induced by the third flash, we find that the recently reported formation of an S4-intermediate prior to the onset of O-O bond formation [M. Haumann, P. Liebisch, C. Müller, M. Barra, M. Grabolle, H. Dau, Science 310, 1019-1021, 2006] is a multiphasic process, as anticipated for proton movements from the manganese complex of PSII to the aqueous bulk phase. The S4-formation involves three or more likely sequential steps; a tri-exponential fit yields time constants of 14, 65, and 200 mus (at 20 degrees C, pH 6.4). We determine that S4-formation is characterized by a sizable difference in Gibbs free energy of more than 90 meV (20 degrees C, pH 6.4). In the second part of the study, the temperature dependence (-2.7 to 27.5 degrees C) of the rate constant of dioxygen formation (600/s at 20 degrees C) was investigated by analysis of DF transients. If the activation energy is assumed to be temperature-independent, a value of 230 meV is determined. There are weak indications for a biphasicity in the Arrhenius plot, but clear-cut evidence for a temperature-dependent switch between two activation energies, which would point to the existence of two distinct rate-limiting steps, is not obtained.

The effects of endothelin-1 on the cardiorespiratory physiology of the freshwater trout (Oncorhynchus mykiss) and the marine dogfish (Squalus acanthias).

PubMed

Perry, S F; Montpetit, C J; McKendry, J; Desforges, P R; Gilmour, K M; Wood, C M; Olson, K R

2001-11-01

The aim of the present study was to evaluate the effects of endothelin-l-elicited cardiovascular events on respiratory gas transfer in the freshwater rainbow trout (Oncorhynchus mykiss) and the marine dogfish (Squalus acanthias). In both species, endothelin-1 (666 pmol kg(-1)) caused a rapid (within 4 min) reduction (ca. 30-50 mmHg) in arterial blood partial pressure of O2. The effects of endothelin-1 on arterial blood partial pressure of CO2 were not synchronised with the changes in O2 partial pressure and the responses were markedly different in trout and dogfish. In trout, arterial CO2 partial pressure was increased transiently by approximately 1.0 mmHg but the onset of the response was delayed and occurred 12 min after endothelin-1 injection. In contrast, CO2 partial pressure remained more-or-less constant in dogfish after injection of endothelin-1 and was increased only slightly (approximately 0.1 mmHg) after 60 min. Pre-treatment of trout with bovine carbonic anhydrase (5 mg ml(-1)) eliminated the increase in CO2 partial pressure that was normally observed after endothelin-1 injection. In both species, endothelin-1 injection caused a decrease in arterial blood pH that mirrored the changes in CO2 partial pressure. Endothelin-1 injection was associated with transient (trout) or persistent (dogfish) hyperventilation as indicated by pronounced increases in breathing frequency and amplitude. In trout, arterial blood pressure remained constant or was decreased slightly and was accompanied by a transient increase in systemic resistance, and a temporary reduction in cardiac output. The decrease in cardiac output was caused solely by a reduction in cardiac frequency; cardiac stroke volume was unaffected. In dogfish, arterial blood pressure was lowered by approximately 10 mmHg at 6-10 min after endothelin-1 injection but then was rapidly restored to pre-injection levels. The decrease in arterial blood pressure reflected an increase in branchial vascular resistance (as determined using in situ perfused gill preparations) that was accompanied by simultaneous decreases in systemic resistance and cardiac output. Cardiac frequency and stroke volume were reduced by endothelin-1 injection and thus both variables contributed to the changes in cardiac output. We conclude that the net consequences of endothelin-1 on arterial blood gases result from the opposing effects of reduced gill functional surface area (caused by vasoconstriction) and an increase in blood residence time within the gill (caused by decreased cardiac output.

Airway exchange of highly soluble gases.

PubMed

Hlastala, Michael P; Powell, Frank L; Anderson, Joseph C

2013-03-01

Highly blood soluble gases exchange with the bronchial circulation in the airways. On inhalation, air absorbs highly soluble gases from the airway mucosa and equilibrates with the blood before reaching the alveoli. Highly soluble gas partial pressure is identical throughout all alveoli. At the end of exhalation the partial pressure of a highly soluble gas decreases from the alveolar level in the terminal bronchioles to the end-exhaled partial pressure at the mouth. A mathematical model simulated the airway exchange of four gases (methyl isobutyl ketone, acetone, ethanol, and propylene glycol monomethyl ether) that have high water and blood solubility. The impact of solubility on the relative distribution of airway exchange was studied. We conclude that an increase in water solubility shifts the distribution of gas exchange toward the mouth. Of the four gases studied, ethanol had the greatest decrease in partial pressure from the alveolus to the mouth at end exhalation. Single exhalation breath tests are inappropriate for estimating alveolar levels of highly soluble gases, particularly for ethanol.

Airway exchange of highly soluble gases

PubMed Central

Powell, Frank L.; Anderson, Joseph C.

2013-01-01

Highly blood soluble gases exchange with the bronchial circulation in the airways. On inhalation, air absorbs highly soluble gases from the airway mucosa and equilibrates with the blood before reaching the alveoli. Highly soluble gas partial pressure is identical throughout all alveoli. At the end of exhalation the partial pressure of a highly soluble gas decreases from the alveolar level in the terminal bronchioles to the end-exhaled partial pressure at the mouth. A mathematical model simulated the airway exchange of four gases (methyl isobutyl ketone, acetone, ethanol, and propylene glycol monomethyl ether) that have high water and blood solubility. The impact of solubility on the relative distribution of airway exchange was studied. We conclude that an increase in water solubility shifts the distribution of gas exchange toward the mouth. Of the four gases studied, ethanol had the greatest decrease in partial pressure from the alveolus to the mouth at end exhalation. Single exhalation breath tests are inappropriate for estimating alveolar levels of highly soluble gases, particularly for ethanol. PMID:23305981

Oxidation Behavior of Carbon Fiber-Reinforced Composites

NASA Technical Reports Server (NTRS)

Sullivan, Roy M.

2008-01-01

OXIMAP is a numerical (FEA-based) solution tool capable of calculating the carbon fiber and fiber coating oxidation patterns within any arbitrarily shaped carbon silicon carbide composite structure as a function of time, temperature, and the environmental oxygen partial pressure. The mathematical formulation is derived from the mechanics of the flow of ideal gases through a chemically reacting, porous solid. The result of the formulation is a set of two coupled, non-linear differential equations written in terms of the oxidant and oxide partial pressures. The differential equations are solved simultaneously to obtain the partial vapor pressures of the oxidant and oxides as a function of the spatial location and time. The local rate of carbon oxidation is determined at each time step using the map of the local oxidant partial vapor pressure along with the Arrhenius rate equation. The non-linear differential equations are cast into matrix equations by applying the Bubnov-Galerkin weighted residual finite element method, allowing for the solution of the differential equations numerically.

Effects of various oxygen partial pressures on Ti-doped ZnO thin film transistors fabricated on flexible plastic substrate

NASA Astrophysics Data System (ADS)

Cui, Guodong; Han, Dedong; Yu, Wen; Shi, Pan; Zhang, Yi; Huang, Lingling; Cong, Yingying; Zhou, Xiaoliang; Zhang, Xiaomi; Zhang, Shengdong; Zhang, Xing; Wang, Yi

2016-04-01

By applying a novel active layer of titanium zinc oxide (TiZO), we have successfully fabricated fully transparent thin-film transistors (TFTs) with a bottom gate structure fabricated on a flexible plastic substrate at low temperatures. The effects of various oxygen partial pressures during channel deposition were studied to improve the device performance. We found that the oxygen partial pressure during channel deposition has a significant impact on the performance of TiZO TFTs, and that the TFT developed under 10% oxygen partial pressure exhibits superior performance with a low threshold voltage (V th) of 2.37 V, a high saturation mobility (μsat) of 125.4 cm2 V-1 s-1, a steep subthreshold swing (SS) of 195 mV/decade and a high I on/I off ratio of 3.05 × 108. These results suggest that TiZO thin films are promising for high-performance fully transparent flexible TFTs and displays.

[Correlation between the inspired fraction of oxygen, maternal partial oxygen pressure, and fetal partial oxygen pressure during cesarean section of normal pregnancies].

PubMed

Castro, Carlos Henrique Viana de; Cruvinel, Marcos Guilherme Cunha; Carneiro, Fabiano Soares; Silva, Yerkes Pereira; Cabral, Antônio Carlos Vieira; Bessa, Roberto Cardoso

2009-01-01

Despite changes in pulmonary function, maternal oxygenation is maintained during obstetric regional blocks. But in those situations, the administration of supplementary oxygen to parturients is a common practice. Good fetal oxygenation is the main justification; however, this has not been proven. The objective of this randomized, prospective study was to test the hypothesis of whether maternal hyperoxia is correlated with an increase in fetal gasometric parameters in elective cesarean sections. Arterial blood gases of 20 parturients undergoing spinal block with different inspired fractions of oxygen were evaluated and correlated with fetal arterial blood gases. An increase in maternal inspired fraction of oxygen did not show any correlation with an increase of fetal partial oxygen pressure. Induction of maternal hyperoxia by the administration of supplementary oxygen did not increase fetal partial oxygen pressure. Fetal gasometric parameters did not change even when maternal parameters changed, induced by hyperoxia, during cesarean section under spinal block.

Respiratory gas exchange of high altitude adapted chick embryos

NASA Technical Reports Server (NTRS)

Wangensteen, O. D.; Rahn, H.; Burton, R. R.; Smith, A. H.

1974-01-01

Study of gas exchange by embryos from chickens acclimatized to an altitude of 3800 m. The oxygen partial pressure and carbon dioxide partial pressure differences across the egg shell were measured and found to be less than the values previously reported for sea-level eggs by about a factor of two. Further measurements of embryonic oxygen consumption and shell conductivity to oxygen indicated that, compared to eggs at sea level, oxygen consumption was reduced by a factor of 0.58 while conductivity to oxygen was increased only by a factor of 1.07 in the high-altitude eggs. These independent measurements predict the change in oxygen partial pressure across the egg shell of the high-altitude eggs to be only 0.54 times that of sea-level eggs; the directly measured factor was 0.53. The authors conclude that at high altitude, a major adaptation of the chick embryo is a reduced metabolism which decreases the change in oxygen partial pressure across the egg shell since its gas conductivity remains essentially unchanged.

Biomass hydrolysis inhibition at high hydrogen partial pressure in solid-state anaerobic digestion.

PubMed

Cazier, E A; Trably, E; Steyer, J P; Escudie, R

2015-08-01

In solid-state anaerobic digestion, so-called ss-AD, biogas production is inhibited at high total solids contents. Such inhibition is likely caused by a slow diffusion of dissolved reaction intermediates that locally accumulate. In this study, we investigated the effect of H2 and CO2 partial pressure on ss-AD. Partial pressure of H2 and/or CO2 was artificially fixed, from 0 to 1 557mbars for H2 and from 0 to 427mbars for CO2. High partial pressure of H2 showed a significant effect on methanogenesis, while CO2 had no impact. At high [Formula: see text] , the overall substrate degradation decreased with no accumulation of metabolites from acidogenic bacteria, indicating that the hydrolytic activity was specifically impacted. Interestingly, such inhibition did not occur when CO2 was added with H2. This result suggests that CO2 gas transfer is probably a key factor in ss-AD from biomass. Copyright © 2015 Elsevier Ltd. All rights reserved.

Measurement of partial pressures in vacuum technology and vacuum physics

NASA Technical Reports Server (NTRS)

Huber, W. K.

1986-01-01

It is pointed out that the measurement of gaseous pressures of less than 0.0001 torr is based on the ionization of gas atoms and molecules due to collisions with electrons. The particle density is determined in place of the pressure. The ionization cross sections for molecules of various gases are discussed. It is found that the true pressure in a vacuum system cannot be determined with certainty if it is unknown which gas is present. Effects of partial pressure determination on the condition of the vacuum system are discussed together with ion sources, systems of separation, and ion detection.

Partial Molar Volumes of Aqua Ions from First Principles.

PubMed

Wiktor, Julia; Bruneval, Fabien; Pasquarello, Alfredo

2017-08-08

Partial molar volumes of ions in water solution are calculated through pressures obtained from ab initio molecular dynamics simulations. The correct definition of pressure in charged systems subject to periodic boundary conditions requires access to the variation of the electrostatic potential upon a change of volume. We develop a scheme for calculating such a variation in liquid systems by setting up an interface between regions of different density. This also allows us to determine the absolute deformation potentials for the band edges of liquid water. With the properly defined pressures, we obtain partial molar volumes of a series of aqua ions in very good agreement with experimental values.

Densification and Electrical Properties of Zinc Oxide Varistors Microwave-Sintered Under Different Oxygen Partial Pressures

NASA Astrophysics Data System (ADS)

Lin, Cong; Wang, Bo; Xu, Zheng; Peng, Hu

2012-11-01

ZnO varistors were prepared by microwave sintering under different oxygen partial pressures. The temperature profile and the densification behavior in different atmospheres were investigated. It was found that the density of ZnO varistors during sintering was the key factor affecting the absorption of microwave energy. The electrical properties, including the nonlinear properties and capacitance-voltage ( C- V) characteristics, were also carefully studied. The results showed that the oxygen partial pressure has significant effects on the electrical properties of ZnO varistors by changing the concentration of defects through a series of reactions involving oxygen during sintering.

Control of magnetization reversal in oriented strontium ferrite thin films

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

Roy, Debangsu, E-mail: debangsu@physics.iisc.ernet.in; Anil Kumar, P. S.

2014-02-21

Oriented Strontium Ferrite films with the c axis orientation were deposited with varying oxygen partial pressure on Al{sub 2}O{sub 3}(0001) substrate using Pulsed Laser Deposition technique. The angle dependent magnetic hysteresis, remanent coercivity, and temperature dependent coercivity had been employed to understand the magnetization reversal of these films. It was found that the Strontium Ferrite thin film grown at lower (higher) oxygen partial pressure shows Stoner-Wohlfarth type (Kondorsky like) reversal. The relative importance of pinning and nucleation processes during magnetization reversal is used to explain the type of the magnetization reversal with different oxygen partial pressure during growth.

DEVICE FOR CONTROL OF OXYGEN PARTIAL PRESSURE

DOEpatents

Bradner, H.; Gordon, H.S.

1957-12-24

A device is described that can sense changes in oxygen partial pressure and cause a corresponding mechanical displacement sufficient to actuate meters, valves and similar devices. A piston and cylinder arrangement contains a charge of crystalline metal chelate pellets which have the peculiar property of responding to variations in the oxygen content of the ambient atmosphere by undergoing a change in dimension. A lever system amplifies the relative displacement of the piston in the cylinder, and actuates the controlled valving device. This partial pressure oxygen sensing device is useful in controlled chemical reactions or in respiratory devices such as the oxygen demand meters for high altitude aircraft.

Mass separation of deuterium and helium with conventional quadrupole mass spectrometer by using varied ionization energy

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

Yu, Yaowei; Hu, Jiansheng, E-mail: hujs@ipp.ac.cn; Wan, Zhao

2016-03-15

Deuterium pressure in deuterium-helium mixture gas is successfully measured by a common quadrupole mass spectrometer (model: RGA200) with a resolution of ∼0.5 atomic mass unit (AMU), by using varied ionization energy together with new developed software and dedicated calibration for RGA200. The new software is developed by using MATLAB with the new functions: electron energy (EE) scanning, deuterium partial pressure measurement, and automatic data saving. RGA200 with new software is calibrated in pure deuterium and pure helium 1.0 × 10{sup −6}–5.0 × 10{sup −2} Pa, and the relation between pressure and ion current of AMU4 under EE = 25 eVmore » and EE = 70 eV is obtained. From the calibration result and RGA200 scanning with varied ionization energy in deuterium and helium mixture gas, both deuterium partial pressures (P{sub D{sub 2}}) and helium partial pressure (P{sub He}) could be obtained. The result shows that deuterium partial pressure could be measured if P{sub D{sub 2}} > 10{sup −6} Pa (limited by ultimate pressure of calibration vessel), and helium pressure could be measured only if P{sub He}/P{sub D{sub 2}} > 0.45, and the measurement error is evaluated as 15%. This method is successfully employed in EAST 2015 summer campaign to monitor deuterium outgassing/desorption during helium discharge cleaning.« less

Synthesis and Characterization of Hexagonal Boron Nitride as a Gate Dielectric

PubMed Central

Jang, Sung Kyu; Youn, Jiyoun; Song, Young Jae; Lee, Sungjoo

2016-01-01

Two different growth modes of large-area hexagonal boron nitride (h-BN) film, a conventional chemical vapor deposition (CVD) growth mode and a high-pressure CVD growth mode, were compared as a function of the precursor partial pressure. Conventional self-limited CVD growth was obtained below a critical partial pressure of the borazine precursor, whereas a thick h-BN layer (thicker than a critical thickness of 10 nm) was grown beyond a critical partial pressure. An interesting coincidence of a critical thickness of 10 nm was identified in both the CVD growth behavior and in the breakdown electric field strength and leakage current mechanism, indicating that the electrical properties of the CVD h-BN film depended significantly on the film growth mode and the resultant film quality. PMID:27458024

UV absorption control of thin film growth

DOEpatents

Biefeld, Robert M.; Hebner, Gregory A.; Killeen, Kevin P.; Zuhoski, Steven P.

1991-01-01

A system for monitoring and controlling the rate of growth of thin films in an atmosphere of reactant gases measures the UV absorbance of the atmosphere and calculates the partial pressure of the gases. The flow of reactant gases is controlled in response to the partial pressure.

Photosynthesis and growth response of almond to increased atmospheric ozone partial pressures

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

Retzlaff, W.A.; Williams, L.E.; DeJong, T.M.

Uniform nursery stock of five almond cultivars [Prunus dulcis (Mill) D.A. Webb syn. P. amygdalus Batsch, cv. Butte, Carmel, Mission, Nonpareil, and Sonora] propagated on peach (P. domstica L. Batsch.) rootstock were exposed to three different atmospheric ozone (O[sub 3]) partial pressures. The trees were planted in open-top fumigation chambers on 19 Apr. 1989 at the University of California Kearny Agricultural Center located in the San Joaquin Valley of California. Exposures of the trees to three atmospheric O[sub 3] partial pressures lasted from 1 June to 2 Nov. 1989. The mean 12-h [0800-2000 h Pacific Daylight Time (PDT)] O[sub 3]more » partial pressures measured in the open-top chambers during the experimental period were 0.038, 0.060, and 0.112 [mu]Pa Pa[sup [minus]1] O[sub 3] in the charcoal filtered, ambient, and ambient + O[sub 3] treatments, respectively. Leaf net CO[sub 2] assimilation, trunk cross-sectional area growth, and root, trunk, foliage, and total dry weight of Nonpareil were reduced by increased atmospheric O[sub 3] partial pressures. Mission was unaffected by O[sub 3] and Butte, Carmel, and Sonora were intermediate in their responses. Foliage of Nonpareil also abscised prematurely in the ambient and ambient + O[sub 3] treatments. The results indicate that there are almond cultivars that are sensitive to O[sub 3] exposure.« less

Oxygen Partial Pressure Is a Rate-Limiting Parameter for Cell Proliferation in 3D Spheroids Grown in Physioxic Culture Condition

PubMed Central

Gomes, Aurélie; Guillaume, Ludivine; Grimes, David Robert; Fehrenbach, Jérôme; Lobjois, Valérie; Ducommun, Bernard

2016-01-01

The in situ oxygen partial pressure in normal and tumor tissues is in the range of a few percent. Therefore, when studying cell growth in 3D culture systems, it is essential to consider how the physiological oxygen concentration, rather than the one in the ambient air, influences the proliferation parameters. Here, we investigated the effect of reducing oxygen partial pressure from 21% to 5% on cell proliferation rate and regionalization in a 3D tumor spheroid model. We found that 5% oxygen concentration strongly inhibited spheroid growth, changed the proliferation gradient and reduced the 50% In Depth Proliferation index (IDP50), compared with culture at 21% oxygen. We then modeled the oxygen partial pressure profiles using the experimental data generated by culturing spheroids in physioxic and normoxic conditions. Although hypoxia occurred at similar depth in spheroids grown in the two conditions, oxygen partial pressure was a major rate-limiting factor with a critical effect on cell proliferation rate and regionalization only in spheroids grown in physioxic condition and not in spheroids grown at atmospheric normoxia. Our findings strengthen the need to consider conducting experiment in physioxic conditions (i.e., tissue normoxia) for proper understanding of cancer cell biology and the evaluation of anticancer drugs in 3D culture systems. PMID:27575790

Germination and growth of lettuce (Lactuca sativa) at low atmospheric pressure

NASA Technical Reports Server (NTRS)

Spanarkel, Robert; Drew, Malcolm C.

2002-01-01

The response of lettuce (Lactuca sativa L. cv. Waldmann's Green) to low atmospheric pressure was examined during the initial 5 days of germination and emergence, and also during subsequent growth to vegetative maturity at 30 days. Growth took place inside a 66-l-volume low pressure chamber maintained at 70 kPa, and plant response was compared to that of plants in a second, matching chamber that was at ambient pressure (approximately 101 kPa) as a control. In other experiments, to determine short-term effects of low pressure transients, plants were grown at ambient pressure until maturity and then subjected to alternating periods of 24 h of low and ambient atmospheric pressures. In all treatments the partial pressure of O2 was maintained at 21 kPa (approximately the partial pressure in air at normal pressure), and the partial pressure of CO2 was in the range 66.5-73.5 Pa (about twice that in normal air) in both chambers, with the addition of CO2 during the light phase. With continuous exposure to low pressure, shoot and root growth was at least as rapid as at ambient pressure, with an overall trend towards slightly greater performance at the lower pressure. Dark respiration rates were greater at low pressure. Transient periods at low pressure decreased transpiration and increased dark respiration but only during the period of exposure to low pressure. We conclude that long-term or short-term exposure to subambient pressure (70 kPa) was without detectable detriment to vegetative growth and development.

Measurements of Pressure Distributions and Force Coefficients in a Squeeze Film Damper. Part 1: Fully Open Ended Configuration

NASA Technical Reports Server (NTRS)

Jung, S. Y.; Sanandres, Luis A.; Vance, J. M.

1991-01-01

Measurements of pressure distributions and force coefficients were carried out in two types of squeeze film dampers, executing a circular centered orbit, an open-ended configuration, and a partially sealed one, in order to investigate the effect of fluid inertia and cavitation on pressure distributions and force coefficients. Dynamic pressure measurements were carried out for two orbit radii, epsilon 0.5 and 0.8. It was found that the partially sealed configuration was less influenced by fluid inertia than the open ended configuration.

Gas pressure and electron density at the level of the active zone of hollow cathode arc discharges

NASA Technical Reports Server (NTRS)

Minoo, M. H.

1984-01-01

A model for the longitudinal variations of the partial pressures of electrons, ions, and neutral particles is proposed as a result of an experimental study of pressure variations at the level of the active zone as a function of the various discharge parameters of a hollow cathode arc. The cathode region where the temperature passes through its maximum is called active zone. The proposed model embodies the very important variations which the partial electron and neutral particles pressures undergo at the level of the active zone.

Solubility of oxygen in a seawater medium in equilibrium with a high-pressure oxy-helium atmosphere.

PubMed

Taylor, C D

1979-06-01

The molar oxygen concentration in a seawater medium in equilibrium with a high-pressure oxygen-helium atmosphere was measured directly in pressurized subsamples, using a modified version of the Winkler oxygen analysis. At a partial pressure of oxygen of 1 atm or less, its concentration in the aqueous phase was adequately described by Henry's Law at total pressures up to 600 atm. This phenomenon, which permits a straightforward determination of dissolved oxygen within hyperbaric systems, resulted from pressure-induced compensatory alterations in the Henry's Law variables rather than from a true obedience to the Ideal Gas Law. If the partial pressure of a gas contributes significantly to the hydrostatic pressure, Henry's Law is no longer adequate for determining its solubility within the compressed medium.

Catecholase activity of dicopper(II)-bispidine complexes: stabilities and structures of intermediates, kinetics and reaction mechanism.

PubMed

Born, Karin; Comba, Peter; Daubinet, André; Fuchs, Alexander; Wadepohl, Hubert

2007-01-01

A mechanism for the oxidation of 3,5-di-tert-butylcatechol (dtbc) with dioxygen to the corresponding quinone (dtbq), catalyzed by bispidine-dicopper complexes (bispidines are various mono- and dinucleating derivatives of 3,7-diazabicyclo[3.3.1]nonane with bis-tertiary-amine-bispyridyl or bis-tertiary-amine-trispyridyl donor sets), is proposed on the basis of (1) the stoichiometry of the reaction as well as the stabilities and structures [X-ray, density functional theory (B3LYP, TZV)] of the bispidine-dicopper(II)-3,4,5,6-tetrachlorcatechol intermediates, (2) formation kinetics and structures (molecular mechanics, MOMEC) of the end-on peroxo-dicopper(II) complexes and (3) kinetics of the stoichiometric (anaerobic) and catalytic (aerobic) copper-complex-assisted oxidation of dtbc. This involves (1) the oxidation of the dicopper(I) complexes with dioxygen to the corresponding end-on peroxo-dicopper(II) complexes, (2) coordination of dtbc as a bridging ligand upon liberation of H(2)O(2) and (3) intramolecular electron transfer to produce dtbq, which is liberated, and the dicopper(I) catalyst. Although the bispidine complexes have reactivities comparable to those of recently published catalysts with macrocyclic ligands, which seem to reproduce the enzyme-catalyzed process in various reaction sequences, a strikingly different oxidation mechanism is derived from the bispidine-dicopper-catalyzed reaction.

The water-water cycle as alternative photon and electron sinks.

PubMed

Asada, K

2000-10-29

The water-water cycle in chloroplasts is the photoreduction of dioxygen to water in photosystem I (PS I) by the electrons generated in photosystem II (PS II) from water. In the water-water cycle, the rate of photoreduction of dioxygen in PS I is several orders of magnitude lower than those of the disproportionation of superoxide catalysed by superoxide dismutase, the reduction of hydrogen peroxide to water catalysed by ascorbate peroxidase, and the reduction of the resulting oxidized forms of ascorbate by reduced ferredoxin or catalysed by either dehydroascorbate reductase or monodehydroascorbate reductase. The water-water cycle therefore effectively shortens the lifetimes of photoproduced superoxide and hydrogen peroxide to suppress the production of hydroxyl radicals, their interactions with the target molecules in chloroplasts, and resulting photoinhibition. When leaves are exposed to photon intensities of sunlight in excess of that required to support the fixation of CO2, the intersystem electron carriers are over-reduced, resulting in photoinhibition. Under such conditions, the water-water cycle not only scavenges active oxygens, but also safely dissipates excess photon energy and electrons, in addition to downregulation of PS II and photorespiration. The dual functions of the water-water cycle for protection from photoinhibition under photon excess stress are discussed, along with its functional evolution.

A novel dioxygenation product of arachidonic acid possesses potent chemotactic activity for human polymorphonuclear leukocytes.

PubMed

Shak, S; Perez, H D; Goldstein, I M

1983-12-25

We have found that a novel dioxygenation product of arachidonic acid, 8(S),15(S)-dihydroxy-5,11-cis-9,13-trans-eicosatetraenoic acid (8,15-diHETE), possesses chemotactic activity for human polymorphonuclear leukocytes comparable to that of leukotriene B4. Authentic 8,15-diHETE, identified by gas chromatography-mass spectrometry, was prepared by treating arachidonic acid with soybean lipoxygenase and was purified by reverse-phase high performance liquid chromatography. Using a "leading front" assay, 8,15-diHETE exhibited significant chemotactic activity at a concentration of 5.0 ng/ml. Maximum chemotactic activity was observed at a concentration of 30 ng/ml. The 8,15-diHETE generated by mixed human leukocytes after stimulation with arachidonic acid and the calcium ionophore, A23187, exhibited quantitatively similar chemotactic activity. Two synthetic all-trans conjugated isomers of 8,15-diHETE, however, were not chemotactic at concentrations up to 500 ng/ml. In contrast to its potent chemotactic activity, 8,15-diHETE (at concentrations up to 10 micrograms/ml) was relatively inactive with respect to its ability to provoke either degranulation or generation of superoxide anion radicals by cytochalasin B-treated leukocytes. Both leukotriene B4 and 8,15-diHETE may be important mediators of inflammation.

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

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

Kumar, Pravindra; Mohammadi, Mahmood; Dhindwal, Sonali

2012-06-28

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

Yeast and Mammalian Metallothioneins Functionally Substitute for Yeast Copper-Zinc Superoxide Dismutase

NASA Astrophysics Data System (ADS)

Tamai, Katherine T.; Gralla, Edith B.; Ellerby, Lisa M.; Valentine, Joan S.; Thiele, Dennis J.

1993-09-01

Copper-zinc superoxide dismutase catalyzes the disproportionation of superoxide anion to hydrogen peroxide and dioxygen and is thought to play an important role in protecting cells from oxygen toxicity. Saccharomyces cerevisiae strains lacking copper-zinc superoxide dismutase, which is encoded by the SOD1 gene, are sensitive to oxidative stress and exhibit a variety of growth defects including hypersensitivity to dioxygen and to superoxide-generating drugs such as paraquat. We have found that in addition to these known phenotypes, SOD1-deletion strains fail to grow on agar containing the respiratory carbon source lactate. We demonstrate here that expression of the yeast or monkey metallothionein proteins in the presence of copper suppresses the lactate growth defect and some other phenotypes associated with SOD1-deletion strains, indicating that copper metallothioneins substitute for copper-zinc superoxide dismutase in vivo to protect cells from oxygen toxicity. Consistent with these results, we show that yeast metallothionein mRNA levels are dramatically elevated under conditions of oxidative stress. Furthermore, in vitro assays demonstrate that yeast metallothionein, purified or from whole-cell extracts, exhibits copper-dependent antioxidant activity. Taken together, these data suggest that both yeast and mammalian metallothioneins may play a direct role in the cellular defense against oxidative stress by functioning as antioxidants.

Fuel Production from Seawater and Fuel Cells Using Seawater.

PubMed

Fukuzumi, Shunichi; Lee, Yong-Min; Nam, Wonwoo

2017-11-23

Seawater is the most abundant resource on our planet and fuel production from seawater has the notable advantage that it would not compete with growing demands for pure water. This Review focuses on the production of fuels from seawater and their direct use in fuel cells. Electrolysis of seawater under appropriate conditions affords hydrogen and dioxygen with 100 % faradaic efficiency without oxidation of chloride. Photoelectrocatalytic production of hydrogen from seawater provides a promising way to produce hydrogen with low cost and high efficiency. Microbial solar cells (MSCs) that use biofilms produced in seawater can generate electricity from sunlight without additional fuel because the products of photosynthesis can be utilized as electrode reactants, whereas the electrode products can be utilized as photosynthetic reactants. Another important source for hydrogen is hydrogen sulfide, which is abundantly found in Black Sea deep water. Hydrogen produced by electrolysis of Black Sea deep water can also be used in hydrogen fuel cells. Production of a fuel and its direct use in a fuel cell has been made possible for the first time by a combination of photocatalytic production of hydrogen peroxide from seawater and dioxygen in the air and its direct use in one-compartment hydrogen peroxide fuel cells to obtain electric power. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evolutionary ecology during the rise of dioxygen in the Earth's atmosphere.

PubMed

Sleep, Norman H; Bird, Dennis K

2008-08-27

Pre-photosynthetic niches were meagre with a productivity of much less than 10(-4) of modern photosynthesis. Serpentinization, arc volcanism and ridge-axis volcanism reliably provided H(2). Methanogens and acetogens reacted CO(2) with H(2) to obtain energy and make organic matter. These skills pre-adapted a bacterium for anoxygenic photosynthesis, probably starting with H(2) in lieu of an oxygen 'acceptor'. Use of ferrous iron and sulphide followed as abundant oxygen acceptors, allowing productivity to approach modern levels. The 'photobacterium' proliferated rooting much of the bacterial tree. Land photosynthetic microbes faced a dearth of oxygen acceptors and nutrients. A consortium of photosynthetic and soil bacteria aided weathering and access to ferrous iron. Biologically enhanced weathering led to the formation of shales and, ultimately, to granitic rocks. Already oxidized iron-poor sedimentary rocks and low-iron granites provided scant oxygen acceptors, as did freshwater in their drainages. Cyanobacteria evolved dioxygen production that relieved them of these vicissitudes. They did not immediately dominate the planet. Eventually, anoxygenic and oxygenic photosynthesis oxidized much of the Earth's crust and supplied sulphate to the ocean. Anoxygenic photosynthesis remained important until there was enough O(2) in downwelling seawater to quantitatively oxidize massive sulphides at mid-ocean ridge axes.

Biosynthesis of 3-acetyldeoxynivalenol and sambucinol. Identification of the two oxygenation steps after trichodiene.

PubMed

Zamir, L O; Nikolakakis, A; Huang, L; St-Pierre, P; Sauriol, F; Sparace, S; Mamer, O

1999-04-30

The first two oxygenation steps post-trichodiene in the biosyntheses of the trichothecenes 3-acetyldeoxynivalenol and sambucinol were investigated. The plausible intermediates 2-hydroxytrichodiene (2alpha- and 2beta-) and 12,13-epoxytrichodiene and the dioxygenated compounds 12,13-epoxy-9,10-trichoene-2-ol (2alpha- and 2beta-) were prepared specifically labeled with stable isotopes. They were then fed separately and/or together to Fusarium culmorum cultures, and the derived trichothecenes were isolated, purified, and analyzed. The stable isotopes enable easy localization of the labels in the products by 2H NMR, 13C NMR, and mass spectrometry. We found that 2alpha-hydroxytrichodiene is the first oxygenated step in the biosynthesis of both 3-acetyldeoxynivalenol and sambucinol. The stereoisomer 2beta-hydroxytrichodiene and 12,13-epoxytrichodiene are not biosynthetic intermediates and have not been isolated as metabolites. We also demonstrated that the dioxygenated 12, 13-epoxy-9,10-trichoene-2alpha-ol is a biosynthetic precursor to trichothecenes as had been suggested in a preliminary work. Its stereoisomer was not found in the pathway. A further confirmation of our results was the isolation of both oxygenated trichodiene derivatives 2alpha-hydroxytrichodiene and 12,13-epoxy-9, 10-trichoene-2alpha-ol as natural metabolites in F. culmorum cultures.

Randomized trial of low versus high carbon dioxide insufflation pressures in posterior retroperitoneoscopic adrenalectomy.

PubMed

Fraser, Sheila; Norlén, Olov; Bender, Kyle; Davidson, Joanne; Bajenov, Sonya; Fahey, David; Li, Shawn; Sidhu, Stan; Sywak, Mark

2018-05-01

Posterior retroperitoneoscopic adrenalectomy has gained widespread acceptance for the removal of benign adrenal tumors. Higher insufflation pressures using carbon dioxide (CO 2 ) are required, although the ideal starting pressure is unclear. This prospective, randomized, single-blinded, study aims to compare physiologic differences with 2 different CO 2 insufflation pressures during posterior retroperitoneoscopic adrenalectomy. Participants were randomly assigned to a starting insufflation pressure of 20 mm Hg (low pressure) or 25 mm Hg (high pressure). The primary outcome measure was partial pressure of arterial CO 2 at 60 minutes. Secondary outcomes included end-tidal CO 2 , arterial pH, blood pressure, and peak airway pressure. Breaches of protocol to change insufflation pressure were permitted if required and were recorded. A prospective randomized trial including 31 patients (low pressure: n = 16; high pressure: n = 15) was undertaken. At 60 minutes, the high pressure group had greater mean partial pressure of arterial CO 2 (64 vs 50 mm Hg, P = .003) and end-tidal CO 2 (54 vs 45 mm Hg, P = .008) and a lesser pH (7.21 vs 7.29, P = .0005). There were no significant differences in base excess, peak airway pressure, operative time, or duration of hospital stay. Clinically indicated protocol breaches were more common in the low pressure than the high pressure group (8 vs 3, P = .03). In posterior retroperitoneoscopic adrenalectomy, greater insufflation pressures are associated with greater partial pressure of arterial CO 2 and end-tidal CO 2 and lesser pH at 60 minutes, be significant. Commencing with lesser CO 2 insufflation pressures decreases intraoperative acidosis. Copyright © 2017 Elsevier Inc. All rights reserved.

Pressure dependence of the electro-optic response function in partially exposed polymer dispersed ferroelectric liquid crystals

NASA Technical Reports Server (NTRS)

Parmar, D. S.; Holmes, H. K.

1993-01-01

Ferroelectric liquid crystals in a new configuration, termed partially exposed polymer dispersed ferroelectric liquid crystal (PEPDFLC), respond to external pressures and demonstrate pressure-induced electro-optic switching response. When the PEPDFLC thin film is sandwiched between two transparent conducting electrodes, one a glass plate and the other a flexible sheet such as polyvenylidene fluoride, the switching characteristics of the thin film are a function of the pressure applied to the flexible transparent electrode and the bias voltage across the electrodes. Response time measurements reveal a linear dependence of the change in electric field with external pressure.

Geometry of α-Cr2O3(0001) as a Function of H2O Partial Pressure

PubMed Central

2015-01-01

Surface X-ray diffraction has been employed to elucidate the surface structure of α-Cr2O3(0001) as a function of water partial pressure at room temperature. In ultra high vacuum, following exposure to ∼2000 Langmuir of H2O, the surface is found to be terminated by a partially occupied double layer of chromium atoms. No evidence of adsorbed OH/H2O is found, which is likely due to either adsorption at minority sites, or X-ray induced desorption. At a water partial pressure of ∼30 mbar, a single OH/H2O species is found to be bound atop each surface Cr atom. This adsorption geometry does not agree with that predicted by ab initio calculations, which may be a result of some differences between the experimental conditions and those modeled. PMID:26877825

21 CFR 868.1150 - Indwelling blood carbon dioxide partial pressure (PCO2) analyzer.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Indwelling blood carbon dioxide partial pressure (PCO2) analyzer. 868.1150 Section 868.1150 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF... “Class II Special Controls Guidance Document: Indwelling Blood Gas Analyzers; Final Guidance for Industry...

Classifying Acute Respiratory Distress Syndrome Severity: Correcting the Arterial Oxygen Partial Pressure to Fractional Inspired Oxygen at Altitude.

PubMed

Pérez-Padilla, Rogelio; Hernández-Cárdenas, Carmen Margarita; Lugo-Goytia, Gustavo

2016-01-01

In the well-known Berlin definition of acute respiratory distress syndrome (ARDS), there is a recommended adjustment for arterial oxygen partial pressure to fractional inspired oxygen (PaO2/FIO2) at altitude, but without a reference as to how it was derived.

Solubility of carbon dioxide in aqueous mixtures of alkanolamines

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

Dawodu, O.F.; Meisen, A.

1994-07-01

The solubility of CO[sub 2] in water + N-methyldiethanolamine + monoethanolamine (MDEA + MEA) and water + N-methyldiethanolamine + diethanolamine (MDEA + DEA) are reported at two compositions of 3.4 M MDEA + 0.8 M MEA or DEA and 2.1 M MDEA + 2.1 M MEA or DEA at temperatures from 70 to 180 C and CO[sub 2] partial pressures from 100 to 3,850 kPa. The solubility of CO[sub 2] in the blends decreased with an increase in temperature but increased with an increase in CO[sub 2] partial pressure. At low partial pressures of CO[sub 2] and the same totalmore » amine concentration, the equilibrium CO[sub 2] loadings were in the order MDEA + MEA > MDEA + DEA > MDEA. However, at high CO[sub 2] partial pressures, the equilibrium CO[sub 2] loadings in the MDEA solutions were higher than those of the MDEA + MEA and MDEA + DEA blends of equal molar strengths due to the stoichiometric loading limitations of MEA and DEA. The nonadditivity of the equilibrium loadings for single amine systems highlights the need for independent measurements on amine blends.« less

Method for sensing and measuring a concentration or partial pressure of a reactant used in a redox reaction

DOEpatents

Findl, E.

1984-12-21

A method for sensing or measuring the partial pressure or concentration of an electroactive species used in conjunction with an electrolyte, the method being characterized by providing a constant current between an anode and a cathode of an electrolyte-containing cell, while measuring changes in voltage that occur between either the anode and cathode or between a reference electrode and one of the main electrodes of the cell, thereby to determine the concentration or partial pressure of the electro-active species as a function of said measured voltage changes. The method of the invention can be practiced using either a cell having only an anode and a cathode, or using a cell having an anode and a cathode in combination with a reference electrode. Accurate measurements of small concentrations or partial pressures of electro-active species are obtainable with the method of the invention, by using constant currents of only a few microamperes between the anode and cathode of the cell, while the concentration-determining voltage is measured.

Oxidation of C/SiC Composites at Reduced Oxygen Partial Pressures

NASA Technical Reports Server (NTRS)

Opila, E. J.; Serra, J. L.

2007-01-01

T-300 carbon fibers and T-300 carbon fiber reinforced silicon carbide composites (C/SiC) were oxidized in flowing reduced oxygen partial pressure environments at a total pressure of one atmosphere (0.5 atm O2, 0.05 atm O2 and 0.005 atm O2, balance argon). Experiments were conducted at four temperatures (816deg, 1149deg, 1343deg, and 1538 C). The oxidation kinetics were monitored using thermogravimetric analysis. T-300 fibers were oxidized to completion for times between 0.6 and 90 h. Results indicated that fiber oxidation kinetics were gas phase diffusion controlled. Oxidation rates had an oxygen partial pressure dependence with a power law exponent close to one. In addition, oxidation rates were only weakly dependent on temperature. The C/SiC coupon oxidation kinetics showed some variability, attributed to differences in the number and width of cracks in the SiC seal coat. In general, weight losses were observed indicating oxidation of the carbon fibers dominated the oxidation behavior. Low temperatures and high oxygen pressures resulted in the most rapid consumption of the carbon fibers. At higher temperatures, the lower oxidation rates were primarily attributed to crack closure due to SiC thermal expansion, rather than oxidation of SiC since these reduced rates were observed even at the lowest oxygen partial pressures where SiC oxidation is minimal.

Pressure effects on the structure, kinetic, and thermodynamic properties of heat-induced aggregation of protein studied by FT-IR spectroscopy

NASA Astrophysics Data System (ADS)

Taniguchi, Y.; Okuno, A.; Kato, M.

2010-03-01

Pressure can retrain the heat-induced aggregation and dissociate the heat-induced aggregates. We observed the aggregation-preventing pressure effect and the aggregates-dissociating pressure effect to characterize the heat-induced aggregation of equine serum albumin (ESA) by FT-IR spectroscopy. The results suggest the α-helical structure collapses at the beginning of heat-induced aggregation through the swollen structure, and then the rearrangement of structure to the intermolecular β-sheet takes place through partially unfolded structure. We determined the activation volume for the heat-induced aggregation (ΔV# = +93 ml/mol) and the partial molar volume difference between native state and heat-induced aggregates (ΔV=+32 ml/mol). This positive partial molar volume difference suggests that the heat-induced aggregates have larger internal voids than the native structure. Moreover, the positive volume change implies that the formation of the intermolecular β-sheet is unfavorable under high pressure.

Optimizing the physical ergonomics indices for the use of partial pressure suits.

PubMed

Ding, Li; Li, Xianxue; Hedge, Alan; Hu, Huimin; Feathers, David; Qin, Zhifeng; Xiao, Huajun; Xue, Lihao; Zhou, Qianxiang

2015-03-01

This study developed an ergonomic evaluation system for the design of high-altitude partial pressure suits (PPSs). A total of twenty-one Chinese males participated in the experiment which tested three types of ergonomics indices (manipulative mission, operational reach and operational strength) were studied using a three-dimensional video-based motion capture system, a target-pointing board, a hand dynamometer, and a step-tread apparatus. In total, 36 ergonomics indices were evaluated and optimized using regression and fitting analysis. Some indices that were found to be linearly related and redundant were removed from the study. An optimal ergonomics index system was established that can be used to conveniently and quickly evaluate the performance of different pressurized/non-pressurized suit designs. The resulting ergonomics index system will provide a theoretical basis and practical guidance for mission planners, suit designers and engineers to design equipment for human use, and to aid in assessing partial pressure suits. Copyright © 2014 Elsevier Ltd and The Ergonomics Society. All rights reserved.

Effects of Environmental Oxygen Content and Dissolved Oxygen on the Surface Tension and Viscosity of Liquid Nickel

NASA Astrophysics Data System (ADS)

SanSoucie, M. P.; Rogers, J. R.; Kumar, V.; Rodriguez, J.; Xiao, X.; Matson, D. M.

2016-07-01

The NASA Marshall Space Flight Center's electrostatic levitation (ESL) laboratory has recently added an oxygen partial pressure controller. This system allows the oxygen partial pressure within the vacuum chamber to be measured and controlled in the range from approximately 10^{-28} {to} 10^{-9} bar, while in a vacuum atmosphere. The oxygen control system installed in the ESL laboratory's main chamber consists of an oxygen sensor, oxygen pump, and a control unit. The sensor is a potentiometric device that determines the difference in oxygen activity in two gas compartments (inside the chamber and the air outside of the chamber) separated by an electrolyte. The pump utilizes coulometric titration to either add or remove oxygen. The system is controlled by a desktop control unit, which can also be accessed via a computer. The controller performs temperature control for the sensor and pump, has a PID-based current loop and a control algorithm. Oxygen partial pressure has been shown to play a significant role in the surface tension of liquid metals. Oxide films or dissolved oxygen may lead to significant changes in surface tension. The effects on surface tension and viscosity by oxygen partial pressure in the surrounding environment and the melt dissolved oxygen content will be evaluated, and the results will be presented. The surface tension and viscosity will be measured at several different oxygen partial pressures while the sample is undercooled. Surface tension and viscosity will be measured using the oscillating droplet method.

Analyzing the dependence of oxygen incorporation current density on overpotential and oxygen partial pressure in mixed conducting oxide electrodes.

PubMed

Guan, Zixuan; Chen, Di; Chueh, William C

2017-08-30

The oxygen incorporation reaction, which involves the transformation of an oxygen gas molecule to two lattice oxygen ions in a mixed ionic and electronic conducting solid, is a ubiquitous and fundamental reaction in solid-state electrochemistry. To understand the reaction pathway and to identify the rate-determining step, near-equilibrium measurements have been employed to quantify the exchange coefficients as a function of oxygen partial pressure and temperature. However, because the exchange coefficient contains contributions from both forward and reverse reaction rate constants and depends on both oxygen partial pressure and oxygen fugacity in the solid, unique and definitive mechanistic assessment has been challenging. In this work, we derive a current density equation as a function of both oxygen partial pressure and overpotential, and consider both near and far from equilibrium limits. Rather than considering specific reaction pathways, we generalize the multi-step oxygen incorporation reaction into the rate-determining step, preceding and following quasi-equilibrium steps, and consider the number of oxygen ions and electrons involved in each. By evaluating the dependence of current density on oxygen partial pressure and overpotential separately, one obtains the reaction orders for oxygen gas molecules and for solid-state species in the electrode. We simulated the oxygen incorporation current density-overpotential curves for praseodymium-doped ceria for various candidate rate-determining steps. This work highlights a promising method for studying the exchange kinetics far away from equilibrium.

Efficient absorption of SO2 with low-partial pressures by environmentally benign functional deep eutectic solvents.

PubMed

Zhang, Kai; Ren, Shuhang; Hou, Yucui; Wu, Weize

2017-02-15

Sulfur dioxide (SO 2 ) emitted from the burning of fossil fuels is one of the main air contaminants. In this work, we found that environmentally benign solvents, deep eutectic solvents (DESs) could be designed with a function to absorb low-partial pressure SO 2 from simulated flue gas. Two kinds of biodegradable functional DESs based on betaine (Bet) and l-carnitine (L-car) as hydrogen bond accepters (HBA) and ethylene glycol (EG) as a hydrogen bond donor (HBD) were prepared with mole ratios of HBA to HBD from 1:3 to 1:5, and they were investigated to absorb SO 2 with different partial pressures at various temperatures. The results showed that the two DESs could absorb low-partial pressure SO 2 efficiently. SO 2 absorption capacities of the DESs with HBA/HBD mole ratio of 1:3 were 0.332mol SO 2 /mol HBA for Bet+EG DES and 0.820mol SO 2 /mol HBA for L-car+EG DES at 40°C with a SO 2 partial pressure of 0.02atm. In addition, the regeneration experiments demonstrated that the absorption capacities of DESs did not change after five absorption and desorption cycles. Furthermore, the absorption mechanism of SO 2 by DESs was studied by FT-IR, 1 H NMR and 13 C NMR spectra. It was found that there are strong acid-base interactions between SO 2 and -COO - on HBA. Copyright © 2016 Elsevier B.V. All rights reserved.

Effects of oxygen on responses to heating in two lizard species sampled along an elevational gradient.

PubMed

DuBois, P Mason; Shea, Tanner K; Claunch, Natalie M; Taylor, Emily N

2017-08-01

Thermal tolerance is an important variable in predictive models about the effects of global climate change on species distributions, yet the physiological mechanisms responsible for reduced performance at high temperatures in air-breathing vertebrates are not clear. We conducted an experiment to examine how oxygen affects three variables exhibited by ectotherms as they heat-gaping threshold, panting threshold, and loss of righting response (the latter indicating the critical thermal maximum)-in two lizard species along an elevational (and therefore environmental oxygen partial pressure) gradient. Oxygen partial pressure did not impact these variables in either species. We also exposed lizards at each elevation to severely hypoxic gas to evaluate their responses to hypoxia. Severely low oxygen partial pressure treatments significantly reduced the gaping threshold, panting threshold, and critical thermal maximum. Further, under these extreme hypoxic conditions, these variables were strongly and positively related to partial pressure of oxygen. In an elevation where both species overlapped, the thermal tolerance of the high elevation species was less affected by hypoxia than that of the low elevation species, suggesting the high elevation species may be adapted to lower oxygen partial pressures. In the high elevation species, female lizards had higher thermal tolerance than males. Our data suggest that oxygen impacts the thermal tolerance of lizards, but only under severely hypoxic conditions, possibly as a result of hypoxia-induced anapyrexia. Copyright © 2017. Published by Elsevier Ltd.

Oxygen vacancy induced phase formation and room temperature ferromagnetism in undoped and Co-doped TiO2 thin films

NASA Astrophysics Data System (ADS)

Mohanty, P.; Mishra, N. C.; Choudhary, R. J.; Banerjee, A.; Shripathi, T.; Lalla, N. P.; Annapoorni, S.; Rath, Chandana

2012-08-01

TiO2 and Co-doped TiO2 (CTO) thin films deposited at various oxygen partial pressures by pulsed laser deposition exhibit room temperature ferromagnetism (RTFM) independent of their phase. Films deposited at 0.1 mTorr oxygen partial pressure show a complete rutile phase confirmed from glancing angle x-ray diffraction and Raman spectroscopy. At the highest oxygen partial pressure, i.e. 300 mTorr, although the TiO2 film shows a complete anatase phase, a small peak corresponding to the rutile phase along with the anatase phase is identified in the case of CTO film. An increase in O to Ti/(Ti+Co) ratio with increase in oxygen partial pressure is observed from Rutherford backscattering spectroscopy. It is revealed from x-ray photoelectron spectroscopy (XPS) that oxygen vacancies are found to be higher in the CTO film than TiO2, while the valency of cobalt remains in the +2 state. Therefore, the CTO film deposited at 300 mTorr does not show a complete anatase phase unlike the TiO2 film deposited at the same partial pressure. We conclude that RTFM in both films is not due to impurities/contaminants, as confirmed from XPS depth profiling and cross-sectional transmission electron microscopy (TEM), but due to oxygen vacancies. The magnitude of moment, however, depends not only on the phase of TiO2 but also on the crystallinity of the films.

Phase development in the Bi 2Sr 2CaCu 2O y system . Effects of oxygen pressure

NASA Astrophysics Data System (ADS)

List, F. A.; Hsu, H.; Cavin, O. B.; Porter, W. D.; Hubbard, C. R.; Kroeger, D. M.

1992-11-01

Studies have been undertaken using thermal analysis, in conjunction with high-temperature and room temperature X-ray diffraction, fraction, to elucidate phase relationships during thermal processing of thick films of initially phase pure Bi 2Sr 2CaCu 2O y (2212) on silver substrates in various oxygen-containing atmospheres (0.001 to 100% O 2). Exothermic events on cooling at 10°C/min from a partially liquid state vary with oxygen partial pressure and can be grouped into three sets (I-III). Set I is prominent for 0.001% and 0.1% O 2 in the range of 740-775°C and is believed to be associated with the crystallization of a Cu-free ∼ Bi 5Sr 3Ca 1 oxide phase. Set II results from the crystallization of 2212; it is observed for p(O 2)≥1.0% in the temperature range 800-870°C. Set III appears for 21% and 100% O 2 in the temperature range 880-910°C, and its origin is not clear from the results of this study. Subsequent room temperature X-ray diffraction from these samples suggests that in general high oxygen partial pressures (100% O 2) tend to favor the formation of Bi 2Sr 2CuO 6 (2201), whereas low oxygen partial pressures (0.001-0.1% O 2) lead to the formation of a Cu-free, Bi-Sr-Ca oxide phase. The 2212 phase forms at this cooling rate predominantly for intermediate oxygen partial pressures (7.6-21% O 2). High-temperature X-ray diffraction during cooling (2°C/h) from the partially liquid state shows a pronounced dependence of the order of evolution of crystalline 2212 and 2201 phases on p(O 2). For an oxygen partial pressure of 1.0% the formation of 2212 precedes that of 2201, whereas for 0.01% O 2 2201 crystallizes at a higher temperature than 2212. The implications of these results pertaining to thermal processing of thick 2212 films are discussed.

Reproducing early Martian atmospheric carbon dioxide partial pressure by modeling the formation of Mg-Fe-Ca carbonate identified in the Comanche rock outcrops on Mars

NASA Astrophysics Data System (ADS)

Berk, Wolfgang; Fu, Yunjiao; Ilger, Jan-Michael

2012-10-01

The well defined composition of the Comanche rock's carbonate (Magnesite0.62Siderite0.25Calcite0.11Rhodochrosite0.02) and its host rock's composition, dominated by Mg-rich olivine, enable us to reproduce the atmospheric CO2partial pressure that may have triggered the formation of these carbonates. Hydrogeochemical one-dimensional transport modeling reveals that similar aqueous rock alteration conditions (including CO2partial pressure) may have led to the formation of Mg-Fe-Ca carbonate identified in the Comanche rock outcrops (Gusev Crater) and also in the ultramafic rocks exposed in the Nili Fossae region. Hydrogeochemical conditions enabling the formation of Mg-rich solid solution carbonate result from equilibrium species distributions involving (1) ultramafic rocks (ca. 32 wt% olivine; Fo0.72Fa0.28), (2) pure water, and (3) CO2partial pressures of ca. 0.5 to 2.0 bar at water-to-rock ratios of ca. 500 molH2O mol-1rock and ca. 5°C (278 K). Our modeled carbonate composition (Magnesite0.64Siderite0.28Calcite0.08) matches the measured composition of carbonates preserved in the Comanche rocks. Considerably different carbonate compositions are achieved at (1) higher temperature (85°C), (2) water-to-rock ratios considerably higher and lower than 500 mol mol-1 and (3) CO2partial pressures differing from 1.0 bar in the model set up. The Comanche rocks, hosting the carbonate, may have been subjected to long-lasting (>104 to 105 years) aqueous alteration processes triggered by atmospheric CO2partial pressures of ca. 1.0 bar at low temperature. Their outcrop may represent a fragment of the upper layers of an altered olivine-rich rock column, which is characterized by newly formed Mg-Fe-Ca solid solution carbonate, and phyllosilicate-rich alteration assemblages within deeper (unexposed) units.

Measurement and Control of Oxygen Partial Pressure in an Electrostatic Levitator

NASA Technical Reports Server (NTRS)

SanSoucie, Michael P.; Rogers, Jan R.

2014-01-01

Recently the NASA Marshall Space Flight Center electrostatic levitation (ESL) laboratory has been upgraded to include an oxygen control system. This system allows the oxygen partial pressure within the vacuum chamber to be measured and controlled, at elevated temperatures, theoretically in the range from 10(exp -36) to 10(exp 0) bar. The role of active surface agents in liquid metals is fairly well known; however, published surface tension data typically has large scatter, which has been hypothesized to be caused by the presence of oxygen. The surface tension of metals is affected by even a small amount of adsorption of oxygen. It has even been shown that oxygen partial pressures may need to be as low as 10(exp -24) bar to avoid oxidation. While electrostatic levitation is done under high vacuum, oxide films or dissolved oxygen may have significant effects on materials properties, such as surface tension and viscosity. Therefore, the ability to measure and control the oxygen partial pressure within the chamber is highly desirable. The oxygen control system installed at MSFC contains a potentiometric sensor, which measures the oxygen partial pressure, and an oxygen ion pump. In the pump, a pulse-width modulated electric current is applied to yttrium-stabilized zirconia, resulting in oxygen transfer into or out of the system. Also part of the system is a control unit, which consists of temperature controllers for the sensor and pump, PID-based current loop for the ion pump, and a control algorithm. This system can be used to study the effects of oxygen on the thermophysical properties of metals, ceramics, glasses, and alloys. It can also be used to provide more accurate measurements by processing the samples at very low oxygen partial pressures. The oxygen control system will be explained in more detail and an overview of its use and limitations in an electrostatic levitator will be described. Some preliminary measurements have been made, and the results to date will be provided.

Electrical conductivity of cobalt doped La 0.8Sr 0.2Ga 0.8Mg 0.2O 3- δ

NASA Astrophysics Data System (ADS)

Wang, Shizhong; Wu, Lingli; Liang, Ying

La 0.8Sr 0.2Ga 0.8Mg 0.2O 3- δ (LSGM8282), La 0.8Sr 0.2Ga 0.8Mg 0.15Co 0.05O 3- δ (LSGMC5) and La 0.8Sr 0.2Ga 0.8Mg 0.115Co 0.085O 3- δ (LSGMC8.5) were prepared using a conventional solid-state reaction. Electrical conductivities and electronic conductivities of the samples were measured using four-probe impedance spectrometry, four-probe dc polarization and Hebb-Wagner polarization within the temperature range of 973-1173 K. The electrical conductivities in LSGMC5 and LSGMC8.5 increased with decreasing oxygen partial pressures especially in the high (>10 -5 atm) and low oxygen partial pressure regions (<10 -15 atm). However, the electrical conductivity in LSGM8282 had no dependency on the oxygen partial pressure. At temperatures higher than 1073 K, PO2 dependencies of the free electron conductivities in LSGM8282, LSGMC5 and LSGMC8.5 were about -1/4, and PO2 dependencies of the electron hole conductivities were about 0.25, 0.12 and 0.07, respectively. Oxygen ion conductivities in LSGMC5 and LSGMC8.5 increased with decreasing oxygen partial pressures especially in the high and low oxygen partial pressure regions, which was due to the increase in the concentration of oxygen vacancies. The change in the concentration of oxygen vacancies and the valence of cobalt with oxygen partial pressure were determined using a thermo-gravimetric technique. Both the electronic conductivity and oxygen ion conductivity in cobalt doped lanthanum gallate samples increased with increasing concentration of cobalt, suggesting that the concentration of cobalt should be optimized carefully to maintain a high electrical conductivity and close to 1 oxygen ion transference number.

Oxygen-Partial-Pressure Sensor for Aircraft Oxygen Mask

NASA Technical Reports Server (NTRS)

Kelly, Mark; Pettit, Donald

2003-01-01

A device that generates an alarm when the partial pressure of oxygen decreases to less than a preset level has been developed to help prevent hypoxia in a pilot or other crewmember of a military or other high-performance aircraft. Loss of oxygen partial pressure can be caused by poor fit of the mask or failure of a hose or other component of an oxygen distribution system. The deleterious physical and mental effects of hypoxia cause the loss of a military aircraft and crew every few years. The device is installed in the crewmember s oxygen mask and is powered via communication wiring already present in all such oxygen masks. The device (see figure) includes an electrochemical sensor, the output potential of which is proportional to the partial pressure of oxygen. The output of the sensor is amplified and fed to the input of a comparator circuit. A reference potential that corresponds to the amplified sensor output at the alarm oxygen-partial-pressure level is fed to the second input of the comparator. When the sensed partial pressure of oxygen falls below the minimum acceptable level, the output of the comparator goes from the low state (a few millivolts) to the high state (near the supply potential, which is typically 6.8 V for microphone power). The switching of the comparator output to the high state triggers a tactile alarm in the form of a vibration in the mask, generated by a small 1.3-Vdc pager motor spinning an eccentric mass at a rate between 8,000 and 10,000 rpm. The sensation of the mask vibrating against the crewmember s nose is very effective at alerting the crewmember, who may already be groggy from hypoxia and is immersed in an environment that is saturated with visual cues and sounds. Indeed, the sensation is one of rudeness, but such rudeness could be what is needed to stimulate the crewmember to take corrective action in a life-threatening situation.

Carbon Monoxide, Hydrogen, and Formate Metabolism during Methanogenesis from Acetate by Thermophilic Cultures of Methanosarcina and Methanothrix Strains.

PubMed

Zinder, S H; Anguish, T

1992-10-01

CO and H(2) have been implicated in methanogenesis from acetate, but it is unclear whether they are directly involved in methanogenesis or electron transfer in acetotrophic methanogens. We compared metabolism of H(2), CO, and formate by cultures of the thermophilic acetotrophic methanogens Methanosarcina thermophila TM-1 and Methanothrix sp. strain CALS-1. M. thermophila accumulated H(2) to partial pressures of 40 to 70 Pa (1 Pa = 0.987 x 10 atm), as has been previously reported for this and other Methanosarcina cultures. In contrast, Methanothrix sp. strain CALS-1 accumulated H(2) to maximum partial pressures near 1 Pa. Growing cultures of Methanothrix sp. strain CALS-1 initially accumulated CO, which reached partial pressures near 0.6 Pa (some CO came from the rubber stopper) during the middle of methanogenesis; this was followed by a decrease in CO partial pressures to less than 0.01 Pa by the end of methanogenesis. Accumulation or consumption of CO by cultures of M. thermophila growing on acetate was not detected. Late-exponential-phase cultures of Methanothrix sp. strain CALS-1, in which the CO partial pressure was decreased by flushing with N(2)-CO(2), accumulated CO to 0.16 Pa, whereas cultures to which ca. 0.5 Pa of CO was added consumed CO until it reached this partial pressure. Cyanide (1 mM) blocked CO consumption but not production. High partial pressures of H(2) (40 kPa) inhibited methanogenesis from acetate by M. thermophila but not by Methanothrix sp. strain CALS-1, and 2 kPa of CO was not inhibitory to M. thermophila but was inhibitory to Methanothrix sp. strain CALS-1. Levels of CO dehydrogenase, hydrogenase, and formate dehydrogenase in Methanothrix sp. strain CALS-1 were 9.1, 0.045, and 5.8 mumol of viologen reduced min mg of protein. These results suggest that CO plays a role in Methanothrix sp. strain CALS-1 similar to that of H(2) in M. thermophila and are consistent with the conclusion that CO is an intermediate in a catabolic or anabolic pathway in Methanothrix sp. strain CALS-1; however, they could also be explained by passive equilibration of CO with a metabolic intermediate.

Carbon Monoxide, Hydrogen, and Formate Metabolism during Methanogenesis from Acetate by Thermophilic Cultures of Methanosarcina and Methanothrix Strains

PubMed Central

Zinder, S. H.; Anguish, T.

1992-01-01

CO and H2 have been implicated in methanogenesis from acetate, but it is unclear whether they are directly involved in methanogenesis or electron transfer in acetotrophic methanogens. We compared metabolism of H2, CO, and formate by cultures of the thermophilic acetotrophic methanogens Methanosarcina thermophila TM-1 and Methanothrix sp. strain CALS-1. M. thermophila accumulated H2 to partial pressures of 40 to 70 Pa (1 Pa = 0.987 × 10-5 atm), as has been previously reported for this and other Methanosarcina cultures. In contrast, Methanothrix sp. strain CALS-1 accumulated H2 to maximum partial pressures near 1 Pa. Growing cultures of Methanothrix sp. strain CALS-1 initially accumulated CO, which reached partial pressures near 0.6 Pa (some CO came from the rubber stopper) during the middle of methanogenesis; this was followed by a decrease in CO partial pressures to less than 0.01 Pa by the end of methanogenesis. Accumulation or consumption of CO by cultures of M. thermophila growing on acetate was not detected. Late-exponential-phase cultures of Methanothrix sp. strain CALS-1, in which the CO partial pressure was decreased by flushing with N2-CO2, accumulated CO to 0.16 Pa, whereas cultures to which ca. 0.5 Pa of CO was added consumed CO until it reached this partial pressure. Cyanide (1 mM) blocked CO consumption but not production. High partial pressures of H2 (40 kPa) inhibited methanogenesis from acetate by M. thermophila but not by Methanothrix sp. strain CALS-1, and 2 kPa of CO was not inhibitory to M. thermophila but was inhibitory to Methanothrix sp. strain CALS-1. Levels of CO dehydrogenase, hydrogenase, and formate dehydrogenase in Methanothrix sp. strain CALS-1 were 9.1, 0.045, and 5.8 μmol of viologen reduced min-1 mg of protein-1. These results suggest that CO plays a role in Methanothrix sp. strain CALS-1 similar to that of H2 in M. thermophila and are consistent with the conclusion that CO is an intermediate in a catabolic or anabolic pathway in Methanothrix sp. strain CALS-1; however, they could also be explained by passive equilibration of CO with a metabolic intermediate. PMID:16348788

Spatial and Temporal Variations in the Partial Pressure and Emission of CO2 and CH4 in and Amazon Floodplain Lake

NASA Astrophysics Data System (ADS)

Forsberg, B. R.; Amaral, J. H.; Barbosa, P.; Kasper, D.; MacIntyre, S.; Cortes, A.; Sarmento, H.; Borges, A. V.; Melack, J. M.; Farjalla, V.

2015-12-01

The Amazon floodplain contains a variety of wetland environments which contribute CO2 and CH4 to the regional and global atmospheres. The partial pressure and emission of these greenhouse gases (GHGs) varies: 1) between habitats, 2) seasonally, as the characteristics these habitats changes and 3) diurnally, in response to diurnal stratification. In this study, we investigated the combined influence of these factors on the partial pressure and emission of GHGs in Lago Janauacá, a central Amazon floodplain lake (3o23' S; 60o18' O). All measurements were made between August of 2014 and April of 2015 at two different sites and in three distinct habitats: open water, flooded forest, flooded macrophytes. Concentrations of CO2 and CH4 in air were measured continuously with a cavity enhanced absorption spectrometer, Los Gatos Research´s Ultraportable Greenhouse Gas Analyzer (UGGA). Vertical profiles o pCO2 and pCH4 were measured using the UGGA connected to an electric pump and equilibrator. Diffusive surface emissions were estimated with the UGGA connected to a static floating chamber. To investigate the influence of vertical stratification and mixing on GHG partial pressure and emissions, a meteorological station and submersible sensor chain were deployed at each site. Meteorological sensors included wind speed and direction. The submersible chains included thermistors and oxygen sensors. Depth profiles of partial pressure and diffusive emissions for both CO2 and CH4 varied diurnally, seasonally and between habitats. Both pCO2 and pCH4 were consistently higher in bottom than surface waters with the largest differences occurring at high water when thermal stratification was most stable. Methane emissions and partial pressures were highest at low water while pCO2 and CO2 fluxes were highest during high water periods, with 35% of CO2 fluxes at low water being negative. The highest average surface value of pCO2 (5491 μatm), encountered during rising water, was ~3 times higher than that encountered at low water (1708 μatm). Partial pressures and emissions of both CO2 and CH4 were greatest in open water habitats and consistently higher at night. These patterns reflected the higher levels of wind driven mixing and turbulence in open water environments and higher convective mixing at night which promoted diffusive emission.

High-pressure NaCl-phase of tetrahedral compounds

NASA Astrophysics Data System (ADS)

Soma, T.; -Matsuo Kagaya, H.

1984-04-01

The phase transition of tetrahedral compounds such as GaP, InP, ZnS, ZnSe, ZnTe and CdTe under pressure is investigated from the electronic theory of solids by using our recently presented binding force, which includes mainly covalent interactions in the pseudopotential formalism and partially ionic interactions. The partially ionic forces give the important contributions to the high-pressure phase and stabilize the NaCl-type structure for the high-pressure phase of these compounds, although not reported for GaP experimentally. Then, the numerical results such as the transition pressure, the volume-discontinuity, the transition heat with respect to the pressure-induced phase transition from the zinc-blende-to the NaCl-type lattice are obtained theoretically.

The Relationship of Mucus Concentration (Hydration) to Mucus Osmotic Pressure and Transport in Chronic Bronchitis

PubMed Central

Coakley, Raymond D.; Button, Brian; Henderson, Ashley G.; Zeman, Kirby L.; Alexis, Neil E.; Peden, David B.; Lazarowski, Eduardo R.; Davis, C. William; Bailey, Summer; Fuller, Fred; Almond, Martha; Qaqish, Bahjat; Bordonali, Elena; Rubinstein, Michael; Bennett, William D.; Kesimer, Mehmet; Boucher, Richard C.

2015-01-01

Rationale: Chronic bronchitis (CB) is characterized by persistent cough and sputum production. Studies were performed to test whether mucus hyperconcentration and increased partial osmotic pressure, in part caused by abnormal purine nucleotide regulation of ion transport, contribute to the pathogenesis of CB. Objectives: We tested the hypothesis that CB is characterized by mucus hyperconcentration, increased mucus partial osmotic pressures, and reduced mucus clearance. Methods: We measured in subjects with CB as compared with normal and asymptomatic smoking control subjects indices of mucus concentration (hydration; i.e., percentage solids) and sputum adenine nucleotide/nucleoside concentrations. In addition, sputum partial osmotic pressures and mucus transport rates were measured in subjects with CB. Measurements and Results: CB secretions were hyperconcentrated as indexed by an increase in percentage solids and total mucins, in part reflecting decreased extracellular nucleotide/nucleoside concentrations. CB mucus generated concentration-dependent increases in partial osmotic pressures into ranges predicted to reduce mucus transport. Mucociliary clearance (MCC) in subjects with CB was negatively correlated with mucus concentration (percentage solids). As a test of relationships between mucus concentration and disease, mucus concentrations and MCC were compared with FEV1, and both were significantly correlated. Conclusions: Abnormal regulation of airway surface hydration may slow MCC in CB and contribute to disease pathogenesis. PMID:25909230

Oxygen partial pressure influence on the character of InGaZnO thin films grown by PLD

NASA Astrophysics Data System (ADS)

Lu, Yi; Wang, Li

2012-11-01

The amorphous oxide semiconductors (AOSs) are promising for emerging large-area optoelectronic applications because of capability of large-area, uniform deposition at low temperatures such as room temperature (RT). Indium-gallium-zinc oxide (InGaZnO) thin film is a promising amorphous semiconductors material in thin film transistors (TFT) for its excellent electrical properties. In our work, the InGaZnO thin films are fabricated on the SiO2 glass using pulsed laser deposition (PLD) in the oxygen partial pressure altered from 1 to 10 Pa at RT. The targets were prepared by mixing Ga2O3, In2O3, and ZnO powder at a mol ratio of 1: 7: 2 before the solid-state reactions in a tube furnace at the atmospheric pressure. The targets were irradiated by an Nd:YAG laser(355nm). Finally, we have three films of 270nm, 230nm, 190nm thick for 1Pa, 5Pa, 10Pa oxygen partial pressure. The product thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), Hall-effect investigation. The comparative study demonstrated the character changes of the structure and electronic transport properties, which is probably occurred as a fact of the different oxygen partial pressure used in the PLD.

O 1s core levels in Bi2Sr2CaCu2O8+δ single crystals

NASA Astrophysics Data System (ADS)

Parmigiani, F.; Shen, Z. X.; Mitzi, D. B.; Lindau, I.; Spicer, W. E.; Kapitulnik, A.

1991-02-01

High-quality Bi2Sr2CaCu2O8+δ superconducting single crystals, annealed at different oxygen partial pressures, have been studied using angular-resolved x-ray photoelectron spectroscopy with a resolution higher than that used in any previous study. Two states of the oxygen, separated by ~=0.7 eV, are unambiguously observed. Examining these components at different angles makes it possible to distinguish bulk from surface components. Using this capability we discover that annealing under lower oxygen partial pressure (1 atm) results in oxygen intercalation beneath the Bi-O surface layer of the crystal, whereas for higher-pressure anneals (12 atm) additional oxygen is found on the Bi-O surfaces. This steplike intercalation mechanism is also confirmed by the changes observed in the Cu and Bi core lines as a function of the annealing oxygen partial pressure.

Theoretical study of the partial molar volume change associated with the pressure-induced structural transition of ubiquitin

PubMed Central

Imai, Takashi; Ohyama, Shusaku; Kovalenko, Andriy; Hirata, Fumio

2007-01-01

The partial molar volume (PMV) change associated with the pressure-induced structural transition of ubiquitin is analyzed by the three-dimensional reference interaction site model (3D-RISM) theory of molecular solvation. The theory predicts that the PMV decreases upon the structural transition, which is consistent with the experimental observation. The volume decomposition analysis demonstrates that the PMV reduction is primarily caused by the decrease in the volume of structural voids in the protein, which is partially canceled by the volume expansion due to the hydration effects. It is found from further analysis that the PMV reduction is ascribed substantially to the penetration of water molecules into a specific part of the protein. Based on the thermodynamic relation, this result implies that the water penetration causes the pressure-induced structural transition. It supports the water penetration model of pressure denaturation of proteins proposed earlier. PMID:17660257

Theoretical study of the partial molar volume change associated with the pressure-induced structural transition of ubiquitin.

PubMed

Imai, Takashi; Ohyama, Shusaku; Kovalenko, Andriy; Hirata, Fumio

2007-09-01

The partial molar volume (PMV) change associated with the pressure-induced structural transition of ubiquitin is analyzed by the three-dimensional reference interaction site model (3D-RISM) theory of molecular solvation. The theory predicts that the PMV decreases upon the structural transition, which is consistent with the experimental observation. The volume decomposition analysis demonstrates that the PMV reduction is primarily caused by the decrease in the volume of structural voids in the protein, which is partially canceled by the volume expansion due to the hydration effects. It is found from further analysis that the PMV reduction is ascribed substantially to the penetration of water molecules into a specific part of the protein. Based on the thermodynamic relation, this result implies that the water penetration causes the pressure-induced structural transition. It supports the water penetration model of pressure denaturation of proteins proposed earlier.

Aerobic oxidations catalyzed by chromium corroles.

PubMed

Mahammed, Atif; Gray, Harry B; Meier-Callahan, Alexandre E; Gross, Zeev

2003-02-05

Oxochromium(V) complexes of 5,10,15-tris(pentafluorophenyl)corrole and brominated derivatives oxygenate substrates (triphenylphosphine and norbornene) with concomitant production of chromium(III). Regeneration of CrVO by reaction of dioxygen with CrIII completes an aerobic catalytic cycle, with very large solvent effects; in acetonitrile, rapid initial turnovers observed initially are shut down by formation of CrIVO, while in toluene, THF, and methanol, relatively slow reactions are further inhibited by product formation.

Spatial Distribution of Oxygen Chemical Potential under Potential Gradients and Theoretical Maximum Power Density with 8YSZ Electrolyte

NASA Astrophysics Data System (ADS)

Lim, Dae-Kwang; Im, Ha-Ni; Song, Sun-Ju

2016-01-01

The maximum power density of SOFC with 8YSZ electrolyte as the function of thickness was calculated by integrating partial conductivities of charge carriers under various DC bias conditions at a fixed oxygen chemical potential gradient at both sides of the electrolyte. The partial conductivities were successfully taken using the Hebb-Wagner polarization method as a function of temperature and oxygen partial pressure, and the spatial distribution of oxygen partial pressure across the electrolyte was calculated based on Choudhury and Patterson’s model by considering zero electrode polarization. At positive voltage conditions corresponding to SOFC and SOEC, the high conductivity region was expanded, but at negative cell voltage condition, the low conductivity region near n-type to p-type transition was expanded. In addition, the maximum power density calculated from the current-voltage characteristic showed approximately 5.76 W/cm2 at 700 oC with 10 μm thick-8YSZ, while the oxygen partial pressure of the cathode and anode sides maintained ≈0.21 and 10-22 atm.

The Role of the Pressure in the Partial Regularity Theory for Weak Solutions of the Navier-Stokes Equations

NASA Astrophysics Data System (ADS)

Chamorro, Diego; Lemarié-Rieusset, Pierre-Gilles; Mayoufi, Kawther

2018-04-01

We study the role of the pressure in the partial regularity theory for weak solutions of the Navier-Stokes equations. By introducing the notion of dissipative solutions, due to D uchon and R obert (Nonlinearity 13:249-255, 2000), we will provide a generalization of the Caffarelli, Kohn and Nirenberg theory. Our approach sheels new light on the role of the pressure in this theory in connection to Serrin's local regularity criterion.

Solubility of carbon monoxide in n-hexane between 293 and 473 K and CO pressures up to 200 bar

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

Koelliker, R.; Thies, H.

The solubility of carbon monoxide, CO, in n-hexane was measured at 293, 323, 373, 423, and 473 K for CO partial pressures up to 200 bar. The enthalpy of solution was calculated between 293 and 473 K. Using the Krichevsky-Ilinskaya equation of state, the solubility of CO in n-hexane can be calculated between 293 and 423 K for CO partial pressures up to 200 bar with an accuracy better than 5%.

Variable range hopping in ZnO films

NASA Astrophysics Data System (ADS)

Ali, Nasir; Ghosh, Subhasis

2018-04-01

We report the variable range hopping in ZnO films grown by RF magnetron sputtering in different argon and oxygen partial pressure. It has been found that Mott variable range hopping dominant over Efros variable range hopping in all ZnO films. It also has been found that hopping distance and energy increases with increasing oxygen partial pressure.

[Device to assess in-socket pressure distribution for partial foot amputation].

PubMed

Alvarez-Camacho, Michelín; Urrusti, José Luis; Acero, María Del Carmen; Galván Duque-Gastélum, Carlos; Rodríguez-Reyes, Gerardo; Mendoza-Cruz, Felipe

2014-07-01

A device for dynamic acquisition and distribution analysis of in-socket pressure for patients with partial foot amputation is presented in this work. By using the developed system, we measured and generated pressure distribution graphs, obtained maximal pressure, and calculated pressure-time integral (PTI) of three subjects with partial foot amputation and of a group of Healthy subjects (Hs) (n = 10). Average maximal pressure in the healthy group was 19.4 ± 4.11 PSI, while for the three amputated patients, this was 27.8 ± 1.38, 17.6 ± 1.15, 29.10 ± 3.9 PSI, respectively. Maximal pressure-time integral for healthy subjects was 11.56 ± 2.83 PSI*s, and for study subjects was 19.54 ± 1.9, 12.35 ± 1.48, and 13.17 ± 1.31 PSI*s, respectively. The results of the control group agree with those previously reported in the literature. The pressure distribution pattern showed clear differences between study subjects and those of the control group; these graphs allowed us to identify the pressure in regions-of-interest that could be critical, such as surgical scars. The system presented in this work will aid to assess the effectiveness with which prosthetic systems distribute load, given that the formation of ulcers is highly linked to the pressure exercised at the point of contact; in addition, these results will help to investigate the comfort perception of the prosthesis, a factor directly influenced by the stump's pressure distribution.

Aerodynamic forces and flows of the full and partial clap-fling motions in insects

PubMed Central

Sun, Mao

2017-01-01

Most of the previous studies on Weis-Fogh clap-fling mechanism have focused on the vortex structures and velocity fields. Detailed pressure distribution results are provided for the first time in this study to reveal the differences between the full and the partial clap-fling motions. The two motions are studied by numerically solving the Navier–Stokes equations in moving overset grids. The Reynolds number is set to 20, relevant to the tiny flying insects. The following has been shown: (1) During the clap phase, the wings clap together and create a high pressure region in the closing gap between wings, greatly increasing the positive pressure on the lower surface of wing, while pressure on the upper surface is almost unchanged by the interaction; during the fling phase, the wings fling apart and create a low pressure region in the opening gap between wings, greatly increasing the suction pressure on the upper surface of wing, while pressure on the lower surface is almost unchanged by the interaction; (2) The interference effect between wings is most severe at the end of clap phase and the start of the fling phase: two sharp force peaks (8–9 times larger than that of the one-winged case) are generated. But the total force peaks are manifested mostly as drag and barely as lift of the wing, owing to the vertical orientation of the wing section; (3) The wing–wing interaction effect in the partial clap-fling case is much weaker than that in the full clap-fling case, avoiding the generation of huge drag. Compared with a single wing flapping with the same motion, mean lift in the partial case is enhanced by 12% without suffering any efficiency degradation, indicating that partial clap-fling is a more practical choice for tiny insects to employ. PMID:28289562

Thermodynamic models for bounding pressurant mass requirements of cryogenic tanks

NASA Technical Reports Server (NTRS)

Vandresar, Neil T.; Haberbusch, Mark S.

1994-01-01

Thermodynamic models have been formulated to predict lower and upper bounds for the mass of pressurant gas required to pressurize a cryogenic tank and then expel liquid from the tank. Limiting conditions are based on either thermal equilibrium or zero energy exchange between the pressurant gas and initial tank contents. The models are independent of gravity level and allow specification of autogenous or non-condensible pressurants. Partial liquid fill levels may be specified for initial and final conditions. Model predictions are shown to successfully bound results from limited normal-gravity tests with condensable and non-condensable pressurant gases. Representative maximum collapse factor maps are presented for liquid hydrogen to show the effects of initial and final fill level on the range of pressurant gas requirements. Maximum collapse factors occur for partial expulsions with large final liquid fill fractions.

Laser-Induced Dynamics of Peroxodicopper(II) Complexes Vary with the Ligand Architecture. One-Photon Two-Electron O2 Ejection and Formation of Mixed-Valent Cu(I)Cu(II)-Superoxide Intermediates.

PubMed

Saracini, Claudio; Ohkubo, Kei; Suenobu, Tomoyoshi; Meyer, Gerald J; Karlin, Kenneth D; Fukuzumi, Shunichi

2015-12-23

Photoexcitation of end-on trans-μ-1,2-peroxodicopper(II) complex [(tmpa)2Cu(II)2(O2)](2+) (1) (λmax = 525 and 600 nm) and side-on μ-η(2):η(2)-peroxodicopper(II) complexes [(N5)Cu(II)2(O2)](2+) (2) and [(N3)Cu(II)2(O2)](2+) (3) at -80 °C in acetone led to one-photon two-electron peroxide-to-dioxygen oxidation chemistry (O2(2-) + hν → O2 + 2e(-)). Interestingly, light excitation of 2 and 3 (having side-on μ-η(2):η(2)-peroxo ligation) led to release of dioxygen, while photoexcitation of 1 (having an end-on trans-1,2-peroxo geometry) did not, even though spectroscopic studies revealed that both reactions proceeded through previously unknown mixed-valent superoxide species: [Cu(II)(O2(•-))Cu(I)](2+) (λmax = 685-740 nm). For 1, this intermediate underwent further fast intramolecular electron transfer to yield an "O2-caged" dicopper(I) adduct, Cu(I)2-O2, and a barrierless stepwise back electron transfer to regenerate 1 occurred. Femtosecond laser excitation of 2 and 3 under the same conditions still led to [Cu(II)(O2(•-))Cu(I)](2+) intermediates that, instead, underwent O2 release with a quantum yield of 0.14 ± 0.1 for 3. Such remarkable differences in reaction pathways likely result from the well-known ligand-derived stability of 2 and 3 vs 1 indicated by ligand-Cu(II/I) redox potentials; (N5)Cu(I) and (N3)Cu(I) complexes are far more stable than (tmpa)Cu(I) species. The fast Cu(I)2/O2 rebinding kinetics was also measured after photoexcitation of 2 and 3, with the results closely tracking those known for the dicopper proteins hemocyanin and tyrosinase, for which the synthetic dicopper(I) precursors [(N5)Cu(I)2](2+) and [(N3)Cu(I)2](2+) and their dioxygen adducts serve as models. The biological relevance of the present findings is discussed, including the potential impact on the solar water splitting process.

Separating the roles of nitrogen and oxygen in high pressure-induced blood-borne microparticle elevations, neutrophil activation, and vascular injury in mice.

PubMed

Yang, Ming; Bhopale, Veena M; Thom, Stephen R

2015-08-01

An elevation in levels of circulating microparticles (MPs) due to high air pressure exposure and the associated inflammatory changes and vascular injury that occur with it may be due to oxidative stress. We hypothesized that these responses arise due to elevated partial pressures of N2 and not because of high-pressure O2. A comparison was made among high-pressure air, normoxic high-pressure N2, and high-pressure O2 in causing an elevation in circulating annexin V-positive MPs, neutrophil activation, and vascular injury by assessing the leakage of high-molecular-weight dextran in a murine model. After mice were exposed for 2 h to 790 kPa air, there were over 3-fold elevations in total circulating MPs as well as subgroups bearing Ly6G, CD41, Ter119, CD31, and CD142 surface proteins-evidence of neutrophil activation; platelet-neutrophil interaction; and vascular injury to brain, omentum, psoas, and skeletal muscles. Similar changes were found in mice exposed to high-pressure N2 using a gas mixture so that O2 partial pressure was the same as that of ambient air, whereas none of these changes occurred after exposures to 166 kPa O2, the same partial pressure that occurs during high-pressure air exposures. We conclude that N2 plays a central role in intra- and perivascular changes associated with exposure to high air pressure and that these responses appear to be a novel form of oxidative stress. Copyright © 2015 the American Physiological Society.

Calibration Of Partial-Pressure-Of-Oxygen Sensors

NASA Technical Reports Server (NTRS)

Yount, David W.; Heronimus, Kevin

1995-01-01

Report and analysis of, and discussion of improvements in, procedure for calibrating partial-pressure-of-oxygen sensors to satisfy Spacelab calibration requirements released. Sensors exhibit fast drift, which results in short calibration period not suitable for Spacelab. By assessing complete process of determining total drift range available, calibration procedure modified to eliminate errors and still satisfy requirements without compromising integrity of system.

Real-Time Monitoring of Singlet Oxygen and Oxygen Partial Pressure During the Deep Photodynamic Therapy In Vitro.

PubMed

Li, Weitao; Huang, Dong; Zhang, Yan; Liu, Yangyang; Gu, Yueqing; Qian, Zhiyu

2016-09-01

Photodynamic therapy (PDT) is an effective noninvasive method for the tumor treatment. The major challenge in current PDT research is how to quantitatively evaluate therapy effects. To our best knowledge, this is the first time to combine multi-parameter detection methods in PDT. More specifically, we have developed a set of system, including the high-sensitivity measurement of singlet oxygen, oxygen partial pressure and fluorescence image. In this paper, the detection ability of the system was validated by the different concentrations of carbon quantum dots. Moreover, the correlation between singlet oxygen and oxygen partial pressure with laser irradiation was observed. Then, the system could detect the signal up to 0.5 cm tissue depth with 660 nm irradiation and 1 cm tissue depth with 980 nm irradiation by using up-conversion nanoparticles during PDT in vitro. Furthermore, we obtained the relationship among concentration of singlet oxygen, oxygen partial pressure and tumor cell viability under certain conditions. The results indicate that the multi-parameter detection system is a promising asset to evaluate the deep tumor therapy during PDT. Moreover, the system might be potentially used for the further study in biology and molecular imaging.

Positron beam study of indium tin oxide films on GaN

NASA Astrophysics Data System (ADS)

Cheung, C. K.; Wang, R. X.; Beling, C. D.; Djurisic, A. B.; Fung, S.

2007-02-01

Variable energy Doppler broadening spectroscopy has been used to study open-volume defects formed during the fabrication of indium tin oxide (ITO) thin films grown by electron-beam evaporation on n-GaN. The films were prepared at room temperature, 200 and 300 °C without oxygen and at 200 °C under different oxygen partial pressures. The results show that at elevated growth temperatures the ITO has fewer open volume sites and grows with a more crystalline structure. High temperature growth, however, is not sufficient in itself to remove open volume defects at the ITO/GaN interface. Growth under elevated temperature and under partial pressure of oxygen is found to further reduce the vacancy type defects associated with the ITO film, thus improving the quality of the film. Oxygen partial pressures of 6 × 10-3 mbar and above are found to remove open volume defects associated with the ITO/GaN interface. The study suggests that, irrespective of growth temperature and oxygen partial pressure, there is only one type of defect in the ITO responsible for trapping positrons, which we tentatively attribute to the oxygen vacancy.

Measurement of Local Partial Pressure of Oxygen in the Brain Tissue under Normoxia and Epilepsy with Phosphorescence Lifetime Microscopy.

PubMed

Zhang, Cong; Bélanger, Samuel; Pouliot, Philippe; Lesage, Frédéric

2015-01-01

In this work a method for measuring brain oxygen partial pressure with confocal phosphorescence lifetime microscopy system is reported. When used in conjunction with a dendritic phosphorescent probe, Oxyphor G4, this system enabled minimally invasive measurements of oxygen partial pressure (pO2) in cerebral tissue with high spatial and temporal resolution during 4-AP induced epileptic seizures. Investigating epileptic events, we characterized the spatio-temporal distribution of the "initial dip" in pO2 near the probe injection site and along nearby arterioles. Our results reveal a correlation between the percent change in the pO2 signal during the "initial dip" and the duration of seizure-like activity, which can help localize the epileptic focus and predict the length of seizure.

Oxidation of C/SiC Composites at Reduced Oxygen Partial Pressures

NASA Technical Reports Server (NTRS)

Opila, Elizabeth J.; Serra, Jessica

2009-01-01

Carbon-fiber reinforced SiC (C/SiC) composites are proposed for leading edge applications of hypersonic vehicles due to the superior strength of carbon fibers at high temperatures (greater than 1500 C). However, the vulnerability of the carbon fibers in C/SiC to oxidation over a wide range of temperatures remains a problem. Previous oxidation studies of C/SiC have mainly been conducted in air or oxygen, so that the oxidation behavior of C/SiC at reduced oxygen partial pressures of the hypersonic flight regime are less well understood. In this study, both carbon fibers and C/SiC composites were oxidized over a wide range of temperatures and oxygen partial pressures to facilitate the understanding and modeling of C/SiC oxidation kinetics for hypersonic flight conditions.

Pressure induced swelling in microporous materials

DOEpatents

Vogt, Thomas; Hriljac, Joseph A.; Lee, Yongjae

2006-07-11

A method for capturing specified materials which includes contacting a microporous material with a hydrostatic fluid having at least one specified material carried therein, under pressure which structurally distorts the lattice sufficiently to permit entry of the at least one specified material. The microporous material is capable of undergoing a temporary structural distortion which alters resting lattice dimensions under increased ambient pressure and at least partially returning to rest lattice dimensions when returned to ambient pressure. The pressure of the fluid is then reduced to permit return to at least partial resting lattice dimension while the at least one specified material is therein. By this method, at least one specified material is captured in the microporous material to form a modified microporous material.

What does the Sr-substituted 2.1 Å resolution crystal structure of photosystem II reveal about the water oxidation mechanism?

PubMed

Terrett, Richard; Petrie, Simon; Pace, Ron J; Stranger, Robert

2014-03-25

A density functional study of the Sr-substituted photosystem II water oxidising complex demonstrates that its recent X-ray crystal structure is consistent with a (Mn(III))4 oxidation state pattern, and with a Sr-bound hydroxide ion. The Sr-water-hydroxide interactions rationalize differences in the exchange rates of substrate water and kinetics of dioxygen bond formation relative to the Ca-containing structure.

The methionine salvage pathway in Bacillus subtilis

PubMed Central

Sekowska, Agnieszka; Danchin, Antoine

2002-01-01

Background Polyamine synthesis produces methylthioadenosine, which has to be disposed of. The cell recycles it into methionine through methylthioribose (MTR). Very little was known about MTR recycling for methionine salvage in Bacillus subtilis. Results Using in silico genome analysis and transposon mutagenesis in B. subtilis we have experimentally uncovered the major steps of the dioxygen-dependent methionine salvage pathway, which, although similar to that found in Klebsiella pneumoniae, recruited for its implementation some entirely different proteins. The promoters of the genes have been identified by primer extension, and gene expression was analyzed by Northern blotting and lacZ reporter gene expression. Among the most remarkable discoveries in this pathway is the role of an analog of ribulose diphosphate carboxylase (Rubisco, the plant enzyme used in the Calvin cycle which recovers carbon dioxide from the atmosphere) as a major step in MTR recycling. Conclusions A complete methionine salvage pathway exists in B. subtilis. This pathway is chemically similar to that in K. pneumoniae, but recruited different proteins to this purpose. In particular, a paralogue or Rubisco, MtnW, is used at one of the steps in the pathway. A major observation is that in the absence of MtnW, MTR becomes extremely toxic to the cell, opening an unexpected target for new antimicrobial drugs. In addition to methionine salvage, this pathway protects B. subtilis against dioxygen produced by its natural biotope, the surface of leaves (phylloplane). PMID:12022921

Spectroscopic properties and conformational stability of Concholepas concholepas hemocyanin.

PubMed

Idakieva, Krassimira; Nikolov, Peter; Chakarska, Irena; Genov, Nicolay; Shnyrov, Valery L

2008-01-01

The structure in solution and conformational stability of the hemocyanin from the Chilean gastropod mollusk Concholepas concholepas (CCH) and its structural subunits, CCH-A and CCH-B, were studied using fluorescence spectroscopy and differential scanning calorimetry (DSC). The fluorescence properties of the oxygenated and apo-form (copper-deprived) of the didecamer and its subunits were characterized. Besides tryptophan residues buried in the hydrophobic interior of the protein molecule also exposed fluorophores determine the fluorescence emission of the oxy- and apo-forms of the investigated hemocyanins. The copper-dioxygen system at the binuclear active site quenches the tryptophan emission of the oxy-forms of CCH and its subunits. The removal of this system increases the fluorescence quantum yield and causes structural rearrangement of the microenvironment of the emitting tryptophan residues in the respective apo-forms. Time-resolved fluorescence measurements show that the oxygenated and copper-deprived forms of the CCH and its subunits exist in different conformations. The thermal denaturation of the hemocyanin is an irreversible process, under kinetic control. A successive annealing procedure was applied to obtain the experimental deconvolution of the irreversible thermal transitions. Arrhenius equation parameter for the two-state irreversible model of the thermal denaturation of oxy-CCH at pH 7.2 was estimated. Both factors, oligomerization and the copper-dioxygen system at the active site, are important for stabilizing the structure of the hemocyanin molecule.

NO Dioxygenase Activity in Hemoglobins Is Ubiquitous In Vitro, but Limited by Reduction In Vivo

PubMed Central

Smagghe, Benoit J.; Trent, James T.; Hargrove, Mark S.

2008-01-01

Genomics has produced hundreds of new hemoglobin sequences with examples in nearly every living organism. Structural and biochemical characterizations of many recombinant proteins reveal reactions, like oxygen binding and NO dioxygenation, that appear general to the hemoglobin superfamily regardless of whether they are related to physiological function. Despite considerable attention to “hexacoordinate” hemoglobins, which are found in nearly every plant and animal, no clear physiological role(s) has been assigned to them in any species. One popular and relevant hypothesis for their function is protection against NO. Here we have tested a comprehensive representation of hexacoordinate hemoglobins from plants (rice hemoglobin), animals (neuroglobin and cytoglobin), and bacteria (Synechocystis hemoglobin) for their abilities to scavenge NO compared to myoglobin. Our experiments include in vitro comparisons of NO dioxygenation, ferric NO binding, NO-induced reduction, NO scavenging with an artificial reduction system, and the ability to substitute for a known NO scavenger (flavohemoglobin) in E. coli. We conclude that none of these tests reveal any distinguishing predisposition toward a role in NO scavenging for the hxHbs, but that any hemoglobin could likely serve this role in the presence of a mechanism for heme iron re-reduction. Hence, future research to test the role of Hbs in NO scavenging would benefit more from the identification of cognate reductases than from in vitro analysis of NO and O2 binding. PMID:18446211

The Rate of Oxygen Utilization by Cells

PubMed Central

Wagner, Brett A.; Venkataraman, Sujatha; Buettner, Garry R.

2011-01-01

The discovery of oxygen is considered by some to be the most important scientific discovery of all time – from both physical-chemical/astrophysics and biology/evolution viewpoints. One of the major developments during evolution is the ability to capture dioxygen in the environment and deliver it to each cell in the multicellular, complex mammalian body -- on demand, i.e. just-in-time. Humans use oxygen to extract approximately 2550 Calories (10.4 MJ) from food to meet daily energy requirements. This combustion requires about 22 moles of dioxygen per day, or 2.5 × 10-4 mol s-1. This is an average rate of oxygen utilization of 2.5 × 10-18 mol cell-1 s-1, i.e. 2.5 amol cell-1 s-1. Cells have a wide range of oxygen utilization, depending on cell type, function, and biological status. Measured rates of oxygen utilization by mammalian cells in culture range from <1 to >350 amol cell-1 s-1. There is a loose positive linear correlation of the rate of oxygen consumption (OCR) by mammalian cells in culture with cell volume and cell protein. The use of oxygen by cells and tissues is an essential aspect of the basic redox biology of cells and tissues. This type of quantitative information is fundamental to investigations in quantitative redox biology, especially redox systems biology. PMID:21664270

Compositional dependent partial molar volume and compressibility of CO2 in rhyolite, phonolite and basalt glasses

NASA Astrophysics Data System (ADS)

Lerch, P.; Seifert, R.; Malfait, W. J.; Sanchez-Valle, C.

2012-12-01

Carbon dioxide is the second most abundant volatile in magmatic systems and plays an important role in many magmatic processes, e.g. partial melting, volatile saturation, outgassing. Despite this relevance, the volumetric properties of carbon-bearing silicates at relevant pressure and temperature conditions remain largely unknown because of considerable experimental difficulties associated with in situ measurements. Density and elasticity measurements on quenched glasses can provide an alternative source of information. For dissolved water, such measurements indicate that the partial molar volume is independent of compositions at ambient pressure [1], but the partial molar compressibility is not [2, 3]. Thus the partial molar volume of water may depend on melt composition at elevated pressure. For dissolved CO2, no such data is available. In order to constrain the effect of magma composition on the partial molar volume and compressibility of dissolved carbon, we determined the density and elasticity for three series of carbon-bearing basalt, phonolite and rhyolite glasses, quenched from 3.5 GPa and relaxed at ambient pressure. The CO2 content varies between 0 to 3.90 wt% depending on the glass composition. Glass densities were determined using the sink/float method in a diiodomethane (CH2I2) - acetone mixture. Brillouin measurements were conducted on relaxed and unrelaxed silicate glasses in platelet geometry to determine the compressional (VP) and shear (VS) wave velocities and elastic moduli. The partial molar volume of CO2 in rhyolite, phonolite and basalt glasses is 25.4 ± 0.9, 22.1 ± 0.6 and 26.6 ±1.8 cm3/mol, respectively. Thus, unlike for dissolved water, the partial molar volume of CO2 displays a resolvable compositional effect. Although the composition and CO2/carbonate speciation of the phonolite glasses is intermediate between that of the rhyolite and basalt glasses, the molar volume is not. Similar to dissolved water, the partial molar bulk modulus of CO2 displays a strong compositional effect. If these compositional dependencies persist in the analogue melts, the partial molar volume of dissolved CO2 will depend on melt composition, both at low and elevated pressure. Thus, for CO2-bearing melts, a full quantitative understanding of density dependent magmatic processes, such as crystal fractionation, magma mixing and melt extraction will require in situ measurements for a range of melt compositions. [1] Richet, P. et al., 2000, Contrib Mineral Petrol, 138, 337-347. [2] Malfait et al. 2011, Am. Mineral. 96, 1402-1409. [3] Whittington et al., 2012, Am. Mineral. 97, 455-467.

Clinical recommendations for high altitude exposure of individuals with pre-existing cardiovascular conditions

PubMed Central

Parati, Gianfranco; Agostoni, Piergiuseppe; Basnyat, Buddha; Bilo, Grzegorz; Brugger, Hermann; Coca, Antonio; Festi, Luigi; Giardini, Guido; Lironcurti, Alessandra; Luks, Andrew M; Maggiorini, Marco; Modesti, Pietro A; Swenson, Erik R; Williams, Bryan; Bärtsch, Peter; Torlasco, Camilla

2018-01-01

Abstract Take home figureAdapted from Bärtsch and Gibbs2 Physiological response to hypoxia. Life-sustaining oxygen delivery, in spite of a reduction in the partial pressure of inhaled oxygen between 25% and 60% (respectively at 2500 m and 8000 m), is ensured by an increase in pulmonary ventilation, an increase in cardiac output by increasing heart rate, changes in vascular tone, as well as an increase in haemoglobin concentration. BP, blood pressure; HR, heart rate; PaCO2, partial pressure of arterial carbon dioxide. PMID:29340578

Petrologic Constraints on Magma Plumbing Systems Beneath Hawaiian Volcanoes

NASA Astrophysics Data System (ADS)

Li, Y.; Peterman, K. J.; Scott, J. L.; Barton, M.

2016-12-01

We have calculated the pressures of partial crystalliztion of basaltic magmas from Hawaii using a petrological method. A total of 1576 major oxide analyses of glasses from four volcanoes (Kilauea and the Puna Ridge, Loihi, Mauna Loa, and Mauna Kea, on the Big Island) were compiled and used as input data. Glasses represent quenched liquid compositions and are ideal for calculation of pressures of partial crystallization. The results were filtered to exclude samples that yielded unrealistic high errors associated with the calculated pressure or negative value of pressure, and to exclude samples with non-basaltic compositions. Calculated pressures were converted to depths of partial crystallization. The majority (68.2%) of pressures for the shield-stage subaerial volcanoes Kilauea, Mauna Loa, and Mauna Kea, fall in the range 0-140 MPa, corresponding to depths of 0-5 km. Glasses from the Puna Ridge yield pressures ranging from 18 to 126 MPa and are virtually identical to pressures determined from glasses from Kilauea (0 to 129 MPa). These results are consistent with the presence of magma reservoirs at depths of 0-5 km beneath the large shield volcanoes. The inferred depth of the magma reservoir beneath the summit of Kilauea (average = 1.8 km, maximum = 5 km) agrees extremely well with depths ( 2-6 km) estimated from seismic studies. The results for Kilauea and Mauna Kea indicate that significant partial crystallization also occurs beneath the summit reservoirs at depths up to 11 km. These results are consistent with seismic evidence for the presence of a magma reservoir at 8-11 km beneath Kilauea at the base of the volcanic pile. The results for Loihi indicate crystallization at higher average pressures (100-400 MPa) and depths (3-14 km) than the large shield volcanoes, suggesting that the plumbing system is not yet fully developed, and that the Hawaiian volcanic plumbing systems evolve over time.

LIF measurements and chemical kinetic analysis of methylidyne formation in high-pressure counter-flow partially premixed and non-premixed flames

NASA Astrophysics Data System (ADS)

Naik, S. V.; Laurendeau, N. M.

2004-11-01

We report quantitative, spatially resolved, linear laser-induced fluorescence (LIF) measurements of methylidyne concentration ([CH]) in laminar, methane air, counter-flow partially premixed and non-premixed flames using excitation near 431.5 nm in the A X (0,0) band. For partially premixed flames, fuel-side equivalence ratios (ϕB) of 1.45, 1.6 and 2.0 are studied at pressures of 1, 3, 6, 9 and 12 atm. For non-premixed flames, the fuel-side mixture consists of 25% CH4 and 75% N2; measurements are obtained at pressures of 1, 2, 3, 4, 5, 6, 9 and 12 atm. The quantitative CH measurements are compared with predictions from an opposed-flow flame code utilizing two GRI chemical kinetic mechanisms (versions 2.11 and 3.0). LIF measurements of [CH] are corrected for variations in the quenching rate coefficient by using major species concentrations and temperatures generated by the code along with suitable quenching cross sections for CH available from the literature. A pathway analysis provides relative contributions from important elementary reactions to the total amount of CH produced at various pressures. Key reactions controlling peak CH concentrations are also identified by using a sensitivity analysis. For the partially premixed flames, measured CH profiles are reproduced reasonably well by GRI 3.0, although some quantitative disagreement exists at all pressures. Two CH radical peaks are observed for ϕB=1.45 and ϕB=1.6 at pressures above 3 atm. Peak CH concentrations for the non-premixed flames are significantly underpredicted by GRI 3.0. The latter agrees with previously reported NO concentrations, which are also underpredicted in these same high-pressure counter-flow diffusion flames.

Introduction to total- and partial-pressure measurements in vacuum systems

NASA Technical Reports Server (NTRS)

Outlaw, R. A.; Kern, F. A.

1989-01-01

An introduction to the fundamentals of total and partial pressure measurement in the vacuum regime (760 x 10 to the -16th power Torr) is presented. The instrument most often used in scientific fields requiring vacuum measurement are discussed with special emphasis on ionization type gauges and quadrupole mass spectrometers. Some attention is also given to potential errors in measurement as well as calibration techniques.

A negative feedback mechanism for the long-term stabilization of the earth's surface temperature

NASA Technical Reports Server (NTRS)

Walker, J. C. G.; Hays, P. B.; Kasting, J. F.

1981-01-01

It is suggested that the partial pressure of carbon dioxide in the atmosphere is buffered, over geological time scales, by a negative feedback mechanism, in which the rate of weathering of silicate minerals (followed by deposition of carbonate minerals) depends on surface temperature, which in turn depends on the carbon dioxide partial pressure through the greenhouse effect. Although the quantitative details of this mechanism are speculative, it appears able to partially stabilize the earth's surface temperature against the steady increase of solar luminosity, believed to have occurred since the origin of the solar system.

Design development and test: Two-gas atmosphere control subsystem

NASA Technical Reports Server (NTRS)

Jackson, J. K.

1974-01-01

An atmosphere control subsystem (ACS) was developed for NASA-IBJSC which is designed to measure the major atmospheric constituents in the manned cabin of the space shuttle orbiter and control the addition of oxygen and nitrogen to maintain the partial pressures of these gases within very close limits. The ACS includes a mass spectrometer sensor (MSS) which analyzes the atmosphere of a shuttle vehicle pressurized cabin, and an electronic control assembly (ECA). The MSS was built and tested to meet the requirements for flight equipment for the M-171 Metabolic Analyzer experiment for the Skylab flight program. The instrument analyzes an atmospheric gas sample and produces continuous 0-5 vdc analog signals proportional to the partial pressures of H2, O2, N2, H2O, CO2 and total hydrocarbons having a m/e ratio between 50 and 120. It accepts signals from the MSS proportional to the partial pressures of N2 and O2 and controls the supply of these gases to the closed cabin.

Preflight studies on tolerance of pocket mice to oxygen and heat. IV - Observations on the brain

NASA Technical Reports Server (NTRS)

Bailey, O. T.; Ordy, J. M.; Haymaker, W.

1975-01-01

Experiments designed to ascertain the effects of oxygen at 8, 10, and 12 psi partial pressure on the brains of pocket mice (Perognathus longimembris) were carried out at room temperature (24 C, 75 F) and at 32 C (90 F). The animals exposed to 8-12 psi at 32 C had been in earlier KO2 oxygen tests. Five animals exposed either to 10 or 12 psi (517 mm or 620 mm Hg) O2 partial pressure at 32 C died during the course of the tests, possibly as a consequence of injury sustained by the earlier O2 partial pressure testing. Autopsy was not carried out. In the other 36 exposed animals, no pathological changes were observed in the brain. It is thus highly probable that oxygen pressures at the hyperbaric levels to which the pocket mice would be exposed during the Apollo XVII mission would not result in any lesions in the brain.

An ion interaction model for the volumetric properties of natural waters: Density of the solution and partial molal volumes of electrolytes to high concentrations at 25°C

NASA Astrophysics Data System (ADS)

Monnin, Christophe

1989-06-01

Literature density data for binary and common ion ternary solutions in the Na-K-Ca-Mg-Cl-SO 4-HCO 3-CO3-H 2O system at 25°C have been analysed with Pitzer's ion interaction model, which provides an adequate representation of the experimental data for binary and common ion ternary solutions up to high concentration. This analysis yields Pitzer's interaction parameters for the apparent and partial molal volumes, which are the first derivatives with respect to pressure of the interaction parameters for the free energy. From this information, densities of natural waters as well as partial molal volumes of their solutes can be predicted with good accuracy, as shown by several comparisons of calculated and measured values. It is shown that V¯MX - V¯0mx, the excess partial molal volume of the salt MX, depends more on the type of salt than on the electrolyte itself and that it increases with the charges of the salt components. The influence of concentration and composition on the variation of activity coefficients with pressure and on the partial molal volumes of the salts is discussed, using as an example the partial molal volume of CaSO 4(aq) in solutions of various compositions. The increase of V¯CaSO 4, with ionic strength is very large but is not very different for a NaCl-dominated natural water like the Red Sea lower brine than for a simple NaCl solution. Although the variation of activity coefficients with pressure is usually ignored for moderate pressures, like those found in hydrothermal environments, the present example shows that it can be as large as 30% for a 2-2 salt for a pressure increase from 1 to 500 bars at high ionic strength.

Study of Chromium Oxide Activities in EAF Slags

NASA Astrophysics Data System (ADS)

Yan, Baijun; Li, Fan; Wang, Hui; Sichen, Du

2016-02-01

The activity coefficients of chromium in Cu-Cr melts were determined by equilibrating liquid copper with solid Cr2O3 in CO-CO2 atmosphere. The temperature dependence of the activity coefficients of chromium in Cu-Cr melts could be expressed as lg γ_{Cr}(s)^{0} = { 3 2 5 9( ± 1 8 6} )/T - 0. 5 9( { ± 0. 1} ). Based on the above results, the activities of bivalent and trivalent chromium oxide in some slags at 1873 K (1600 °C) were measured. The slags were equilibrated with Cu-Cr melts under two oxygen partial pressures ( {p_{O}_{ 2} }} } = 6.9 × 10-4 and 1.8 × 10-6 Pa, respectively). The morphology of the quenched slags and the solubility of chromium oxide in the melts were investigated by EPMA, SEM, and XRD. Under both oxygen partial pressures, the slags were saturated by the solid solution MgAl2- x Cr x O4- δ . At the low oxygen partial pressure (1.8 × 10-6 Pa), the content of Cr in the liquid phase varied from 0.4 to 1.6 mass pct with the total Cr content in the slags increasing from 1.3 to 10.8 mass pct. At the high oxygen partial pressure (6.9 × 10-4 Pa), the content of Cr in the liquid phase decreased to the level of 0.2 to 0.6 mass pct. Both the activities of CrO and Cr2O3 in slag were found to increase approximately linearly with the increase of the total Cr content in slag. While the oxygen partial pressure had minor effect on the activity of Cr2O3 in the slag, it had significant effect on the activity of CrO.

Oxygen supply in aquatic ectotherms: partial pressure and solubility together explain biodiversity and size patterns.

PubMed

Verberk, Wilco C E P; Bilton, David T; Calosi, Piero; Spicer, John I

2011-08-01

Aquatic ectotherms face the continuous challenge of capturing sufficient oxygen from their environment as the diffusion rate of oxygen in water is 3 x 10(5) times lower than in air. Despite the recognized importance of oxygen in shaping aquatic communities, consensus on what drives environmental oxygen availability is lacking. Physiologists emphasize oxygen partial pressure, while ecologists emphasize oxygen solubility, traditionally expressing oxygen in terms of concentrations. To resolve the question of whether partial pressure or solubility limits oxygen supply in nature, we return to first principles and derive an index of oxygen supply from Fick's classic first law of diffusion. This oxygen supply index (OSI) incorporates both partial pressure and solubility. Our OSI successfully explains published patterns in body size and species across environmental clines linked to differences in oxygen partial pressure (altitude, organic pollution) or oxygen solubility (temperature and salinity). Moreover, the OSI was more accurately and consistently related to these ecological patterns than other measures of oxygen (oxygen saturation, dissolved oxygen concentration, biochemical oxygen demand concentrations) and similarly outperformed temperature and altitude, which covaried with these environmental clines. Intriguingly, by incorporating gas diffusion rates, it becomes clear that actually more oxygen is available to an organism in warmer habitats where lower oxygen concentrations would suggest the reverse. Under our model, the observed reductions in aerobic performance in warmer habitats do not arise from lower oxygen concentrations, but instead through organismal oxygen demand exceeding supply. This reappraisal of how organismal thermal physiology and oxygen demands together shape aerobic performance in aquatic ectotherms and the new insight of how these components change with temperature have broad implications for predicting the responses of aquatic communities to ongoing global climate shifts.

Facile O-atom insertion into CC and CH bonds by a trinuclear copper complex designed to harness a singlet oxene

PubMed Central

Chen, Peter P.-Y.; Yang, Richard B.-G.; Lee, Jason C.-M.; Chan, Sunney I.

2007-01-01

Two trinuclear copper [CuICuICuI(L)]1+ complexes have been prepared with the multidentate ligands (L) 3,3′-(1,4-diazepane-1,4-diyl)bis(1-((2-(dimethylamino)ethyl)(methyl)amino)propan-2-ol) (7-Me) and (3,3′-(1,4-diazepane-1,4-diyl)bis(1-((2-(diethylamino) ethyl)(ethyl) amino)propan-2-ol) (7-Et) as models for the active site of the particulate methane monooxygenase (pMMO). The ligands were designed to form the proper spatial and electronic geometry to harness a “singlet oxene,” according to the mechanism previously suggested by our laboratory. Consistent with the design strategy, both [CuICuICuI(L)]1+ reacted with dioxygen to form a putative bis(μ3-oxo)CuIICuIICuIII species, capable of facile O-atom insertion across the central CC bond of benzil and 2,3-butanedione at ambient temperature and pressure. These complexes also catalyze facile O-atom transfer to the CH bond of CH3CN to form glycolonitrile. These results, together with our recent biochemical studies on pMMO, provide support for our hypothesis that the hydroxylation site of pMMO contains a trinuclear copper cluster that mediates CH bond activation by a singlet oxene mechanism. PMID:17804786

Measurements of Pressure Distributions and Force Coefficients in a Squeeze Film Damper. Part 2: Partially Sealed Configuration

NASA Technical Reports Server (NTRS)

Jung, S. Y.; Sanandres, Luis A.; Vance, J. M.

1991-01-01

Experimental results from a partially sealed squeeze film damper (SFD) test rig, executing a circular centered orbit are presented and discussed. A serrated piston ring is installed at the damper exit. This device involves a new sealing concept which produces high damping values while allowing for oil flow to cool the damper. In the partially sealed damper, large cavitation regions are observed in the pressure fields at orbit radii epsilon equals 0.5 and epsilon equals 0.8. The cavitated pressure distributions and the corresponding force coefficients are compared with a cavitated bearing solution. The experimental results show the significance of fluid inertia and vapor cavitation in the operation of squeeze film dampers. Squeeze film Reynolds numbers tested reach up to Re equals 50, spanning the range of contemporary applications.

Measurement of Local Partial Pressure of Oxygen in the Brain Tissue under Normoxia and Epilepsy with Phosphorescence Lifetime Microscopy

PubMed Central

Zhang, Cong; Bélanger, Samuel; Pouliot, Philippe; Lesage, Frédéric

2015-01-01

In this work a method for measuring brain oxygen partial pressure with confocal phosphorescence lifetime microscopy system is reported. When used in conjunction with a dendritic phosphorescent probe, Oxyphor G4, this system enabled minimally invasive measurements of oxygen partial pressure (pO2) in cerebral tissue with high spatial and temporal resolution during 4-AP induced epileptic seizures. Investigating epileptic events, we characterized the spatio-temporal distribution of the "initial dip" in pO2 near the probe injection site and along nearby arterioles. Our results reveal a correlation between the percent change in the pO2 signal during the "initial dip" and the duration of seizure-like activity, which can help localize the epileptic focus and predict the length of seizure. PMID:26305777

Gas concentration measurement instrument based on the effects of a wave-mixing interference on stimulated emissions

DOEpatents

Garrett, W. Ray

1997-01-01

A method and apparatus for measuring partial pressures of gaseous components within a mixture. The apparatus comprises generally at least one tunable laser source, a beam splitter, mirrors, optical filter, an optical spectrometer, and a data recorder. Measured in the forward direction along the path of the laser, the intensity of the emission spectra of the gaseous component, at wavelengths characteristic of the gas component being measured, are suppressed. Measured in the backward direction, the peak intensities characteristic of a given gaseous component will be wavelength shifted. These effects on peak intensity wavelengths are linearly dependent on the partial pressure of the compound being measured, but independent of the partial pressures of other gases which are present within the sample. The method and apparatus allow for efficient measurement of gaseous components.

Gas concentration measurement instrument based on the effects of a wave-mixing interference on stimulated emissions

DOEpatents

Garrett, W.R.

1997-11-11

A method and apparatus are disclosed for measuring partial pressures of gaseous components within a mixture. The apparatus comprises generally at least one tunable laser source, a beam splitter, mirrors, optical filter, an optical spectrometer, and a data recorder. Measured in the forward direction along the path of the laser, the intensity of the emission spectra of the gaseous component, at wavelengths characteristic of the gas component being measured, are suppressed. Measured in the backward direction, the peak intensities characteristic of a given gaseous component will be wavelength shifted. These effects on peak intensity wavelengths are linearly dependent on the partial pressure of the compound being measured, but independent of the partial pressures of other gases which are present within the sample. The method and apparatus allow for efficient measurement of gaseous components. 9 figs.

Isochoric Burn, an Internally Consistent Method for the Reactant to Product Transformation in Reactive Flow

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

Reaugh, J E; Lee, E L

2002-07-01

Mixture rules for partially reacted explosives differ amongst various models. For instance, JWL++ uses a partial pressure addition to compute an average zonal pressure, Ignition and Growth requires pressure equilibration and thermal equilibration of temperature dependent JWL EOSs, CHEETAH In Line RF also assumes temperature and pressure equilibration. It has been suggested in the past that a more realistic equilibration scheme should comprise isentropic pressure equilibration of the separate reacted and unreacted phases. This turns out not to be a proper path for equilibration. Rather, we find that the only internally consistent method is the evaluation of the equilibrium pressuremore » that satisfies the particular conditions of reactant and product resulting from deflagration in a fixed volume.« less

Feasibility of Lettuce Growth at Hypoxic and Sub-Ambient Total Gas Pressures

NASA Technical Reports Server (NTRS)

Hoffman, Anne

1997-01-01

Lettuce (Lactuca saliva L. cv. 'Waldmann's Green') plants were grown (1) either from seed to 5 days old to study the effect of low atmospheric pressure (70 kPa) on their germination and early growth, or (2) until maturity at 30 days old to determine any long-term growth effects. The data were compared to plants grown in a second matching chamber which was maintained at ambient pressure (101 kPa) that served as a control. In other experiments, plants were grown at ambient pressure until maturity and then subjected to low atmospheric pressure for periods of 24 hours to determine possible effects of intermittent low pressure. The O2 and CO2 partial pressures in the low pressure chamber were adjusted to levels equal to those in the ambient pressure chamber to prevent differences in plant response which would have resulted from differences in the partial pressure of those gasses. The O2 partial pressure in the ambient chamber was maintained at 21 kPa and provision was made for additional CO2 during the fight phase. The germination rate and early seedling growth were insensitive to a low pressure environment. The rate of root elongation of plants grown at 70 kPa and at 101 kPa was also approximately the same. The rate of net carbon assimilation (per unit leaf area) of plants grown at low atmospheric pressure was unaffected at all growth stages even though plants grown at 70 kPa had slightly greater fresh and dry weights. There were consistent differences in assimilate partitioning, as shown by higher root/shoot ratios of plants grown at low pressure. Transpiration rates of plants grown until maturity under either constant or intermittent low pressure were reduced. Dark respiration rates of plants grown until maturity under either constant or intermittent low pressure were approximately 20% higher than the control plants.

Filterability of freshly-collected sickle erythrocytes under venous oxygen pressure without exposure to air.

PubMed

Shah, Siddharth; Acholonu, Rhonda Graves; Ohene-Frempong, Kwaku; Asakura, Toshio

2015-12-01

We previously found that blood samples collected from steady-state patients with sickle cell disease (SCD) without exposure to air contain a new type of reversibly sickled cells (RSCs) with blunt edges at a level of as high as 78%. Since partial oxygenation of once-deoxygenated sickled cells with pointy edges to near venous oxygen pressure generates similar sickled cells with blunt edges in vitro, we named them as partially oxygenated sickled cells (POSCs). On the other hand, partial deoxygenation of once-oxygenated SS cells to venous oxygen pressure generates partially deoxygenated sickled cells (PDSCs) with pointy edges. In this study, we obtained blood samples from 6 steady-state patients with SCD under venous oxygen pressure without exposure to air, subjected them to various oxygenation/deoxygenation/reoxygenation cycles, and studied their filterability through a membrane filter with pore diameter of 3μm, the theoretical minimum diameter of a capillary. Our results indicated that discocytes, POSCs with blunt edges, and irreversibly sickled cells could deform and pass through the filter, while PDSCs with pointy edges were rigid and could not. The filterability of SS cells seems to be related to the length and amount of deoxy-hemoglobin S fibers in the cells. Copyright © 2015. Published by Elsevier Inc.

Novel application of lower body positive-pressure in the rehabilitation of an individual with multiple lower extremity fractures.

PubMed

Takacs, Judit; Leiter, Jeff R S; Peeler, Jason D

2011-06-01

Lower extremity fractures, if not treated appropriately, can increase the risk of morbidity. Partial weight-bearing after surgical repair is recommended; however, current methods of partial weight-bearing may cause excessive loads through the lower extremity. A new rehabilitation tool that uses lower body positive-pressure is described, that may allow partial weight-bearing while preventing excessive loads, thereby improving functional outcomes. A patient with multiple lower extremity fractures underwent a 6-month rehabilitation programme using bodyweight support technology 3 times per week, post-surgery. The patient experienced a reduction in pain and an improvement in ankle range of motion (p=0.002), walking speed (p>0.05) and physical function (p=0.004), as assessed by the Foot and Ankle Module of the American Academy of Orthopaedic Surgeons Lower Limb Outcomes Assessment Instrument. Training did not appear to affect fracture healing, as was evident on radiograph. The effect of lower body positive-pressure on effusion, which has not previously been reported in the literature, was also investigated. No significant difference in effusion of the foot and ankle when using lower body positive-pressure was found. Initial results suggest that this new technology may be a useful rehabilitation tool that allows partial weight-bearing during the treatment of lower extremity injuries.

Effects of hypobaria and hypoxia on seed germination of six plant species

NASA Astrophysics Data System (ADS)

Tang, Yongkang; Gao, Feng; Guo, Shuangsheng; Li, Fang

2014-10-01

Hypobaria (low pressure) is typically associated with hypoxia (low oxygen partial pressure). There are several advantages of growing higher plants under hypobaria in the moon or mars habitat. The objectives of this research were to investigate the seed germination of six plant species under hypobaric and ambient total pressure conditions. Seeds were sown and germinated under three levels of total atmospheric pressure (101, 30 and 10 kPa) and three levels of oxygen partial pressures (21, 6 and 2 kPa) in an 8-day study. Hypoxia (6 or 2 kPa) significantly inhibited all seed germination under three levels of total atmospheric pressure by increasing the electrical conductivity and the optical density, decreasing the seed germination percentage and seed dehydrogenase activity and inhibiting the growth of the shoots and roots. Hypobaria (30 or 10 kPa) markedly improved seed germination and root growth by enhancing the oxygen diffusion rate under hypoxic conditions (6 or 2 kPa). The seeds of three dicot plants (lettuce, Chinese cabbage and cucumber) were more sensitive to hypoxia caused by hypobaria than were those of three monocot plants (maize, wheat and rice); lettuce and cucumber seeds had the highest sensitivity, whereas rice seeds had the lowest sensitivity. This research demonstrates that six experimental seeds can germinate normally under hypobaria (30 kPa), but the oxygen partial pressure should not be less than 6 kPa.

Melt-Vapor Phase Diagram of the Te-S System

NASA Astrophysics Data System (ADS)

Volodin, V. N.; Trebukhov, S. A.; Kenzhaliyev, B. K.; Nitsenko, A. V.; Burabaeva, N. M.

2018-03-01

The values of partial pressure of saturated vapor of the constituents of the Te-S system are determined from boiling points. The boundaries of the melt-vapor phase transition at atmospheric pressure and in vacuum of 2000 and 100 Pa are calculated on the basis of partial pressures. A phase diagram that includes vapor-liquid equilibrium fields whose boundaries allow us to assess the behavior of elements upon distillation fractioning is plotted. It is established that the separation of elements is possible at the first evaporation-condensation cycle. Complications can be caused by crystallization of a sulfur solid solution in tellurium.

Dynamic calibration of fast-response probes in low-pressure shock tubes

NASA Astrophysics Data System (ADS)

Persico, G.; Gaetani, P.; Guardone, A.

2005-09-01

Shock tube flows resulting from the incomplete burst of the diaphragm are investigated in connection with the dynamic calibration of fast-response pressure probes. As a result of the partial opening of the diaphragm, pressure disturbances are observed past the shock wave and the measured total pressure profile deviates from the envisaged step signal required by the calibration process. Pressure oscillations are generated as the initially normal shock wave diffracts from the diaphragm's orifice and reflects on the shock tube walls, with the lowest local frequency roughly equal to the ratio of the sound speed in the perturbed region to the shock tube diameter. The energy integral of the perturbations decreases with increasing distance from the diaphragm, as the diffracted leading shock and downwind reflections coalesce into a single normal shock. A procedure is proposed to calibrate fast-response pressure probes downwind of a partially opened shock tube diaphragm.

Partial pressure analysis in space testing

NASA Technical Reports Server (NTRS)

Tilford, Charles R.

1994-01-01

For vacuum-system or test-article analysis it is often desirable to know the species and partial pressures of the vacuum gases. Residual gas or Partial Pressure Analyzers (PPA's) are commonly used for this purpose. These are mass spectrometer-type instruments, most commonly employing quadrupole filters. These instruments can be extremely useful, but they should be used with caution. Depending on the instrument design, calibration procedures, and conditions of use, measurements made with these instruments can be accurate to within a few percent, or in error by two or more orders of magnitude. Significant sources of error can include relative gas sensitivities that differ from handbook values by an order of magnitude, changes in sensitivity with pressure by as much as two orders of magnitude, changes in sensitivity with time after exposure to chemically active gases, and the dependence of the sensitivity for one gas on the pressures of other gases. However, for most instruments, these errors can be greatly reduced with proper operating procedures and conditions of use. In this paper, data are presented illustrating performance characteristics for different instruments and gases, operating parameters are recommended to minimize some errors, and calibrations procedures are described that can detect and/or correct other errors.

Oxygen stoichiometry, phase stability, and thermodynamic behavior of the lead-doped Bi-2223 and Ag/Bi-2223 systems

NASA Astrophysics Data System (ADS)

Tetenbaum, M.; Hash, M.; Tani, B. S.; Luo, J. S.; Maroni, V. A.

1995-02-01

Electromotive-force (EMF) measurements of oxygen fugacities as a function of stoichiometry have been made in the lead-doped Bi-2223 superconducting system in the temperature range 700-815°C by means of an oxygen titration technique that employs an yttria-stabilized zirconia electrolyte. The results of our studies indicate that processing or annealing lead-doped Bi-2223 at temperatures ranging from 750 to 815°C and at oxygen partial pressures ranging from ∼ 0.02 to 0.2 atm should preserve Bi-2223 as essentially single-phase material. Thermodynamic assessments of the partial molar quantities ΔS¯( O2) andΔH¯( O2) indicate that the plateau regions in the plot of oxygen partial pressure versus oxygen stoichiometry ( x) can be represented by the diphasic CuOCu 2O system. In accord with the EMF measurements, it was found that lead-doped Bi-2223 in a silver sheath is stable at 815°C for oxygen partial pressures between 0.02 and 0.13 atm.

Thermodynamic and nonstoichiometric behavior of the lead-doped Bi-2223 system

NASA Astrophysics Data System (ADS)

Tetenbaum, M.; Hash, M.; Tani, B. S.; Luo, J. S.; Maroni, V. A.

1994-12-01

Electromotive force (EMF) measurements of oxygen fugacities as a function of stoichiometry have been made in the lead-doped Bi-2223 superconducting system in the temperature range 700-815°C by means of an oxygen titration technique. The results of our studies indicate that processing or annealing lead-doped Bi-2223 at temperatures ranging from 700 to 815°C and at oxygen partial pressures ranging from ∼0.02 to 0.2 atm should tend to preserve Bi-2223 as essentially single-phase material. Thermodynamic assessments of partial molar quantities indicate that the plateau regions can be represented by the diphasic CuOCu 2O system. In accord with the EMF measurements, it was found that lead-doped Bi-2223 in a silver sheath is stable at 815°C for oxygen partial pressures between 0.02 and 0.13 atm. Long-duration post anneals of silver-clad Bi-2223 filaments at 825°C and an oxygen partial pressure of 0.075 atm eliminated Bi-2212 intergrowths with a concomitant increase in the superconducting transition sharpness.

Influence of defunctionalization and mechanical forces on intestinal epithelial wound healing

PubMed Central

Kovalenko, Pavlo L.; Flanigan, Thomas L.; Chaturvedi, Lakshmi

2012-01-01

The influence on mucosal healing of luminal nutrient flow and the forces it creates are poorly understood. We hypothesized that altered deformation and extracellular pressure mediate, in part, the effects of defunctionalization on mucosal healing. We created patent or partially obstructing defunctionalizing jejunal Roux-en-Y anastomoses in rats to investigate mucosal healing in the absence or presence of luminal nutrient flow and measured luminal pressures to document partial obstruction. We used serosal acetic acid to induce ulcers in the proximal, distal, and defunctionalized intestinal segments. After 3 days, we assessed ulcer area, proliferation, and phosphorylated ERK. In vitro, we measured proliferation and migration in Caco-2 and IEC-6 intestinal epithelial cells subjected to cyclic strain, increased extracellular pressure, or strain and pressure together. Defunctionalization of intestine without obstruction reduced phosphorylated ERK, slowed ulcer healing, and inhibited mucosal proliferation. This outcome was blocked by PD-98059. Partial obstruction delayed ulcer healing but stimulated proliferation independently of ERK. In vitro, strain increased Caco-2 and IEC-6 proliferation and reduced migration across collagen but reduced proliferation and increased migration across fibronectin. In contrast, increased pressure and the combination of pressure and strain increased proliferation and reduced migration independently of substrate. PD-98059 reduced basal migration but increased migration under pressure. These results suggest that loss of the repetitive distension may decrease mucosal healing in defunctionalized bowel, while increased luminal pressure above anastomoses or in spastic bowel disease could further inhibit mucosal healing, despite peristaltic repetitive strain. ERK may mediate the effects of repetitive deformation but not the effects of pressure. PMID:22997197

Flow-independent dynamics in aneurysm (FIDA): pressure measurements following partial and complete flow impairment in experimental aneurysm model

PubMed Central

Watanabe, Masaki; Chaudhry, Saqib A; Qureshi, Adnan I

2014-01-01

Background: There have been growing concerns regarding delayed aneurysm rupture subsequent to the flow-diverting stent deployment. Therefore, more investigations are needed regarding hemodynamic changes secondary to flow-diverting stent deployment. Objective: To study intra-aneurysmal and perianeurysmal pressures after partial and complete flow impairment into the aneurysm. Methods A silicone model of an 8-mm-sized aneurysm (neck diameter: 5 mm, vessel size: 4 mm) was used. The aneurysm wall was encapsulated and sealed within a 5 ml syringe filled with saline and a pressure sensor guide wire (ComboWire, Volcano Corp.) to detect pressure changes in the perivascular compartment (outer aneurysm wall). A second pressure sensor guide wire was advanced inside the aneurysm sac. Both pressure sensors were continuously measuring pressure inside and outside the aneurysm under pulsatile flow under the following conditions: 1) baseline (reference); 2) a 16 mm by 3.75 mm flow-diverting stent (ev3/Covidien Vascular, Mansfield, MA) deployed in front of the aneurysm; 3) two flow-diverting stents (16 mm by 3.5 mm) were deployed; and 4) a covered stent (4 mm by 16 mm VeriFlex coronary artery stent covered with rubber sheet) was deployed. Results: Mean (±SD) baseline pressures inside and outside the aneurysm were 53.9 (±2.4) mmHg (range 120–40 mmHg) and 15.4 (±0.7) mmHg (range 40–8mmHg), respectively. There was no change in pressure inside and outside the aneurysm after deploying the first and second flow-diverting stents (partial flow impairment) and it remained at 53.9 (±2.7) mmHg and 14.9 (±1) mmHg for the pressure inside and outside the aneurysm, respectively. The pressure recording from outside the aneurysm dropped from 15.4 (±0.7) mmHg to 0.3 (±0.7) mmHg after deploying the covered stent (complete flow impairment). There was no change in pressure inside the aneurysm after deploying the covered stent. Mean (±SD) pressure within the aneurysm was 55.1 (±1.7) mmHg and it remained 54.7 (±1.7) mmHg after covered stent deployment. Conclusion: Our findings suggest a major discordance between the pressures within the aneurysm and partial or complete flow impairment (flow independent). The outer wall pressure is reduced after covered stent placement. These finding may assist clinicians in better understanding of aneurysm hemodynamics and rupture after flow-diverting stent deployment. PMID:25298859

Biological nitrogen fixation under primordial Martian partial pressures of dinitrogen

NASA Technical Reports Server (NTRS)

Klingler, J. M.; Mancinelli, R. L.; White, M. R.

1989-01-01

One of the most striking differences between the conditions on early Mars and earth was a low (18 mb) partial pressure of N2 (pN2) on early Mars, as opposed to 780 mb N2 on earth. To investigate the possibility of biological nitrogen fixation under conditions of early Mars, experiments were carried out on the growth of Azotobacter vinelandii and Azomonas agilis in nitrogen-free synthetic medium under various partial pressures of N2 (ranging from 780 to 0 mb). It was found that, although the biomass, cell number, and growth rate of these bacteria decreased with decreasing pN2 values below pN2 of 400 mb, both microorganisms were capable of growing at pN2 as low as 5 mb (but not at of below 1 mb), indicating that biological fixation of nitrogen could have occurred on primordial Mars.

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

PubMed

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

2016-01-01

The EPR spin-trapping technique and EPR-oximetry were used to study generation of superoxide radicals in heart mitochondria isolated from Wistar rats under conditions of variable oxygen concentration. Lithium phthalocyanine and TEMPONE-15N-D16 were chosen to determine oxygen content in a gas-permeable capillary tube containing mitochondria. TIRON was used as a spin trap. We investigated the influence of different oxygen concentrations in incubation mixture and demonstrated that heart mitochondria can generate superoxide in complex III at different partial pressure of oxygen as well as under the conditions of deep hypoxia (< 5% O2). Dinitrosyl iron complexes with glutathione (the pharmaceutical drug "Oxacom") exerted an antioxidant effect, regardless of the value of the partial pressure of oxygen, but the magnitude and kinetic characteristics of the effect depended on the concentration of the drug.

Method for forming bismuth-based superconducting ceramics

DOEpatents

Maroni, Victor A.; Merchant, Nazarali N.; Parrella, Ronald D.

2005-05-17

A method for reducing the concentration of non-superconducting phases during the heat treatment of Pb doped Ag/Bi-2223 composites having Bi-2223 and Bi-2212 superconducting phases is disclosed. A Pb doped Ag/Bi-2223 composite having Bi-2223 and Bi-2212 superconducting phases is heated in an atmosphere having an oxygen partial pressure not less than about 0.04 atmospheres and the temperature is maintained at the lower of a non-superconducting phase take-off temperature and the Bi-2223 superconducting phase grain growth take-off temperature. The oxygen partial pressure is varied and the temperature is varied between about 815.degree. C. and about 835.degree. C. to produce not less than 80 percent conversion to Pb doped Bi-2223 superconducting phase and not greater than about 20 volume percent non-superconducting phases. The oxygen partial pressure is preferably varied between about 0.04 and about 0.21 atmospheres. A product by the method is disclosed.

Oxygen partial pressure modulates 67-kDa laminin receptor expression, leading to altered activity of the green tea polyphenol, EGCG.

PubMed

Tsukamoto, Shuntaro; Yamashita, Shuya; Kim, Yoon Hee; Kumazoe, Motofumi; Huang, Yuhui; Yamada, Koji; Tachibana, Hirofumi

2012-09-21

(-)-Epigallocatechin-3-O-gallate (EGCG) exhibits anti-tumor activity mediated via the 67-kDa laminin receptor (67LR). In this study, we found that 67LR protein levels are reduced by exposure to low O(2) levels (5%), without affecting the expression of HIF-1α. We also found that EGCG-induced anti-cancer activity is abrogated under low O(2) levels (5%) in various cancer cells. Notably, treatment with the proteasome inhibitor, prevented down-regulation of 67LR and restored sensitivity to EGCG under 5% O(2). In summary, 67LR expression is highly sensitive to O(2) partial pressure, and the activity of EGCG can be regulated in cancer cells by O(2) partial pressure. Copyright © 2012 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

The change of steel surface chemistry regarding oxygen partial pressure and dew point

NASA Astrophysics Data System (ADS)

Norden, Martin; Blumenau, Marc; Wuttke, Thiemo; Peters, Klaus-Josef

2013-04-01

By investigating the surface state of a Ti-IF, TiNb-IF and a MnCr-DP after several series of intercritical annealing, the impact of the annealing gas composition on the selective oxidation process is discussed. On behalf of the presented results, it can be concluded that not the general oxygen partial pressure in the annealing furnace, which is a result of the equilibrium reaction of water and hydrogen, is the main driving force for the selective oxidation process. It is shown that the amounts of adsorbed gases at the strip surface and the effective oxygen partial pressure resulting from the adsorbed gases, which is mainly dependent on the water content of the annealing furnace, is driving the selective oxidation processes occurring during intercritical annealing. Thus it is concluded, that for industrial applications the dew point must be the key parameter value for process control.

Two Phase Flow Modeling: Summary of Flow Regimes and Pressure Drop Correlations in Reduced and Partial Gravity

NASA Technical Reports Server (NTRS)

Balasubramaniam, R.; Rame, E.; Kizito, J.; Kassemi, M.

2006-01-01

The purpose of this report is to provide a summary of state-of-the-art predictions for two-phase flows relevant to Advanced Life Support. We strive to pick out the most used and accepted models for pressure drop and flow regime predictions. The main focus is to identify gaps in predictive capabilities in partial gravity for Lunar and Martian applications. Following a summary of flow regimes and pressure drop correlations for terrestrial and zero gravity, we analyze the fully developed annular gas-liquid flow in a straight cylindrical tube. This flow is amenable to analytical closed form solutions for the flow field and heat transfer. These solutions, valid for partial gravity as well, may be used as baselines and guides to compare experimental measurements. The flow regimes likely to be encountered in the water recovery equipment currently under consideration for space applications are provided in an appendix.

A defect model for UO2+x based on electrical conductivity and deviation from stoichiometry measurements

NASA Astrophysics Data System (ADS)

Garcia, Philippe; Pizzi, Elisabetta; Dorado, Boris; Andersson, David; Crocombette, Jean-Paul; Martial, Chantal; Baldinozzi, Guido; Siméone, David; Maillard, Serge; Martin, Guillaume

2017-10-01

Electrical conductivity of UO2+x shows a strong dependence upon oxygen partial pressure and temperature which may be interpreted in terms of prevailing point defects. A simulation of this property along with deviation from stoichiometry is carried out based on a model that takes into account the presence of impurities, oxygen interstitials, oxygen vacancies, holes, electrons and clusters of oxygen atoms. The equilibrium constants for each defect reaction are determined to reproduce the experimental data. An estimate of defect concentrations and their dependence upon oxygen partial pressure can then be determined. The simulations carried out for 8 different temperatures (973-1673 K) over a wide range of oxygen partial pressures are discussed and resulting defect equilibrium constants are plotted in an Arrhenius diagram. This provides an estimate of defect formation energies which may further be compared to other experimental data or ab-initio and empirical potential calculations.

Development of a three-man preprototype CO2 collection subsystem for spacecraft application

NASA Technical Reports Server (NTRS)

Schubert, F. H.; Wynveen, R. A.; Quattrone, P. D.; Marshall, R. D.

1977-01-01

Future long-duration manned space missions will require regenerable carbon dioxide (CO2) collection concepts such as the Electrochemical Depolarized CO2 Concentrator (EDC). A three-man-capacity preprototype CO2 Collection Subsystem (CS-3) is being developed for eventual flight demonstration as part of the Air Revitalization System (ARS) of the Regenerative Life Support Evaluation (RLSE) experiment. The CS-3 employs an EDC to concentrate CO2 from the low partial-pressure levels required of spacecraft atmospheres to high partial-pressure levels needed for oxygen (O2) recovery through CO2 reduction processes. The CS-3 is sized to remove a nominal 3.0 kg/day (6.6 lb/day) of the CO2 to maintain the CO2 partial pressure (pCO2) of the cabin atmosphere at 400 Pa (3 mm Hg) or less. This paper presents the preprototype design, configuration, operation, and projected performance characteristics.

Pathophysiological effect of fat embolism in a canine model of pulmonary contusion.

PubMed

Elmaraghy, A W; Aksenov, S; Byrick, R J; Richards, R R; Schemitsch, E H

1999-08-01

The objective of this study was to determine the individual and combined effects of pulmonary contusion and fat embolism on the hemodynamics and pulmonary pathophysiology in a canine model of acute traumatic pulmonary injury. After a thoracotomy, twenty-one skeletally mature dogs were randomly assigned to one of three groups. Unilateral pulmonary contusion alone was produced in Group 1 (seven dogs); pulmonary contusion and fat embolism, in Group 2 (seven dogs); and fat embolism alone, in Group 3 (seven dogs). Pulmonary contusion was produced by standardized compression of the left lung with a piezoelectric force transducer. Fat embolism was produced by femoral and tibial reaming followed by pressurization of the intramedullary canals. Cardiac output, systolic blood pressure, peak airway pressure, pulmonary arterial pressure, pulmonary capillary wedge pressure, partial pressure of arterial oxygen, and partial pressure of carbon dioxide were monitored for all groups. From these data, several outcome parameters were calculated: total thoracic compliance, alveolar-arterial oxygen gradient, and ratio of partial pressure of arterial oxygen to fractional inspired oxygen concentration. All of the dogs were killed after eight hours, and tissue samples were obtained from the brain, kidneys, and lungs for histological analysis. Lung samples were assigned scores for pulmonary edema (the presence of fluid in the alveoli) and inflammation (the presence of neutrophils or hyaline membranes, or both). The percentage of the total area occupied by fat was determined. Pulmonary contusion alone caused a significant increase in the alveolar-arterial oxygen gradient but only after seven hours (p = 0.034). Fat embolism alone caused a significant transient decrease in systolic blood pressure (p = 0.001) and a significant transient increase in pulmonary arterial pressure (p = 0.01) and pulmonary capillary wedge pressure (p = 0.015). Fat embolism alone also caused a significant sustained decrease in the ratio of partial pressure of arterial oxygen to fractional inspired oxygen concentration (p = 0.0001) and a significant increase in the alveolar-arterial oxygen gradient (p = 0.0001). The combination of pulmonary contusion and fat embolism caused a significant transient increase in pulmonary capillary wedge pressure (p = 0.0013) as well as a significant sustained decrease in partial pressure of arterial oxygen (p = 0.0001) and a significant decrease in systolic blood pressure (p = 0.001) that lasted for an hour. Pulmonary contusion followed by fat embolism caused a significant increase in peak airway pressure (p = 0.015), alveolar-arterial oxygen gradient (p = 0.0001), and pulmonary arterial pressure (p = 0.01), and these effects persisted for five hours. Total thoracic compliance was decreased 6.4 percent by pulmonary contusion alone, 4.6 percent by fat embolism alone, and 23.5 percent by pulmonary contusion followed by fat embolism. The ratio of partial pressure of arterial oxygen to fractional inspired oxygen concentration was decreased 23.7 percent by pulmonary contusion alone, 52.3 percent by fat embolism alone, and 65.8 percent by pulmonary contusion followed by fat embolism. The mean pulmonary edema score was significantly higher with the combined injury than with either injury alone (p = 0.0001). None of the samples from the lungs demonstrated inflammation. Fat embolism combined with pulmonary contusion resulted in a significantly greater mean percentage of the area occupied by fat in the noncontused right lung than in the contused left lung (p = 0.001); however, no significant difference between the right and left lungs could be detected with fat embolism alone. The mean percentage of the glomerular and cerebral areas occupied by fat was greater with fat embolism combined with pulmonary contusion than with fat embolism alone (p = 0.0001 and p = 0.01, respectively). (ABSTRACT TRUNCATED)

Effect of Nitrogen Content on Physical and Chemical Properties of TiN Thin Films Prepared by DC Magnetron Sputtering with Supported Discharge

NASA Astrophysics Data System (ADS)

Kavitha, A.; Kannan, R.; Gunasekhar, K. R.; Rajashabala, S.

2017-10-01

Amorphous titanium nitride (TiN) thin films have been prepared on silicon (Si) and glass substrates by direct-current (DC) reactive magnetron sputtering with a supported discharge (triode). Nitrogen gas (N2) at partial pressure of 0.3 Pa, 0.4 Pa, 0.5 Pa, and 0.6 Pa was used to prepare the TiN thin films, maintaining total pressure of argon and N2 of about 0.7 Pa. The chemical, microstructural, optical, and electrical properties of the TiN thin films were systematically studied. Presence of different phases of Ti with nitrogen (N), oxygen (O2), and carbon (C) elements was revealed by x-ray photoelectron spectroscopy characterization. Increase in the nitrogen pressure from 0.3 Pa to 0.6 Pa reduced the optical bandgap of the TiN thin film from 2.9 eV to 2.7 eV. Photoluminescence study showed that TiN thin film deposited at N2 partial pressure of 0.3 Pa exhibited three shoulder peaks at 330 nm, 335 nm, and 340 nm, which disappeared when the sample was deposited with N2 partial pressure of 0.6 Pa. Increase in the nitrogen content decreased the electrical resistivity of the TiN thin film from 3200 μΩ cm to 1800 μΩ cm. Atomic force microscopy studies of the TiN thin films deposited with N2 partial pressure of 0.6 Pa showed a uniform surface pattern associated with accumulation of fine grains. The results and advantages of this method of preparing TiN thin films are also reported.

Predicting Intracranial Pressure and Brain Tissue Oxygen Crises in Patients With Severe Traumatic Brain Injury.

PubMed

Myers, Risa B; Lazaridis, Christos; Jermaine, Christopher M; Robertson, Claudia S; Rusin, Craig G

2016-09-01

To develop computer algorithms that can recognize physiologic patterns in traumatic brain injury patients that occur in advance of intracranial pressure and partial brain tissue oxygenation crises. The automated early detection of crisis precursors can provide clinicians with time to intervene in order to prevent or mitigate secondary brain injury. A retrospective study was conducted from prospectively collected physiologic data. intracranial pressure, and partial brain tissue oxygenation crisis events were defined as intracranial pressure of greater than or equal to 20 mm Hg lasting at least 15 minutes and partial brain tissue oxygenation value of less than 10 mm Hg for at least 10 minutes, respectively. The physiologic data preceding each crisis event were used to identify precursors associated with crisis onset. Multivariate classification models were applied to recorded data in 30-minute epochs of time to predict crises between 15 and 360 minutes in the future. The neurosurgical unit of Ben Taub Hospital (Houston, TX). Our cohort consisted of 817 subjects with severe traumatic brain injury. Our algorithm can predict the onset of intracranial pressure crises with 30-minute advance warning with an area under the receiver operating characteristic curve of 0.86 using only intracranial pressure measurements and time since last crisis. An analogous algorithm can predict the start of partial brain tissue oxygenation crises with 30-minute advanced warning with an area under the receiver operating characteristic curve of 0.91. Our algorithms provide accurate and timely predictions of intracranial hypertension and tissue hypoxia crises in patients with severe traumatic brain injury. Almost all of the information needed to predict the onset of these events is contained within the signal of interest and the time since last crisis.

[Effect of oxygen tubing connection site on percutaneous oxygen partial pressure and percutaneous carbon dioxide partial pressure in patients with chronic obstructive pulmonary disease during noninvasive positive pressure ventilation].

PubMed

Mi, S; Zhang, L M

2017-04-12

Objective: We evaluated the effects of administering oxygen through nasal catheters inside the mask or through the mask on percutaneous oxygen partial pressure (PcO(2))and percutaneous carbon dioxide partial pressure (PcCO(2)) during noninvasive positive pressure ventilation (NPPV) to find a better way of administering oxygen, which could increase PcO(2) by increasing the inspired oxygen concentration. Methods: Ten healthy volunteers and 9 patients with chronic obstructive pulmonary disease complicated by type Ⅱ respiratory failure were included in this study. Oxygen was administered through a nasal catheter inside the mask or through the mask (oxygen flow was 3 and 5 L/min) during NPPV. PcO(2) and PcCO(2) were measured to evaluate the effects of administering oxygen through a nasal catheter inside the mask or through the mask, indirectly reflecting the effects of administering oxygen through nasal catheter inside the mask or through the mask on inspired oxygen concentration. Results: Compared to administering oxygen through the mask during NPPV, elevated PcO(2) was measured in administering oxygen through the nasal catheter inside the mask, and the differences were statistically significant ( P <0.05). At the same time, there was no significant change in PcCO(2) ( P >0.05). Conclusion: Administering oxygen through a nasal catheter inside the mask during NPPV increased PcO(2) by increasing the inspired oxygen concentration but did not increase PcCO(2). This method of administering oxygen could conserve oxygen and be suitable for family NPPV. Our results also provided theoretical basis for the development of new masks.

In-Line Ozonation for Sensitive Air-Monitoring of a Mustard-Gas Simulant by Atmospheric Pressure Chemical Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Okumura, Akihiko

2015-09-01

A highly sensitive method for real-time air-monitoring of mustard gas (bis(2-chloroethyl) sulfide, HD), which is a lethal blister agent, is proposed. Humidified air containing a HD simulant, 2-chloroethyl ethyl sulfide (2CEES), was mixed with ozone and then analyzed by using an atmospheric pressure chemical ionization ion trap tandem mass spectrometer. Mass-spectral ion peaks attributable to protonated molecules of intact, monooxygenated, and dioxygenated 2CEES (MH+, MOH+, and MO2H+, respectively) were observed. As ozone concentration was increased from zero to 30 ppm, the signal intensity of MH+ sharply decreased, that of MOH+ increased once and then decreased, and that of MO2H+ sharply increased until reaching a plateau. The signal intensity of MO2H+ at the plateau was 40 times higher than that of MH+ and 100 times higher than that of MOH+ in the case without in-line ozonation. Twenty-ppm ozone gas was adequate to give a linear calibration curve for 2CEES obtained by detecting the MO2H+ signal in the concentration range up to 60 μg/m3, which is high enough for hygiene management. In the low concentration range lower than 3 μg/m3, which is equal to the short-term exposure limit for HD, calibration plots unexpectedly fell off the linear calibration curve, but 0.6-μg/m3 vapor was actually detected with the signal-to-noise ratio of nine. Ozone was generated from instrumentation air by using a simple and inexpensive home-made generator. 2CEES was ozonated in 1-m extended sampling tube in only 1 s.

Carbon dioxide exchange of lettuce plants under hypobaric conditions

NASA Technical Reports Server (NTRS)

Corey, K. A.; Bates, M. E.; Adams, S. L.; MacElroy, R. D. (Principal Investigator)

1996-01-01

Growth of plants in a Controlled Ecological Life Support System (CELSS) may involve the use of hypobaric pressures enabling lower mass requirements for atmospheres and possible enhancement of crop productivity. A controlled environment plant growth chamber with hypobaric capability designed and built at Ames Research Center was used to determine if reduced pressures influence the rates of photosynthesis (Ps) and dark respiration (DR) of hydroponically grown lettuce plants. The chamber, referred to as a plant volatiles chamber (PVC), has a growing area of about 0.2 m2, a total gas volume of about 0.7 m3, and a leak rate at 50 kPa of <0.1%/day. When the pressure in the chamber was reduced from ambient to 51 kPa, the rate of net Ps increased by 25% and the rate of DR decreased by 40%. The rate of Ps increased linearly with decreasing pressure. There was a greater effect of reduced pressure at 41 Pa CO2 than at 81 Pa CO2. This is consistent with reports showing greater inhibition of photorespiration (Pr) in reduced O2 at low CO2 concentrations. When the partial pressure of O2 was held constant but the total pressure was varied between 51 and 101 kPa, the rate of CO2 uptake was nearly constant, suggesting that low pressure enhancement of Ps may be mainly attributable to lowered partial pressure of O2 and the accompanying reduction in Pr. The effects of lowered partial pressure of O2 on Ps and DR could result in substantial increases in the rates of biomass production, enabling rapid throughput of crops or allowing flexibility in the use of mass and energy resources for a CELSS.

Low Pressure Flame Blowoff from the Forward Stagnation Region of a Blunt-Nosed Cast PMMA Cylinder in Axial Mixed Convective Flow

NASA Technical Reports Server (NTRS)

Marcum, J. W.; Rachow, P.; Ferkul, P. V.; Olson, S. L.

2017-01-01

Low-pressure blowoff experiments were conducted with a stagnation flame stabilized on the forward tip of cast PMMA rods in a vertical wind tunnel. Pressure, forced flow velocity, gravity, and ambient oxygen concentration were varied. Stagnation flame blowoff is determined from a time-stamped video recording of the test. The blowoff pressure is determined from test section pressure transducer data that is synchronized with the time stamp. The forced flow velocity is also determined from the choked flow orifice pressure. Most of the tests were performed in normal gravity, but a handful of microgravity tests were also conducted to determine the influence of buoyant flow velocity on the blowoff limits. The blowoff limits are found to have a linear dependence between the partial pressure of oxygen and the total pressure, regardless of forced flow velocity and gravity level. The flow velocity (forced and/or buoyant) affects the blowoff pressure through the critical Damkohler number residence time, which dictates the partial pressure of oxygen at blowoff. This is because the critical stretch rate increases linearly with increasing pressure at low pressure (sub-atmospheric pressures) since a second-order overall reaction rate with two-body reactions dominates in this pressure range.

PH2O and simulated hypobaric hypoxia.

PubMed

Conkin, Johnny

2011-12-01

Some manufacturers of reduced oxygen (O2) breathing devices claim a comparable hypobaric hypoxia (HH) training experience by providing F1O2 < 0.209 at or near sea level pressure to match the ambient oxygen partial pressure (iso-PO2) of the target altitude. I conclude after a review of literature from investigators and manufacturers that these devices may not properly account for the 47 mmHg of water vapor partial pressure that reduces the inspired partial pressure of oxygen (P1O2), which is substantial at higher altitude relative to sea level. Consequently, some devices claiming an equivalent HH experience under normobaric conditions would significantly overestimate the HH condition, especially when simulating altitudes above 10,000 ft (3048 m). At best, the claim should be that the devices provide an approximate HH experience since they only duplicate the ambient PO2 at sea level as at altitude. An approach to reduce the overestimation and standardize the operation is to at least provide machines that create the same P1O2 conditions at sea level as at the target altitude, a simple software upgrade.

Formulation of steam-methane reforming rate in Ni-YSZ porous anode of solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Sugihara, Shinichi; Kawamura, Yusuke; Iwai, Hiroshi

2018-02-01

The steam-methane reforming reaction on a Ni-YSZ (yttria-stabilized zirconia) cermet was experimentally investigated under atmospheric pressure and in the temperature range from 650 to 750 °C. We examined the effects of the partial pressures of methane and steam in the supply gas on the reaction rate. The experiments were conducted with a low Ni contained Ni-YSZ cermet sheet of thickness 0.1 mm. Its porous microstructure and accompanied parameters were quantified using the FIB-SEM (focused ion beam scanning electron microscopy) technique. A power-law-type rate equation incorporating the reaction-rate-limiting conditions was obtained on the basis of the unit surface area of the Ni-pore contact surface in the cermet. The kinetics indicated a strong positive dependence on the methane partial pressure and a negative dependence on the steam partial pressure. The obtained rate equation successfully reproduced the experimental results for Ni-YSZ samples having different microstructures in the case of low methane consumption. The equation also reproduced the limiting-reaction behaviours at different temperatures.

Variable character of O—O and M—O bonding in side-on (η2) 1:1 metal complexes of O2

PubMed Central

Cramer, Christopher J.; Tolman, William B.; Theopold, Klaus H.; Rheingold, Arnold L.

2003-01-01

The structures and the O—O and M—O bonding characters of a series of reported side-on (η2) 1:1 metal complexes of O2 are analyzed by using density functional theory calculations. Comparison of the calculated and experimental systems with respect to O—O bond distance, O—O stretching frequency, and O—O and M—O bond orders provides new insights into subtle influences relevant to O2 activation processes in biology and catalysis. The degree of charge transfer from the generally electron-rich metals to the dioxygen fragment is found to be variable, such that there are species well described as superoxides, others well described as peroxides, and several cases having intermediate character. Increased charge transfer to dioxygen takes place via overlap of the metal dxy orbital with the in-plane π* orbital of O2 and results in increased M—O bond orders and decreased O—O bond orders. Comparison of theory and experiment over the full range of compounds studied suggests that reevaluation of the O—O bond lengths determined from certain x-ray crystal structures is warranted; in one instance, an x-ray crystal structure redetermination was performed at low temperature, confirming the theoretical prediction. Librational motion of the coordinated O2 is identified as a basis for significant underestimation of the O—O distance at high temperature. PMID:12634422

Transient species involved in catalytic dioxygen/peroxide activation by hemoproteins: possible involvement of protonated Compound I species.

PubMed

Silaghi-Dumitrescu, Radu; Cooper, Chris E

2005-11-07

Interaction of hemoproteins with peroxide leads in several cases to transient formation of ferric peroxo, ferric hydroperoxo, and "high-valent", formally Fev, oxo or hydroxo Compound species. Here, density functional calculations on ferric peroxo, ferric hydroperoxo, Compound and protonated Compound heme active site models are reported. The theoretical results, including calculated isotropic Fermi contact couplings and anisotropic spin dipole couplings, are found to generally correlate well with experimental EPR/ENDOR data. Hydrogen bonding and solvation affect the ferric-peroxo/ferrous-superoxo electromerism. The transition between the two electromers appears smooth, but neither hydrogen bonding to up to two water molecules, nor solvation appear able to dramatically alter the redox state of the superoxo ligand or of the iron. The presence of almost one full unpaired electron on the iron and of one full unpaired electron on the dioxygenic ligand in the "ferric-peroxo" state suggests a possible description of non-protonated "ferric-peroxo" as {ferric-superoxo+porphyrin radical}. Emerging from the DFT data is the possibility that a protonated Compound has already been detected in ENDOR experiments on cytochrome P450. The general feasibility of a protonated Compound in P450 monooxygenases is probed in light of these findings. To encompass the multiple mechanisms available in P450 for substrate oxidation, we define "mechanistic promiscuity" as the feature allowing an enzyme to perform the same reaction, with the same product, using more than one mechanism.

Mechanism of superoxide and hydrogen peroxide generation by human electron-transfer flavoprotein and pathological variants.

PubMed

Rodrigues, João V; Gomes, Cláudio M

2012-07-01

Reactive oxygen species production by mitochondrial enzymes plays a fundamental role both in cellular signaling and in the progression of dysfunctional states. However, sources of reactive oxygen species and the mechanisms by which enzymes produce these reactive species still remain elusive. We characterized the generation of reactive oxygen species by purified human electron-transfer flavoprotein (ETF), a mitochondrial enzyme that has a central role in the metabolism of lipids, amino acids, and choline. The results showed that ETF produces significant amounts of both superoxide and hydrogen peroxide in the presence of its partner enzyme medium-chain acyl-CoA dehydrogenase (MCAD). ETF-mediated production of reactive oxygen species is partially inhibited at high MCAD/ETF ratios, whereas it is enhanced at high ionic strength. Determination of the reduction potentials of ETF showed that thermodynamic properties of the FAD cofactor are changed upon formation of a complex between ETF and MCAD, supporting the notion that protein:protein interactions modulate the reactivity of the protein with dioxygen. Two pathogenic ETF variants were also studied to determine which factors modulate the reactivity toward molecular oxygen and promote reactive oxygen species production. The results obtained show that destabilized conformations and defective protein:protein interactions increase the ability of ETF to generate reactive oxygen species. A possible role for these processes in mitochondrial dysfunction in metabolic disorders of fatty acid β-oxidation is discussed. Copyright © 2012 Elsevier Inc. All rights reserved.

Measured pressure distributions inside nonaxisymmetric nozzles with partially deployed thrust reversers

NASA Technical Reports Server (NTRS)

Green, Robert S.; Carson, George T., Jr.

1987-01-01

An investigation was conducted in the Langley 16-Foot Transonic Tunnel at static conditions to measure the pressure distributions inside a nonaxisymmetric nozzle with simultaneous partial thrust reversing (50-percent deployment) and thrust vectoring of the primary (forward-thrust) nozzle flow. Geometric forward-thrust-vector angles of 0 and 15 deg. were tested. Test data were obtained at static conditions while nozzle pressure ratio was varied from 2.0 to 4.0. Results indicate that, unlike the 0 deg. vector angle nozzle, a complicated, asymmetric exhaust flow pattern exists in the primary-flow exhaust duct of the 15 deg. vectored nozzle.

Hydrostatic Paradox: Experimental Verification of Pressure Equilibrium

ERIC Educational Resources Information Center

Kodejška, C.; Ganci, S.; Ríha, J.; Sedlácková, H.

2017-01-01

This work is focused on the experimental verification of the balance between the atmospheric pressure acting on the sheet of paper, which encloses the cylinder completely or partially filled with water from below, where the hydrostatic pressure of the water column acts against the atmospheric pressure. First of all this paper solves a theoretical…

40 CFR 86.344-79 - Humidity calculations.

Code of Federal Regulations, 2012 CFR

2012-07-01

... = Molecular weight of air = 28.9645 M H2O = Molecular weight of water = 18.01534 P DB = Saturation vapor pressure of water at the dry bulb temperature (Pa) P DP = saturation vapor pressure of water at the dewpoint temperature (Pa) P v = partial pressure of water vapor (Pa) P WB = saturation vapor pressure of...

40 CFR 86.344-79 - Humidity calculations.

Code of Federal Regulations, 2013 CFR

2013-07-01

... = Molecular weight of air = 28.9645 M H2O = Molecular weight of water = 18.01534 P DB = Saturation vapor pressure of water at the dry bulb temperature (Pa) P DP = saturation vapor pressure of water at the dewpoint temperature (Pa) P v = partial pressure of water vapor (Pa) P WB = saturation vapor pressure of...

Effects of ambient temperature and water vapor on chamber pressure and oxygen level during low atmospheric pressure stunning of poultry.

PubMed

Holloway, Paul H; Pritchard, David G

2017-08-01

The characteristics of the vacuum used in a low atmospheric pressure stunning system to stun (render unconscious) poultry prior to slaughter are described. A vacuum chamber is pumped by a wet screw compressor. The vacuum pressure is reduced from ambient atmospheric pressure to an absolute vacuum pressure of ∼250 Torr (∼33 kPa) in ∼67 sec with the vacuum gate valve fully open. At ∼250 Torr, the sliding gate valve is partially closed to reduce effective pumping speed, resulting in a slower rate of decreasing pressure. Ambient temperature affects air density and water vapor pressure and thereby oxygen levels and the time at the minimum total pressure of ∼160 Torr (∼21 kPa) is varied from ∼120 to ∼220 sec to ensure an effective stun within the 280 seconds of each cycle. The reduction in total pressure results in a gradual reduction of oxygen partial pressure that was measured by a solid-state electrochemical oxygen sensor. The reduced oxygen pressure leads to hypoxia, which is recognized as a humane method of stunning poultry. The system maintains an oxygen concentration of <5% for at least 2 minutes, which ensures that birds are irreversibly stunned. Calculated pump down (pressure versus time) data match experimental data very closely because the programmable logic controller and the human machine interface enable precise and accurate control. The vacuum system operates in the turbulent viscous flow regime, and is best characterized by absolute vacuum pressure rather than gauge pressure. Neither the presence of broiler chickens nor different fore-line pipe designs of four parallel commercial systems affected the pressure-time data. Water in wet air always reduces the oxygen concentrations to a value lower than in dry air. The partial pressure of water and oxygen were found to depend on the pump down parameters due to the formation of fog in the chamber and desorption of water from the birds and the walls of the vacuum chamber. © The Author 2017. Published by Oxford University Press on behalf of Poultry Science Association.

Effects of ambient temperature and water vapor on chamber pressure and oxygen level during low atmospheric pressure stunning of poultry

PubMed Central

Holloway, Paul H.; Pritchard, David G.

2017-01-01

Abstract The characteristics of the vacuum used in a low atmospheric pressure stunning system to stun (render unconscious) poultry prior to slaughter are described. A vacuum chamber is pumped by a wet screw compressor. The vacuum pressure is reduced from ambient atmospheric pressure to an absolute vacuum pressure of ∼250 Torr (∼33 kPa) in ∼67 sec with the vacuum gate valve fully open. At ∼250 Torr, the sliding gate valve is partially closed to reduce effective pumping speed, resulting in a slower rate of decreasing pressure. Ambient temperature affects air density and water vapor pressure and thereby oxygen levels and the time at the minimum total pressure of ∼160 Torr (∼21 kPa) is varied from ∼120 to ∼220 sec to ensure an effective stun within the 280 seconds of each cycle. The reduction in total pressure results in a gradual reduction of oxygen partial pressure that was measured by a solid-state electrochemical oxygen sensor. The reduced oxygen pressure leads to hypoxia, which is recognized as a humane method of stunning poultry. The system maintains an oxygen concentration of <5% for at least 2 minutes, which ensures that birds are irreversibly stunned. Calculated pump down (pressure versus time) data match experimental data very closely because the programmable logic controller and the human machine interface enable precise and accurate control. The vacuum system operates in the turbulent viscous flow regime, and is best characterized by absolute vacuum pressure rather than gauge pressure. Neither the presence of broiler chickens nor different fore-line pipe designs of four parallel commercial systems affected the pressure-time data. Water in wet air always reduces the oxygen concentrations to a value lower than in dry air. The partial pressure of water and oxygen were found to depend on the pump down parameters due to the formation of fog in the chamber and desorption of water from the birds and the walls of the vacuum chamber. PMID:28521045

Cullin 5 Expression in the Rat: Cellular and Tissue Distribution, and Changes in Response to Water Deprivation and Hemorrhagic Shock

DTIC Science & Technology

2003-02-28

of Health p53 tumor suppressor PBS phosphate buffered saline PCO2 partial pressure of carbon dioxide PO2 partial pressure of oxygen PCR...buffered saline TTBS tween-20 tris buffered saline TonEBP tonicity-response enhancer binding protein TSNRP TriService Nursing Research Program...growth and metabolism (Hochstrasser, 1995; Deshaies, 1999). Although traditionally seen as no more than a means of eliminating no longer needed

A partial pressure monitor and controller for stable ozone flow from a silica gel trap

NASA Astrophysics Data System (ADS)

Stevens, R. E.; Hsiao, C.-W.; Le, Linh; Curro, N. J.; Monton, B. J.; Chang, B.-Y.; Kung, C.-Y.; Kittrell, C.; Kinsey, J. L.

1998-06-01

A new ozone trapping system designed for safe and consistent delivery to a reaction vessel is described. Silica gel is used to trap the ozone because of its known safety advantages over traps that store ozone in liquid form. The new design is free of any liquid baths, such as freon or flammable solvents. A circuit design for monitoring and controlling the ozone partial pressure of 6-25 Torr is also described.

A new approach to non-invasive oxygenated mixed venous PCO(sub)2

NASA Technical Reports Server (NTRS)

Fisher, Joseph A.; Ansel, Clifford A.

1986-01-01

A clinically practical technique was developed to calculate mixed venous CO2 partial pressure for the calculation of cardiac output by the Fick technique. The Fick principle states that the cardiac output is equal to the CO2 production divided by the arterio-venous CO2 content difference of the pulmonary vessels. A review of the principles involved in the various techniques used to estimate venous CO2 partial pressure is presented.

Mechanical Integrity of Flexible In-Zn-Sn-O Film for Flexible Transparent Electrode

NASA Astrophysics Data System (ADS)

Kim, Young Sung; Oh, Se-In; Choa, Sung-Hoon

2013-05-01

The mechanical integrity of transparent In-Zn-Sn-O (IZTO) films is investigated using outer/inner bending, stretching, and twisting tests. Amorphous IZTO films are grown using a pulsed DC magnetron sputtering system with an IZTO target on a polyimide substrate at room temperature. Changes in the optical and electrical properties of IZTO films depend on the oxygen partial pressure applied during the film deposition process. In the case of 3% oxygen partial pressure, the IZTO films exhibit s resistivity of 8.3×10-4 Ω cm and an optical transmittance of 86%. The outer bending test shows that the critical bending radius decreases from 10 to 7.5 mm when the oxygen partial pressure is increased from 1 to 3%. The inner bending test reveals that the critical bending radius of all IZTO films is 3.5 mm regardless of oxygen partial pressure. The IZTO films also show excellent mechanical reliability in the bending fatigue tests of more than 10,000 cycles. In the uniaxial stretching tests, the electrical resistance of the IZTO film does not change until a strain of 2.4% is reached. The twisting tests demonstrate that the electrical resistance of IZTO films remains unchanged up to 25°. These results suggest that IZTO films have excellent mechanical durability and flexibility in comparison with already reported crystallized indium tin oxide (ITO) films.

Oxygen availability and spreading depolarizations provide complementary prognostic information in neuromonitoring of aneurysmal subarachnoid hemorrhage patients.

PubMed

Winkler, Maren Kl; Dengler, Nora; Hecht, Nils; Hartings, Jed A; Kang, Eun J; Major, Sebastian; Martus, Peter; Vajkoczy, Peter; Woitzik, Johannes; Dreier, Jens P

2017-05-01

Multimodal neuromonitoring in neurocritical care increasingly includes electrocorticography to measure epileptic events and spreading depolarizations. Spreading depolarization causes spreading depression of activity (=isoelectricity) in electrically active tissue. If the depression is long-lasting, further spreading depolarizations occur in still isoelectric tissue where no activity can be suppressed. Such spreading depolarizations are termed isoelectric and are assumed to indicate energy compromise. However, experimental and clinical recordings suggest that long-lasting spreading depolarization-induced depression and isoelectric spreading depolarizations are often recorded outside of the actual ischemic zones, allowing the remote diagnosis of delayed cerebral ischemia after aneurysmal subarachnoid hemorrhage. Here, we analyzed simultaneous electrocorticography and tissue partial pressure of oxygen recording in 33 aneurysmal subarachnoid hemorrhage patients. Multiple regression showed that both peak total depression duration per recording day and mean baseline tissue partial pressure of oxygen were independent predictors of outcome. Moreover, tissue partial pressure of oxygen preceding spreading depolarization was similar and differences in tissue partial pressure of oxygen responses to spreading depolarization were only subtle between isoelectric spreading depolarizations and spreading depressions. This further supports that, similar to clustering of spreading depolarizations, long spreading depolarization-induced periods of isoelectricity are useful to detect energy compromise remotely, which is valuable because the exact location of future developing pathology is unknown at the time when the neurosurgeon implants recording devices.

Derivation of intermediate to silicic magma from the basalt analyzed at the Vega 2 landing site, Venus.

PubMed

Shellnutt, J Gregory

2018-01-01

Geochemical modeling using the basalt composition analyzed at the Vega 2 landing site indicates that intermediate to silicic liquids can be generated by fractional crystallization and equilibrium partial melting. Fractional crystallization modeling using variable pressures (0.01 GPa to 0.5 GPa) and relative oxidation states (FMQ 0 and FMQ -1) of either a wet (H2O = 0.5 wt%) or dry (H2O = 0 wt%) parental magma can yield silicic (SiO2 > 60 wt%) compositions that are similar to terrestrial ferroan rhyolite. Hydrous (H2O = 0.5 wt%) partial melting can yield intermediate (trachyandesite to andesite) to silicic (trachydacite) compositions at all pressures but requires relatively high temperatures (≥ 950°C) to generate the initial melt at intermediate to low pressure whereas at high pressure (0.5 GPa) the first melts will be generated at much lower temperatures (< 800°C). Anhydrous partial melt modeling yielded mafic (basaltic andesite) and alkaline compositions (trachybasalt) but the temperature required to produce the first liquid is very high (≥ 1130°C). Consequently, anhydrous partial melting is an unlikely process to generate derivative liquids. The modeling results indicate that, under certain conditions, the Vega 2 composition can generate silicic liquids that produce granitic and rhyolitic rocks. The implication is that silicic igneous rocks may form a small but important component of the northeast Aphrodite Terra.

Derivation of intermediate to silicic magma from the basalt analyzed at the Vega 2 landing site, Venus

PubMed Central

2018-01-01

Geochemical modeling using the basalt composition analyzed at the Vega 2 landing site indicates that intermediate to silicic liquids can be generated by fractional crystallization and equilibrium partial melting. Fractional crystallization modeling using variable pressures (0.01 GPa to 0.5 GPa) and relative oxidation states (FMQ 0 and FMQ -1) of either a wet (H2O = 0.5 wt%) or dry (H2O = 0 wt%) parental magma can yield silicic (SiO2 > 60 wt%) compositions that are similar to terrestrial ferroan rhyolite. Hydrous (H2O = 0.5 wt%) partial melting can yield intermediate (trachyandesite to andesite) to silicic (trachydacite) compositions at all pressures but requires relatively high temperatures (≥ 950°C) to generate the initial melt at intermediate to low pressure whereas at high pressure (0.5 GPa) the first melts will be generated at much lower temperatures (< 800°C). Anhydrous partial melt modeling yielded mafic (basaltic andesite) and alkaline compositions (trachybasalt) but the temperature required to produce the first liquid is very high (≥ 1130°C). Consequently, anhydrous partial melting is an unlikely process to generate derivative liquids. The modeling results indicate that, under certain conditions, the Vega 2 composition can generate silicic liquids that produce granitic and rhyolitic rocks. The implication is that silicic igneous rocks may form a small but important component of the northeast Aphrodite Terra. PMID:29584745

Oxidase uncoupling in heme monooxygenases: Human cytochrome P450 CYP3A4 in Nanodiscs

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

Grinkova, Yelena V.; Denisov, Ilia G.; McLean, Mark A.

Highlights: ► Substantial reducing equivalents are lost in human P450 CYP3A4 via an oxidase channel. ► Substrate binding has a pronounced effect on uncoupling in cytochrome P450. ► Anionic phospholipids improve the overall coupling in CYP3A4 Nanodiscs. -- Abstract: The normal reaction mechanism of cytochrome P450 operates by utilizing two reducing equivalents to reduce atmospheric dioxygen, producing one molecule of water and an oxygenated product in an overall stoichiometry of 2 electrons:1 dioxygen:1 product. However, three alternate unproductive pathways exist where the intermediate iron–oxygen states in the catalytic cycle can yield reduced oxygen products without substrate metabolism. The first involvesmore » release of superoxide from the oxygenated intermediate while the second occurs after input of the second reducing equivalent. Superoxide rapidly dismutates and hence both processes produce hydrogen peroxide that can be cytotoxic to the organism. In both cases, the formation of hydrogen peroxide involves the same overall stoichiometry as oxygenases catalysis. The key step in the catalytic cycle of cytochrome P450 involves scission of the oxygen–oxygen bond of atmospheric dioxygen to produce a higher valent iron-oxo state termed “Compound I”. This intermediate initiates a radical reaction in the oxygenase pathway but also can uptake two additional reducing equivalents from reduced pyridine nucleotide (NADPH) and the flavoprotein reductase to produce a second molecule of water. This non-productive decay of Compound I thus yields an overall oxygen to NADPH ratio of 1:2 and does not produce hydrocarbon oxidation. This water uncoupling reaction provides one of a limited means to study the reactivity of the critical Compound I intermediate in P450 catalysis. We measured simultaneously the rates of NADPH and oxygen consumption as a function of substrate concentration during the steady-state hydroxylation of testosterone catalyzed by human P450 CYP3A4 reconstituted in Nanodiscs. We discovered that the “oxidase” uncoupling pathway is also operating in the substrate free form of the enzyme with rate of this pathway substantially increasing with the first substrate binding event. Surprisingly, a large fraction of the reducing equivalents used by the P450 system is wasted in this oxidase pathway. In addition, the overall coupling with testosterone and bromocryptine as substrates is significantly higher in the presence of anionic lipids, which is attributed to the changes in the redox potential of CYP3A4 and reductase.« less

SSMILES.

ERIC Educational Resources Information Center

Sunal, Dennis W., Ed.; Tracy, Dyanne M., Ed.

1993-01-01

Describes an activity in which the students utilize the mathematics concepts of ratio, proportion, and data tabulation to examine the relationship between air pressure, temperature, and humidity. Students learn to approximate partial pressure by using humidity and temperature readings and by interpolating from the vapor pressure-temperature table.…

Method to Estimate the Dissolved Air Content in Hydraulic Fluid

NASA Technical Reports Server (NTRS)

Hauser, Daniel M.

2011-01-01

In order to verify the air content in hydraulic fluid, an instrument was needed to measure the dissolved air content before the fluid was loaded into the system. The instrument also needed to measure the dissolved air content in situ and in real time during the de-aeration process. The current methods used to measure the dissolved air content require the fluid to be drawn from the hydraulic system, and additional offline laboratory processing time is involved. During laboratory processing, there is a potential for contamination to occur, especially when subsaturated fluid is to be analyzed. A new method measures the amount of dissolved air in hydraulic fluid through the use of a dissolved oxygen meter. The device measures the dissolved air content through an in situ, real-time process that requires no additional offline laboratory processing time. The method utilizes an instrument that measures the partial pressure of oxygen in the hydraulic fluid. By using a standardized calculation procedure that relates the oxygen partial pressure to the volume of dissolved air in solution, the dissolved air content is estimated. The technique employs luminescent quenching technology to determine the partial pressure of oxygen in the hydraulic fluid. An estimated Henry s law coefficient for oxygen and nitrogen in hydraulic fluid is calculated using a standard method to estimate the solubility of gases in lubricants. The amount of dissolved oxygen in the hydraulic fluid is estimated using the Henry s solubility coefficient and the measured partial pressure of oxygen in solution. The amount of dissolved nitrogen that is in solution is estimated by assuming that the ratio of dissolved nitrogen to dissolved oxygen is equal to the ratio of the gas solubility of nitrogen to oxygen at atmospheric pressure and temperature. The technique was performed at atmospheric pressure and room temperature. The technique could be theoretically carried out at higher pressures and elevated temperatures.

Contributions of aortic pulse wave velocity and backward wave pressure to variations in left ventricular mass are independent of each other.

PubMed

Bello, Hamza; Norton, Gavin R; Ballim, Imraan; Libhaber, Carlos D; Sareli, Pinhas; Woodiwiss, Angela J

2017-05-01

Aortic pulse wave velocity (PWV) and backward waves, as determined from wave separation analysis, predict cardiovascular events beyond brachial blood pressure. However, the extent to which these aortic hemodynamic variables contribute independent of each other is uncertain. In 749 randomly selected participants of African ancestry, we therefore assessed the extent to which relationships between aortic PWV or backward wave pressures (Pb) (and hence central aortic pulse pressure [PPc]) and left ventricular mass index (LVMI) occur independent of each other. Aortic PWV, PPc, forward wave pressure (Pf), and Pb were determined using radial applanation tonometry and SphygmoCor software and LVMI using echocardiography; 44.5% of participants had an increased left ventricular mass indexed to height 1.7 . With adjustments for age, brachial systolic blood pressure or PP, and additional confounders, PPc and Pb, but not Pf, were independently related to LVMI and left ventricular hypertrophy (LVH) in both men and women. However, PWV was independently associated with LVMI in women (partial r = 0.16, P < .001), but not in men (partial r = 0.03), and PWV was independently associated with LVH in women (P < .05), but not in men (P = .07). With PWV and Pb included in the same multivariate regression models, PWV (partial r = 0.14, P < .005) and Pb (partial r = 0.10, P < .05) contributed to a similar extent to variations in LVMI in women. In addition, with PWV and Pb included in the same multivariate regression models, PWV (P < .05) and Pb (P < .02) contributed to LVH in women. In conclusion, aortic PWV and Pb (and hence pulse pressure) although both associated with LVMI and LVH produce effects which are independent of each other. Copyright © 2017 American Society of Hypertension. Published by Elsevier Inc. All rights reserved.

Scaling of Two-Phase Flows to Partial-Earth Gravity

NASA Technical Reports Server (NTRS)

Hurlbert, Kathryn M.; Witte, Larry C.

2003-01-01

A report presents a method of scaling, to partial-Earth gravity, of parameters that describe pressure drops and other characteristics of two-phase (liquid/ vapor) flows. The development of the method was prompted by the need for a means of designing two-phase flow systems to operate on the Moon and on Mars, using fluid-properties and flow data from terrestrial two-phase-flow experiments, thus eliminating the need for partial-gravity testing. The report presents an explicit procedure for designing an Earth-based test bed that can provide hydrodynamic similarity with two-phase fluids flowing in partial-gravity systems. The procedure does not require prior knowledge of the flow regime (i.e., the spatial orientation of the phases). The method also provides for determination of pressure drops in two-phase partial-gravity flows by use of a generalization of the classical Moody chart (previously applicable to single-phase flow only). The report presents experimental data from Mars- and Moon-activity experiments that appear to demonstrate the validity of this method.

A Theoretical Study of Methanol Oxidation on RuO 2(110): Bridging the Pressure Gap

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

Latimer, Allegra A.; Abild-Pedersen, Frank; Norskov, Jens K.

Partial oxidation catalysis is often fraught with selectivity problems, largely because there is a tendency of oxidation products to be more reactive than the starting material. One industrial process that has successfully overcome this problem is partial oxidation of methanol to formaldehyde. This process has become a global success, with an annual production of 30 million tons. Although ruthenium catalysts have not shown activity as high as the current molybdena or silver-based industrial standards, the study of ruthenium systems has the potential to elucidate which catalyst properties facilitate the desired partial oxidation reaction as opposed to deep combustion due tomore » a pressure-dependent selectivity “switch” that has been observed in ruthenium-based catalysts. In this work, we find that we are able to successfully rationalize this “pressure gap” using near-ab initio steady-state microkinetic modeling on RuO 2(110). We obtain molecular desorption prefactors from experiment and determine all other energetics using density functional theory. We show that, under ambient pressure conditions, formaldehyde production is favored on RuO 2(110), whereas under ultrahigh vacuum pressure conditions, full combustion to CO 2 takes place. We glean from our model several insights regarding how coverage effects, oxygen activity, and rate-determining steps influence selectivity and activity. As a result, we believe the understanding gained in this work might advise and inspire the greater partial oxidation community and be applied to other catalytic processes which have not yet found industrial success.« less

In situ metrology to characterize water vapor delivery during atomic layer deposition

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

Ahmido, Tariq, E-mail: tariq.ahmido@nist.gov; Kimes, William A.; Sperling, Brent A.

Water is often employed as the oxygen source in metal oxide atomic layer deposition (ALD) processes. It has been reported that variations in the amount of water delivered during metal oxide ALD can impact the oxide film properties. Hence, one contribution to optimizing metal oxide ALD processes would be to identify methods to better control water dose. The development of rapid, quantitative techniques for in situ water vapor measurements during ALD processes would be beneficial to achieve this goal. In this report, the performance of an in situ tunable diode laser absorption spectroscopy (TDLAS) scheme for performing rapid, quantitative watermore » partial pressure measurements in a representative quarter-inch ALD delivery line is described. This implementation of TDLAS, which utilizes a near-infrared distributed-feedback diode laser and wavelength modulation spectroscopy, provides measurements of water partial pressure on a timescale comparable to or shorter than the timescale of the gas dynamics in typical ALD systems. Depending on the degree of signal averaging, this TDLAS system was capable of measuring the water partial pressure with a detection limit in the range of ∼0.80 to ∼0.08 Pa. The utility of this TDLAS scheme was demonstrated by using it to identify characteristics of a representative water delivery system that otherwise would have been difficult to predict. Those characteristics include (1) the magnitude and time dependence of the pressure transient that can occur during water injection, and (2) the dependence of the steady-state water partial pressure on the carrier gas flow rate and the setting of the water ampoule flow restriction.« less

A Theoretical Study of Methanol Oxidation on RuO 2(110): Bridging the Pressure Gap

DOE PAGES

Latimer, Allegra A.; Abild-Pedersen, Frank; Norskov, Jens K.

2017-05-26

Partial oxidation catalysis is often fraught with selectivity problems, largely because there is a tendency of oxidation products to be more reactive than the starting material. One industrial process that has successfully overcome this problem is partial oxidation of methanol to formaldehyde. This process has become a global success, with an annual production of 30 million tons. Although ruthenium catalysts have not shown activity as high as the current molybdena or silver-based industrial standards, the study of ruthenium systems has the potential to elucidate which catalyst properties facilitate the desired partial oxidation reaction as opposed to deep combustion due tomore » a pressure-dependent selectivity “switch” that has been observed in ruthenium-based catalysts. In this work, we find that we are able to successfully rationalize this “pressure gap” using near-ab initio steady-state microkinetic modeling on RuO 2(110). We obtain molecular desorption prefactors from experiment and determine all other energetics using density functional theory. We show that, under ambient pressure conditions, formaldehyde production is favored on RuO 2(110), whereas under ultrahigh vacuum pressure conditions, full combustion to CO 2 takes place. We glean from our model several insights regarding how coverage effects, oxygen activity, and rate-determining steps influence selectivity and activity. As a result, we believe the understanding gained in this work might advise and inspire the greater partial oxidation community and be applied to other catalytic processes which have not yet found industrial success.« less

Infinite dilution partial molar volumes of platinum(II) 2,4-pentanedionate in supercritical carbon dioxide.

PubMed

Kong, Chang Yi; Siratori, Tomoya; Funazukuri, Toshitaka; Wang, Guosheng

2014-10-03

The effects of temperature and density on retention of platinum(II) 2,4-pentanedionate in supercritical fluid chromatography were investigated at temperatures of 308.15-343.15K and pressure range from 8 to 40MPa by the chromatographic impulse response method with curve fitting. The retention factors were utilized to derive the infinite dilution partial molar volumes of platinum(II) 2,4-pentanedionate in supercritical carbon dioxide. The determined partial molar volumes were small and positive at high pressures but exhibited very large and negative values in the highly compressible near critical region of carbon dioxide. Copyright © 2014 Elsevier B.V. All rights reserved.

Flight test evaluation of an RAF high altitude partial pressure protective assembly

NASA Technical Reports Server (NTRS)

Ashworth, G. R.; Putnam, T. W.; Dana, W. J.; Enevoldson, E. K.; Winter, W. R.

1979-01-01

A partial pressure suit was evaluated during tests in an F-104 and F-15 as a protective garment for emergency descents. The garment is an pressure jerkin and modified anti-g suit combined with an oronasal mask. The garment can be donned and doffed at the aircraft to minimize thermal buildup. The oronasal mask was favored by the pilots due to its immobility on the face during high g-loading. The garment was chosen to provide optimum dexterity for the pilot, which is not available in a full pressure suit, while protecting the pilot at altitudes up to 18,288 meters, during a cabin decompression, and subsequent aircraft descent. During cabin decompressions in the F-104 and F-15, cabin pressure altitude was measured at various aircraft angles of attack, Mach numbers, and altitudes to determine the effect of the aerodynamic slipstream on the cabin altitude.

Diaphragm electrical activity during negative lower torso pressure in quadriplegic men.

PubMed

Banzett, R B; Inbar, G F; Brown, R; Goldman, M; Rossier, A; Mead, J

1981-09-01

We recorded the diaphragm electromyogram (EMG) of quadriplegic men before and during exposure of the lower torso to continuous negative pressure, which caused shortening of the inspiratory muscles by expanding the respiratory system by one tidal volume. The moving-time-averaged diaphragm EMG was larger during expansion of the respiratory system. When we repeated the experiment with subjects who breathed through a mouthpiece, we found qualitatively similar EMG changes and little or no change in tidal volume or end-tidal CO2 partial pressure. When the pressure was applied or removed rapidly, changes in EMG occurred within one or two breaths. Because end-tidal CO2 partial pressure did not increase, and because the response was rapid, we suggest that the response results from proprioceptive, rather than chemoreceptive, reflexes. As most of these men had complete spinal lesions at C6 or C7 the afferent pathways are likely to be vagal or phrenic.

Glaucoma (image)

MedlinePlus

Glaucoma is a condition of increased fluid pressure inside the eye. The increased pressure causes compression of ... nerve which can eventually lead to nerve damage. Glaucoma can cause partial vision loss, with blindness as ...

Role of low O 2 pressure and growth temperature on electrical transport of PLD grown ZnO thin films on Si substrates

NASA Astrophysics Data System (ADS)

Pandis, Ch.; Brilis, N.; Tsamakis, D.; Ali, H. A.; Krishnamoorthy, S.; Iliadis, A. A.

2006-06-01

Undoped ZnO thin films have been grown on (100) Si substrates by pulsed laser deposition. The effect of growth parameters such as temperature, O 2 partial pressure and laser fluence on the structural and electrical properties of the films has been investigated. It is shown that the well-known native n-type conductivity, attributed to the activation of hydrogenic donor states, exhibits a conversion from n-type to p-type when the O 2 partial pressure is reduced from 10 -4 to 10 -7 Torr at growth temperatures lower than 400 °C. The p-type conductivity could be attributed to the dominant role of the acceptor Zn vacancies for ZnO films grown at very low O 2 pressures.

Oxygen transport membrane based advanced power cycle with low pressure synthesis gas slip stream

DOEpatents

Kromer, Brian R.; Litwin, Michael M.; Kelly, Sean M.

2016-09-27

A method and system for generating electrical power in which a high pressure synthesis gas stream generated in a gasifier is partially oxidized in an oxygen transport membrane based reactor, expanded and thereafter, is combusted in an oxygen transport membrane based boiler. A low pressure synthesis gas slip stream is split off downstream of the expanders and used as the source of fuel in the oxygen transport membrane based partial oxidation reactors to allow the oxygen transport membrane to operate at low fuel pressures with high fuel utilization. The combustion within the boiler generates heat to raise steam to in turn generate electricity by a generator coupled to a steam turbine. The resultant flue gas can be purified to produce a carbon dioxide product.

Generation, ascent and eruption of magma on the Moon: New insights into source depths, magma supply, intrusions and effusive/explosive eruptions (Part 1: Theory)

NASA Astrophysics Data System (ADS)

Wilson, Lionel; Head, James W.

2017-02-01

We model the ascent and eruption of lunar mare basalt magmas with new data on crustal thickness and density (GRAIL), magma properties, and surface topography, morphology and structure (Lunar Reconnaissance Orbiter). GRAIL recently measured the broad spatial variation of the bulk density structure of the crust of the Moon. Comparing this with the densities of lunar basaltic and picritic magmas shows that essentially all lunar magmas were negatively buoyant everywhere within the lunar crust. Thus positive excess pressures must have been present in melts at or below the crust-mantle interface to enable them to erupt. The source of such excess pressures is clear: melt in any region experiencing partial melting or containing accumulated melt, behaves as though an excess pressure is present at the top of the melt column if the melt is positively buoyant relative to the host rocks and forms a continuously interconnected network. The latter means that, in partial melt regions, probably at least a few percent melting must have taken place. Petrologic evidence suggests that both mare basalts and picritic glasses may have been derived from polybaric melting of source rocks in regions extending vertically for at least a few tens of km. This is not surprising: the vertical extent of a region containing inter-connected partial melt produced by pressure-release melting is approximately inversely proportional to the acceleration due to gravity. Translating the ∼25 km vertical extent of melting in a rising mantle diapir on Earth to the Moon then implies that melting could have taken place over a vertical extent of up to 150 km. If convection were absent, melting could have occurred throughout any region in which heat from radioisotope decay was accumulating; in the extreme this could have been most of the mantle. The maximum excess pressure that can be reached in a magma body depends on its environment. If melt percolates upward from a partial melt zone and accumulates as a magma reservoir, either at the density trap at the base of the crust or at the rheological trap at the base of the elastic lithosphere, the excess pressure at the top of the magma body will exert an elastic stress on the overlying rocks. This will eventually cause them to fail in tension when the excess pressure has risen to close to twice the tensile strength of the host rocks, perhaps up to ∼10 MPa, allowing a dike to propagate upward from this point. If partial melting occurs in a large region deep in the mantle, however, connections between melt pockets and veins may not occur until a finite amount, probably a few percent, of melting has occurred. When interconnection does occur, the excess pressure at the top of the partial melt zone will rise abruptly to a high value, again initiating a brittle fracture, i.e. a dike. That sudden excess pressure is proportional to the vertical extent of the melt zone, the difference in density between the host rocks and the melt, and the acceleration due to gravity, and could readily be ∼100 MPa, vastly greater than the value needed to initiate a dike. We therefore explored excess pressures in the range ∼10 to ∼100 MPa. If eruptions take place through dikes extending upward from the base of the crust, the mantle magma pressure at the point where the dike is initiated must exceed the pressure due to the weight of the magmatic liquid column. This means that on the nearside the excess pressure must be at least ∼19 ± 9 MPa and on the farside must be ∼29 ± 15 MPa. If the top of the magma body feeding an erupting dike is a little way below the base of the crust, slightly smaller excess pressures are needed because the magma is positively buoyant in the part of the dike within the upper mantle. Even the smallest of these excess pressures is greater than the ∼10 MPa likely maximum value in a magma reservoir at the base of the crust or elastic lithosphere, but the values are easily met by the excess pressures in extensive partial melt zones deeper within the mantle. Thus magma accumulations at the base of the crust would have been able to intrude dikes part-way through the crust, but not able to feed eruptions to the surface; in order to be erupted, magma must have been extracted from deeper mantle sources, consistent with petrologic evidence. Buoyant dikes growing upward from deep mantle sources of partial melt can disconnect from their source regions and travel through the mantle as isolated bodies of melt that encounter and penetrate the crust-mantle density boundary. They adjust their lengths and internal pressure excesses so that the stress intensity at the lower tip is zero. The potential total vertical extent of the resulting melt body depends on the vertical extent of the source region from which it grew. For small source extents, the upper tip of the resulting dike crossing the crust-mantle boundary cannot reach the surface anywhere on the Moon and therefore can only form a dike intrusion; for larger source extents, the dike can reach the surface and erupt on the nearside but still cannot reach the surface on the farside; for even larger source extents, eruptions could occur on both the nearside and the farside. The paucity of farside eruptions therefore implies a restricted range of vertical extents of partial melt source region sizes, between ∼16 and ∼36 km. When eruptions can occur, the available pressure in excess of what is needed to support a static magma column to the surface gives the pressure gradient driving magma flow. The resulting typical turbulent magma rise speeds are ∼10 to a few tens of m s-1, dike widths are of order 100 m, and eruption rates from 1 to 10 km long fissure vents are of order 105 to 106 m3 s-1. Volume fluxes in lunar eruptions derived from lava flow thicknesses and surface slopes or rille lengths and depths are found to be of order 105 to 106 m3 s-1 for volume-limited lava flows and >104 to 105 m3 s-1 for sinuous rilles, with dikes widths of ∼50 m. The lower end of the volume flux range for sinuous rilles corresponds to magma rise speeds approaching the limit set by the fact that excessive cooling would occur during flow up a 30 km long dike kept open by a very low excess pressure. These eruptions were thus probably fed by partial melt zones deep in the mantle. Longer eruption durations, rather than any subtle topographic slope effects, appear to be the key to the ability of these flows to erode sinuous rille channels. We conclude that: (1) essentially all lunar magmas were negatively buoyant everywhere within the crust; (2) positive excess pressures of at least 20-30 MPa must have been present in mantle melts at or below the crust-mantle interface to drive magmas to the surface; (3) such pressures are easily produced in zones of partial melting by pressure-release during mantle convection or simple heat accumulation from radioisotopes; (4) magma volume fluxes available from dikes forming at the tops of partial melt zones are consistent with the 105 to 106 m3 s-1 volume fluxes implied by earlier analyses of surface flows; (5) eruptions producing thermally-eroded sinuous rille channels involved somewhat smaller volume fluxes of magma where the supply rate may be limited by the rate of extraction of melt percolating through partial melt zones.

Simultaneous velocity and pressure quantification using pressure-sensitive flow tracers in air

NASA Astrophysics Data System (ADS)

Zhang, Peng; Peterson, Sean; Porfiri, Maurizio

2017-11-01

Particle-based measurement techniques for assessing the velocity field of a fluid have advanced rapidly over the past two decades. Full-field pressure measurement techniques have remained elusive, however. In this work, we aim to demonstrate the possibility of direct simultaneous planar velocity and pressure measurement of a high speed aerodynamic flow by employing novel pressure-sensitive tracer particles for particle image velocimetry (PIV). Specifically, the velocity and pressure variations of an airflow through a converging-diverging channel are studied. Polystyrene microparticles embedded with a pressure-sensitive phosphorescent dye-platinum octaethylporphyrin (PtOEP)-are used as seeding particles. Due to the oxygen quenching effect, the emission lifetime of PtOEP is highly sensitive to the oxygen concentration, that is, the partial pressure of oxygen, in the air. Since the partial pressure of oxygen is linearly proportional to the air pressure, we can determine the air pressure through the phosphorescence emission lifetime of the dye. The velocity field is instead obtained using traditional PIV methods. The particles have a pressure resolution on the order of 1 kPa, which may be improved by optimizing the particle size and dye concentration to suit specific flow scenarios. This work was supported by the National Science Foundation under Grant Number CBET-1332204.

Cystic fibrosis airway secretions exhibit mucin hyperconcentration and increased osmotic pressure

PubMed Central

Henderson, Ashley G.; Ehre, Camille; Button, Brian; Abdullah, Lubna H.; Cai, Li-Heng; Leigh, Margaret W.; DeMaria, Genevieve C.; Matsui, Hiro; Donaldson, Scott H.; Davis, C. William; Sheehan, John K.; Boucher, Richard C.; Kesimer, Mehmet

2014-01-01

The pathogenesis of mucoinfective lung disease in cystic fibrosis (CF) patients likely involves poor mucus clearance. A recent model of mucus clearance predicts that mucus flow depends on the relative mucin concentration of the mucus layer compared with that of the periciliary layer; however, mucin concentrations have been difficult to measure in CF secretions. Here, we have shown that the concentration of mucin in CF sputum is low when measured by immunologically based techniques, and mass spectrometric analyses of CF mucins revealed mucin cleavage at antibody recognition sites. Using physical size exclusion chromatography/differential refractometry (SEC/dRI) techniques, we determined that mucin concentrations in CF secretions were higher than those in normal secretions. Measurements of partial osmotic pressures revealed that the partial osmotic pressure of CF sputum and the retained mucus in excised CF lungs were substantially greater than the partial osmotic pressure of normal secretions. Our data reveal that mucin concentration cannot be accurately measured immunologically in proteolytically active CF secretions; mucins are hyperconcentrated in CF secretions; and CF secretion osmotic pressures predict mucus layer–dependent osmotic compression of the periciliary liquid layer in CF lungs. Consequently, mucin hypersecretion likely produces mucus stasis, which contributes to key infectious and inflammatory components of CF lung disease. PMID:24892808

A Double-Blinded, Randomized Comparison of Medetomidine-Tiletamine-Zolazepam and Dexmedetomidine-Tiletamine-Zolazepam Anesthesia in Free-Ranging Brown Bears (Ursus Arctos)

PubMed Central

Cattet, Marc; Zedrosser, Andreas; Stenhouse, Gordon B.; Küker, Susanne; Evans, Alina L.; Arnemo, Jon M.

2017-01-01

We compared anesthetic features, blood parameters, and physiological responses to either medetomidine-tiletamine-zolazepam or dexmedetomidine-tiletamine-zolazepam using a double-blinded, randomized experimental design during 40 anesthetic events of free-ranging brown bears (Ursus arctos) either captured by helicopter in Sweden or by culvert trap in Canada. Induction was smooth and predictable with both anesthetic protocols. Induction time, the need for supplemental drugs to sustain anesthesia, and capture-related stress were analyzed using generalized linear models, but anesthetic protocol did not differentially affect these variables. Arterial blood gases and acid-base status, and physiological responses were examined using linear mixed models. We documented acidemia (pH of arterial blood < 7.35), hypoxemia (partial pressure of arterial oxygen < 80 mmHg), and hypercapnia (partial pressure of arterial carbon dioxide ≥ 45 mmHg) with both protocols. Arterial pH and oxygen partial pressure were similar between groups with the latter improving markedly after oxygen supplementation (p < 0.001). We documented dose-dependent effects of both anesthetic protocols on induction time and arterial oxygen partial pressure. The partial pressure of arterial carbon dioxide increased as respiratory rate increased with medetomidine-tiletamine-zolazepam, but not with dexmedetomidine-tiletamine-zolazepam, demonstrating a differential drug effect. Differences in heart rate, respiratory rate, and rectal temperature among bears could not be attributed to the anesthetic protocol. Heart rate increased with increasing rectal temperature (p < 0.001) and ordinal day of capture (p = 0.002). Respiratory rate was significantly higher in bears captured by helicopter in Sweden than in bears captured by culvert trap in Canada (p < 0.001). Rectal temperature significantly decreased over time (p ≤ 0.05). Overall, we did not find any benefit of using dexmedetomidine-tiletamine-zolazepam instead of medetomidine-tiletamine-zolazepam in the anesthesia of brown bears. Both drug combinations appeared to be safe and reliable for the anesthesia of free-ranging brown bears captured by helicopter or by culvert trap. PMID:28118413

Partial melting of TTG gneisses: crustal contamination and the production of granitic melts

NASA Astrophysics Data System (ADS)

Meade, F. C.; Masotta, M.; Troll, V. R.; Freda, C.; Johnson, T. E.; Dahren, B.

2011-12-01

Understanding partial melting of ancient TTG gneiss terranes is crucial when considering crustal contamination in volcanic systems, as these rocks are unlikely to melt completely at magmatic temperatures (1000-1200 °C) and crustal pressures (<500 MPa). Variations in the bulk composition of the gneiss, magma temperature, pressure (depth) and the composition and abundance of any fluids present will produce a variety of melt compositions, from partial melts enriched in incompatible elements to more complete melts, nearing the bulk chemistry of the parent gneiss. We have used piston cylinder experiments to simulate partial melting in a suite of 12 gneisses from NW Scotland (Lewisian) and Eastern Greenland (Ammassalik, Liverpool Land) under magma chamber temperature and pressure conditions (P=200 MPa, T=975 °C). These gneisses form the basement to much of the North Atlantic Igneous Province, where crustal contamination of magmas was commonplace but the composition of the crustal partial melts are poorly constrained [1]. The experiments produced partial melts in all samples (e.g. Fig 1). Electron microprobe analyses of glasses indicate they are compositionally heterogeneous and are significantly different from the whole rock chemistry of the parent gneisses. The melts have variably evolved compositions but are typically trachy-dacitic to rhyolitic (granitic). This integrated petrological, experimental and in-situ geochemical approach allows quantification of the processes of partial melting of TTG gneiss in a volcanic context, providing accurate major/trace element and isotopic (Sr, Pb) end-members for modeling crustal contamination. The experimental melts and restites will be compared geochemically with a suite of natural TTG gneisses, providing constraints on the extent to which the gneisses have produced and subsequently lost melt. [1] Geldmacher et al. (2002) Scottish Journal of Geology, v.38, p.55-61.

STRUCTURE AND PHYSICAL PROPERTIES OF SOLID AND LIQUID VANADIUM PENTOXIDE.

DTIC Science & Technology

The electrical resistivity of near-stoichiometric crystalline V2O5 was measured as a function of crystal orientation and oxygen partial pressure from...25C to 300C. Conductivity is insensitive to ambient atmosphere. The activation energy for conduction is 0.20 ev. Molten V2O5 , however, is...sensitive to oxygen partial pressure. Its conductivity is proportional to P-O2 to the -1/6th power. Anomalously high electrical resistivity was observed for glassy V2O5 films. (Author)

Assessment of Correlation of Distal Mean Arterial Pressure with Aortic Blood Flow during Partial Resuscitative Endovascular Balloon Aortic Occlusion (P-REBOA) in a Swine (Sus scrofa) Controlled Hemorrhage Model

DTIC Science & Technology

2017-11-06

60th Medical Group (AMC), Travis AFB, CA INSTITUTIONAL ANIMAL CARE AND USE COMMITTEE (IACUC) FINAL REPORT SUMMARY (Please type all information. Use...Pressure with Aortic Blood Flow during Partial Resuscitative Endovascular Balloon Aortic Occlusion (P-REBOA) in a Swine (Sus scrofa) Controlled Hemorrhage...to Date Sus scrofa 8 8 2. PROTOCOL TYPE /CHARACTERISTICS: (Check all applicable terms in EACH column) _ Training: Live Animal Medical Readiness

Shear Banding in a Partially Molten Mantle

NASA Astrophysics Data System (ADS)

Alisic, L.; Rudge, J. F.; Wells, G.; Katz, R. F.; Rhebergen, S.

2013-12-01

We investigate the nonlinear behaviour of partially molten mantle material under shear. Numerical models of compaction and advection-diffusion of a porous matrix with a spherical inclusion are built using the automated code generation package FEniCS. The time evolution of melt distribution with increasing shear in these models is compared to laboratory experiments that show high-porosity shear banding in the medium and pressure shadows around the inclusion. We focus on understanding the interaction between these shear bands and pressure shadows as a function of rheological parameters.

Cu-catalyzed esterification reaction via aerobic oxygenation and C-C bond cleavage: an approach to α-ketoesters.

PubMed

Zhang, Chun; Feng, Peng; Jiao, Ning

2013-10-09

The Cu-catalyzed novel aerobic oxidative esterification reaction of 1,3-diones for the synthesis of α-ketoesters has been developed. This method combines C-C σ-bond cleavage, dioxygen activation and oxidative C-H bond functionalization, as well as provides a practical, neutral, and mild synthetic approach to α-ketoesters which are important units in many biologically active compounds and useful precursors in a variety of functional group transformations. A plausible radical process is proposed on the basis of mechanistic studies.

Bio-mimicking galactose oxidase and hemocyanin, two dioxygen-processing copper proteins.

PubMed

Gamez, Patrick; Koval, Iryna A; Reedijk, Jan

2004-12-21

The modelling of the active sites of metalloproteins is one of the most challenging tasks in bio-inorganic chemistry. Copper proteins form part of this stimulating field of research as copper enzymes are mainly involved in oxidation bio-reactions. Thus, the understanding of the structure-function relationship of their active sites will allow the design of effective and environmental friendly oxidation catalysts. This perspective illustrates some outstanding structural and functional synthetic models of the active site of copper proteins, with special attention given to models of galactose oxidase and hemocyanin.

Mechanism for chelated sulfate formation from SO2 and bis (triphenylphosphine) platinum

NASA Technical Reports Server (NTRS)

Mehandru, S. P.; Anderson, A. B.

1985-01-01

Structure and energy surface calculations using the atom superposition and electron delocalization molecular orbital theory show that the first step in the reaction between SO2 and the dioxygen complex (PPh3)2PtO2 is the coordination of SO2 with one oxygen atom of the complex, followed by metal-oxygen bond breaking and reorientation, leading to a five-membered cyclic structure. This then rearranges to form the bidentate coordinated sulfate. Alternative pathways are considered and are found to be less favorable.

The human Krebs cycle 2-oxoglutarate dehydrogenase complex creates an additional source of superoxide/hydrogen peroxide from 2-oxoadipate as alternative substrate.

PubMed

Nemeria, Natalia S; Gerfen, Gary; Guevara, Elena; Nareddy, Pradeep Reddy; Szostak, Michal; Jordan, Frank

2017-07-01

Recently, we reported that the human 2-oxoglutarate dehydrogenase (hE1o) component of the 2-oxoglutarate dehydrogenase complex (OGDHc) could produce the reactive oxygen species superoxide and hydrogen peroxide (detected by chemical means) from its substrate 2-oxoglutarate (OG), most likely concurrently with one-electron oxidation by dioxygen of the thiamin diphosphate (ThDP)-derived enamine intermediate to a C2α-centered radical (detected by Electron Paramagnetic Resonance) [Nemeria et al., 2014 [17]; Ambrus et al. 2015 [18

New iron-sulfur clusters help hydrogenases tolerate oxygen.

PubMed

Grubel, Katarzyna; Holland, Patrick L

2012-04-02

One S less: recent crystallographic studies have revealed a new, oxygen-tolerant kind of iron-sulfide cluster [4Fe-3S], which contains only three rather than four sulfur atoms in its cage (see picture; yellow=S, red=Fe, blue=N, green=cysteine). It is proposed that the cluster's ability to transfer multiple electrons increases the oxygen tolerance by enabling the enzyme to reduce O(2) rapidly, converting the dioxygen into harmless water before it can damage the protein. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The development of a three-dimensional partially elliptic flow computer program for combustor research

NASA Technical Reports Server (NTRS)

Pan, Y. S.

1978-01-01

A three dimensional, partially elliptic, computer program was developed. Without requiring three dimensional computer storage locations for all flow variables, the partially elliptic program is capable of predicting three dimensional combustor flow fields with large downstream effects. The program requires only slight increase of computer storage over the parabolic flow program from which it was developed. A finite difference formulation for a three dimensional, fully elliptic, turbulent, reacting, flow field was derived. Because of the negligible diffusion effects in the main flow direction in a supersonic combustor, the set of finite-difference equations can be reduced to a partially elliptic form. Only the pressure field was governed by an elliptic equation and requires three dimensional storage; all other dependent variables are governed by parabolic equations. A numerical procedure which combines a marching integration scheme with an iterative scheme for solving the elliptic pressure was adopted.

Measuring N2 Pressure Using Cyanobacteria

NASA Astrophysics Data System (ADS)

Silverman, S. N.; Kopf, S.; Gordon, R.; Bebout, B.; Som, S.

2017-11-01

We have shown that cyanobacteria can record information about N2 partial pressure both morphologically and isotopically, and thus may serve as useful geobarometers to help us better understand Earth's ancient atmosphere.

Effects of changing body position on oxygenation and arterial blood pressures in foals anesthetized with guaifenesin, ketamine, and xylazine.

PubMed

Braun, Christina; Trim, Cynthia M; Eggleston, Randy B

2009-01-01

To investigate the impact of a change in body position on blood gases and arterial blood pressures in foals anesthetized with guaifenesin, ketamine, and xylazine. Prospective, randomized experimental study. Twelve Quarter Horse foals, age of 5.4 +/-0.9 months and weighing 222 +/- 48 kg. Foals were anesthetized with guaifenesin, ketamine, and xylazine for 40 minutes in lateral recumbency and then assigned to a change in lateral recumbency after hoisting (Group 1, n = 6), or no change (Group 2, n = 6). Oxygen 15 L minute(-1) was insufflated into the endotracheal tube throughout anesthesia. Arterial blood pressure, heart rate, respiratory rate (f(R)), inspired fraction of oxygen (FIO(2)), and end-tidal carbon dioxide (PE'CO(2)) were measured every 5 minutes. Arterial pH and blood gases [arterial partial pressure of oxygen (PaO(2)), arterial partial pressure of carbon dioxide (PaCO(2))] were measured at 10, 30, and 40 minutes after induction, and 5 minutes after hoisting. Alveolar dead space ventilation and PaO(2)/FIO(2) were calculated. Two repeated measures models were used. All hypothesis tests were two-sided and significance level was alpha = 0.05. All values are presented as least square means +/- SE. Values at time-matched points from the two groups were not significantly different so they were combined. Arterial partial pressure of oxygen decreased significantly from 149 +/- 14.4 mmHg before hoisting to 92 +/- 11.6 mmHg after hoisting (p = 0.0013). The PaO(2)/FIO(2) ratio decreased from 275 +/- 30 to 175 +/- 24 (p = 0.0055). End-tidal carbon dioxide decreased significantly from 48.7 +/- 1.6 to 44.5 +/- 1.2 mmHg (p = 0.021). Arterial partial pressure of carbon dioxide, blood pressures and heart rates measured 5 minutes after hoisting were not different from measurements obtained before hoisting. Hoisting decreased PaO(2) in anesthetized healthy foals. Administration of supplemental oxygen is recommended to counter the decrease in oxygenation and PaO(2) measurement is necessary to detect early changes.

The System Forsterite-Diopside-Enstatite up to 70 kbar and its Significance to the Genesis of Komatiites

NASA Astrophysics Data System (ADS)

Dasgupta, S.; Gupta, A. K.

2011-12-01

Liquidus phase relations in the system forsterite-diopside-enstatite has been made at 70 kbar under anhydrous conditions using a Walker-type multi-anvil high pressure apparatus. Positions of the pseudoeutectic/ invariant, minimum points and amount of solid solutions of appearing phases are summarized in table 1. Comparison of these phase relations with those conducted by previous investigators at lower pressures and temperatures shows that the fosterite-pyroxene liquidus boundary shifts toward forsterite and away from the diopside apex with increasing pressure. Microprobe analyses indicate that the maximum amount of MgSiO3 that can be incorporated in diopside increases with pressure, and at the solidus (70 kbar, 2010°C), it is about 82%. On the basis of EPMA analyses of coexisting liquid and crystalline phases, three-phase triangles have been constructed. It is observed that at 70 kbar, the early partial melt generated from a model peridotite does not precipitate orthopyroxene. If such a melt instead of crystallizing in-situ, ascend to the surface, then the polybaric-polythermal crystallization path should never intersect the liquidus phase field of orthopyroxene, enstatitess may then appear in the solidus as an exsolution product. Our calculation shows that at 31% partial melting of a model mantle, orthopyroxene should appear as a liquidus phase. With further increase in the degree of partial melting (42-60%), proportion of orthopyroxene crystallizing from the melt progressively increases. With reference to the above discussion we propose that the Gorgona komatiites which are primarily orthopyroxene-deficient komatiites, are an outcome of low degree of partial melting, whereas the orthopyroxene-bearing Commondale komatiites of the southern Kaapvaal Craton, South Africa, are the outcome of a larger degree of partial melting, both generated from melting of an anhydrous mantle.

Gd Ba Cu O bulk superconductors fabricated by a seeded infiltration growth technique under reduced oxygen partial pressure

NASA Astrophysics Data System (ADS)

Iida, K.; Babu, N. H.; Shi, Y. H.; Cardwell, D. A.; Murakami, M.

2006-06-01

Single-grain Gd-Ba-Cu-O (GdBCO) bulk superconductors have been grown by a seeded infiltration and growth (SIG) technique under a 1% O2+N2 atmosphere using a generic MgO-doped Nd-Ba-Cu-O (MgO-NdBCO) seed placed on the sample surface at room temperature (the so-called the cold-seeding method). Partial melting of the MgO-NdBCO seeds fabricated in air under notionally identical thermal processing conditions, however, limited the reliability of this bulk GdBCO single-grain process. The observed seed decomposition is attributed to the dependence of the peritectic temperature Tp of MgO-doped Nd1+xBa2-xCu3Oy solid solution (MgO-doped Nd-123ss, where ss indicates solid solution) compounds on both oxygen partial pressure during the melt process and the level of solid solution (x). The peritectic decomposition temperature of MgO-doped Nd-123ss, with x ranging from 0 to 0.5 under p(O2) = 1.00 atm, was observed to remain constant at 1120 °C. Tp was observed to decrease linearly as a function of solid solution level, on the other hand, under oxygen partial pressures of both p(O2) = 0.21 and 0.01 atm. Based on these results, MgO-doped NdBCO seed crystals should be grown under reduced oxygen partial pressure in order to obtain a stable MgO-doped NdBCO seed crystal suitable for cold-seeding processes of large-grain (RE)BCO bulk superconductors (where RE is a rare earth element).

Studying pressure denaturation of a protein by molecular dynamics simulations.

PubMed

Sarupria, Sapna; Ghosh, Tuhin; García, Angel E; Garde, Shekhar

2010-05-15

Many globular proteins unfold when subjected to several kilobars of hydrostatic pressure. This "unfolding-up-on-squeezing" is counter-intuitive in that one expects mechanical compression of proteins with increasing pressure. Molecular simulations have the potential to provide fundamental understanding of pressure effects on proteins. However, the slow kinetics of unfolding, especially at high pressures, eliminates the possibility of its direct observation by molecular dynamics (MD) simulations. Motivated by experimental results-that pressure denatured states are water-swollen, and theoretical results-that water transfer into hydrophobic contacts becomes favorable with increasing pressure, we employ a water insertion method to generate unfolded states of the protein Staphylococcal Nuclease (Snase). Structural characteristics of these unfolded states-their water-swollen nature, retention of secondary structure, and overall compactness-mimic those observed in experiments. Using conformations of folded and unfolded states, we calculate their partial molar volumes in MD simulations and estimate the pressure-dependent free energy of unfolding. The volume of unfolding of Snase is negative (approximately -60 mL/mol at 1 bar) and is relatively insensitive to pressure, leading to its unfolding in the pressure range of 1500-2000 bars. Interestingly, once the protein is sufficiently water swollen, the partial molar volume of the protein appears to be insensitive to further conformational expansion or unfolding. Specifically, water-swollen structures with relatively low radii of gyration have partial molar volume that are similar to that of significantly more unfolded states. We find that the compressibility change on unfolding is negligible, consistent with experiments. We also analyze hydration shell fluctuations to comment on the hydration contributions to protein compressibility. Our study demonstrates the utility of molecular simulations in estimating volumetric properties and pressure stability of proteins, and can be potentially extended for applications to protein complexes and assemblies. Proteins 2010. (c) 2009 Wiley-Liss, Inc.

Tested Demonstrations.

ERIC Educational Resources Information Center

Gilbert, George L.

1983-01-01

An apparatus is described in which effects of pressure, volume, and temperature changes on a gas can be observed simultaneously. Includes use of the apparatus in demonstrating Boyle's, Gay-Lussac's, and Charles' Laws, attractive forces, Dalton's Law of Partial pressures, and in illustrating measurable vapor pressures of liquids and some solids.…

High pressure effects on U L 3 x-ray absorption in partial fluorescence yield mode and single crystal x-ray diffraction in the heavy fermion compound UCd 11

DOE PAGES

Nasreen, Farzana; Antonio, Daniel; VanGennep, Derrick; ...

2016-02-15

© 2016 IOP Publishing Ltd. We report a study of high pressure x-ray absorption (XAS) performed in the partial fluorescence yield mode (PFY) at the U L 3 edge (0-28.2 GPa) and single crystal x-ray diffraction (SXD) (0-20 GPa) on the UCd 11 heavy fermion compound at room temperature. Under compression, the PFY-XAS results show that the white line is shifted by +4.1(3) eV at the highest applied pressure of 28.2 GPa indicating delocalization of the 5f electrons. The increase in full width at half maxima and decrease in relative amplitude of the white line with respect to the edgemore » jump point towards 6d band broadening under high pressure. A bulk modulus of K 0 = 62(1) GPa and its pressure derivative, = 4.9(2) was determined from high pressure SXD results. Both the PFY-XAS and diffraction results do not show any sign of a structural phase transition in the applied pressure range.« less

Effect of prolonged hypokinesia on resistance of resistive vessels in rats

NASA Technical Reports Server (NTRS)

Saltykova, V. A.

1982-01-01

Under the effect of prolonged hypokinesia, the perfusion pressure in resistive vessels, measured under conditions of deep anesthesia and complete denervation, increased by approximately the same degree as arterial pressure in non-anesthetized animals. The increase in arterial, perfusion pressure and the resistance of resistive vessels in animals subjected to prolonged hypokinesia was accompanied by an increase in adrenoreactivity. During prolonged hypokinesia, partial obliteration of the vascular bed of the skeletal muscles plays a significant role in the observed increase in resistance of vessels of the extremities. The increase in adrenoreactivity of the vessels during hypokinesia may be realized as a partial case of an increase in the adrenoreactivity of structures whose innervation is disturbed.

Mass flow and velocity profiles in Neurospora hyphae: partial plug flow dominates intra-hyphal transport.

PubMed

Abadeh, Aryan; Lew, Roger R

2013-11-01

Movement of nuclei, mitochondria and vacuoles through hyphal trunks of Neurospora crassa were vector-mapped using fluorescent markers and green fluorescent protein tags. The vectorial movements of all three were strongly correlated, indicating the central role of mass (bulk) flow in cytoplasm movements in N. crassa. Profiles of velocity versus distance from the hyphal wall did not match the parabolic shape predicted by the ideal Hagen-Poiseuille model of flow at low Reynolds number. Instead, the profiles were flat, consistent with a model of partial plug flow due to the high concentration of organelles in the flowing cytosol. The intra-hyphal pressure gradients were manipulated by localized external osmotic treatments to demonstrate the dependence of velocity (and direction) on pressure gradients within the hyphae. The data support the concept that mass transport, driven by pressure gradients, dominates intra-hyphal transport. The transport occurs by partial plug flow due to the organelles in the cytosol.

Undergraduate students' misconceptions about respiratory physiology.

PubMed

Michael, J A; Richardson, D; Rovick, A; Modell, H; Bruce, D; Horwitz, B; Hudson, M; Silverthorn, D; Whitescarver, S; Williams, S

1999-12-01

Approximately 700 undergraduates studying physiology at community colleges, a liberal arts college, and universities were surveyed to determine the prevalence of our misconceptions about respiratory phenomena. A misconception about the changes in breathing frequency and tidal volume (physiological variables whose changes can be directly sensed) that result in increased minute ventilation was found to be present in this population with comparable prevalence (approximately 60%) to that seen in a previous study. Three other misconceptions involving phenomena that cannot be experienced directly and therefore were most likely learned in some educational setting were found to be of varying prevalence. Nearly 90% of the students exhibited a misconception about the relationship between arterial oxygen partial pressure and hemoglobin saturation. Sixty-six percent of the students believed that increasing alveolar oxygen partial pressure leads to a decrease in alveolar carbon dioxide partial pressure. Nearly 33% of the population misunderstood the relationship between metabolism and ventilation. The possible origins of these respiratory misconceptions are discussed and suggestions for how to prevent and/or remediate them are proposed.

Nanocrystalline films for gas-reactive applications

DOEpatents

Eastman, Jeffrey A.; Thompson, Loren J.

2004-02-17

A gas sensor for detection of oxidizing and reducing gases, including O.sub.2, CO.sub.2, CO, and H.sub.2, monitors the partial pressure of a gas to be detected by measuring the temperature rise of an oxide-thin-film-coated metallic line in response to an applied electrical current. For a fixed input power, the temperature rise of the metallic line is inversely proportional to the thermal conductivity of the oxide coating. The oxide coating contains multi-valent cation species that change their valence, and hence the oxygen stoichiometry of the coating, in response to changes in the partial pressure of the detected gas. Since the thermal conductivity of the coating is dependent on its oxygen stoichiometry, the temperature rise of the metallic line depends on the partial pressure of the detected gas. Nanocrystalline (<100 nm grain size) oxide coatings yield faster sensor response times than conventional larger-grained coatings due to faster oxygen diffusion along grain boundaries rather than through grain interiors.

A comparative study on NbOx films reactively sputtered from sintered and cold gas sprayed targets

NASA Astrophysics Data System (ADS)

Lorenz, Roland; O'Sullivan, Michael; Fian, Alexander; Sprenger, Dietmar; Lang, Bernhard; Mitterer, Christian

2018-04-01

The aim of this work is to evaluate novel cold gas sprayed Nb targets in a reactive sputter deposition process of thin films with respect to the widely used sintered Nb targets. With the exception of a higher target discharge voltage of ∼100 V for the cold gas sprayed targets and the thus higher film growth rate compared to sintered targets, NbOx films with comparable microstructure and properties were obtained for both target variants. The amorphous films with thicknesses between 2.9 and 4.9 μm present an optical shift from dark and non-transparent towards transparent properties, as the oxygen partial pressure increases. X-ray photoelectron spectroscopy confirms the occurrence of the Nb5+ oxidation state for the highest oxygen partial pressure, while Nb4+ is additionally present at lower oxygen partial pressure settings. With a maximal transparency of ∼80% and a refractive index of ∼2.5, the transparent films show characteristics similar to Nb2O5.

A flowing liquid test system for assessing the linearity and time-response of rapid fibre optic oxygen partial pressure sensors.

PubMed

Chen, R; Hahn, C E W; Farmery, A D

2012-08-15

The development of a methodology for testing the time response, linearity and performance characteristics of ultra fast fibre optic oxygen sensors in the liquid phase is presented. Two standard medical paediatric oxygenators are arranged to provide two independent extracorporeal circuits. Flow from either circuit can be diverted over the sensor under test by means of a system of rapid cross-over solenoid valves exposing the sensor to an abrupt change in oxygen partial pressure, P O2. The system is also capable of testing the oxygen sensor responses to changes in temperature, carbon dioxide partial pressure P CO2 and pH in situ. Results are presented for a miniature fibre optic oxygen sensor constructed in-house with a response time ≈ 50 ms and a commercial fibre optic sensor (Ocean Optics Foxy), when tested in flowing saline and stored blood. Copyright © 2012 Elsevier B.V. All rights reserved.

Chemical reactions and morphological stability at the Cu/Al2O3 interface.

PubMed

Scheu, C; Klein, S; Tomsia, A P; Rühle, M

2002-10-01

The microstructures of diffusion-bonded Cu/(0001)Al2O3 bicrystals annealed at 1000 degrees C at oxygen partial pressures of 0.02 or 32 Pa have been studied with various microscopy techniques ranging from optical microscopy to high-resolution transmission electron microscopy. The studies revealed that for both oxygen partial pressures a 20-35 nm thick interfacial CuAlO2 layer formed, which crystallises in the rhombohedral structure. However, the CuAlO2 layer is not continuous, but interrupted by many pores. In the samples annealed in the higher oxygen partial pressure an additional reaction phase with a needle-like structure was observed. The needles are several millimetres long, approximately 10 microm wide and approximately 1 microm thick. They consist of CuAlO2 with alternating rhombohedral and hexagonal structures. Solid-state contact angle measurements were performed to derive values for the work of adhesion. The results show that the adhesion is twice as good for the annealed specimen compared to the as-bonded sample.

Lunar mass spectrometer test program

NASA Technical Reports Server (NTRS)

Torney, F. L.; Dobrott, J. R.

1972-01-01

The procedures are described along with results obtained in a test program conducted to demonstrate the performance of a candidate lunar mass spectrometer. The instrument was designed to sample and measure gases believed to exist in the lunar atmosphere at the surface. The subject instrument consists of a cold cathode ion source, a small quadrupole mass analyzer and an off axis electron multiplier ion counting detector. The major program emphasis was placed on demonstrating instrument resolution, sensitivity and S/N ratio over the mass range 0-150 amu and over a partial pressure range from 10 to the minus 9th power to 10 to the minus 13th power torr. Ultrahigh vacuum tests were conducted and the minimum detectable partial pressure for neon, argon, krypton and xenon was successfully determined for the spectrometer using isotopes of these gases. With the exception of neon, the minimum detectable partial pressure is approximately 4 x 10 to the minus 14th power torr for the above gases.

Experimental study of catalytic hydrogenation by using an in-situ hydrogen measuring technique. Final report

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

Chiang, S.H.; Klinzing, G.E.; Cheng, Y.S.

1984-12-01

An in-situ technique for measuring hydrogen concentration (partial pressure) had been previously used to measure static properties (hydrogen solubilities, vapor pressures of hydrocarbons, etc.). Because of its good precision (2% relative error) and relatively short respond time (9.7 to 2.0 seconds at 589 to 728K), the technique was successfully applied to a dynamic study of hydrogenation reactions in this work. Furthermore, the technique is to be tested for industrial uses. Hydrogen/1-methylnaphthalene system was experimentally investigated in a one-liter autoclave equipped with a magnetically driven stirrer and temperature controlling devices. Catalytic hydrogenation of 1-methylnaphthalene was studied in the presence of sulfidedmore » Co-Mo-Al2O3 catalyst. In addition, the vapor/liquid equilibrium relationship was determined by using this technique. Hydrogenation reaction runs were performed at temperatures of 644.1, 658.0 and 672.0K and pressures up to 9.0 MPa. The ring hydrogenation, resulting in 1- and 5-methyltetralin, was found to be the dominant reaction. This is in agreement with cited literature. Effects of hydrogen partial pressure, operating temperature, as well as presulfided catalyst are also investigated and discussed in this work. The vapor pressure of 1-methylnaphthalene was measured over a temperature range of 555.2 to 672.0K. The results are in good agreement with literature data. Measurements for hydrogen solubility in 1-methylnaphthalene were conducted over temperature and pressure range of 598 to 670K and 5.2 to 8.8 MPa, respectively. Similar to previously reported results, the hydrogen solubility increases with increasing temperature when total pressure is held constant. A linear relation is found between the hydrogen solubility and hydrogen partial pressure. 21 refs., 13 figs., 10 tabs.« less

Comparison of cardiorespiratory variables in dorsally recumbent horses anesthetized with guaifenesin-ketamine-xylazine spontaneously breathing 50% or maximal oxygen concentrations.

PubMed

Karrasch, Nicole M; Hubbell, John A E; Aarnes, Turi K; Bednarski, Richard M; Lerche, Phillip

2015-04-01

This study compared cardiorespiratory variables in dorsally recumbent horses anesthetized with guaifenesin-ketamine-xylazine and spontaneously breathing 50% or maximal (> 90%) oxygen (O2) concentrations. Twelve healthy mares were randomly assigned to breathe 50% or maximal O2 concentrations. Horses were sedated with xylazine, induced to recumbency with ketamine-diazepam, and anesthesia was maintained with guaifenesin-ketamine-xylazine to effect. Heart rate, arterial blood pressures, respiratory rate, lithium dilution cardiac output (CO), inspired and expired O2 and carbon dioxide partial pressures, and tidal volume were measured. Arterial and mixed-venous blood samples were collected prior to sedation (baseline), during 30 minutes of anesthesia, 10 minutes after disconnection from O2, and 30 minutes after standing. Shunt fraction, O2 delivery, and alveolar-arterial O2 partial pressures difference [P(A-a)O2] were calculated. Recovery times were recorded. There were no significant differences between groups in cardiorespiratory parameters or in P(A-a)O2 at baseline or 30 minutes after standing. Oxygen partial pressure difference in the 50% group was significantly less than in the maximal O2 group during anesthesia.

Comparison of cardiorespiratory variables in dorsally recumbent horses anesthetized with guaifenesin-ketamine-xylazine spontaneously breathing 50% or maximal oxygen concentrations

PubMed Central

Karrasch, Nicole M.; Hubbell, John A.E.; Aarnes, Turi K.; Bednarski, Richard M.; Lerche, Phillip

2015-01-01

This study compared cardiorespiratory variables in dorsally recumbent horses anesthetized with guaifenesin-ketamine-xylazine and spontaneously breathing 50% or maximal (> 90%) oxygen (O2) concentrations. Twelve healthy mares were randomly assigned to breathe 50% or maximal O2 concentrations. Horses were sedated with xylazine, induced to recumbency with ketamine-diazepam, and anesthesia was maintained with guaifenesin-ketamine-xylazine to effect. Heart rate, arterial blood pressures, respiratory rate, lithium dilution cardiac output (CO), inspired and expired O2 and carbon dioxide partial pressures, and tidal volume were measured. Arterial and mixed-venous blood samples were collected prior to sedation (baseline), during 30 minutes of anesthesia, 10 minutes after disconnection from O2, and 30 minutes after standing. Shunt fraction, O2 delivery, and alveolar-arterial O2 partial pressures difference [P(A-a)O2] were calculated. Recovery times were recorded. There were no significant differences between groups in cardiorespiratory parameters or in P(A-a)O2 at baseline or 30 minutes after standing. Oxygen partial pressure difference in the 50% group was significantly less than in the maximal O2 group during anesthesia. PMID:25829559

Experimental petrology and origin of rocks from the Descartes Highlands

NASA Technical Reports Server (NTRS)

Walker, D.; Longhi, J.; Grove, T. L.; Stolper, E.; Hays, J. F.

1973-01-01

Petrographic studies of Apollo 16 samples indicate that rocks 62295 and 68415 are crystallization products of highly aluminous melts. 60025 is a shocked, crushed and partially annealed plagioclase cumulate. 60315 is a recrystallized noritic breccia of disputed origin. 60335 is a feldspathic basalt filled with xenoliths and xenocrysts of anorthosite, breccia, and anorthite. The Fe/(Fe+Mg) of plagioclase appears to be a relative crystallization index. Low pressure melting experiments with controlled Po2 indicate that the igneous samples crystallized at oxygen fugacities well below the Fe/FeO buffer. Crystallization experiments at various pressures suggest that the 62295 and 68415 compositions were produced by partial or complete melting of lunar crustal materials, and not by partial melting of the deep lunar interior.

Solubilities of carbon dioxide in aqueous potassium carbonate solutions mixed with physical solvents

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

Park, S.B.; Lee, H.; Lee, K.H.

1998-09-01

The removal of acidic gases such as CO{sub 2}, H{sub 2}S, and COS from gas streams is a very important operation for petrochemical, oil refineries, ammonia manufacture, coal gasification, and natural gas purification plants. Here, the solubilities of carbon dioxide in aqueous potassium carbonate (K{sub 2}CO{sub 3}) solutions mixed with physical solvents were measured at 298.2 and 323.2 K with a CO{sub 2} partial-pressure range of 5 kPa to 2 MPa. 1,2-propanediol and propylene carbonate were selected as physical solvents. The aqueous solutions treated in this study were 5 mass% K{sub 2}CO{sub 3}-15 mass% 1,2-propanediol and propylene carbonate were selectedmore » as physical solvents. The aqueous solutions treated in this study were 5 mass% K{sub 2}CO{sub 3}-15 mass% propylene carbonate. The experimental solubility results were presented by the mole ratio of CO{sub 2} and K{sub 2}CO{sub 3} contained in the liquid mixture. The addition of 1,2-propanediol to 5 mass% K{sub 2}CO{sub 3} solution lowered the solubility of CO{sub 2} at constant temperature and pressure conditions when CO{sub 2} partial-pressure range of 5 kPa to 2 MPa. In the case of propylene carbonate the addition of propylene carbonate increased the experimental solubilities in the region of low CO{sub 2} partial pressures and decreased as the CO{sub 2} partial pressure was increased above atmospheric. The solubilities of CO{sub 2} decreased with increasing temperature in the range of 298.2 to 323.2 K.« less

Hyperoxia is Associated with Increased Mortality in Patients Treated with Mild Therapeutic Hypothermia after Sudden Cardiac Arrest

PubMed Central

Janz, David R.; Hollenbeck, Ryan D.; Pollock, Jeremy S.; McPherson, John A.; Rice, Todd W.

2012-01-01

Objective To determine if higher levels of partial pressure of arterial oxygen are associated with in-hospital mortality and poor neurologic status at hospital discharge in patients treated with mild therapeutic hypothermia after sudden cardiac arrest. Design Retrospective analysis of a prospective cohort study Patients A total of 170 consecutive patients treated with therapeutic hypothermia in the cardiovascular care unit of an academic tertiary care hospital. Interventions None. Measurements and Main Results Of 170 patients, 77 (45.2%) survived to hospital discharge. Survivors had a significantly lower maximum partial pressure of arterial oxygen(198 mmHg, IQR 152.5–282) measured in the first 24 hours following cardiac arrest compared to nonsurvivors (254 mmHg, IQR 172–363, p = .022). A multivariable analysis including age, time to return of spontaneous circulation, the presence of shock, bystander CPR, and initial rhythm revealed that higher levels of the partial pressure of arterial oxygen were significantly associated with increased in-hospital mortality (odds ratio 1.439, 95% confidence interval 1.028–2.015, p = 0.034) and poor neurologic status at hospital discharge (odds ratio 1.485, 95% confidence interval 1.032–2.136, p = 0.033). Conclusions Higher levels of the maximum measured partial pressure of arterial oxygen are associated with increased in-hospital mortality and poor neurologic status on hospital discharge in patients treated with mild therapeutic hypothermia after sudden cardiac arrest. PMID:22971589

Hydromechanics in dentine: role of dentinal tubules and hydrostatic pressure on mechanical stress-strain distribution.

PubMed

Kishen, A; Vedantam, S

2007-10-01

This investigation is to understand the role of free water in the dentinal tubules on the mechanical integrity of bulk dentine. Three different experiments were conducted in this study. In experiment 1, three-dimensional models of dentine with gradient elastic modulus, homogenous elastic modulus, and with and without hydrostatic pressure were simulated using the finite element method. Static compressive loads of 15, 50 and 100 N were applied and the distribution of the principal stresses, von Mises stresses, and strains in loading direction were determined. In experiment 2, experimental compression testing of fully hydrated and partially dehydrated dentine (21 degrees C for 72 h) was conducted using a Universal testing machine. In experiment 3, Fourier transform infrared spectroscopic analysis of hydrated and partially dehydrated dentine was carried out. The finite element analysis revealed that the dentine model with simulated hydrostatic pressure displayed residual tensile stresses and strains in the inner region adjacent to the root canal. When external compressive loads were applied to the model, the residual stresses and strains counteracted the applied loads. Similarly the hydrated specimens subjected to experimental compression loads showed greater toughness when compared to the partially dehydrated specimens. The stress at fracture was significantly higher in partially dehydrated specimens (p=0.014), while the strain at fracture was significantly higher in hydrated dentine specimens (p=0.037). These experiments highlighted the distinct role of free water in the dentinal tubules and hydrostatic pressure on the stress-strain distribution within the bulk dentine.

Influence of Oxygen Partial Pressure during Processing on the Thermoelectric Properties of Aerosol-Deposited CuFeO₂.

PubMed

Stöcker, Thomas; Exner, Jörg; Schubert, Michael; Streibl, Maximilian; Moos, Ralf

2016-03-24

In the field of thermoelectric energy conversion, oxide materials show promising potential due to their good stability in oxidizing environments. Hence, the influence of oxygen partial pressure during synthesis on the thermoelectric properties of Cu-Delafossites at high temperatures was investigated in this study. For these purposes, CuFeO₂ powders were synthetized using a conventional mixed-oxide technique. X-ray diffraction (XRD) studies were conducted to determine the crystal structures of the delafossites associated with the oxygen content during the synthesis. Out of these powders, films with a thickness of about 25 µm were prepared by the relatively new aerosol-deposition (AD) coating technique. It is based on a room temperature impact consolidation process (RTIC) to deposit dense solid films of ceramic materials on various substrates without using a high-temperature step during the coating process. On these dense CuFeO₂ films deposited on alumina substrates with electrode structures, the Seebeck coefficient and the electrical conductivity were measured as a function of temperature and oxygen partial pressure. We compared the thermoelectric properties of both standard processed and aerosol deposited CuFeO₂ up to 900 °C and investigated the influence of oxygen partial pressure on the electrical conductivity, on the Seebeck coefficient and on the high temperature stability of CuFeO₂. These studies may not only help to improve the thermoelectric material in the high-temperature case, but may also serve as an initial basis to establish a defect chemical model.

Experimental validation of Critical Temperature-Pressure theory of scuffing

NASA Astrophysics Data System (ADS)

Lee, Si C.; Chen, Huanliang

1995-07-01

A series of experiments was conducted for validating a newly developed theory of scuffing. The Critical temperature-Pressure (CTP) theory is based on the physisorption behavior of lubricants and is capable of predicting the onset of scuffing failures over a wide range of operating conditions, including the contacts operating in the boundary lubrication and in the partial elastohydrodynamic lubrication (EHL) regimes. According to the CTP theory, failures occur when the contact temperature exceeds a certain critical value which is a function of the lubricant pressure generated by the hydrodynamic action of the EHL contact. A special device capable of simulating the ambient conditions of the partial EHL conjunctions (of contact temperature, pressure, and the lubricant pressure) was constructed. A ball-on-flat type wear tester was put inside a pressure vessel, completely immersed in a highly pressurized bath of mineral oil. The temperature on the flat specimen was gradually increased while the ball was slowly traversed. At a certain critical temmperature, the friction force abruptly jumped indicating the incipiency of the lubrication breakdown. This experiment was repeated for several levels of hydrostatic pressure and the corresponding critical temperatures were obtained. The test results showed an excellent correlation with the newly developed CTP theory.

[Clinical efficacy of partial resection of puborectalis combined with mutilation of internal anal sphincter in the treatment of puborectalis syndrome with high anal pressure].

PubMed

Ye, Hui; Liu, Weicheng; Qian, Qun; Liu, Zhisu; Jiang, Congqing; Zheng, Keyan; Qin, Qianbo; Ding, Zhao; Gong, Zhilin

2017-03-25

To explore the efficacy of partial resection of puborectalis combined with mutilation of internal anal sphincter(IAS) in the treatment of puborectalis syndrome with high anal pressure. Twenty-five cases of puborectalis syndrome with high anal resting pressure in the preoperative examination received the operation of partial resection of puborectalis combined with mutilation of IAS in Zhongnan Hospital of Wuhan University between January 2013 and May 2015. The position of puborectalis was confirmed by touching with the exposure under the transfixion device, and a transverse incision was made by electrotome between 3 and 5 o'clock direction of puborectalis, then partial puborectalis was lifted by vessel clamp at 5 o'clock direction, and about 0.5 cm of muscular tissue was resected. Between 8 to 10 o'clock direction of anal tube, about 1 cm length of transverse incision was made by electrotome, then partial IAS was lifted by vessel clamp and cut off. Preoperative and postoperative 3-month anorectal manometry and defecography were carried out. Wexner constipation score and Cleveland Clinic incontinence score were implemented before surgery and 3, 6, 12 months after operation. This study was registered in the Chinese Clinical Trial Registry (registration number: ChiCTR-ORB-16007695). Of the 25 cases, 18 were male and 7 were female, the average age was 55 years old and the average course of disease was 9 years. Compared with pre-operation, the postoperative 3-month anal resting pressure and maximal squeeze pressure were significantly decreased [(53.56±9.05) mmHg vs. (92.44±7.06) mmHg, (142.80±20.35) mmHg vs. (210.88±20.56) mmHg, respectively, both P=0.000]; anorectal angulation at resting state and forced defecation state increased significantly [(102.32±4.96)degree vs. (95.88±4.01)degree, (117.88±5.95)degree vs. (89.52±3.25)degree, respectively, both P=0.000]. Wexner constipation score of postoperative 3-month, 6-month, 12-month (8.28±3.91, 7.40±3.64 and 8.04±4.74) was significantly lower than the preoperative score (16.00±3.69, all P<0.05), while the score was not significantly different among 3 time points after operation (P>0.05). Cleveland Clinic incontinence score was 0 at postoperative 6 and 12 months, and revealed 20 cases were effective among all the surgical patients(80%). Partial resection of puborectalis combined with mutilation of internal anal sphincter can effectively reduce anal pressure and improve symptoms of outlet obstruction, which is an effective method in the treatment of puborectalis syndrome with high anal pressure.

Spectroscopic definition of the biferrous and biferric sites in de novo designed four-helix bundle DFsc peptides: implications for O2 reactivity of binuclear non-heme iron enzymes.

PubMed

Bell, Caleb B; Calhoun, Jennifer R; Bobyr, Elena; Wei, Pin-Pin; Hedman, Britt; Hodgson, Keith O; Degrado, William F; Solomon, Edward I

2009-01-13

DFsc is a single chain de novo designed four-helix bundle peptide that mimics the core protein fold and primary ligand set of various binuclear non-heme iron enzymes. DFsc and the E11D, Y51L, and Y18F single amino acid variants have been studied using a combination of near-IR circular dichroism (CD), magnetic circular dichroism (MCD), variable temperature variable field MCD (VTVH MCD), and X-ray absorption (XAS) spectroscopies. The biferrous sites are all weakly antiferromagnetically coupled with mu-1,3 carboxylate bridges and one 4-coordinate and one 5-coordinate Fe, very similar to the active site of class I ribonucleotide reductase (R2) providing open coordination positions on both irons for dioxygen to bridge. From perturbations of the MCD and VTVH MCD the iron proximal to Y51 can be assigned as the 4-coordinate center, and XAS results show that Y51 is not bound to this iron in the reduced state. The two open coordination positions on one iron in the biferrous state would become occupied by dioxygen and Y51 along the O(2) reaction coordinate. Subsequent binding of Y51 functions as an internal spectral probe of the O(2) reaction and as a proton source that would promote loss of H(2)O(2). Coordination by a ligand that functions as a proton source could be a structural mechanism used by natural binuclear iron enzymes to drive their reactions past peroxo biferric level intermediates.

Spectroscopic definition of the biferrous and biferric sites of de novo designed 4-helix bundle DFsc peptides: Implications for O2 reactivity of binuclear non-heme iron enzymes

PubMed Central

Bell, Caleb B.; Calhoun, Jennifer R.; Bobyr, Elena; Wei, Pin-pin; Hedman, Britt; Hodgson, Keith O.; DeGrado, William F.; Solomon, Edward I.

2009-01-01

DFsc is a single chain de novo designed 4-helix bundle peptide that mimics the core protein fold and primary ligand set of various binuclear non-heme iron enzymes. DFsc and the E11D, Y51L and Y18F single amino acid variants have been studied using a combination of near-IR circular dichroism (CD), magnetic circular dichroism (MCD), variable temperature variable field MCD (VTVH MCD) and x-ray absorption (XAS) spectroscopies. The biferrous sites are all weakly antiferromagnetically coupled with μ-1,3 carboxylate bridges and one 4-coordinate and one 5-coordinate Fe, very similar to the active site of Class I ribonucleotide reductase (R2) providing open coordination positions on both irons for dioxygen to bridge. From perturbations of the MCD and VTVH MCD the iron proximal to Y51 can be assigned as the 4-coordinate center and XAS results show that Y51 is not bound to this iron in the reduced state. The two open coordination positions on one iron in the biferrous state would become occupied by dioxygen and Y51 along the O2 reaction coordinate. Subsequent binding of Y51 functions as an internal spectral probe of the O2 reaction and as a proton source that would promote loss of H2O2. Coordination by a ligand that functions as a proton source could be a structural mechanism used by natural binuclear iron enzymes to drive their reactions past peroxo biferric level intermediates. PMID:19090676

Reactivity of Toluate Dioxygenase with Substituted Benzoates and Dioxygen

PubMed Central

Ge, Yong; Vaillancourt, Frédéric H.; Agar, Nathalie Y. R.; Eltis, Lindsay D.

2002-01-01

Toluate dioxygenase (TADO) of Pseudomonas putida mt-2 catalyzes the dihydroxylation of a broad range of substituted benzoates. The two components of this enzyme were hyperexpressed and anaerobically purified. Reconstituted TADO had a specific activity of 3.8 U/mg with m-toluate, and each component had a full complement of their respective Fe2S2 centers. Steady-state kinetics data obtained by using an oxygraph assay and by varying the toluate and dioxygen concentrations were analyzed by a compulsory order ternary complex mechanism. TADO had greatest specificity for m-toluate, displaying apparent parameters of KmA = 9 ± 1 μM, kcat = 3.9 ± 0.2 s−1, and KmO2 = 16 ± 2 μM (100 mM sodium phosphate, pH 7.0; 25°C), where KmO2 represents the Km for O2 and KmA represents the Km for the aromatic substrate. The enzyme utilized benzoates in the following order of specificity: m-toluate > benzoate ≃ 3-chlorobenzoate > p-toluate ≃ 4-chlorobenzoate ≫ o-toluate ≃ 2-chlorobenzoate. The transformation of each of the first five compounds was well coupled to O2 utilization and yielded the corresponding 1,2-cis-dihydrodiol. In contrast, the transformation of ortho-substituted benzoates was poorly coupled to O2 utilization, with >10 times more O2 being consumed than benzoate. However, the apparent Km of TADO for these benzoates was >100 μM, indicating that they do not effectively inhibit the turnover of good substrates. PMID:12107126

Finding molecular dioxygen tunnels in homoprotocatechuate 2,3-dioxygenase: implications for different reactivity of identical subunits.

PubMed

Xu, Liang; Zhao, Weijie; Wang, Xicheng

2010-01-01

Extradiol dioxygenases facilitate microbial aerobic degradation of catechol and its derivatives by activating molecular dioxygen and incorporating both oxygen atoms into their substrates. Experimental and theoretical studies have focused on the mechanism of the reaction at the active site. However, whether the catalytic rate is limited by O(2) access to the active site has not yet been explored. Here, we choose a recently solved X-ray structure of homoprotocatechuate 2,3-dioxygenase as a typical example to determine potential pathways for O(2) migration from the solvent into the enzyme center. On the basis of the trajectories of two 10-ns molecular dynamics simulations, implicit ligand sampling was used to calculate the 3D free energy map for O(2) inside the protein. The energetically optimal routes for O(2) diffusion were identified for each subunit of the homotetrameric protein structure. The O(2) tunnels formed because of thermal fluctuations were also characterized by connecting elongated cavities inside the protein. By superimposing the favorable O(2) tunnels on to the free energy map, both energetically and geometrically preferred O(2) pathways were determined, as also were the amino acids that may be critical for O(2) passage along these paths. Our results demonstrate that identical subunits possess quite distinct O(2) tunnels. The order of O(2) affinity of these tunnels is generally consistent with the order of the catalytic rate of each subunit. As a consequence, the probability of finding the reaction product is highest in the subunit containing the highest O(2) affinity pathway.

On Dioxygen and Substrate Access to Soluble Methane Monooxygenases: An all-Atom Molecular Dynamics Investigation in Water Solution.

PubMed

Pietra, Francesco

2017-01-01

In a preliminary exploration of the dummy model for diiron proteins, random-acceleration molecular dynamics (RAMD) revealed that a pure four-helix bundle structure, like hemerythrin, constitutes an efficient cage for dioxygen (O 2 ), which can only leave from defined, albeit very broad, gates. However, this well ordered structure does not constitute an archetype on which to compare O 2 permeation of other diiron proteins, like the complex of soluble methane monooxygenase hydroxylase with the regulatory protein (sMMOH-MMOB). The reason is that with this complex, unlike hemerythrin, the four helices of the four-helix bundle are heavily bent, and RAMD showed that most traps for O 2 lie outside them. It was also observed that, in spite of a nearly identical van der Waals radius for O 2 and the natural substrate CH 4 , the latter behaves under RAMD as a bulkier molecule than O 2 , requiring a higher external force to be brought out of sMMOH-MMOB along trajectories of viable length. All that determined with sMMOH-MMOB multiple gates and multiple pathways to each of them through several binding pockets, for both O 2 and CH 4 . Of the two equally preferred pathways for O 2 , at right angle with one another, one proved to be in accordance with the Xe-atom mapping for sMMOH. In contrast, none of the pathways identified for CH 4 proved to be in accordance with such mapping, CH 4 looking for more open avenues instead. © 2017 Wiley-VHCA AG, Zurich, Switzerland.

The Effects of Bougie Diameters on Tissue Oxygen Levels After Sleeve Gastrectomy: A Randomized Experimental Trial

PubMed

Konca, Can; Yılmaz, Ali Abbas; Çelik, Süleyman Utku; Kayılıoğlu, Selami Ilgaz; Paşaoğlu, Özge Tuğçe; Ceylan, Halil Arda; Genç, Volkan

2018-05-29

Staple-line leak is the most frightening complication of laparoscopic sleeve gastrectomy and several predisposing factors such as using improper staple sizes regardless of gastric wall thickness, narrower bougie diameter and ischemia of the staple line are asserted. To evaluate the effects of different bougie diameters on tissue oxygen partial pressure at the esophagogastric junction after sleeve gastrectomy. A randomized and controlled animal experiment with 1:1:1:1 allocation ratio. Thirty-two male Wistar Albino rats were randomly divided into 4 groups of 8 each. While 12-Fr bougies were used in groups 1 and 3, 8-Fr bougies were used in groups 2 and 4. Fibrin sealant application was also carried out around the gastrectomy line after sleeve gastrectomy in groups 3 and 4. Burst pressure of gastrectomy line, tissue oxygen partial pressure and hydroxyproline levels at the esophagogastric junction were measured and compared among groups. Mortality was detected in 2 out of 32 rats (6.25%) and one of them was in group 2 and the cause of this mortality was gastric leak. Gastric leak was detected in 2 out of 32 rats (6.25%). There was no significant difference in terms of burst pressures, tissue oxygen partial pressure and tissue hydroxyproline levels among the 4 groups. The use of narrower bougie along with fibrin sealant has not had a negative effect on tissue perfusion and wound healing.

40 CFR 61.341 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... to industrial organic chemicals, organic pesticide products, pharmaceutical preparations, paint and allied products, fertilizers, and agricultural chemicals. Examples of chemical manufacturing plants...). Maximum organic vapor pressure means the equilibrium partial pressure exerted by the waste at the...

EXTINGUISHMENT OF ALKALI METAL FIRES

DTIC Science & Technology

low O2 partial pressures on alkali metal fires Extinguishment of alkali metal fires using in organic salt mixtures Extinguishment of alkali metal ... fires using inorganic salt foams Alkali metal jet stream ignition at various pressure conditions Bibliography

Pressure relief and other joint rehabilitation techniques

DOT National Transportation Integrated Search

1987-02-01

A study of four major concrete pavement joint rehabilitation techniques has been conducted, including: pressure relief joints, full-depth repairs, partial-depth repairs and joint resealing. The products of this research include the following for each...

Toxicity of elevated partial pressures of carbon dioxide to invasive New Zealand mudsnails

USGS Publications Warehouse

Nielson, R. Jordan; Moffitt, Christine M.; Watten, Barnaby J.

2012-01-01

The authors tested the efficacy of elevated partial pressures of CO2 to kill invasive New Zealand mudsnails. The New Zealand mudsnails were exposed to 100 kPa at three water temperatures, and the survival was modeled versus dose as cumulative °C-h. We estimated an LD50 of 59.4°C-h for adult and juvenile New Zealand mudsnails. The results suggest that CO2 may be an effective and inexpensive lethal tool to treat substrates, tanks, or materials infested with New Zealand mudsnails.

Methods for enhancing P-type doping in III-V semiconductor films

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

Liu, Feng; Stringfellow, Gerald; Zhu, Junyi

2017-08-01

Methods of doping a semiconductor film are provided. The methods comprise epitaxially growing the III-V semiconductor film in the presence of a dopant, a surfactant capable of acting as an electron reservoir, and hydrogen, under conditions that promote the formation of a III-V semiconductor film doped with the p-type dopant. In some embodiments of the methods, the epitaxial growth of the doped III-V semiconductor film is initiated at a first hydrogen partial pressure which is increased to a second hydrogen partial pressure during the epitaxial growth process.

Influence of hydrostatic pressure on dynamics and spatial distribution of protein partial molar volume: time-resolved surficial Kirkwood-Buff approach.

PubMed

Yu, Isseki; Tasaki, Tomohiro; Nakada, Kyoko; Nagaoka, Masataka

2010-09-30

The influence of hydrostatic pressure on the partial molar volume (PMV) of the protein apomyoglobin (AMb) was investigated by all-atom molecular dynamics (MD) simulations. Using the time-resolved Kirkwood-Buff (KB) approach, the dynamic behavior of the PMV was identified. The simulated time average value of the PMV and its reduction by 3000 bar pressurization correlated with experimental data. In addition, with the aid of the surficial KB integral method, we obtained the spatial distributions of the components of PMV to elucidate the detailed mechanism of the PMV reduction. New R-dependent PMV profiles identified the regions that increase or decrease the PMV under the high pressure condition. The results indicate that besides the hydration in the vicinity of the protein surface, the outer space of the first hydration layer also significantly influences the total PMV change. These results provide a direct and detailed picture of pressure induced PMV reduction.

Thermodynamic Equilibrium Solubility of Diethanolamine – N-Butyl-1-Methylpyrrolidinium Dicyanamide [DEABMPYRR DCA] Mixtures for Carbon Dioxide Capture

NASA Astrophysics Data System (ADS)

Salleh, R. M.; Jamaludin, S. N.

2018-05-01

Solubility data of carbon dioxide (CO2) in aqueous Diethanolamine (DEA) blended with pyrrolidinium-based ionic liquid: N-Butyl-1-Methylpyrrolidinium Dıcyanamıde [Bmpyrr][DCA] are presented at various temperatures (313.15K-333.15K) and pressure up to about 700 psi. The concentration of [Bmpyrr][DCA] ranges from 0-10wt% and 30-40wt% for DEA. The solubility of CO2 was evaluated by measuring the pressure drop in high pressure stirred absorption cell reactor. The CO2 loading in all studied mixtures increases with an increase in CO2 partial pressure and decreases with temperature. It was also found that the CO2 loading capacity decrease as the concentration of [Bmpyrr][DCA] increases. The experimental data were correlated as a function of temperature and CO2 partial pressure to predict the solubility of CO2 in the mixtures. It was found that the model predicted results in a good agreement with experimental value.

Low-Tidal-Volume Ventilation in the Acute Respiratory Distress Syndrome

PubMed Central

Malhotra, Atul

2008-01-01

A 55-year-old man who is 178 cm tall and weighs 95 kg is hospitalized with community-acquired pneumonia and progressively severe dyspnea. His arterial oxygen saturation while breathing 100% oxygen through a face mask is 76%; a chest radiograph shows diffuse alveolar infiltrates with air bronchograms. He is intubated and receives mechanical ventilation; ventilator settings include a tidal volume of 1000 ml, a positive end-expiratory pressure (PEEP) of 5 cm of water, and a fraction of inspired oxygen (FiO2) of 0.8. With these settings, peak airway pressure is 50 to 60 cm of water, plateau airway pressure is 38 cm of water, partial pressure of arterial oxygen is 120 mm Hg, partial pressure of carbon dioxide is 37 mm Hg, and arterial blood pH is 7.47. The diagnosis of the acute respiratory distress syndrome (ARDS) is made. An intensive care specialist evaluates the patient and recommends changing the current ventilator settings and implementing a low-tidal-volume ventilation strategy. PMID:17855672

Large boron--epoxy filament-wound pressure vessels

NASA Technical Reports Server (NTRS)

Jensen, W. M.; Bailey, R. L.; Knoell, A. C.

1973-01-01

Advanced composite material used to fabricate pressure vessel is prepeg (partially cured) consisting of continuous, parallel boron filaments in epoxy resin matrix arranged to form tape. To fabricate chamber, tape is wound on form which must be removable after composite has been cured. Configuration of boron--epoxy composite pressure vessel was determined by computer program.

The gaseous explosive reaction at constant pressure : the reaction order and reaction rate

NASA Technical Reports Server (NTRS)

Stevens, F W

1931-01-01

The data given in this report covers the explosive limits of hydrocarbon fuels. Incidental to the purpose of the investigation here reported, the explosive limits will be found to be expressed for the condition of constant pressure, in the fundamental terms of concentrations (partial pressures) of fuel and oxygen.

REVIEW: High pressure NMR study of proteins - seeking roots for function, evolution, disease and food applications

NASA Astrophysics Data System (ADS)

Akasaka, Kazuyuki

2010-12-01

NMR experiments at variable pressure reveal a wide range of conformation of a globular protein spanning from within the folded ensemble to the fully unfolded ensemble, herewith collectively called "high-energy conformers". The observation of "high-energy conformers" in a wide variety of globular proteins has led to the "volume theorem": the partial molar volume of a protein decreases with the decrease in its conformational order. Since "high-energy conformers" are intrinsically more reactive than the basic folded conformer, they could play decisive roles in all phenomena of proteins, namely function, environmental adaptation and misfolding. Based on the information on high-energy conformers and the rules on their partial volume in its monomeric state and amyloidosis, one may have a general view on what is happening on proteins under pressure. Moreover, one may even choose a high-energy conformer of a protein with pressure as variable for a particular purpose. Bridging "high-energy conformers" to macroscopic pressure effects could be a key to success in pressure application to biology, medicine, food technology and industry in the near future.

Mathematical modeling of human brain physiological data

NASA Astrophysics Data System (ADS)

Böhm, Matthias; Faltermeier, Rupert; Brawanski, Alexander; Lang, Elmar W.

2013-12-01

Recently, a mathematical model of the basic physiological processes regulating the cerebral perfusion and oxygen supply was introduced [Jung , J. Math. Biol.JMBLAJ0303-681210.1007/s00285-005-0343-5 51, 491 (2005)]. Although this model correctly describes the interdependence of arterial blood pressure (ABP) and intracranial pressure (ICP), it fails badly when it comes to explaining certain abnormal correlations seen in about 80% of the recordings of ABP together with ICP and the partial oxygen pressure (TiPO2) of the neuronal tissue, taken at an intensive care unit during neuromonitoring of patients with a severe brain trauma. Such recordings occasionally show segments, where the mean arterial blood pressure is correlated with the partial oxygen pressure in tissue but anticorrelated with the intracranial pressure. The origin of such abnormal correlations has not been fully understood yet. Here, two extensions to the previous approach are proposed which can reproduce such abnormal correlations in simulations quantitatively. Furthermore, as the simulations are based on a mathematical model, additional insight into the physiological mechanisms from which such abnormal correlations originate can be gained.

Effect of water on the composition of partial melts of greenstone and amphibolite

NASA Technical Reports Server (NTRS)

Beard, James S.; Lofgren, Gary E.

1989-01-01

Closed-system partial melts of hydrated, metamorphosed arc basalts and andesites (greenstones and amphibolites), where only water structurally bound in metamorphic minerals is available for melting (dehydration melting), are generally water-undersaturated, coexist with plagioclase-rich, anhydrous restites, and have compositions like island arc tonalites. In contrast, water-saturated melting at water pressures of 3 kilobars yields strongly peraluminous, low iron melts that coexist with an amphibole-bearing, plagioclase-poor restite. These melt compositions are unlike those of most natural silicic rocks. Thus, dehydration melting over a range of pressures in the crust of island arcs is a plausible mechanism for the petrogenesis of islands arc tonalite, whereas water-saturated melting at pressure of 3 kilobars and above is not.

The feasibility of desorption on Zeolite-water pair using dry gas

NASA Astrophysics Data System (ADS)

Oktariani, E.; Nakashima, K.; Noda, A.; Xue, B.; Tahara, K.; Nakaso, K.; Fukai, J.

2018-04-01

The increase in temperature, reduction in partial pressure, reduction in concentration, purging with an inert fluid, and displacement with a more strongly adsorbing species are the basic things that occur in the practical method of desorption. In this study, dry gas at constant temperature and pressure was employed as the aid to reduce the partial pressure in the water desorption on the zeolite 13X. The objective of this study is to confirm the feasibility of desorption using dry gas experimentally and numerically. The implication of heat and mass transfers were numerically investigated to find the most influential. The results of numerical simulation agree with the experimental ones for the distribution of local temperature and average water adsorbed in the packed bed.

Carbon acceptor incorporation in GaAs grown by metalorganic chemical vapor deposition: Arsine versus tertiarybutylarsine

NASA Astrophysics Data System (ADS)

Watkins, S. P.; Haacke, G.

1991-10-01

Undoped p-type GaAs epilayers were grown by low-pressure metalorganic chemical vapor deposition (MOCVD) at 650 °C and 76 Torr using either arsine or tertiarybutylarsine (TBA), and trimethylgallium (TMG). Extremely high-purity precursors were used in order to eliminate extrinsic doping effects. Carbon acceptors from the TMG were the dominant residual electrical impurities under all growth conditions. Temperature-dependent Hall measurements were used to make a quantitative comparison of the carbon acceptor concentrations for arsine- and TBA-grown epilayers over a range of As partial pressures. For a given group V partial pressure, we report a significant reduction in carbon acceptor incorporation using TBA compared with arsine under identical growth conditions.

An Investigation Into Low Fuel Pressure Warnings on a Macchi-Viper Aircraft

DTIC Science & Technology

1988-05-01

was sufficient To activate the low pressure warning light. The pressure switch is normally set to a differential of between 2.5 - 3 psi. Partial...only a 2.1 psig margin for light illumination, if the pressure switch is set at 3 psig, and gives little scope for extra pipe or filter losses when... pressure switch is set between 2.5 - 3 psig. Any untoward pressure resistance in the fuel delivery line and filtering system would soon erode this

EXTINGUISHMENT OF ALKALI METAL FIRES

DTIC Science & Technology

Contents: Effect of inert gas nket and ow O2 partial pressures on alkali metal fires Extinguishment of small scale fires Extinguishment of alkali... metal fires using inorganic salt foam Alkali metal jet stream ignition at various pressure conditions

Pressure relief and other joint rehabilitation techniques : appendices

DOT National Transportation Integrated Search

1987-02-01

Appendices of a study of four major concrete pavement joint rehabilitation techniques has been conducted, including: pressure relief joints, full-depth repairs, partial-depth repairs and joint resealing. The products of this research include the foll...

Rare-gas effects on metabolism and inert gas narcosis

NASA Technical Reports Server (NTRS)

1972-01-01

The detailed examination is reported of the theory that narcosis results from expansion of the cell membrane under high partial pressures. The research is partially based on the hypothesis that, like oxygen toxicity, the mechanism of metabolic effects of rare gases may be similar at both low and high pressures and are simply more observable at high pressures. Using adult female goats, the parameters measured include oxygen consumption, CO2 production, respiration rate, heart rate, rectal and skin temperatures and the analysis of electroencephalograms and evoked response. Additionally, the specific activity is measured of plasma glucose subsequent to injection of glucose-UL-C-14, intravenous infusion, specific activity of expired CO2, unesterified fatty acid levels and whole blood lactate-to-pyruvate ratios. Also studied were the effects of acetylsalicylic acid, vitamin E and cationic detergents (which alleviate narcosis) upon metabolic changes induced by high pressure narcosis.

Curved and conformal high-pressure vessel

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

Croteau, Paul F.; Kuczek, Andrzej E.; Zhao, Wenping

A high-pressure vessel is provided. The high-pressure vessel may comprise a first chamber defined at least partially by a first wall, and a second chamber defined at least partially by the first wall. The first chamber and the second chamber may form a curved contour of the high-pressure vessel. A modular tank assembly is also provided, and may comprise a first mid tube having a convex geometry. The first mid tube may be defined by a first inner wall, a curved wall extending from the first inner wall, and a second inner wall extending from the curved wall. The firstmore » inner wall may be disposed at an angle relative to the second inner wall. The first mid tube may further be defined by a short curved wall opposite the curved wall and extending from the second inner wall to the first inner wall.« less

Two dimensional radial gas flows in atmospheric pressure plasma-enhanced chemical vapor deposition

NASA Astrophysics Data System (ADS)

Kim, Gwihyun; Park, Seran; Shin, Hyunsu; Song, Seungho; Oh, Hoon-Jung; Ko, Dae Hong; Choi, Jung-Il; Baik, Seung Jae

2017-12-01

Atmospheric pressure (AP) operation of plasma-enhanced chemical vapor deposition (PECVD) is one of promising concepts for high quality and low cost processing. Atmospheric plasma discharge requires narrow gap configuration, which causes an inherent feature of AP PECVD. Two dimensional radial gas flows in AP PECVD induces radial variation of mass-transport and that of substrate temperature. The opposite trend of these variations would be the key consideration in the development of uniform deposition process. Another inherent feature of AP PECVD is confined plasma discharge, from which volume power density concept is derived as a key parameter for the control of deposition rate. We investigated deposition rate as a function of volume power density, gas flux, source gas partial pressure, hydrogen partial pressure, plasma source frequency, and substrate temperature; and derived a design guideline of deposition tool and process development in terms of deposition rate and uniformity.

Water Vapor Effects on Silica-Forming Ceramics

NASA Technical Reports Server (NTRS)

Opila, E. J.; Greenbauer-Seng, L. (Technical Monitor)

2000-01-01

Silica-forming ceramics such as SiC and Si3N4 are proposed for applications in combustion environments. These environments contain water vapor as a product of combustion. Oxidation of silica-formers is more rapid in water vapor than in oxygen. Parabolic oxidation rates increase with the water vapor partial pressure with a power law exponent value close to one. Molecular water vapor is therefore the mobile species in silica. Rapid oxidation rates and large amounts of gases generated during the oxidation reaction in high water vapor pressures may result in bubble formation in the silica and nonprotective scale formation. It is also shown that silica reacts with water vapor to form Si(OH)4(g). Silica volatility has been modeled using a laminar flow boundary layer controlled reaction equation. Silica volatility depends on the partial pressure of water vapor, the total pressure, and the gas velocity. Simultaneous oxidation and volatilization reactions have been modeled with paralinear kinetics.

Hydraulic effects in a radiative atmosphere with ionization

NASA Astrophysics Data System (ADS)

Bhat, P.; Brandenburg, A.

2016-03-01

Context. In his 1978 paper, Eugene Parker postulated the need for hydraulic downward motion to explain magnetic flux concentrations at the solar surface. A similar process has also recently been seen in simplified (e.g., isothermal) models of flux concentrations from the negative effective magnetic pressure instability (NEMPI). Aims: We study the effects of partial ionization near the radiative surface on the formation of these magnetic flux concentrations. Methods: We first obtain one-dimensional (1D) equilibrium solutions using either a Kramers-like opacity or the H- opacity. The resulting atmospheres are then used as initial conditions in two-dimensional (2D) models where flows are driven by an imposed gradient force that resembles a localized negative pressure in the form of a blob. To isolate the effects of partial ionization and radiation, we ignore turbulence and convection. Results: Because of partial ionization, an unstable stratification always forms near the surface. We show that the extrema in the specific entropy profiles correspond to the extrema in the degree of ionization. In the 2D models without partial ionization, strong flux concentrations form just above the height where the blob is placed. Interestingly, in models with partial ionization, such flux concentrations always form at the surface well above the blob. This is due to the corresponding negative gradient in specific entropy. Owing to the absence of turbulence, the downflows reach transonic speeds. Conclusions: We demonstrate that, together with density stratification, the imposed source of negative pressure drives the formation of flux concentrations. We find that the inclusion of partial ionization affects the entropy profile dramatically, causing strong flux concentrations to form closer to the surface. We speculate that turbulence effects are needed to limit the strength of flux concentrations and homogenize the specific entropy to a stratification that is close to marginal.

High rates of non-adherence to antihypertensive treatment revealed by high-performance liquid chromatography-tandem mass spectrometry (HP LC-MS/MS) urine analysis

PubMed Central

Tomaszewski, Maciej; White, Christobelle; Patel, Prashanth; Masca, Nicholas; Damani, Ravi; Hepworth, Joanne; Samani, Nilesh J; Gupta, Pankaj; Madira, Webster; Stanley, Adrian; Williams, Bryan

2014-01-01

Objectives Non-adherence to therapy is an important cause of suboptimal blood pressure control but few practical tools exist to accurately and routinely detect it. We used a simple urine-based assay to evaluate the prevalence of antihypertensive treatment non-adherence and its impact on blood pressure in a specialist hypertension centre. Methods 208 hypertensive patients (125 new referrals, 66 follow-up patients with inadequate blood pressure control and 17 renal denervation referrals) underwent assessment of antihypertensive drug intake using high-performance liquid chromatography-tandem mass spectrometry (HP LC-MS/MS) urine analysis at the time of clinical appointment. A total of 40 most commonly prescribed antihypertensive medications (or their metabolites) were screened for in spot urine samples. Results Overall, 25% of patients were totally or partially non-adherent to antihypertensive treatment (total non-adherence 10.1%, partial non-adherence 14.9%). The highest prevalence of partial and total non-adherence was among follow-up patients with inadequate blood pressure control (28.8%) and those referred for consideration of renal denervation (23.5%), respectively. There was a linear relationship between blood pressure and the numerical difference in detected/prescribed antihypertensive medications—every unit increase in this difference was associated with 3.0 (1.1) mm Hg, 3.1 (0.7) mm Hg and 1.9 (0.7) mm Hg increase in adjusted clinic systolic blood pressure, clinic diastolic blood pressure (DBP) and 24 h mean daytime DBP (p=0.0051, p=8.62×10−6, p=0.0057), respectively. Conclusions Non-adherence to blood pressure lowering therapy is common, particularly in patients with suboptimal blood pressure control and those referred for renal denervation. HP LC-MS/MS urine analysis could be used to exclude non-adherence and better stratify further investigations and intervention. PMID:24694797

Role of partial miscibility on pressure buildup due to constant rate injection of CO2 into closed and open brine aquifers

NASA Astrophysics Data System (ADS)

Mathias, Simon A.; Gluyas, Jon G.; GonzáLez MartíNez de Miguel, Gerardo J.; Hosseini, Seyyed A.

2011-12-01

This work extends an existing analytical solution for pressure buildup because of CO2 injection in brine aquifers by incorporating effects associated with partial miscibility. These include evaporation of water into the CO2 rich phase and dissolution of CO2 into brine and salt precipitation. The resulting equations are closed-form, including the locations of the associated leading and trailing shock fronts. Derivation of the analytical solution involves making a number of simplifying assumptions including: vertical pressure equilibrium, negligible capillary pressure, and constant fluid properties. The analytical solution is compared to results from TOUGH2 and found to accurately approximate the extent of the dry-out zone around the well, the resulting permeability enhancement due to residual brine evaporation, the volumetric saturation of precipitated salt, and the vertically averaged pressure distribution in both space and time for the four scenarios studied. While brine evaporation is found to have a considerable effect on pressure, the effect of CO2 dissolution is found to be small. The resulting equations remain simple to evaluate in spreadsheet software and represent a significant improvement on current methods for estimating pressure-limited CO2 storage capacity.

Plant and environment interactions: Growth and yield response of commercial bearing-age {open_quote}Casselman{close_quote} plum trees to various ozone partial pressures

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

Retzlaff, W.A.; Williams, L.E.; DeJong, T.M.

1997-05-01

Nursery stock of plum (Prunus salicina Lindel., cv. Casselman) was planted 1 Apr. 1988 in an experimental orchard at the Univ. of California Kearney Agricultural Center near Fresno, CA. Trees in this study were enclosed in open-top fumigation chambers on 1 May 1989, and exposed to three atmospheric ozone partial pressures (charcoal filtered air, ambient air, and ambient air + ozone) during the 1989 through 1992 growing seasons (typically 1 Apr. - 1 Nov.). A nonchamber treatment plot was used to assess chamber effects on tree performance. This study details the results of the exposures during the initial commercial bearingmore » period (1991 through 1993) in this orchard. The mean 12-h (0800-2000 h Pacific Daylight Time [PDT]) ozone partial pressures during the experimental periods in the charcoal filtered, ambient, ambient + ozone, and nonchamber treatments averaged 0.031, 0.048, 0.091, and 0.056 {mu}Pa Pa{sup {minus}1} in 1991 and 1992, respectively. Fruit number per tree decreased as atmospheric ozone partial pressure increased from the charcoal filtered to ambient + ozone treatment, significantly affecting yield. Yield of plum trees averaged 23.6, 19.8, 13.7, and 17.9 kg tree{sup {minus}1} in 1991 and 1992 in the charcoal filtered, ambient, ambient + ozone, and nonchamber treatments, respectively. Only one out of the five original treatment plots was exposed to ozone treatments during the 1993 growing season. Yield of plum trees in this single replicate in 1993 was reduced by increased atmospheric ozone partial pressure. Yield of plum trees in the four remaining unexposed treatment plots in 1993 was 16.7, 17.9, and 16.0 kg tree{sup {minus}1} in the previous charcoal filtered, ambient, and ambient + ozone treatments respectively. The similarity in yield of the post-chamber treatments indicates that a change in air quality in the current growing season can affect yield of Casselman plum trees. 26 refs., 6 figs., 4 tabs.« less

Partial melting of deeply subducted eclogite from the Sulu orogen in China

PubMed Central

Wang, Lu; Kusky, Timothy M.; Polat, Ali; Wang, Songjie; Jiang, Xingfu; Zong, Keqing; Wang, Junpeng; Deng, Hao; Fu, Jianmin

2014-01-01

We report partial melting of an ultrahigh pressure eclogite in the Mesozoic Sulu orogen, China. Eclogitic migmatite shows successive stages of initial intragranular and grain boundary melt droplets, which grow into a three-dimensional interconnected intergranular network, then segregate and accumulate in pressure shadow areas and then merge to form melt channels and dikes that transport magma to higher in the lithosphere. Here we show, using zircon U–Pb dating and petrological analyses, that partial melting occurred at 228–219 Myr ago, shortly after peak metamorphism at 230 Myr ago. The melts and residues are complimentarily enriched and depleted in light rare earth element (LREE) compared with the original rock. Partial melting of deeply subducted eclogite is an important process in determining the rheological structure and mechanical behaviour of subducted lithosphere and its rapid exhumation, controlling the flow of deep lithospheric material, and for generation of melts from the upper mantle, potentially contributing to arc magmatism and growth of continental crust. PMID:25517619

Ru nucleation and thin film smoothness improvement with ammonia during chemical vapor deposition

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

Liao, Wen; Ekerdt, John G., E-mail: ekerdt@utexas.edu

This study reports the use of ammonia to inhibit the growth of previously nucleated ruthenium islands and force the nucleation of additional islands such that thinner films form as the islands coalesce with continued growth. Ruthenium films are grown at 448 K in a chemical vapor deposition process on SiO{sub 2}/Si(001) using triruthenium dodecacarbonyl, Ru{sub 3}(CO){sub 12}, with and without a constant partial pressure of ammonia. Film growth was performed at a Ru{sub 3}(CO){sub 12}/Ar pressure of 47.2 mTorr. The ammonia partial pressure varied from 0 to 27.8 mTorr. X-ray photoelectron spectroscopy was used to analyze the samples in situ. Exmore » situ characterization included scanning electron microscopy, atomic force microscopy, and x-ray diffraction and x-ray reflectivity. Nucleation studies limited to the first 10 min of growth revealed the maximum nanoparticle (island) density of 8.1 × 10{sup 11 }cm{sup −2} occurred at an intermediate ammonia pressure (5.25 mTorr) compared to a density of 3.1 × 10{sup 11 }cm{sup −2} for no ammonia addition. Extending film growth to 120 min and varying the ammonia partial pressure during the first 10 min followed by 5.25 mTorr ammonia pressure for the final 110 min reveals the importance of nucleation on film smoothness. A model describing the inhibition effects of ammonia during nucleation and growth is presented.« less

Inaccuracy of a physical strain trainer for the monitoring of partial weight bearing.

PubMed

Pauser, Johannes; Jendrissek, Andreas; Swoboda, Bernd; Gelse, Kolja; Carl, Hans-Dieter

2011-11-01

To investigate the use of a physical strain trainer for the monitoring of partial weight bearing. Case series with healthy volunteers. Orthopedic clinic. Healthy volunteers (N=10) with no history of foot complaints. Volunteers were taught to limit weight bearing to 10% body weight (BW) and 50% BW, monitored by a physical strain trainer. The parameters peak pressure, maximum force, force-time integral, and pressure-time integral were assessed by dynamic pedobarography when volunteers walked with full BW (condition 1), 50% BW (condition 2), and 10% BW (condition 3). With 10% BW (condition 3), forces with normative gait (condition 1) were statistically significantly reduced under the hindfoot where the physical strain trainer is placed. All pedobarographic parameters were, however, exceeded when the total foot was measured. A limitation to 10% BW with the physical strain trainer (condition 3) was equal to a bisection of peak pressure and maximum force for the total foot with normative gait (condition 1). Halved BW (condition 2) left a remaining mean 82% of peak pressure and mean 59% of maximum force from full BW (condition 1). The concept of controlling partial weight bearing with the hindfoot-addressing device does not represent complete foot loading. Such devices may be preferably applied in cases when the hindfoot in particular must be off-loaded. Other training devices (eg, biofeedback soles) that monitor forces of the total foot have to be used to control partial weight bearing of the lower limb accurately. Copyright © 2011 American Congress of Rehabilitation Medicine. Published by Elsevier Inc. All rights reserved.

Sensor for measuring hydrogen partial pressure in parabolic trough power plant expansion tanks

NASA Astrophysics Data System (ADS)

Glatzmaier, Greg C.; Cooney, Daniel A.

2017-06-01

The National Renewable Energy Laboratory and Acciona Energy North America are working together to design and implement a process system that provides a permanent solution to the issue of hydrogen buildup at parabolic trough power plants. We are pursuing a method that selectively removes hydrogen from the expansion tanks that serve as reservoirs for the heat transfer fluid (HTF) that circulates in the collector field and power block components. Our modeling shows that removing hydrogen from the expansion tanks at a design rate reduces and maintains dissolved hydrogen in the circulating HTF to a selected target level. Our collaborative work consists of several tasks that are needed to advance this process concept to a development stage, where it is ready for implementation at a commercial power plant. Our main effort is to design and evaluate likely process-unit operations that remove hydrogen from the expansion tanks at a specified rate. Additionally, we designed and demonstrated a method and instrumentation to measure hydrogen partial pressure and concentration in the expansion-tank headspace gas. We measured hydrogen partial pressure in the headspace gas mixture using a palladium-alloy membrane, which is permeable exclusively to hydrogen. The membrane establishes a pure hydrogen gas phase that is in equilibrium with the hydrogen in the gas mixture. We designed and fabricated instrumentation, and demonstrated its effectiveness in measuring hydrogen partial pressures over a range of three orders of magnitude. Our goal is to install this instrument at the Nevada Solar One power plant and to demonstrate its effectiveness in measuring hydrogen levels in the expansion tanks under normal plant operating conditions.

Average rainwater pH, concepts of atmospheric acidity, and buffering in open systems

NASA Astrophysics Data System (ADS)

Liljestrand, Howard M.

The system of water equilibrated with a constant partial pressure of CO 2, as a reference point for pH acidity-alkalinity relationships, has nonvolatile acidity and alkalinity components as conservative quantities, but not [H +]. Simple algorithms are presented for the determination of the average pH for combinations of samples both above and below pH 5.6. Averaging the nonconservative quantity [H +] yields erroneously low mean pH values. To extend the open CO 2 system to include other volatile atmospheric acids and bases distributed among the gas, liquid and particulate matter phases, a theoretical framework for atmospheric acidity is presented. Within certain oxidation-reduction limitations, the total atmospheric acidity (but not free acidity) is a conservative quantity. The concept of atmospheric acidity is applied to air-water systems approximating aerosols, fogwater, cloudwater and rainwater. The buffer intensity in hydrometeors is described as a function of net strong acidity, partial pressures of acid and base gases and the water to air ratio. For high liquid to air volume ratios, the equilibrium partial pressures of trace acid and base gases are set by the pH or net acidity controlled by the nonvolatile acid and base concentrations. For low water to air volume ratios as well as stationary state systems such as precipitation scavenging with continuous emissions, the partial pressures of trace gases (NH 3, HCl, HNO 3, SO 2 and CH 3COOH) appear to be of greater or equal importance as carbonate species as buffers in the aqueous phase.

Impact of the hydrogen partial pressure on lactate degradation in a coculture of Desulfovibrio sp. G11 and Methanobrevibacter arboriphilus DH1.

PubMed

Junicke, H; Feldman, H; van Loosdrecht, M C M; Kleerebezem, R

2015-04-01

In this study, the impact of the hydrogen partial pressure on lactate degradation was investigated in a coculture of Desulfovibrio sp. G11 and Methanobrevibacter arboriphilus DH1. To impose a change of the hydrogen partial pressure, formate was added to the reactor. Hydrogen results from the bioconversion of formate besides lactate in the liquid phase. In the presence of a hydrogen-consuming methanogen, this approach allows for a better estimation of low dissolved hydrogen concentrations than under conditions where hydrogen is supplied externally from the gas phase, resulting in a more accurate determination of kinetic parameters. A change of the hydrogen partial pressure from 1,200 to 250 ppm resulted in a threefold increase of the biomass-specific lactate consumption rate. The 50 % inhibition constant of hydrogen on lactate degradation was determined as 0.692 ± 0.064 μM dissolved hydrogen (831 ± 77 ppm hydrogen in the gas phase). Moreover, for the first time, the maximum biomass-specific lactate consumption rate of Desulfovibrio sp. G11 (0.083 ± 0.006 mol-Lac/mol-XG11/h) and the affinity constant for hydrogen uptake of Methanobrevibacter arboriphilus DH1 (0.601 ± 0.022 μM dissolved hydrogen) were determined. Contrary to the widely established view that the biomass-specific growth rate of a methanogenic coculture is determined by the hydrogen-utilizing partner; here, it was found that the hydrogen-producing bacterium determined the biomass-specific growth rate of the coculture grown on lactate and formate.

Electrical and optical properties of nitrogen doped SnO{sub 2} thin films deposited on flexible substrates by magnetron sputtering

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

Fang, Feng, E-mail: fangfeng@seu.edu.cn; Zhang, Yeyu; Wu, Xiaoqin

2015-08-15

Graphical abstract: The best SnO{sub 2}:N TCO film: about 80% transmittance and 9.1 × 10{sup −4} Ω cm. - Highlights: • Nitrogen-doped tin oxide film was deposited on PET by RF-magnetron sputtering. • Effects of oxygen partial pressure on the properties of thin films were investigated. • For SnO{sub 2}:N film, visible light transmittance was 80% and electrical resistivity was 9.1 × 10{sup −4} Ω cm. - Abstract: Nitrogen-doped tin oxide (SnO{sub 2}:N) thin films were deposited on flexible polyethylene terephthalate (PET) substrates at room temperature by RF-magnetron sputtering. Effects of oxygen partial pressure (0–4%) on electrical and optical propertiesmore » of thin films were investigated. Experimental results showed that SnO{sub 2}:N films were amorphous state, and O/Sn ratios of SnO{sub 2}:N films were deviated from the standard stoichiometry 2:1. Optical band gap of SnO{sub 2}:N films increased from approximately 3.10 eV to 3.42 eV as oxygen partial pressure increased from 0% to 4%. For SnO{sub 2}:N thin films deposited on PET, transmittance was about 80% in the visible light region. The best transparent conductive oxide (TCO) deposited on flexible PET substrates was SnO{sub 2}:N thin films preparing at 2% oxygen partial pressure, the transmittance was about 80% and electrical conductivity was about 9.1 × 10{sup −4} Ω cm.« less

Influence of Oxygen Partial Pressure during Processing on the Thermoelectric Properties of Aerosol-Deposited CuFeO2

PubMed Central

Stöcker, Thomas; Exner, Jörg; Schubert, Michael; Streibl, Maximilian; Moos, Ralf

2016-01-01

In the field of thermoelectric energy conversion, oxide materials show promising potential due to their good stability in oxidizing environments. Hence, the influence of oxygen partial pressure during synthesis on the thermoelectric properties of Cu-Delafossites at high temperatures was investigated in this study. For these purposes, CuFeO2 powders were synthetized using a conventional mixed-oxide technique. X-ray diffraction (XRD) studies were conducted to determine the crystal structures of the delafossites associated with the oxygen content during the synthesis. Out of these powders, films with a thickness of about 25 µm were prepared by the relatively new aerosol-deposition (AD) coating technique. It is based on a room temperature impact consolidation process (RTIC) to deposit dense solid films of ceramic materials on various substrates without using a high-temperature step during the coating process. On these dense CuFeO2 films deposited on alumina substrates with electrode structures, the Seebeck coefficient and the electrical conductivity were measured as a function of temperature and oxygen partial pressure. We compared the thermoelectric properties of both standard processed and aerosol deposited CuFeO2 up to 900 °C and investigated the influence of oxygen partial pressure on the electrical conductivity, on the Seebeck coefficient and on the high temperature stability of CuFeO2. These studies may not only help to improve the thermoelectric material in the high-temperature case, but may also serve as an initial basis to establish a defect chemical model. PMID:28773351

Proximate nutritional composition of CELSS crops grown at different CO2 partial pressures

NASA Technical Reports Server (NTRS)

Wheeler, R. M.; Mackowiak, C. L.; Sager, J. C.; Knott, W. M.; Berry, W. L.

1994-01-01

Two Controlled Ecological Life Support System (CELSS) candidate crops, soybean (Glycine max) and potato (Solanum tuberosum), were grown hydroponically in controlled environments maintained at carbon dioxide (CO2) partial pressures ranging from 0.05 to 1.00 kPa (500 to 10,000 ppm at 101 kPa atmospheric pressure). Plants were harvested at maturity (90 days for soybean and 105 days for potato) and all tissues analyzed for proximate nutritional composition (i.e. protein, fat, carbohydrate, crude fiber, and ash content). Soybean seed ash and crude fiber were higher and carbohydrate was lower than values reported for field-grown seed. Potato tubers showed little difference from field-grown tubers. Crude fiber of soybean stems and leaves increased with increased CO2, as did soybean leaf protein (total nitrogen). Potato leaf and stem (combined) protein levels also increased with increased CO2, while leaf and stem carbohydrates decreased. Values for leaf and stem protein and ash were higher than values generally reported for field-grown plants for both species. Results suggest that CO2 partial pressure should have little influence on proximate composition of potato tubers or soybean seed, but that high ash and protein levels might be expected from leaves and stems of crops grown in controlled environments of a CELSS.

Cardiovascular autonomic adaptation in lunar and martian gravity during parabolic flight.

PubMed

Widjaja, Devy; Vandeput, Steven; Van Huffel, Sabine; Aubert, André E

2015-06-01

Weightlessness has a well-known effect on the autonomic control of the cardiovascular system. With future missions to Mars in mind, it is important to know what the effect of partial gravity is on the human body. We aim to study the autonomic response of the cardiovascular system to partial gravity levels, as present on the Moon and on Mars, during parabolic flight. ECG and blood pressure were continuously recorded during parabolic flight. A temporal analysis of blood pressure and heart rate to changing gravity was conducted to study the dynamic response. In addition, cardiovascular autonomic control was quantified by means of heart rate (HR) and blood pressure (BP) variability measures. Zero and lunar gravity presented a biphasic cardiovascular response, while a triphasic response was noted during martian gravity. Heart rate and blood pressure are positively correlated with gravity, while the general variability of HR and BP, as well as vagal indices showed negative correlations with increasing gravity. However, the increase in vagal modulation during weightlessness is not in proportion when compared to the increase during partial gravity. Correlations were found between the gravity level and modulations in the autonomic nervous system during parabolic flight. Nevertheless, with future Mars missions in mind, more studies are needed to use these findings to develop appropriate countermeasures.

Effect of oxygen partial pressure on oxidation of Mo-metal

NASA Astrophysics Data System (ADS)

Sharma, Rabindar Kumar; Kumar, Prabhat; Singh, Megha; Gopal, Pawar; Reddy, G. B.

2018-05-01

This report explains the effect of oxygen partial pressure (PO2 ) on oxidation of Mo-metal in oxygen plasma. XRD results indulge that oxide layers formed on Mo-surfaces at different oxygen partial pressures have two different oxide phases (i.e. orthorhombic MoO3 and monoclinic Mo8O23). Intense XRD peaks at high pressure (i.e. 2.0×10-1 Torr) points out the formation of thick oxide layer on Mo-surface due to presence of large oxygen species in chamber and less oxide volatilization. Whereas, at low PO2 (6.5×10-2 and 7.5×10-2 Torr.) the reduced peak strength is owing to high oxide volatilization rate. SEM micrographs and thickness measurements also support XRD results and confirm that the optimum -2value of PO2 to deposited thicker and uniform oxide film on glass substrate is 7.5×10-2 Torr through plasma assistedoxidation process. Further to study the compositional properties, EDX of the sample M2 (the best sample) is carried out, which confirms that the stoichiometric ratio is less than 3 (i.e. 2.88). Less stoichiometric ratio again confirms the presence of sub oxides in oxide layers on Mo metal as evidenced by XRD results. All the observed results are well in consonance with each other.

Joining of alumina via copper/niobium/copper interlayers

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

Marks, Robert A.; Chapman, Daniel R.; Danielson, David T.

2000-03-15

Alumina has been joined at 1150 degrees C and 1400 degrees C using multilayer copper/niobium/copper interlayers. Four-point bend strengths are sensitive to processing temperature, bonding pressure, and furnace environment (ambient oxygen partial pressure). Under optimum conditions, joints with reproducibly high room temperature strengths (approximately equal 240 plus/minus 20 MPa) can be produced; most failures occur within the ceramic. Joints made with sapphire show that during bonding an initially continuous copper film undergoes a morphological instability, resulting in the formation of isolated copper-rich droplets/particles at the sapphire/interlayer interface, and extensive regions of direct bonding between sapphire and niobium. For optimized aluminamore » bonds, bend tests at 800 degrees C-1100 degrees C indicate significant strength is retained; even at the highest test temperature, ceramic failure is observed. Post-bonding anneals at 1000 degrees C in vacuum or in gettered argon were used to assess joint stability and to probe the effect of ambient oxygen partial pressure on joint characteristics. Annealing in vacuum for up to 200 h causes no significant decrease in room temperature bend strength or change in fracture path. With increasing anneal time in a lower oxygen partial pressure environment, the fracture strength decreases only slightly, but the fracture path shifts from the ceramic to the interface.« less

Method for recovery of actinides from refractory oxides thereof using O.sub. F.sub.2

DOEpatents

Asprey, Larned B.; Eller, Phillip G.

1988-01-01

Method for recovery of actinides from nuclear waste material containing sintered and other oxides thereof using O.sub.2 F.sub.2 to generate the hexafluorides of the actinides present therein. The fluorinating agent, O.sub.2 F.sub.2, has been observed to perform the above-described tasks at sufficiently low temperatures that there is virtually no damage to the containment vessels. Moreover, the resulting actinide hexafluorides are not destroyed by high temperature reactions with the walls of the reaction vessel. Dioxygen difluoride is readily prepared, stored and transferred to the place of reaction.

Simulation of NO and O2 transport facilitated by polymerized hemoglobin solutions in an arteriole that takes into account wall shear stress-induced NO production.

PubMed

Zhou, Yipin; Cabrales, Pedro; Palmer, Andre F

2012-03-01

A mathematical model was developed to study nitric oxide (NO) and oxygen (O(2)) transport in an arteriole and surrounding tissues exposed to a mixture of red blood cells (RBCs) and hemoglobin (Hb)-based O(2) carriers (HBOCs). A unique feature of this model is the inclusion of blood vessel wall shear stress-induced production of endothelial-derived NO, which is very sensitive to the viscosity of the RBC and HBOC mixture traversing the blood vessel lumen. Therefore in this study, a series of polymerized bovine Hb (PolyHb) solutions with high viscosity, varying O(2) affinities, NO dioxygenation rate constants and O(2) dissociation rate constants that were previously synthesized and characterized by our group was evaluated via mathematical modeling, in order to investigate the effect of these biophysical properties on the transport of NO and O(2) in an arteriole and its surrounding tissues subjected to anemia with the commercial HBOC Oxyglobin® and cell-free bovine Hb (bHb) serving as appropriate controls. The computer simulation results indicated that transfusion of high viscosity PolyHb solutions promoted blood vessel wall shear stress dependent generation of the vasodilator NO, especially in the blood vessel wall and should transport enough NO inside the smooth muscle layer to activate vasodilation compared to the commercial HBOC Oxyglobin® and cell-free bHb. However, NO scavenging in the arteriole lumen was unavoidable due to the intrinsic high NO dioxygenation rate constant of the HBOCs being studied. This study also observed that all PolyHbs could potentially improve tissue oxygenation under hypoxic conditions, while low O(2) affinity PolyHbs were more effective in oxygenating tissues under normoxic conditions compared with high O(2) affinity PolyHbs. In addition, all ultrahigh molecular weight PolyHbs displayed higher O(2) transfer rates than the commercial HBOC Oxyglobin® and cell-free bHb. Therefore, these results suggest that ultrahigh molecular weight PolyHb solutions could be used as safe and efficacious O(2) carriers for use in transfusion medicine. It also suggests that future generations of PolyHb solutions should possess lower NO dioxygenation reaction rate constants in order to reduce NO scavenging, while maintaining high solution viscosity to take advantage of wall shear stress-induced NO production. Taken together, we suggest that this mathematical model can be used to predict the vasoactivity of HBOCs and help guide the design and optimization of the next generation of HBOCs for use in transfusion medicine. Copyright © 2011 Elsevier B.V. All rights reserved.

Reaction of tris(bipyridine)ruthenium(III) with hydroxide and its application in a solar energy storage system

PubMed Central

Creutz, Carol; Sutin, Norman

1975-01-01

Irradiation of Ru(bipy)32+ (bipy = 2,2′-bipyridine) with light below 560 nm results in the formation of a charge-transfer excited state potentially capable of reducing water to dihydrogen with concomitant production of Ru(bipy)33+. The latter may be reduced by hydroxide [Formula: see text] to form dioxygen and regenerate the starting complex. The use of these reactions in a cell designed to bring about the photochemical decomposition of water is proposed. The stoichiometry, kinetics, and mechanism of the Ru(bipy)33+-hydroxide reaction have been investigated by conventional and stopped-flow spectrophotometry. The dioxygen yield is a sharp function of pH, attaining its maximum value (about 80%) at pH 9. At low pH (3 and 4.8) the production of ruthenium(II) is first order with kobsd = (1.41 ± 0.04) × 10-4 sec-1 (25°, ionic strength μ = 1.00 M with sodium sulfate). In the intermediate pH range (7.9-10.0) complex kinetics are observed. In the hydroxide range 0.01-0.50 M, ruthenium(II) production is predominantly first order with kobsd = ka[OH-] + kb[OH-]2 sec-1; ka = 148 M-1 sec-1 and kb = 138 M-2 sec-1 (25°, μ = 1.00 M, sodium sulfate). For the ka term, the activation parameters are ΔH‡ = 15.3 ± 1.0 kcal mol-1 and ΔS‡ = 7 ± 3 cal deg-1 mol-1 (1 cal = 4.184 J). An intermediate species (λmax 800 nm) forms at the same rate as ruthenium(II) in this hydroxide range. It disappears with kobsd = 1.2 + 1.1 × 102 [OH-] sec-1 at 25°. Similarly absorbing (λmax 750 to 800 nm) species are generated by the addition of hydroxyl radical to M(bipy)32+/3+ [M = Fe(II), Os(II), Ru(II), Cr(III), Ru(III)] in pulse radiolysis experiments. The kinetics above pH 7 are described in terms of rate-determining nucleophilic attack by hydroxide on the bound bipyridine ring. The hydroxide adduct so generated is tentatively identified with that observed in the pulse radiolysis experiments with Ru(bipy)32+. For reduction of Ru(bipy)33+ by hydrogen peroxide ruthenium(II) production is first order with kobsd = kc[HO2-] + kd[H2O2] where kc = 5.4 × 107 M-1 sec-1 and kd = 8.3 M-1 sec-1 (25°, μ = 1.00 M, pH 3.5 to 9.7). This reaction produces dioxygen in 83 ± 15% yield at pH 6.8 and in 1.0 N sulfuric acid. PMID:16592265

Changes in Contact Area in Meniscus Horizontal Cleavage Tears Subjected to Repair and Resection.

PubMed

Beamer, Brandon S; Walley, Kempland C; Okajima, Stephen; Manoukian, Ohan S; Perez-Viloria, Miguel; DeAngelis, Joseph P; Ramappa, Arun J; Nazarian, Ara

2017-03-01

To assess the changes in tibiofemoral contact pressure and contact area in human knees with a horizontal cleavage tear before and after treatment. Ten human cadaveric knees were tested. Pressure sensors were placed under the medial meniscus and the knees were loaded at twice the body weight for 20 cycles at 0°, 10°, and 20° of flexion. Contact area and pressure were recorded for the intact meniscus, the meniscus with a horizontal cleavage tear, after meniscal repair, after partial meniscectomy (single leaflet), and after subtotal meniscectomy (double leaflet). The presence of a horizontal cleavage tear significantly increased average peak contact pressure and reduced effective average tibiofemoral contact area at all flexion angles tested compared with the intact state (P < .03). There was approximately a 70% increase in contact pressure after creation of the horizontal cleavage tear. Repairing the horizontal cleavage tear restored peak contact pressures and areas to within 15% of baseline, statistically similar to the intact state at all angles tested (P < .05). Partial meniscectomy and subtotal meniscectomy significantly increased average peak contact pressure and reduced average contact area at all degrees of flexion compared with the intact state (P < .05). The presence of a horizontal cleavage tear in the medial meniscus causes a significant reduction in contact area and a significant elevation in contact pressure. These changes may accelerate joint degeneration. A suture-based repair of these horizontal cleavage tears returns the contact area and contact pressure to nearly normal, whereas both partial and subtotal meniscectomy lead to significant reductions in contact area and significant elevations in contact pressure within the knee. Repairing horizontal cleavage tears may lead to improved clinical outcomes by preserving meniscal tissue and the meniscal function. Understanding contact area and peak contact pressure resulting from differing strategies for treating horizontal cleavage tears will allow the surgeon to evaluate the best strategy for treating his or her patients who present with this meniscal pathology. Copyright © 2016 Arthroscopy Association of North America. Published by Elsevier Inc. All rights reserved.

Sickling of red blood cells through rapid oxygen exchange in microfluidic drops.

PubMed

Abbyad, Paul; Tharaux, Pierre-Louis; Martin, Jean-Louis; Baroud, Charles N; Alexandrou, Antigoni

2010-10-07

We have developed a microfluidic approach to study the sickling of red blood cells associated with sickle cell anemia by rapidly varying the oxygen partial pressure within flowing microdroplets. By using the perfluorinated carrier oil as a sink or source of oxygen, the oxygen level within the water droplets quickly equilibrates through exchange with the surrounding oil. This provides control over the oxygen partial pressure within an aqueous drop ranging from 1 kPa to ambient partial pressure, i.e. 21 kPa. The dynamics of the oxygen exchange is characterized through fluorescence lifetime measurements of a ruthenium compound dissolved in the aqueous phase. The gas exchange is shown to occur primarily during and directly after droplet formation, in 0.1 to 0.5 s depending on the droplet diameter and speed. The controlled deoxygenation is used to trigger the polymerization of hemoglobin within sickle red blood cells, encapsulated in drops. This process is observed using polarization microscopy, which yields a robust criterion to detect polymerization based on transmitted light intensity through crossed polarizers.

Effect of oxygen partial pressure on the density of antiphase boundaries in Fe3O4 thin films on Si(100)

NASA Astrophysics Data System (ADS)

Singh, Suraj Kumar; Husain, Sajid; Kumar, Ankit; Chaudhary, Sujeet

2018-02-01

Polycrystalline Fe3O4 thin films were grown on Si(100) substrate by reactive DC sputtering at different oxygen partial pressures PO2 for controlling the growth associated density of antiphase boundaries (APBs). The micro-Raman analyses were performed to study the structural and electronic properties in these films. The growth linked changes in the APBs density are probed by electron-phonon coupling strength (λ) and isothermal magnetization measurements. The estimated values of λ are found to vary from 0.39 to 0.56 with the increase in PO2 from 2.2 × 10-5 to 3.0 × 10-5 Torr, respectively. The saturation magnetization (saturation field) values are found to increase (decrease) from 394 (5.9) to 439 (3.0) emu/cm3 (kOe) with the increase in PO2 . The sharp Verwey transition (∼120 K), low saturation field, high saturation magnetization and low value of λ (comparable to the bulk value ∼0.51) clearly affirm the negligible amount of APBs in the high oxygen partial pressure deposited thin films.

Oxygen partial pressure dependence of thermoelectric power factor in polycrystalline n-type SrTiO3: Consequences for long term stability in thermoelectric oxides

NASA Astrophysics Data System (ADS)

Sharma, Peter A.; Brown-Shaklee, Harlan J.; Ihlefeld, Jon F.

2017-04-01

The Seebeck coefficient and electrical conductivity have been measured as functions of oxygen partial pressure over the range of 10-22 to 10-1 atm at 1173 K for a 10% niobium-doped SrTiO3 ceramic with a grain size comparable to the oxygen diffusion length. Temperature-dependent measurements performed from 320 to 1275 K for as-prepared samples reveal metallic-like conduction and good thermoelectric properties. However, upon exposure to progressively increasing oxygen partial pressure, the thermoelectric power factor decreased over time scales of 24 h, culminating in a three order of magnitude reduction over the entire operating range. Identical measurements on single crystal samples show negligible changes in the power factor so that the instability of ceramic samples is primarily tied to the kinetics of grain boundary diffusion. This work provides a framework for understanding the stability of thermoelectric properties in oxides under different atmospheric conditions. The control of the oxygen atmosphere remains a significant challenge in oxide thermoelectrics.

A Model for the Oxidation of Carbon Silicon Carbide Composite Structures

NASA Technical Reports Server (NTRS)

Sullivan, Roy M.

2004-01-01

A mathematical theory and an accompanying numerical scheme have been developed for predicting the oxidation behavior of carbon silicon carbide (C/SiC) composite structures. The theory is derived from the mechanics of the flow of ideal gases through a porous solid. The result of the theoretical formulation is a set of two coupled nonlinear differential equations written in terms of the oxidant and oxide partial pressures. The differential equations are solved simultaneously to obtain the partial vapor pressures of the oxidant and oxides as a function of the spatial location and time. The local rate of carbon oxidation is determined using the map of the local oxidant partial vapor pressure along with the Arrhenius rate equation. The nonlinear differential equations are cast into matrix equations by applying the Bubnov-Galerkin weighted residual method, allowing for the solution of the differential equations numerically. The numerical method is demonstrated by utilizing the method to model the carbon oxidation and weight loss behavior of C/SiC specimens during thermogravimetric experiments. The numerical method is used to study the physics of carbon oxidation in carbon silicon carbide composites.

Surface reconstruction of GaAs(001) nitrided under the controlled As partial pressure [rapid communication

NASA Astrophysics Data System (ADS)

Imayoshi, Takahiro; Oigawa, Haruhiro; Shigekawa, Hidemi; Tokumoto, Hiroshi

2003-08-01

Under the controlled As partial pressure, the nitridation process of GaAs(0 0 1)-(2 × 4) surface was studied using a scanning tunneling microscope (STM) combined with an electron cyclotron resonance plasma-assisted molecular beam epitaxy system. With either prolonging the nitridation time or decreasing the As partial pressure, the previously reported (3 × 3) structure with two dimers per surface cell ((3 × 3)-2D) was found to progressively convert into a new (3 × 3) structure characterized by one dimer per surface cell ((3 × 3)-1D). Reversely the exposure to arsenic transformed the structure from (3 × 3)-1D to (3 × 3)-2D, suggesting that the topmost layer is composed of As 2-dimers. Based on these STM images together with the X-ray photoelectron spectroscopy data, we propose the new As 2-dimer coverage models to explain both (3 × 3)-1D and -2D structures involving the exchange reaction of arsenic with nitrogen in the subsurface region of GaAs.

46 CFR 39.30-1 - Operational requirements-TB/ALL.

Code of Federal Regulations, 2010 CFR

2010-10-01

... oxygen content of each area of that tank formed by each partial bulkhead must be measured at a point one... the requirements of this part. (b) The pressure drop through the vapor collection system from the most... rate versus the pressure drop. (c) If a vessel carries vapor hoses, the pressure drop through the hoses...

Biomechanical analysis of articular-sided partial-thickness rotator cuff tear and repair.

PubMed

Mihata, Teruhisa; McGarry, Michelle H; Ishihara, Yoko; Bui, Christopher N H; Alavekios, Damon; Neo, Masashi; Lee, Thay Q

2015-02-01

Articular-sided partial-thickness rotator cuff tears are common injuries in throwing athletes. The superior shoulder capsule beneath the supraspinatus and infraspinatus tendons works as a stabilizer of the glenohumeral joint. To assess the effect of articular-sided partial-thickness rotator cuff tear and repair on shoulder biomechanics. The hypothesis was that shoulder laxity might be changed because of superior capsular plication in transtendon repair of articular-sided partial-thickness rotator cuff tears. Controlled laboratory study. Nine fresh-frozen cadaveric shoulders were tested by using a custom shoulder-testing system at the simulated late-cocking phase and acceleration phase of throwing motion. Maximum glenohumeral external rotation angle, anterior translation, position of the humeral head apex with respect to the glenoid, internal impingement area, and glenohumeral and subacromial contact pressures were measured. Each specimen underwent 3 stages of testing: stage 1, with the intact shoulder; stage 2, after creation of articular-sided partial-thickness tears of the supraspinatus and infraspinatus tendons; and stage 3, after transtendon repair of the torn tendons by using 2 suture anchors. Articular-sided partial-thickness tears did not significantly change any of the shoulder biomechanical measurements. In the simulated late-cocking phase, transtendon rotator cuff repair resulted in decreased maximum external rotation angle by 4.2° (P = .03), posterior shift of the humeral head (1.1-mm shift; P = .02), decreased glenohumeral contact pressure by 1.7 MPa (56%; P = .004), and decreased internal impingement area by 26.4 mm(2) (65%; P < .001) compared with values in the torn shoulder. In the acceleration phase, the humeral head shifted inferiorly (1.2-mm shift; P = .03 vs torn shoulder), and glenohumeral anterior translation (1.5-mm decrease; P = .03 vs torn shoulder) and subacromial contact pressure (32% decrease; P = .004 vs intact shoulder) decreased significantly after transtendon repair. Transtendon repair of articular-sided partial-thickness supraspinatus and infraspinatus tears decreased glenohumeral and subacromial contact pressures at time zero; these changes might lead to reduced secondary subacromial and internal impingements and consequently progression to full-thickness rotator cuff tear. However, repair of the tendons decreased anterior translation and external rotation and changed the positional relationship between the humeral head and the glenoid. Careful attention should be paid to shoulder laxity and range of motion when transtendon repair is chosen to treat articular-sided partial-thickness rotator cuff tears, specifically in throwing athletes. © 2014 The Author(s).

Surface Complexation Modeling of Calcite Zeta Potential Measurement in Mixed Brines for Carbonate Wettability Characterization

NASA Astrophysics Data System (ADS)

Song, J.; Zeng, Y.; Biswal, S. L.; Hirasaki, G. J.

2017-12-01

We presents zeta potential measurements and surface complexation modeling (SCM) of synthetic calcite in various conditions. The systematic zeta potential measurement and the proposed SCM provide insight into the role of four potential determining cations (Mg2+, SO42- , Ca2+ and CO32-) and CO2 partial pressure in calcite surface charge formation and facilitate the revealing of calcite wettability alteration induced by brines with designed ionic composition ("smart water"). Brines with varying potential determining ions (PDI) concentration in two different CO2 partial pressure (PCO2) are investigated in experiments. Then, a double layer SCM is developed to model the zeta potential measurements. Moreover, we propose a definition for contribution of charged surface species and quantitatively analyze the variation of charged species contribution when changing brine composition. After showing our model can accurately predict calcite zeta potential in brines containing mixed PDIs, we apply it to predict zeta potential in ultra-low and pressurized CO2 environments for potential applications in carbonate enhanced oil recovery including miscible CO2 flooding and CO2 sequestration in carbonate reservoirs. Model prediction reveals that pure calcite surface will be positively charged in all investigated brines in pressurized CO2 environment (>1atm). Moreover, the sensitivity of calcite zeta potential to CO2 partial pressure in the various brine is found to be in the sequence of Na2CO3 > Na2SO4 > NaCl > MgCl2 > CaCl2 (Ionic strength=0.1M).

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

Groenen, Rik; Smit, Jasper; Orsel, Kasper

The oxidation of species in the plasma plume during pulsed laser deposition controls both the stoichiometry as well as the growth kinetics of the deposited SrTiO{sub 3} thin films, instead of the commonly assumed mass distribution in the plasma plume and the kinetic energy of the arriving species. It was observed by X-ray diffraction that SrTiO{sub 3} stoichiometry depends on the composition of the background gas during deposition, where in a relative small pressure range between 10{sup −2} mbars and 10{sup −1} mbars oxygen partial pressure, the resulting film becomes fully stoichiometric. Furthermore, upon increasing the oxygen (partial) pressure, themore » growth mode changes from 3D island growth to a 2D layer-by-layer growth mode as observed by reflection high energy electron diffraction.« less

Clinical recommendations for high altitude exposure of individuals with pre-existing cardiovascular conditions: A joint statement by the European Society of Cardiology, the Council on Hypertension of the European Society of Cardiology, the European Society of Hypertension, the International Society of Mountain Medicine, the Italian Society of Hypertension and the Italian Society of Mountain Medicine.

PubMed

Parati, Gianfranco; Agostoni, Piergiuseppe; Basnyat, Buddha; Bilo, Grzegorz; Brugger, Hermann; Coca, Antonio; Festi, Luigi; Giardini, Guido; Lironcurti, Alessandra; Luks, Andrew M; Maggiorini, Marco; Modesti, Pietro A; Swenson, Erik R; Williams, Bryan; Bärtsch, Peter; Torlasco, Camilla

2018-05-01

Take home figureAdapted from Bärtsch and Gibbs2 Physiological response to hypoxia. Life-sustaining oxygen delivery, in spite of a reduction in the partial pressure of inhaled oxygen between 25% and 60% (respectively at 2500 m and 8000 m), is ensured by an increase in pulmonary ventilation, an increase in cardiac output by increasing heart rate, changes in vascular tone, as well as an increase in haemoglobin concentration. BP, blood pressure; HR, heart rate; PaCO2, partial pressure of arterial carbon dioxide.

[Peroxynitrite effect on the haemoglobin oxygen affinity in vitro in presence of different partial pressure of carbon dioxide].

PubMed

Stepuro, T L; Zinchuk, V V

2011-08-01

Peroxynitrite (ONOO-) besides its toxic possesses regulatory action that includes the modulation of oxygen binding properties of blood. The aim of this work was to estimate ONOO- effect on the haemoglobin oxygen affinity (HOA) in vitro in presence of different partial pressure of carbon dioxide (CO2). The ONOO- presence in venous blood in conditions of hypercapnia induced oxyhaemoglobin dissociation curve shift leftward while in hypocapnic conditions the result of a different character was obtained. The revealed effect of ONOO- is realized, possibly, through various modifications ofhaemoglobin whose formation is dependent on the CO2 pressure. The ONOO- influences the HOA in different manner that can be important in regulation of blood oxygenation in lungs and maintenance of oxygen consumption in tissues.

Fiber-Optic Based Compact Gas Leak Detection System

NASA Technical Reports Server (NTRS)

deGroot, Wim A.

1995-01-01

A propellant leak detection system based on Raman scattering principles is introduced. The proposed system is flexible and versatile as the result of the use of optical fibers. It is shown that multiple species can be monitored simultaneously. In this paper oxygen, nitrogen, carbon monoxide, and hydrogen are detected and monitored. The current detection sensitivity for both hydrogen and carbon monoxide is 1% partial pressure at ambient conditions. The sensitivity for oxygen and nitrogen is 0.5% partial pressure. The response time to changes in species concentration is three minutes. This system can be used to monitor multiple species at several locations.

[Diagnostic importance of the alveolar-arterial oxygen gradient].

PubMed

Weinans, Marije A E; Drost-de Klerck, Amanda M; ter Maaten, Jan C

2012-01-01

The alveolar-arterial (A-a) oxygen gradient is the difference between the partial pressure of oxygen in the alveoli and the partial pressure of arterial oxygen and can be elevated in the case of pulmonary disease. We describe a 41-year-old patient with pneumonia who presented with abdominal pain, in whom calculation of the A-a gradient could have led to earlier diagnosis. The A-a oxygen gradient is mainly of diagnostic importance and the presented nomogram allows easy and quick interpretation. This might lead to a more frequent use of the A-a oxygen gradient in the future.

Operation and testing of Mark 10 Mod 3 underwater breathing apparatus

NASA Technical Reports Server (NTRS)

Milwee, W. I., Jr.

1972-01-01

Performance tests on a closed circuit, mixed gas underwater breathing apparatus are reported. The equipment is designed to provide a minimum diving duration of four hours at 1500 ft below sea surface; it senses oxygen partial pressure in the breathing gas mix and controls oxygen content of the breathing gas within narrow limits about a preset value. The breathing circuit subsystem provides respirable gas to the diver and removes carbon dioxide and moisture from the expired gas. Test results indicate undesirable variations in oxygen partial pressure with oxygen addition and insufficient carbon dioxide absorption.

Molecular Layer Deposition of Hybrid Organic-Inorganic Alucone Polymer Films Using a Three-Step ABC Reaction Sequence

DTIC Science & Technology

2009-11-02

versus TMA exposure at 150 C is shown in Figure 4a. The TMA exposure is defined by the number of TMA microdoses . EachTMAmicrodosewas a 0.5 s exposure...at 80mTorr of partial pressure. Figure 4a indicates that the TMA reac- tion is self-limiting and reaches completion after 10 TMA microdoses . The...of EA microdoses . Each EA microdose was a 0.5 s exposure at 20 mTorr of partial pressure. Figure 4b indicates that the EA reaction is self-limiting

Oxygen stoichiometry, phase stability, and thermodynamic behavior of the lead-doped and lead-free Bi-2212 systems

NASA Astrophysics Data System (ADS)

Tetenbaum, M.; Hash, M.; Tani, B. S.; Maroni, V. A.

1996-02-01

Electromotive-force (EMF) measurements of oxygen fugacities as a function of stoichiometry have been made on lead-doped and lead-free Bi 2- zPb zSr 2Ca 1Cu 2O x superconducting ceramics in the temperature range ≈ 700-815°C by means of an oxygen-titration techique that employs an yttria-stabilized zirconia electrolyte. Equations for the variation of oxygen partial pressure with composition and temperature have been derived from our EMF measurements. Thermodynamic assessments of the partial molar quantities Δ overlineH(O 2) and Δ overlineS(O 2) for lead-doped Bi-2212 and lead-free Bi-2212 indicate that the solid-state decomposition of these bismuth cuprates at low oxygen partial pressure can be represented by the diphasic CuOCu 2O system.

Some aspects of the thermodynamic behaviour of the lead-doped Bi-2223 system

NASA Astrophysics Data System (ADS)

Tetenbaum, M.; Maroni, V. A.

1996-02-01

A thermodynamic assessment of lead-doped Bi-2223 with emphasis on compositions and oxygen partial pressures within the homogeneity region prior to solid-state decomposition is presented. Equations for the variation of oxygen partial pressure with composition and temperature have been derived from our EMF measurements. Long-term metastability was indicated during cycling over a temperature range of ∼ 700-815°C of a lead-doped Bi-2223 sample having an oxygen-deficient stoichiometry of 9.64 prior to solid-state decomposition corresponding to the diphasic CuOCu 2O system. A trend of increasing negative values of the partial molar enthalpy Δ overlineH( O 2) and entropy Δ overlineS( O2 with increasing oxygen deficiency of the condensed phase indicated an increase in ordering of the cuprate structure prior to solid-state decomposition.

Nonflat equilibrium liquid shapes on flat surfaces.

PubMed

Starov, Victor M

2004-01-15

The hydrostatic pressure in thin liquid layers differs from the pressure in the ambient air. This difference is caused by the actions of surface forces and capillary pressure. The manifestation of the surface force action is the disjoining pressure, which has a very special S-shaped form in the case of partial wetting (aqueous thin films and thin films of aqueous electrolyte and surfactant solutions, both free films and films on solid substrates). In thin flat liquid films the disjoining pressure acts alone and determines their thickness. However, if the film surface is curved then both the disjoining and the capillary pressures act simultaneously. In the case of partial wetting their simultaneous action results in the existence of nonflat equilibrium liquid shapes. It is shown that in the case of S-shaped disjoining pressure isotherm microdrops, microdepressions, and equilibrium periodic films exist on flat solid substrates. Criteria are found for both the existence and the stability of these nonflat equilibrium liquid shapes. It is shown that a transition from thick films to thinner films can go via intermediate nonflat states, microdepressions and periodic films, which both can be more stable than flat films within some range of hydrostatic pressure. Experimental investigations of shapes of the predicted nonflat layers can open new possibilities of determination of disjoining pressure in the range of thickness in which flat films are unstable.

SYNTHESIZING ALCOHOLS AND KETONES BY PHOTOINDUCED CATALYTIC PARTIAL-OXIDATION OF HYDROCARBONS IN TI02 FILM REACTORS PREPARED BY THREE DIFFERENT METHODS

EPA Science Inventory

The partial oxidation of cyclohexane to cyclohexanol and cyclohexanone on UV irradiated titanium dioxide films in the presence of molecular oxygen at ambient temperatures and pressures was studied. Three different coating methodologies (dip coating using titanium isopropoxide an...

Partial discharge detection and analysis in low pressure environments

NASA Astrophysics Data System (ADS)

Liu, Xin

Typical aerospace vehicles (aircraft and spacecraft) experience a wide range of operating pressures during ascending and returning to earth. Compared to the sea-level atmospheric pressure (760 Torr), the pressure at about 60 km altitude is 2 Torr. The performance of the electric power system components of the aerospace vehicles must remain reliable even under such sub-atmospheric operating conditions. It is well known that the dielectric strength of gaseous insulators, while the electrode arrangement remains unchanged, is pressure dependent. Therefore, characterization of the performance and behavior of the electrical insulation in flight vehicles in low-pressure environments is extremely important. Partial discharge testing is one of the practical methods for evaluating the integrity of electrical insulation in aerospace vehicles. This dissertation describes partial discharge (PD) measurements performed mainly with 60 Hz ac energization in air, argon and helium, for pressures between 2 and 760 Torr. Two main electrode arrangements were used. One was a needle-plane electrode arrangement with a Teflon insulating barrier. The other one was a twisted pair of insulated conductors taken from a standard aircraft wiring harness. The measurement results are presented in terms of typical PD current pulse waveforms and waveform analysis for both main electrode arrangements. The evaluation criteria are the waveform polarity, magnitude, shape, rise time, and phase angle (temporal location) relative to the source voltage. Two-variable histograms and statistical averages of the PD parameters are presented. The PD physical mechanisms are analyzed. For PD pattern recognition, both statistical methods (such as discharge parameter dot pattern representation, discharge parameter phase distribution, statistical operator calculations, and PD fingerprint development) and wavelet transform applications are investigated. The main conclusions of the dissertation include: (1) The PD current pulse waveforms are dependent on the pressure. (2) The rise time of the waveform is another effective PD current pulse characteristic indicator. (3) PD fingerprint patterns that are already available for atmospheric pressure (760 Torr) conditions are inadequate for the evaluation of PD pulses at low pressures. (4) Various wavelet transform techniques can be used effectively for PD pulse signal denoising purposes, and for PD pulse waveform transient feature recognition.

Multi-scale diffuse interface modeling of multi-component two-phase flow with partial miscibility

NASA Astrophysics Data System (ADS)

Kou, Jisheng; Sun, Shuyu

2016-08-01

In this paper, we introduce a diffuse interface model to simulate multi-component two-phase flow with partial miscibility based on a realistic equation of state (e.g. Peng-Robinson equation of state). Because of partial miscibility, thermodynamic relations are used to model not only interfacial properties but also bulk properties, including density, composition, pressure, and realistic viscosity. As far as we know, this effort is the first time to use diffuse interface modeling based on equation of state for modeling of multi-component two-phase flow with partial miscibility. In numerical simulation, the key issue is to resolve the high contrast of scales from the microscopic interface composition to macroscale bulk fluid motion since the interface has a nanoscale thickness only. To efficiently solve this challenging problem, we develop a multi-scale simulation method. At the microscopic scale, we deduce a reduced interfacial equation under reasonable assumptions, and then we propose a formulation of capillary pressure, which is consistent with macroscale flow equations. Moreover, we show that Young-Laplace equation is an approximation of this capillarity formulation, and this formulation is also consistent with the concept of Tolman length, which is a correction of Young-Laplace equation. At the macroscopical scale, the interfaces are treated as discontinuous surfaces separating two phases of fluids. Our approach differs from conventional sharp-interface two-phase flow model in that we use the capillary pressure directly instead of a combination of surface tension and Young-Laplace equation because capillarity can be calculated from our proposed capillarity formulation. A compatible condition is also derived for the pressure in flow equations. Furthermore, based on the proposed capillarity formulation, we design an efficient numerical method for directly computing the capillary pressure between two fluids composed of multiple components. Finally, numerical tests are carried out to verify the effectiveness of the proposed multi-scale method.

Multi-scale diffuse interface modeling of multi-component two-phase flow with partial miscibility

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

Kou, Jisheng; Sun, Shuyu, E-mail: shuyu.sun@kaust.edu.sa; School of Mathematics and Statistics, Xi'an Jiaotong University, Xi'an 710049

2016-08-01

In this paper, we introduce a diffuse interface model to simulate multi-component two-phase flow with partial miscibility based on a realistic equation of state (e.g. Peng–Robinson equation of state). Because of partial miscibility, thermodynamic relations are used to model not only interfacial properties but also bulk properties, including density, composition, pressure, and realistic viscosity. As far as we know, this effort is the first time to use diffuse interface modeling based on equation of state for modeling of multi-component two-phase flow with partial miscibility. In numerical simulation, the key issue is to resolve the high contrast of scales from themore » microscopic interface composition to macroscale bulk fluid motion since the interface has a nanoscale thickness only. To efficiently solve this challenging problem, we develop a multi-scale simulation method. At the microscopic scale, we deduce a reduced interfacial equation under reasonable assumptions, and then we propose a formulation of capillary pressure, which is consistent with macroscale flow equations. Moreover, we show that Young–Laplace equation is an approximation of this capillarity formulation, and this formulation is also consistent with the concept of Tolman length, which is a correction of Young–Laplace equation. At the macroscopical scale, the interfaces are treated as discontinuous surfaces separating two phases of fluids. Our approach differs from conventional sharp-interface two-phase flow model in that we use the capillary pressure directly instead of a combination of surface tension and Young–Laplace equation because capillarity can be calculated from our proposed capillarity formulation. A compatible condition is also derived for the pressure in flow equations. Furthermore, based on the proposed capillarity formulation, we design an efficient numerical method for directly computing the capillary pressure between two fluids composed of multiple components. Finally, numerical tests are carried out to verify the effectiveness of the proposed multi-scale method.« less

Water-hammer pressure waves interaction at cross-section changes in series in viscoelastic pipes

NASA Astrophysics Data System (ADS)

Meniconi, S.; Brunone, B.; Ferrante, M.

2012-08-01

In view of scarcity of both experimental data and numerical models concerning transient behavior of cross-section area changes in pressurized liquid flow, the paper presents laboratory data and numerical simulation of the interaction of a surge wave with a partial blockage by a valve, a single pipe contraction or expansion and a series of pipe contraction/expansion in close proximity.With regard to a single change of cross-section area, laboratory data point out the completely different behavior with respect to one of the partially closed in-line valves with the same area ratio. In fact, for the former the pressure wave interaction is not regulated by the steady-state local head loss. With regard to partial blockages, transient tests have shown that the smaller the length, the more intense the overlapping of pressure waves due to the expansion and contraction in series.Numerically, the need for taking into account both the viscoelasticity and unsteady friction is demonstrated, since the classical water-hammer theory does not simulate the relevant damping of pressure peaks and gives rise to a time shifting between numerical and laboratory data. The transient behavior of a single local head loss has been checked by considering tests carried out in a system with a partially closed in-line valve. As a result, the reliability of the quasi steady-state approach for local head loss simulation has been demonstrated in viscoelastic pipes. The model parameters obtained on the basis of transients carried out in single pipe systems have then been used to simulate transients in the more complex pipe systems. These numerical experiments show the great importance of the length of the small-bore pipe with respect to one of the large-bore pipes. Precisely, until a gradually flow establishes in the small-bore pipe, the smaller such a length, the better the quality of the numerical simulation.

Hydrogen Permeability of Incoloy 800H, Inconel 617, and Haynes 230 Alloys

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

Pattrick Calderoni

A potential issue in the design of the NGNP reactor and high-temperature components is the permeation of fission generated tritium and hydrogen product from downstream hydrogen generation through high-temperature components. Such permeation can result in the loss of fission-generated tritium to the environment and the potential contamination of the helium coolant by permeation of product hydrogen into the coolant system. The issue will be addressed in the engineering design phase, and requires knowledge of permeation characteristics of the candidate alloys. Of three potential candidates for high-temperature components of the NGNP reactor design, the hydrogen permeability has been documented well onlymore » for Incoloy 800H, but at relatively high partial pressures of hydrogen. Hydrogen permeability data have been published for Inconel 617, but only in two literature reports and for partial pressures of hydrogen greater than one atmosphere, far higher than anticipated in the NGNP reactor. The hydrogen permeability of Haynes 230 has not been published. To support engineering design of the NGNP reactor components, the hydrogen permeability of Inconel 617 and Haynes 230 were determined using a measurement system designed and fabricated at the Idaho National Laboratory. The performance of the system was validated using Incoloy 800H as reference material, for which the permeability has been published in several journal articles. The permeability of Incoloy 800H, Inconel 617 and Haynes 230 was measured in the temperature range 650 to 950 °C and at hydrogen partial pressures of 10-3 and 10-2 atm, substantially lower pressures than used in the published reports. The measured hydrogen permeability of Incoloy 800H and Inconel 617 were in good agreement with published values obtained at higher partial pressures of hydrogen. The hydrogen permeability of Inconel 617 and Haynes 230 were similar, about 50% greater than for Incoloy 800H and with similar temperature dependence.« less

Early differentiation of the Moon: Experimental and modeling studies

NASA Technical Reports Server (NTRS)

Longhi, J.

1986-01-01

Major accomplishments include the mapping out of liquidus boundaries of lunar and meteoritic basalts at low pressure; the refinement of computer models that simulate low pressure fractional crystallization; the development of a computer model to calculate high pressure partial melting of the lunar and Martian interiors; and the proposal of a hypothesis of early lunar differentiation based upon terrestrial analogs.

49 CFR 176.907 - Polymeric Beads and Plastic Molding Compounds.

Code of Federal Regulations, 2013 CFR

2013-10-01

...: (1) Packed in hermetically sealed packagings or IBC's which conform to packing group II performance level for liquid dangerous goods with a total pressure in the packaging (i.e., the vapor pressure of the material plus the partial pressure of air or other inert gases, less 100kPa (15 psia)) at 55 °C (131 °F...

49 CFR 176.907 - Polymeric Beads and Plastic Molding Compounds.

Code of Federal Regulations, 2014 CFR

2014-10-01

...: (1) Packed in hermetically sealed packagings or IBC's which conform to packing group II performance level for liquid dangerous goods with a total pressure in the packaging (i.e., the vapor pressure of the material plus the partial pressure of air or other inert gases, less 100kPa (15 psia)) at 55 °C (131 °F...

Adaptation of mesenteric lymphatic vessels to prolonged changes in transmural pressure.

PubMed

Dongaonkar, R M; Nguyen, T L; Quick, C M; Hardy, J; Laine, G A; Wilson, E; Stewart, R H

2013-07-15

In vitro studies have revealed that acute increases in transmural pressure increase lymphatic vessel contractile function. However, adaptive responses to prolonged changes in transmural pressure in vivo have not been reported. Therefore, we developed a novel bovine mesenteric lymphatic partial constriction model to test the hypothesis that lymphatic vessels exposed to higher transmural pressures adapt functionally to become stronger pumps than vessels exposed to lower transmural pressures. Postnodal mesenteric lymphatic vessels were partially constricted for 3 days. On postoperative day 3, constricted vessels were isolated, and divided into upstream (UP) and downstream (DN) segment groups, and instrumented in an isolated bath. Although there were no differences between the passive diameters of the two groups, both diastolic diameter and systolic diameter were significantly larger in the UP group than in the DN group. The pump index of the UP group was also higher than that in the DN group. In conclusion, this is the first work to report how lymphatic vessels adapt to prolonged changes in transmural pressure in vivo. Our results suggest that vessel segments upstream of the constriction adapt to become both better fluid conduits and lymphatic pumps than downstream segments.

Absorption of Carbon Dioxide in the aqueous solution of Diethanolamine (DEA) blended with 1-Butyl-1-Methylpyrrolidinium Trifluoromethanesulfonate [BmPyrr][OTf] at high pressure

NASA Astrophysics Data System (ADS)

Jamaludin, S. N.; Salleh, R. M.

2018-03-01

Solubility data of carbon dioxide (CO2) in aqueous Diethanolamine (DEA) blended with 1-Butyl-1-Methylpyrrolidinium Trifluoromethanesulfonate [Bmpyrr][OTf] were measured at temperature 313.15K, 323.15K, 333.15K and pressure from 500psi up to 700 psi. The experiments covered over the concentration range of 0-10wt% for [Bmpyrr][OTf] and 30-40wt% for DEA. The solubility of CO2 was evaluated by measuring the pressure drop in high pressure stirred absorption cell reactor. The experimental results showed that CO2 loading in all DEA-[BmPyrr][OTf] mixtures studied increases with increasing of CO2 partial pressure and temperature. It was also found that the CO2 loading capacity increase significantly as the concentration of [Bmpyrr][OTf] increases. Jou and Mather model was used to predict the solubility of CO2 in the mixtures where the experimental data were correlated as a function of temperature and CO2 partial pressure. It was found that the model was successful in predicting the solubility behavior of the aqueous DEA-[Bmpyrr][OTf] systems considered in this study.

Two Regimes of Bandgap Red Shift and Partial Ambient Retention in Pressure-Treated Two-Dimensional Perovskites

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

Liu, Gang; Kong, Lingping; Guo, Peijun

The discovery of elevated environmental stability in two-dimensional (2D) Ruddlesden–Popper hybrid perovskites represents a significant advance in low-cost, high-efficiency light absorbers. In comparison to 3D counterparts, 2D perovskites of organo-lead-halides exhibit wider, quantum-confined optical bandgaps that reduce the wavelength range of light absorption. Here, we characterize the structural and optical properties of 2D hybrid perovskites as a function of hydrostatic pressure. We observe bandgap narrowing with pressure of 633 meV that is partially retained following pressure release due to an atomic reconfiguration mechanism. We identify two distinct regimes of compression dominated by the softer organic and less compressible inorganic sublattices.more » Our findings, which also include PL enhancement, correlate well with density functional theory calculations and establish structure–property relationships at the atomic scale. These concepts can be expanded into other hybrid perovskites and suggest that pressure/strain processing could offer a new route to improved materials-by-design in applications.« less

Plateau Waves of Intracranial Pressure and Partial Pressure of Cerebral Oxygen.

PubMed

Lang, Erhard W; Kasprowicz, Magdalena; Smielewski, Peter; Pickard, John; Czosnyka, Marek

2016-01-01

This study investigates 55 intracranial pressure (ICP) plateau waves recorded in 20 patients after severe traumatic brain injury (TBI) with a focus on a moving correlation coefficient between mean arterial pressure (ABP) and ICP, called PRx, which serves as a marker of cerebrovascular reactivity, and a moving correlation coefficient between ABP and cerebral partial pressure of oxygen (pbtO2), called ORx, which serves as a marker for cerebral oxygen reactivity. ICP and ICPamplitude increased significantly during the plateau waves, whereas CPP and pbtO2 decreased significantly. ABP, ABP amplitude, and heart rate remained unchanged. In 73 % of plateau waves PRx increased during the wave. ORx showed an increase during and a decrease after the plateau waves, which was not statistically significant. Our data show profound cerebral vasoparalysis on top of the wave and, to a lesser extent, impairment of cerebral oxygen reactivity. The different behavior of the indices may be due to the different latencies of the cerebral blood flow and oxygen level control mechanisms. While cerebrovascular reactivity is a rapidly reacting mechanism, cerebral oxygen reactivity is slower.

Development of Recombinant Hemoglobin-Based Oxygen Carriers

PubMed Central

Varnado, Cornelius L.; Mollan, Todd L.; Birukou, Ivan; Smith, Bryan J.Z.; Henderson, Douglas P.

2013-01-01

Abstract Significance: The worldwide blood shortage has generated a significant demand for alternatives to whole blood and packed red blood cells for use in transfusion therapy. One such alternative involves the use of acellular recombinant hemoglobin (Hb) as an oxygen carrier. Recent Advances: Large amounts of recombinant human Hb can be expressed and purified from transgenic Escherichia coli. The physiological suitability of this material can be enhanced using protein-engineering strategies to address specific efficacy and toxicity issues. Mutagenesis of Hb can (i) adjust dioxygen affinity over a 100-fold range, (ii) reduce nitric oxide (NO) scavenging over 30-fold without compromising dioxygen binding, (iii) slow the rate of autooxidation, (iv) slow the rate of hemin loss, (v) impede subunit dissociation, and (vi) diminish irreversible subunit denaturation. Recombinant Hb production is potentially unlimited and readily subjected to current good manufacturing practices, but may be restricted by cost. Acellular Hb-based O2 carriers have superior shelf-life compared to red blood cells, are universally compatible, and provide an alternative for patients for whom no other alternative blood products are available or acceptable. Critical Issues: Remaining objectives include increasing Hb stability, mitigating iron-catalyzed and iron-centered oxidative reactivity, lowering the rate of hemin loss, and lowering the costs of expression and purification. Although many mutations and chemical modifications have been proposed to address these issues, the precise ensemble of mutations has not yet been identified. Future Directions: Future studies are aimed at selecting various combinations of mutations that can reduce NO scavenging, autooxidation, oxidative degradation, and denaturation without compromising O2 delivery, and then investigating their suitability and safety in vivo. Antioxid. Redox Signal. 18, 2314–2328. PMID:23025383

Generation of a Mn(IV)-Peroxo or Mn(III)-Oxo-Mn(III) Species upon Oxygenation of Mono- and Binuclear Thiolate-Ligated Mn(II) Complexes.

PubMed

Lee, Chien-Ming; Wu, Wun-Yan; Chiang, Ming-Hsi; Bohle, D Scott; Lee, Gene-Hsiang

2017-09-05

A thiolate-bridged binuclear complex [PPN] 2 [(Mn II ( TMS PS3)) 2 ] (1, PPN = bis(triphenylphosphine)iminium and TMS PS3H 3 = (2,2',2″-trimercapto-3,3',3″-tris(trimethylsilyl)triphenylphosphine)), prepared from the reaction of MnCl 2 /[PPN]Cl and Li 3 [ TMS PS3], converts into a mononuclear complex [PPN][Mn II ( TMS PS3)(DABCO)] (2) in the presence of excess amounts of DABCO (DABCO = 1,4-diazabicyclo[2.2.2]octane). Variable temperature studies of solution containing 1 and DABCO by UV-vis spectroscopy indicate that 1 and 2 exist in significant amounts in equilibrium and mononuclear 2 is favored at low temperature. Treatment of 1 or 2 with the monomeric O 2 -side-on-bound [PPN][Mn IV (O 2 )( TMS PS3)] (3) produces the mono-oxo-bridged dimer [PPN] 2 [(Mn III ( TMS PS3)) 2 (μ-O)] (4). The electrochemistry of 1 and 2 reveals anodic peak(s) for a Mn III/ Mn II redox couple at shifted potentials against Fc/Fc + , indicating that both complexes can be oxidized by dioxygen. The O 2 activation mediated by 1 and 2 is investigated in both solution and the solid state. Microcrystals of 2 rapidly react with air or dry O 2 to generate the Mn(IV)-peroxo 3 in high yield, revealing a solid-to-solid transformation and two-electron reduction of O 2 . Oxygenation of 1 or 2 in solution, however, is affected by diffusion and transient concentration of dioxygen in the two different substrates, leading to generation of 3 and 4 in variable ratios.

Structural rearrangements preceding dioxygen formation by the water oxidation complex of photosystem II

PubMed Central

Bao, Han; Burnap, Robert L.

2015-01-01

Photosynthetic water oxidation is catalyzed by the Mn4CaO5 cluster of photosystem II. Recent studies implicate an oxo bridge atom, O5, of the Mn4CaO5 cluster, as the “slowly exchanging” substrate water molecule. The D1-V185N mutant is in close vicinity of O5 and known to extend the lag phase and retard the O2 release phase (slow phase) in this critical last S3+→S0 transition of water oxidation. The pH dependence, hydrogen/deuterium (H/D) isotope effect, and temperature dependence on the O2 release kinetics for this mutant were studied using time-resolved O2 polarography, and comparisons were made with WT and two mutants of the putative proton gate D1-D61. Both kinetic phases in V185N are independent of pH and buffer concentration and have weaker H/D kinetic isotope effects. Each phase is characterized by a parallel or even lower activation enthalpy but a less favorable activation entropy than the WT. The results indicate new rate-determining steps for both phases. It is concluded that the lag does not represent inhibition of proton release but rather, slowing of a previously unrecognized kinetic phase involving a structural rearrangement or tautomerism of the S3+ ground state as it approaches a configuration conducive to dioxygen formation. The parallel impacts on both the lag and O2 formation phases suggest a common origin for the defects surmised to be perturbations of the H-bond network and the water cluster adjacent to O5. PMID:26508637

Series of structural and functional models for the ES (enzyme-substrate) complex of the Co(II)-containing quercetin 2,3-dioxygenase.

PubMed

Sun, Ying-Ji; Huang, Qian-Qian; Zhang, Jian-Jun

2014-03-17

A series of mononuclear Co(II)-flavonolate complexes [Co(II)L(R)(fla)] (L(R)H = 2-{[bis(pyridin-2-ylmethyl)amino]methyl}-p/m-R-benzoic acid; R = p-OMe (1), p-Me (2), m-Br (4), and m-NO2 (5); fla = flavonolate) were designed and synthesized as structural and functional models for the ES (enzyme-substrate) complexes to mimic the active site of the Co(II)-containing quercetin 2,3-dioxygenase (Co-2,3-QD). The metal center Co(II) ion in each complex shows a similar distorted octahedral geometry. The model complexes display high enzyme-type dioxygenation reactivity (oxidative O-heterocyclic ring opening of the coordinated substrate flavonolate) at low temperature, presumably due to the attached carboxylate group in the ligands. The reactivity exhibits a substituent group dependent order of -OMe (1) > -Me (2) > -H (3)14b > -Br (4) > -NO2 (5), and the Hammett plot is linear (ρ = -0.78). This can be explained as the electronic nature of the substituent group in the ligands may influence the conformation and redox potential of the bound flavonolate and finally bring different reactivity. The structures, properties, and reactivity of the model complexes show some dependence on the substituent group in the supporting model ligands, and there is some relationship among them. This study is the first example of a series of structural and functional ES models of Co-2,3-QD, with focus on the effects of the electronic nature of substituted groups and the carboxylate group of the ligands to the dioxygenation reactivity, that will provide important insights into the structure-property-reactivity relationship and the catalytic role of Co-2,3-QD.

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

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

Kumar, Pravindra; Department of Biotechnology, Indian Institute of Technology, Roorkee 247667; Mohammadi, Mahmood

2012-05-18

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

New metabolites in the degradation of fluorene by Arthrobacter sp. strain F101.

PubMed

Casellas, M; Grifoll, M; Bayona, J M; Solanas, A M

1997-03-01

Identification of new metabolites and demonstration of key enzyme activities support and extend the pathways previously reported for fluorene metabolism by Arthrobacter sp. strain F101. Washed-cell suspensions of strain F101 with fluorene accumulated 9-fluorenone, 4-hydroxy-9-fluorenone, 3-hydroxy-1-indanone, 1-indanone, 2-indanone, 3-(2-hydroxyphenyl) propionate, and a compound tentatively identified as a formyl indanone. Incubations with 2-indanone produced 3-isochromanone. The growth yield with fluorene as a sole source of carbon and energy corresponded to an assimilation of about 34% of fluorene carbon. About 7.4% was transformed into 9-fluorenol, 9-fluorenone, and 4-hydroxy-9-fluorenone. Crude extracts from fluorene-induced cells showed 3,4-dihydrocoumarin hydrolase and catechol 2,3-dioxygenase activities. These results and biodegradation experiments with the identified metabolites indicate that metabolism of fluorene by Arthrobacter sp. strain F101 proceeds through three independent pathways. Two productive routes are initiated by dioxygenation at positions 1,2 and 3,4, respectively. meta cleavage followed by an aldolase reaction and loss of C-1 yield the detected indanones. Subsequent biological Baeyer-Villiger reactions produce the aromatic lactones 3,4-dihydrocoumarin and 3-isochromanone. Enzymatic hydrolysis of the former gives 3-(2-hydroxyphenyl) propionate, which could be a substrate for a beta oxidation cycle, to give salicylate. Further oxidation of the latter via catechol and 2-hydroxymuconic semialdehyde connects with the central metabolism, allowing the utilization of all fluorene carbons. Identification of 4-hydroxy-9-fluorenone is consistent with an alternative pathway initiated by monooxygenation at C-9 to give 9-fluorenol and then 9-fluorenone. Although dioxygenation at 3,4 positions of the ketone apparently occurs, this reaction fails to furnish a subsequent productive oxidation of this compound.

New metabolites in the degradation of fluorene by Arthrobacter sp. strain F101.

PubMed Central

Casellas, M; Grifoll, M; Bayona, J M; Solanas, A M

1997-01-01

Identification of new metabolites and demonstration of key enzyme activities support and extend the pathways previously reported for fluorene metabolism by Arthrobacter sp. strain F101. Washed-cell suspensions of strain F101 with fluorene accumulated 9-fluorenone, 4-hydroxy-9-fluorenone, 3-hydroxy-1-indanone, 1-indanone, 2-indanone, 3-(2-hydroxyphenyl) propionate, and a compound tentatively identified as a formyl indanone. Incubations with 2-indanone produced 3-isochromanone. The growth yield with fluorene as a sole source of carbon and energy corresponded to an assimilation of about 34% of fluorene carbon. About 7.4% was transformed into 9-fluorenol, 9-fluorenone, and 4-hydroxy-9-fluorenone. Crude extracts from fluorene-induced cells showed 3,4-dihydrocoumarin hydrolase and catechol 2,3-dioxygenase activities. These results and biodegradation experiments with the identified metabolites indicate that metabolism of fluorene by Arthrobacter sp. strain F101 proceeds through three independent pathways. Two productive routes are initiated by dioxygenation at positions 1,2 and 3,4, respectively. meta cleavage followed by an aldolase reaction and loss of C-1 yield the detected indanones. Subsequent biological Baeyer-Villiger reactions produce the aromatic lactones 3,4-dihydrocoumarin and 3-isochromanone. Enzymatic hydrolysis of the former gives 3-(2-hydroxyphenyl) propionate, which could be a substrate for a beta oxidation cycle, to give salicylate. Further oxidation of the latter via catechol and 2-hydroxymuconic semialdehyde connects with the central metabolism, allowing the utilization of all fluorene carbons. Identification of 4-hydroxy-9-fluorenone is consistent with an alternative pathway initiated by monooxygenation at C-9 to give 9-fluorenol and then 9-fluorenone. Although dioxygenation at 3,4 positions of the ketone apparently occurs, this reaction fails to furnish a subsequent productive oxidation of this compound. PMID:9055403

Isolation and characterization of charge-tagged phenylperoxyl radicals in the gas phase: direct evidence for products and pathways in low temperature benzene oxidation.

PubMed

Kirk, Benjamin B; Harman, David G; Kenttämaa, Hilkka I; Trevitt, Adam J; Blanksby, Stephen J

2012-12-28

The phenylperoxyl radical has long been accepted as a critical intermediate in the oxidation of benzene and an archetype for arylperoxyl radicals in combustion and atmospheric chemistry. Despite being central to many contemporary mechanisms underpinning these chemistries, reports of the direct detection or isolation of phenylperoxyl radicals are rare and there is little experimental evidence connecting this intermediate with expected product channels. We have prepared and isolated two charge-tagged phenyl radical models in the gas phase [i.e., 4-(N,N,N-trimethylammonium)phenyl radical cation and 4-carboxylatophenyl radical anion] and observed their reactions with dioxygen by ion-trap mass spectrometry. Measured reaction rates show good agreement with prior reports for the neutral system (k(2)[(Me(3)N(+))C(6)H(4)˙ + O(2)] = 2.8 × 10(-11) cm(3) molecule(-1) s(-1), Φ = 4.9%; k(2)[((-)O(2)C)C(6)H(4)˙ + O(2)] = 5.4 × 10(-11) cm(3) molecule(-1) s(-1), Φ = 9.2%) and the resulting mass spectra provide unequivocal evidence for the formation of phenylperoxyl radicals. Collisional activation of isolated phenylperoxyl radicals reveals unimolecular decomposition by three pathways: (i) loss of dioxygen to reform the initial phenyl radical; (ii) loss of atomic oxygen yielding a phenoxyl radical; and (iii) ejection of the formyl radical to give cyclopentadienone. Stable isotope labeling confirms these assignments. Quantum chemical calculations for both charge-tagged and neutral phenylperoxyl radicals confirm that loss of formyl radical is accessible both thermodynamically and entropically and competitive with direct loss of both hydrogen atom and carbon dioxide.

The obligate respiratory supercomplex from Actinobacteria.

PubMed

Kao, Wei-Chun; Kleinschroth, Thomas; Nitschke, Wolfgang; Baymann, Frauke; Neehaul, Yashvin; Hellwig, Petra; Richers, Sebastian; Vonck, Janet; Bott, Michael; Hunte, Carola

2016-10-01

Actinobacteria are closely linked to human life as industrial producers of bioactive molecules and as human pathogens. Respiratory cytochrome bcc complex and cytochrome aa3 oxidase are key components of their aerobic energy metabolism. They form a supercomplex in the actinobacterial species Corynebacterium glutamicum. With comprehensive bioinformatics and phylogenetic analysis we show that genes for cyt bcc-aa3 supercomplex are characteristic for Actinobacteria (Actinobacteria and Acidimicrobiia, except the anaerobic orders Actinomycetales and Bifidobacteriales). An obligatory supercomplex is likely, due to the lack of genes encoding alternative electron transfer partners such as mono-heme cyt c. Instead, subunit QcrC of bcc complex, here classified as short di-heme cyt c, will provide the exclusive electron transfer link between the complexes as in C. glutamicum. Purified to high homogeneity, the C. glutamicum bcc-aa3 supercomplex contained all subunits and cofactors as analyzed by SDS-PAGE, BN-PAGE, absorption and EPR spectroscopy. Highly uniform supercomplex particles in electron microscopy analysis support a distinct structural composition. The supercomplex possesses a dimeric stoichiometry with a ratio of a-type, b-type and c-type hemes close to 1:1:1. Redox titrations revealed a low potential bcc complex (Em(ISP)=+160mV, Em(bL)=-291mV, Em(bH)=-163mV, Em(cc)=+100mV) fined-tuned for oxidation of menaquinol and a mixed potential aa3 oxidase (Em(CuA)=+150mV, Em(a/a3)=+143/+317mV) mediating between low and high redox potential to accomplish dioxygen reduction. The generated molecular model supports a stable assembled supercomplex with defined architecture which permits energetically efficient coupling of menaquinol oxidation and dioxygen reduction in one supramolecular entity. Copyright © 2016 Elsevier B.V. All rights reserved.

Comparison of 2 cuff inflation methods of laryngeal mask airway Classic for safe use without cuff manometer in adults.

PubMed

Kim, Min-Soo; Lee, Jeong-Rim; Shin, Yang-Sik; Chung, Ji-Won; Lee, Kyu-Ho; Ahn, Ki Ryang

2014-03-01

This single-center, prospective, randomized, double-blind, 2-arm, parallel group comparison trial was performed to establish whether the adult-sized laryngeal mask airway (LMA) Classic (The Laryngeal Mask Company Ltd, Henley-on-Thames, UK) could be used safely without any consideration of cuff hyperinflation when a cuff of the LMA Classic was inflated using half the maximum inflation volume or the resting volume before insertion of device. Eighty patients aged 20 to 70 years scheduled for general anesthesia using the LMA Classic were included. Before insertion, the cuff was partially filled with half the maximum inflation volume in the half volume group or the resting volume created by opening the pilot balloon valve to equalize with atmospheric pressure in the resting volume group. Several parameters regarding insertion, intracuff pressure, airway leak pressure, and leakage volume/fraction were collected after LMA insertion. The LMA Classic with a partially inflated cuff was successfully inserted in all enrolled patients. Both groups had the same success rate of 95% at the first insertion attempt. The half volume group had a lower mean intracuff pressure compared with the resting volume group (54.5 ± 16.1 cm H2O vs 61.8 ± 16.1 cm H2O; P = .047). There was no difference in airway leak pressure or leakage volume/fraction between the 2 groups under mechanical ventilation. The partially inflated cuff method using half the maximum recommended inflation volume or the resting volume is feasible with the adult-sized LMA Classic, resulting in a high success rate of insertion and adequate range of intracuff pressures. Copyright © 2014 Elsevier Inc. All rights reserved.

Non-contact measurement of partial gas pressure and distribution of elemental composition using energy-resolved neutron imaging

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

Tremsin, A. S.; Losko, A. S.; Vogel, S. C.

Neutron resonance absorption imaging is a non-destructive technique that can characterize the elemental composition of a sample by measuring nuclear resonances in the spectrum of a transmitted beam. Recent developments in pixelated time-of-flight imaging detectors coupled with pulsed neutron sources pose new opportunities for energy-resolved imaging. In this paper we demonstrate non-contact measurements of the partial pressure of xenon and krypton gases encapsulated in a steel pipe while simultaneously passing the neutron beam through high-Z materials. The configuration was chosen as a proof of principle demonstration of the potential to make non-destructive measurement of gas composition in nuclear fuel rods.more » The pressure measured from neutron transmission spectra (~739 ± 98 kPa and ~751 ± 154 kPa for two Xe resonances) is in relatively good agreement with the pressure value of ~758 ± 21 kPa measured by a pressure gauge. This type of imaging has been performed previously for solids with a spatial resolution of ~ 100 μm. In the present study it is demonstrated that the high penetration capability of epithermal neutrons enables quantitative mapping of gases encapsulate within high-Z materials such as steel, tungsten, urania and others. This technique may be beneficial for the non-destructive testing of bulk composition of objects (such as spent nuclear fuel assemblies and others) containing various elements opaque to other more conventional imaging techniques. As a result, the ability to image the gaseous substances concealed within solid materials also allows non-destructive leak testing of various containers and ultimately measurement of gas partial pressures with sub-mm spatial resolution.« less

Non-contact measurement of partial gas pressure and distribution of elemental composition using energy-resolved neutron imaging

DOE PAGES

Tremsin, A. S.; Losko, A. S.; Vogel, S. C.; ...

2017-01-31

Neutron resonance absorption imaging is a non-destructive technique that can characterize the elemental composition of a sample by measuring nuclear resonances in the spectrum of a transmitted beam. Recent developments in pixelated time-of-flight imaging detectors coupled with pulsed neutron sources pose new opportunities for energy-resolved imaging. In this paper we demonstrate non-contact measurements of the partial pressure of xenon and krypton gases encapsulated in a steel pipe while simultaneously passing the neutron beam through high-Z materials. The configuration was chosen as a proof of principle demonstration of the potential to make non-destructive measurement of gas composition in nuclear fuel rods.more » The pressure measured from neutron transmission spectra (~739 ± 98 kPa and ~751 ± 154 kPa for two Xe resonances) is in relatively good agreement with the pressure value of ~758 ± 21 kPa measured by a pressure gauge. This type of imaging has been performed previously for solids with a spatial resolution of ~ 100 μm. In the present study it is demonstrated that the high penetration capability of epithermal neutrons enables quantitative mapping of gases encapsulate within high-Z materials such as steel, tungsten, urania and others. This technique may be beneficial for the non-destructive testing of bulk composition of objects (such as spent nuclear fuel assemblies and others) containing various elements opaque to other more conventional imaging techniques. As a result, the ability to image the gaseous substances concealed within solid materials also allows non-destructive leak testing of various containers and ultimately measurement of gas partial pressures with sub-mm spatial resolution.« less

Is increased positive end-expiratory pressure the culprit? Autoresuscitation in a 44-year-old man after prolonged cardiopulmonary resuscitation: a case report.

PubMed

Hagmann, Henning; Oelmann, Katrin; Stangl, Robert; Michels, Guido

2016-12-20

The phenomenon of autoresuscitation is rare, yet it is known to most emergency physicians. However, the pathophysiology of the delayed return of spontaneous circulation remains enigmatic. Among other causes hyperinflation of the lungs and excessively high positive end-expiratory pressure have been suggested, but reports including cardiopulmonary monitoring during cardiopulmonary resuscitation are scarce to support this hypothesis. We report a case of autoresuscitation in a 44-year-old white man after 80 minutes of advanced cardiac life support accompanied by continuous capnometry and repeated evaluation by ultrasound and echocardiography. After prolonged cardiopulmonary resuscitation, refractory electromechanical dissociation on electrocardiogram and ventricular akinesis were recorded. In addition, a precipitous drop in end-tidal partial pressure of carbon dioxide was noted and cardiopulmonary resuscitation was discontinued. Five minutes after withdrawal of all supportive measures his breathing resumed and a perfusing rhythm ensued. Understanding the underlying pathophysiology of autoresuscitation is hampered by a lack of reports including extensive cardiopulmonary monitoring during cardiopulmonary resuscitation in a preclinical setting. In this case, continuous capnometry was combined with repetitive ultrasound evaluation, which ruled out most assumed causes of autoresuscitation. Our observation of a rapid decline in end-tidal partial pressure of carbon dioxide supports the hypothesis of increased intrathoracic pressure. Continuous capnometry can be performed easily during cardiopulmonary resuscitation, also in a preclinical setting. Knowledge of the pathophysiologic mechanisms may lead to facile interventions to be incorporated into cardiopulmonary resuscitation algorithms. A drop in end-tidal partial pressure of carbon dioxide, for example, might prompt disconnection of the ventilation to allow left ventricular filling. Further reports and research on this topic are encouraged.

Non-contact measurement of partial gas pressure and distribution of elemental composition using energy-resolved neutron imaging

NASA Astrophysics Data System (ADS)

Tremsin, A. S.; Losko, A. S.; Vogel, S. C.; Byler, D. D.; McClellan, K. J.; Bourke, M. A. M.; Vallerga, J. V.

2017-01-01

Neutron resonance absorption imaging is a non-destructive technique that can characterize the elemental composition of a sample by measuring nuclear resonances in the spectrum of a transmitted beam. Recent developments in pixelated time-of-flight imaging detectors coupled with pulsed neutron sources pose new opportunities for energy-resolved imaging. In this paper we demonstrate non-contact measurements of the partial pressure of xenon and krypton gases encapsulated in a steel pipe while simultaneously passing the neutron beam through high-Z materials. The configuration was chosen as a proof of principle demonstration of the potential to make non-destructive measurement of gas composition in nuclear fuel rods. The pressure measured from neutron transmission spectra (˜739 ± 98 kPa and ˜751 ± 154 kPa for two Xe resonances) is in relatively good agreement with the pressure value of ˜758 ± 21 kPa measured by a pressure gauge. This type of imaging has been performed previously for solids with a spatial resolution of ˜ 100 μm. In the present study it is demonstrated that the high penetration capability of epithermal neutrons enables quantitative mapping of gases encapsulate within high-Z materials such as steel, tungsten, urania and others. This technique may be beneficial for the non-destructive testing of bulk composition of objects (such as spent nuclear fuel assemblies and others) containing various elements opaque to other more conventional imaging techniques. The ability to image the gaseous substances concealed within solid materials also allows non-destructive leak testing of various containers and ultimately measurement of gas partial pressures with sub-mm spatial resolution.

Gas exchange and intrapulmonary distribution of ventilation during continuous-flow ventilation

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

Vettermann, J.; Brusasco, V.; Rehder, K.

1988-05-01

In 12 anesthetized paralyzed dogs, pulmonary gas exchange and intrapulmonary inspired gas distribution were compared between continuous-flow ventilation (CFV) and conventional mechanical ventilation (CMV). Nine dogs were studied while they were lying supine, and three dogs were studied while they were lying prone. A single-lumen catheter for tracheal insufflation and a double-lumen catheter for bilateral endobronchial insufflation (inspired O2 fraction = 0.4; inspired minute ventilation = 1.7 +/- 0.3 (SD) 1.kg-1.min-1) were evaluated. Intrapulmonary gas distribution was assessed from regional 133Xe clearances. In dogs lying supine, CO2 elimination was more efficient with endobronchial insufflation than with tracheal insufflation, but themore » alveolar-arterial O2 partial pressure difference was larger during CFV than during CMV, regardless of the type of insufflation. By contrast, endobronchial insufflation maintained both arterial PCO2 and alveolar-arterial O2 partial pressure difference at significantly lower levels in dogs lying prone than in dogs lying supine. In dogs lying supine, the dependent lung was preferentially ventilated during CMV but not during CFV. In dogs lying prone, gas distribution was uniform with both modes of ventilation. The alveolar-arterial O2 partial pressure difference during CFV in dogs lying supine was negatively correlated with the reduced ventilation of the dependent lung, which suggests that increased ventilation-perfusion mismatching was responsible for the increase in alveolar-arterial O2 partial pressure difference. The more efficient oxygenation during CFV in dogs lying prone suggests a more efficient matching of ventilation to perfusion, presumably because the distribution of blood flow is also nearly uniform.« less

Sensor for Measuring Hydrogen Partial Pressure in Parabolic Trough Power Plant Expansion Tanks

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

Glatzmaier, Greg C.; Cooney, Daniel A.

The National Renewable Energy Laboratory and Acciona Energy North America are working together to design and implement a process system that provides a permanent solution to the issue of hydrogen buildup at parabolic trough power plants. We are pursuing a method that selectively removes hydrogen from the expansion tanks that serve as reservoirs for the heat transfer fluid (HTF) that circulates in the collector field and power block components. Our modeling shows that removing hydrogen from the expansion tanks at a design rate reduces and maintains dissolved hydrogen in the circulating HTF to a selected target level. Our collaborative workmore » consists of several tasks that are needed to advance this process concept to a development stage, where it is ready for implementation at a commercial power plant. Our main effort is to design and evaluate likely process-unit operations that remove hydrogen from the expansion tanks at a specified rate. Additionally, we designed and demonstrated a method and instrumentation to measure hydrogen partial pressure and concentration in the expansion-tank headspace gas. We measured hydrogen partial pressure in the headspace gas mixture using a palladium-alloy membrane, which is permeable exclusively to hydrogen. The membrane establishes a pure hydrogen gas phase that is in equilibrium with the hydrogen in the gas mixture. We designed and fabricated instrumentation, and demonstrated its effectiveness in measuring hydrogen partial pressures over a range of three orders of magnitude. Our goal is to install this instrument at the Nevada Solar One power plant and to demonstrate its effectiveness in measuring hydrogen levels in the expansion tanks under normal plant operating conditions.« less

Alteration of striatal dopamine levels under various partial pressure of oxygen in pre-convulsive and convulsive phases in freely-moving rats.

PubMed

Lavoute, Cécile; Weiss, Michel; Risso, Jean-Jacques; Rostain, Jean-Claude

2014-02-01

The purpose of this study was to investigate the change in the striatal dopamine (DA) level in freely-moving rat exposed to different partial pressure of oxygen (from 1 to 5 ATA). Some works have suggested that DA release by the substantia nigra pars compacta (SNc) neurons in the striatum could be disturbed by hyperbaric oxygen (HBO) exposure, altering therefore the basal ganglia activity. Such changes could result in a change in glutamatergic and GABAergic control of the dopaminergic neurons into the SNc. Such alterations could provide more information about the oxygen-induced seizures observed at 5 ATA in rat. DA-sensitive electrodes were implanted into the striatum under general anesthesia. After 1 week rest, awaked rats were exposed to oxygen-nitrogen mixture at a partial pressure of oxygen of 1, 2, 3, 4 and 5 ATA. DA level was monitored continuously (every 3 min) by in vivo voltammetry before and during HBO exposure. HBO induced a decrease in DA level in relationship to the increase in partial pressure of oxygen from 1 ATA to 4 ATA (-15 % at 1 ATA, -30 % at 2 ATA, -40 % at 3 ATA, -45 % at 4 ATA), without signs of oxygen toxicity. At 5 ATA, DA level strongly decreases (-75 %) before seizure which occurred after 27 min ± 7 HBO exposure. After the epileptic seizure the decrease in DA level disappeared. These changes and the biphasic effect of HBO were discussed in function of HBO action on neurochemical regulations of the nigro striatal pathway.

Coronary responses to endothelin-1 and acetylcholine during partial coronary ischaemia and reperfusion in anaesthetized goats.

PubMed

Martínez, Maria Angeles; Fernández, Nuria; Monge, Luis; García-Villalón, Angel Luis; Sanz, Elena; Diéguez, Godofredo

2002-08-01

To examine coronary reactivity to acetylcholine and endothelin-1 (ET-1) during partial ischaemia and reperfusion, flow in the left circumflex coronary artery was measured electromagnetically, and coronary partial ischaemia was induced by stenosis of this artery in anaesthetized goats. In eight animals not treated with N(G)-nitro-l-arginine methyl ester (l-NAME), coronary stenosis reduced coronary flow by 45%, mean arterial pressure by 16% and coronary vascular conductance by 34%. During this ischaemia, coronary vasodilatation to acetylcholine (0.003-0.1 microg) and sodium nitroprusside (SNP; 1-10 microg) was markedly reduced, and coronary vasoconstriction to ET-1 (0.01-0.3 nmol) was attenuated. After 30 min of reperfusion, coronary flow, mean arterial pressure and coronary vascular conductance remained decreased, and the effects of acetylcholine, SNP and ET-1 were as in control animals. In six goats treated with N(G)-nitro-l-arginine methyl ester, coronary stenosis reduced coronary flow by 26% and coronary vascular conductance by 24%, but did not affect mean arterial pressure. During this ischaemia, coronary vasodilatation to acetylcholine and SNP was also markedly reduced, but vasoconstriction to ET-1 was unaffected. After 30 min of reperfusion, coronary flow and coronary vascular conductance remained decreased and mean arterial pressure was normal; in addition, the effects of acetylcholine were lower, those of SNP were similar and those of ET-1 were higher than in control animals. Therefore partial ischaemia reduces the coronary vasodilator reserve and blunts coronary vasoconstriction to ET-1, and reperfusion does not alter the endothelium-dependent and -independent coronary vasodilatation or vasoconstriction to ET-1.

Walking performance in people with diabetic neuropathy: benefits and threats.

PubMed

Kanade, R V; van Deursen, R W M; Harding, K; Price, P

2006-08-01

Walking is recommended as an adjunct therapy to diet and medication in diabetic patients, with the aim of improving physical fitness, glycaemic control and body weight reduction. Therefore we evaluated walking activity on the basis of capacity, performance and potential risk of plantar injury in the diabetic population before it can be prescribed safely. Twenty-three subjects with diabetic neuropathy (DMPN) were compared with 23 patients with current diabetic foot ulcers, 16 patients with partial foot amputations and 22 patients with trans-tibial amputations. The capacity for walking was measured using a total heart beat index (THBI). Gait velocity and average daily strides were measured to assess the performance of walking, and its impact on weight-bearing was studied using maximum peak pressure. THBI increased (p<0.01) and gait velocity and daily stride count fell (p<0.001 for both) with progression of foot complications. The maximum peak pressures over the affected foot of patients with diabetic foot ulcers (p<0.05) and partial foot amputations (p<0.01) were higher than in the group with DMPN. On the contralateral side, the diabetic foot ulcer group showed higher maximum peak pressure over the total foot (p<0.05), and patients with partial foot amputations (p<0.01) and trans-tibial amputations (p<0.05) showed higher maximum peak pressure over the heel. Walking capacity and performance decrease with progression of foot complications. Although walking is recommended to improve fitness, it cannot be prescribed in isolation, considering the increased risk of plantar injury. For essential walking we therefore recommend the use of protective footwear. Walking exercise should be supplemented by partial or non-weight-bearing exercises to improve physical fitness in diabetic populations.

A new device for continuous monitoring the CO2 dissolved in water

NASA Astrophysics Data System (ADS)

de Gregorio, S.; Camarda, M.; Cappuzzo, S.; Giudice, G.; Gurrieri, S.; Longo, M.

2009-04-01

The measurements of dissolved CO2 in water are common elements of industrial processes and scientific research. In order to perform gas dissolved measurements is required to separate the dissolved gaseous phase from water. We developed a new device able to separate the gases phase directly in situ and well suitable for continuous measuring the CO2 dissolved in water. The device is made by a probe of a polytetrafluorethylene (PTFE) tube connected to an I.R. spectrophotometer (I.R.) and a pump. The PTFE is a polymeric semi-permeable membrane and allows the permeation of gas in the system. Hence, this part of the device is dipped in water in order to equilibrate the probe headspace with the dissolved gases. The partial pressure of the gas i in the headspace at equilibrium (Pi) follows the Henry's law: Pi=Hi•Ci, where Hi is the Henry's constant and Ci is the dissolved concentration of gas i. After the equilibrium is achieved, the partial pressure of CO2 inside the tube is equal to the partial pressure of dissolved CO2. The concentration of CO2 is measured by the I.R. connected to the tube. The gas is moved from the tube headspace to the I.R. by using the pump. In order to test the device and assess the best operating condition, several experimental were performed in laboratory. All the test were executed in a special apparatus where was feasible to create controlled atmospheres. Afterward the device has been placed in a draining tunnel sited in the Mt. Etna Volcano edifice (Italy). The monitored groundwater intercepts the Pernicana Fault, along which degassing phenomena are often observed. The values recorded by the station result in agreement with monthly directly measurements of dissolved CO2 partial pressure.

49 CFR 173.133 - Assignment of packing group and hazard zones for Division 6.1 materials.

Code of Federal Regulations, 2011 CFR

2011-10-01

... each component substance is estimated using the formula: ER28SE01.023 where: Pi = partial pressure of the ith component substance in kPa at 20 °C and one atmospheric pressure. Pi may be calculated...

49 CFR 173.133 - Assignment of packing group and hazard zones for Division 6.1 materials.

Code of Federal Regulations, 2010 CFR

2010-10-01

... each component substance is estimated using the formula: ER28SE01.023 where: Pi = partial pressure of the ith component substance in kPa at 20 °C and one atmospheric pressure. Pi may be calculated...

Effect of CO2 partial pressure and different CO2 phases on carbon steel corrosion

NASA Astrophysics Data System (ADS)

Mahlobo, MGR; Premlall, K.; Olubambi, PA

2017-12-01

Carbon capture and storage (CCS) is the recent promising technology aimed at reducing greenhouse gas emission. Like many other developed technologies, CCS is faced with great challenges such as pipeline transportation failure due to corrosion. There are many factors contributing to steel corrosion during the pipeline transportation of carbon dioxide (CO2). This study focuses on CO2 partial pressure and different phases of CO2 as some of the factors contributing to steel corrosion. Carbon steel was used as a testing specimen. High pressure reactor was used in this study to compress CO2 from low to high pressures ultimately changing the CO2 from gaseous phase to gas/liquid phase (subcritical) and to dense phase (supercritical). Weight loss method was employed to determine the corrosion rate while scanning electron microscopy (SEM) and X-Ray diffraction (XRD) were used to study the carbon steel morphology and phase analysis. Using low magnification digital camera, the type of corrosion that took place on the carbon steel surface was identified.

Intradiscal pressure study of percutaneous disc decompression with nucleoplasty in human cadavers.

PubMed

Chen, Yung C; Lee, Sang-heon; Chen, Darwin

2003-04-01

Intradiscal pressure was measured after percutaneous disc decompression by nucleoplasty in human cadavers with different degrees of disc degeneration. To assess intradiscal pressure change after disc decompression, and to analyze the influence of degeneration on the intradiscal pressure change. Partial removal of the nucleus has been shown to decompress herniated discs, relieving pressure on nerve roots and, in some cases, offering relief from disc pain. Nucleoplasty, a new minimally invasive procedure using patented Coblation technology, combines coagulation and ablation for partial removal of the nucleus. Coblated channels remove the tissue volume and may decrease the disc pressure. Three fresh human cadaver spinal specimens (T8-L5; age, 54-84 years; mean age, 70.7 years) were used in this investigation. The intradiscal pressure was measured at three points: before treatment, after each channel was created, and after treatment using a 25-guage 6-inch needle connected to a Merit Medical Systems Intellisystem Inflation Monitor. The needles were calibrated initially to approximately 30 pounds per square inch. For the control, the change in disc pressure was recorded by the same procedure without using Coblation energy. To evaluate the effectiveness of nucleoplasty, disc pressure changes were compared between treatment with and without Coblation energy. Intradiscal pressure was markedly reduced in the younger, healthy disc cadaver. In the older, degenerative disc cadavers, the change in intradiscal pressure after nucleoplasty was very small. There was an inverse correlation between the degree of disc degeneration and the change in intradiscal pressure. Pressure reduction through nucleoplasty is highly dependent on the degree of spine degeneration. Nucleoplasty markedly reduced intradiscal pressure in nondegenerative discs, but had a negligible effect on highly degenerative discs.

Parametric study of orthopedic insole of valgus foot on partial foot amputation.

PubMed

Guo, Jun-Chao; Wang, Li-Zhen; Chen, Wei; Du, Cheng-Fei; Mo, Zhong-Jun; Fan, Yu-Bo

2016-01-01

Orthopedic insole was important for partial foot amputation (PFA) to achieve foot balance and avoid foot deformity. The inapposite insole orthosis was thought to be one of the risk factors of reamputation for foot valgus patient, but biomechanical effects of internal tissues on valgus foot had not been clearly addressed. In this study, plantar pressure on heel and metatarsal regions of PFA was measured using F-Scan. The three-dimensional finite element (FE) model of partial foot evaluated different medial wedge angles (MWAs) (0.0°-10.0°) of orthopedic insole on valgus foot. The effect of orthopedic insole on the internal bone stress, the medial ligament tension of ankle, plantar fascia tension, and plantar pressure was investigated. Plantar pressure on medial heel region was about 2.5 times higher than that of lateral region based on the F-Scan measurements. FE-predicted results showed that the tension of medial ankle ligaments was the lowest, and the plantar pressure was redistributed around the heel, the first metatarsal, and the lateral longitudinal arch regions when MWA of orthopedic insole ranged from 7.5° to 8.0°. The plantar fascias maintained about 3.5% of the total load bearing on foot. However, the internal stresses from foot bones increased. The simulation in this study would provide the suggestion of guiding optimal design of orthopedic insole and therapeutic planning to pedorthist.

A Model for the Oxidation of C/SiC Composite Structures

NASA Technical Reports Server (NTRS)

Sullivan, Roy M.

2003-01-01

A mathematical theory and an accompanying numerical scheme have been developed for predicting the oxidation behavior of C/SiC composite structures. The theory is derived from the mechanics of the flow of ideal gases through a porous solid. Within the mathematical formulation, two diffusion mechanisms are possible: (1) the relative diffusion of one species with respect to the mixture, which is concentration gradient driven and (2) the diffusion associated with the average velocity of the gas mixture, which is total gas pressure gradient driven. The result of the theoretical formulation is a set of two coupled nonlinear differential equations written in terms of the oxidant and oxide partial pressures. The differential equations must be solved simultaneously to obtain the partial vapor pressures of the oxidant and oxides as a function of space and time. The local rate of carbon oxidation is determined as a function of space and time using the map of the local oxidant partial vapor pressure along with the Arrhenius rate equation. The nonlinear differential equations are cast into matrix equations by applying the Bubnov-Galerkin weighted residual method, allowing for the solution of the differential equations numerically. The end result is a numerical scheme capable of determining the variation of the local carbon oxidation rates as a function of space and time for any arbitrary C/SiC composite structures.

Can plants grow in quasi-vacuum?

NASA Technical Reports Server (NTRS)

Andre, M.; Richaud, C.

1986-01-01

It was found that the growth of plants is possible under absolute pressure 14 times lower than the atmospheric pressure. In first approximation, plants ignore the absence of nitrogen and only react to the partial pressure of O2. Hence the growth of plantlets was delayed under low pressures of O2 in both cases with and without nitrogen. The CO2 availability being limited by the carbon content of the seed, the final results after 20 days were very similar.

Investigation of uranium plasma emission from 1050 to 6000 A

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

Mack, J.M. Jr.

1977-12-01

Absolute emission coefficient measurements on arc-generated uranium plasmas in local thermodynamic equilibrium are described for a wavelength bandwidth of 1050 to 6000A. Low- and high-pressure arcs were investigated for their emission properties, characteristic temperatures and uranium partial pressures. Temperatures from 5500 to 8000 K and uranium partial pressures from 0.001 to 0.01 atm were found at the arc centerline. The new emission data are compared with other similar experimental results and to existing theoretical calculations. The effects of cold-layer UF/sub 6/ photoabsorption on uranium plasma emission characteristics are established for UF/sub 6/ molecular densities ranging from 1.0 x 10/sup 16/more » to 1.0 x 10/sup 17/ cm/sup -3/ and layer thickness from 1.0 to 5.0 cm.« less

Correction to the gas phase pressure term in the continuum model for partially saturated granular media presented by Pietruszczak and co-workers

NASA Astrophysics Data System (ADS)

Iveson, Simon M.

2003-06-01

Pietruszczak and coworkers (Internat. J. Numer. Anal. Methods Geomech. 1994; 18(2):93-105; Comput. Geotech. 1991; 12( ):55-71) have presented a continuum-based model for predicting the dynamic mechanical response of partially saturated granular media with viscous interstitial liquids. In their model they assume that the gas phase is distributed uniformly throughout the medium as discrete spherical air bubbles occupying the voids between the particles. However, their derivation of the air pressure inside these gas bubbles is inconsistent with their stated assumptions. In addition the resultant dependence of gas pressure on liquid saturation lies outside of the plausible range of possible values for discrete air bubbles. This results in an over-prediction of the average bulk modulus of the void phase. Corrected equations are presented.

Phase equilibrium constraints on the origin of basalts, picrites, and komatiites

NASA Astrophysics Data System (ADS)

Herzberg, C.; O'Hara, M. J.

1998-07-01

Experimental phase equilibrium studies at pressures ranging from 1 atm to 10 GPa are sufficient to constrain the origin of igneous rocks formed along oceanic ridges and in hotspots. The major element geochemistry of MORB is dominated by partial crystallization at low pressures in the oceanic crust and uppermost mantle, forcing compliance with liquid compositions in low-pressure cotectic equilibrium with olivine, plagioclase and often augite too; parental magmas to MORB formed by partial melting, mixing, and pooling have not survived these effects. Similarly, picrites and komatiites can transform to basalts by partial crystallization in the crust and lithosphere. However, parental picrites and komatiites that were successful in erupting to the surface typically have compositions that can be matched to experimentally-observed anhydrous primary magmas in equilibrium with harzburgite [L+Ol+Opx] at 3.0 to 4.5 GPa. This pressure is likely to represent an average for pooled magmas that collected at the top of a plume head as it flattened below the lithosphere. There is substantial uniformity in the normative olivine content of primary magmas at all depths in a plume melt column, and this results in pooled komatiitic magmas that are equally uniform in normative olivine. However, the imposition of pressure above 3 GPa produces picrites and komatiites with variations in normative enstatite and Al 2O 3 that reveal plume potential temperature and depths of initial melting. Hotter plumes begin to melt deeper than cooler plumes, yielding picrites and komatiites that are enriched in normative enstatite and depleted in Al 2O 3 because of a deeper column within which orthopyroxene can dissolve during decompression. Pressures of initial melting span the 4 to 10 GPa range, increasing in the following order: Iceland, Hawaii, Gorgona, Belingwe, Barberton. Parental komatiites and picrites from a single plume also exhibit internal variability in normative enstatite and Al 2O 3, indicating either a poorly mixed partial melt aggregation process in the plume or the imposition of partial crystallization of olivine-orthopyroxenite on a well-mixed parental magma. Plume shape and thermal structure can also influence the petrology and geochemistry of picrites and komatiites. Liquids extracted from harzburgite residues [L+Ol+Opx] will dominate magmatism in a plume head, and can erupt to form komatiites in oceanic plateaus. Liquids extracted from garnet peridotite residues in a plume axis will gain in importance when the plume head partially solidifies and is removed from the hotspot by a moving lithosphere, as is the case for Hawaii. The paradoxical involvement of garnet indicated by the heavy rare earth elements in picrites that otherwise have a harzburgite signature in Hawaii can be explained by the mixing and collection of magmas from the plume axis. Volcanic rocks from Hawaii and Gorgona and xenoliths from cratonic mantle provide evidence for the importance of partial crystallization of plume magmas when they encounter a cold lithosphere. Harzburgite residua and olivine-orthopyroxene cumulates formed in plumes can yield compositionally distinct lithospheric mantle which is buoyant, and this could have provided an important foundation for the stabilization of the first continents.

75 FR 4793 - Availability for Non-Exclusive, Exclusive, or Partially Exclusive Licensing of U.S. Provisional...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-01-29

... Partially Exclusive Licensing of U.S. Provisional Patent Application Concerning Blast Wave Sensor AGENCY... ``Blast Wave Sensor,'' filed January 4, 2010. The United States Government, as represented by the... wave sensors and their use to detect blast induced pressure changes, and, in particular, a blast wave...

Partial-Vacuum-Gasketed Electrochemical Corrosion Cell

NASA Technical Reports Server (NTRS)

Bonifas, Andrew P.; Calle, Luz M.; Hintze, Paul E.

2006-01-01

An electrochemical cell for making corrosion measurements has been designed to prevent or reduce crevice corrosion, which is a common source of error in prior such cells. The present cell (see figure) includes an electrolyte reservoir with O-ring-edged opening at the bottom. In preparation for a test, the reservoir, while empty, is pressed down against a horizontal specimen surface to form an O-ring seal. A purge of air or other suitable gas is begun in the reservoir, and the pressure in the reservoir is regulated to maintain a partial vacuum. While maintaining the purge and partial vacuum, and without opening the interior of the reservoir to the atmosphere, the electrolyte is pumped into the reservoir. The reservoir is then slowly lifted a short distance off the specimen. The level of the partial vacuum is chosen such that the differential pressure is just sufficient to keep the electrolyte from flowing out of the reservoir through the small O-ring/specimen gap. Electrochemical measurements are then made. Because there is no gasket (and, hence, no crevice between the specimen and the gasket), crevice corrosion is unlikely to occur.

Double silicone tube intubation for the management of partial lacrimal system obstruction.

PubMed

Demirci, Hakan; Elner, Victor M

2008-02-01

To evaluate the effectiveness of double silicone intubation for the management of partial lacrimal drainage system obstruction in adults. Observational retrospective case series. Twenty-four eyes of 18 consecutive adult patients with partial lacrimal system obstruction managed at the University of Michigan. Retrospective review of symptoms and signs, duration of silicone intubation, and complications. Resolution of tearing. Preoperative tearing, negative Jones I testing, positive Jones II testing, and resistance to positive-pressure irrigation were present in all eyes (100%). The first silicone tube was removed after a mean of 11+/-7 months, and the second tube after 16+/-6 months. Postoperatively, at a mean of 21+/-9 months after removal of both tubes, tearing remained resolved in 19 eyes (79%) and remained improved in 2 eyes (8%). In eyes with resolved tearing, Jones I testing became positive, and there was no resistance to positive-pressure irrigation. Persistent tearing in 3 eyes (13%) required treatment with external dacryocystorhinostomy. The only complication was peripunctal pyogenic granulomas in 2 eyes. Double silicone intubation is an effective minimally invasive technique for treatment of partial lacrimal system obstruction in adults.

Containers and systems for the measurement of radioactive gases and related methods

DOEpatents

Mann, Nicholas R; Watrous, Matthew G; Oertel, Christopher P; McGrath, Christopher A

2017-06-20

Containers for a fluid sample containing a radionuclide for measurement of radiation from the radionuclide include an outer shell having one or more ports between an interior and an exterior of the outer shell, and an inner shell secured to the outer shell. The inner shell includes a detector receptacle sized for at least partial insertion into the outer shell. The inner shell and outer shell together at least partially define a fluid sample space. The outer shell and inner shell are configured for maintaining an operating pressure within the fluid sample space of at least about 1000 psi. Systems for measuring radioactivity in a fluid include such a container and a radiation detector received at least partially within the detector receptacle. Methods of measuring radioactivity in a fluid sample include maintaining a pressure of a fluid sample within a Marinelli-type container at least at about 1000 psi.

Exposure of Arabidopsis thaliana to Hypobaric Environments: Implications for Low-Pressure Bioregenerative Life Support Systems for Human Exploration Missions and Terraforming on Mars

NASA Astrophysics Data System (ADS)

Richards, Jeffrey T.; Corey, Kenneth A.; Paul, Anna-Lisa; Ferl, Robert J.; Wheeler, Raymond M.; Schuerger, Andrew C.

2006-12-01

Understanding how hypobaria can affect net photosynthetic (P net) and net evapotranspiration rates of plants is important for the Mars Exploration Program because low-pressured environments may be used to reduce the equivalent system mass of near-term plant biology experiments on landers or future bioregenerative advanced life support systems. Furthermore, introductions of plants to the surface of a partially terraformed Mars will be constrained by the limits of sustainable growth and reproduction of plants to hypobaric conditions. To explore the effects of hypobaria on plant physiology, a low-pressure growth chamber (LPGC) was constructed that maintained hypobaric environments capable of supporting short-term plant physiological studies. Experiments were conducted on Arabidopsis thaliana maintained in the LPGC with total atmospheric pressures set at 101 (Earth sea-level control), 75, 50, 25 or 10 kPa. Plants were grown in a separate incubator at 101 kPa for 6 weeks, transferred to the LPGC, and acclimated to low-pressure atmospheres for either 1 or 16 h. After 1 or 16 h of acclimation, CO2 levels were allowed to drawdown from 0.1 kPa to CO2 compensation points to assess P net rates under different hypobaric conditions. Results showed that P net increased as the pressures decreased from 101 to 10 kPa when CO2 partial pressure (pp) values were below 0.04 kPa (i.e., when ppCO2 was considered limiting). In contrast, when ppCO2 was in the nonlimiting range from 0.10 to 0.07 kPa, the P net rates were insensitive to decreasing pressures. Thus, if CO2 concentrations can be kept elevated in hypobaric plant growth modules or on the surface of a partially terraformed Mars, P net rates may be relatively unaffected by hypobaria. Results support the conclusions that (i) hypobaric plant growth modules might be operated around 10 kPa without undue inhibition of photosynthesis and (ii) terraforming efforts on Mars might require a surface pressure of at least 10 kPa (100 mb) for normal growth of deployed plant species.

Exposure of Arabidopsis thaliana to hypobaric environments: implications for low-pressure bioregenerative life support systems for human exploration missions and terraforming on Mars.

PubMed

Richards, Jeffrey T; Corey, Kenneth A; Paul, Anna-Lisa; Ferl, Robert J; Wheeler, Raymond M; Schuerger, Andrew C

2006-12-01

Understanding how hypobaria can affect net photosynthetic (P (net)) and net evapotranspiration rates of plants is important for the Mars Exploration Program because low-pressured environments may be used to reduce the equivalent system mass of near-term plant biology experiments on landers or future bioregenerative advanced life support systems. Furthermore, introductions of plants to the surface of a partially terraformed Mars will be constrained by the limits of sustainable growth and reproduction of plants to hypobaric conditions. To explore the effects of hypobaria on plant physiology, a low-pressure growth chamber (LPGC) was constructed that maintained hypobaric environments capable of supporting short-term plant physiological studies. Experiments were conducted on Arabidopsis thaliana maintained in the LPGC with total atmospheric pressures set at 101 (Earth sea-level control), 75, 50, 25 or 10 kPa. Plants were grown in a separate incubator at 101 kPa for 6 weeks, transferred to the LPGC, and acclimated to low-pressure atmospheres for either 1 or 16 h. After 1 or 16 h of acclimation, CO(2) levels were allowed to drawdown from 0.1 kPa to CO(2) compensation points to assess P (net) rates under different hypobaric conditions. Results showed that P (net) increased as the pressures decreased from 101 to 10 kPa when CO(2) partial pressure (pp) values were below 0.04 kPa (i.e., when ppCO2 was considered limiting). In contrast, when ppCO(2) was in the nonlimiting range from 0.10 to 0.07 kPa, the P (net) rates were insensitive to decreasing pressures. Thus, if CO(2 )concentrations can be kept elevated in hypobaric plant growth modules or on the surface of a partially terraformed Mars, P (net) rates may be relatively unaffected by hypobaria. Results support the conclusions that (i) hypobaric plant growth modules might be operated around 10 kPa without undue inhibition of photosynthesis and (ii) terraforming efforts on Mars might require a surface pressure of at least 10 kPa (100 mb) for normal growth of deployed plant species.

The unfolding effects on the protein hydration shell and partial molar volume: a computational study.

PubMed

Del Galdo, Sara; Amadei, Andrea

2016-10-12

In this paper we apply the computational analysis recently proposed by our group to characterize the solvation properties of a native protein in aqueous solution, and to four model aqueous solutions of globular proteins in their unfolded states thus characterizing the protein unfolded state hydration shell and quantitatively evaluating the protein unfolded state partial molar volumes. Moreover, by using both the native and unfolded protein partial molar volumes, we obtain the corresponding variations (unfolding partial molar volumes) to be compared with the available experimental estimates. We also reconstruct the temperature and pressure dependence of the unfolding partial molar volume of Myoglobin dissecting the structural and hydration effects involved in the process.

On the anomaly of velocity-pressure decoupling in collocated mesh solutions

NASA Technical Reports Server (NTRS)

Kim, Sang-Wook; Vanoverbeke, Thomas

1991-01-01

The use of various pressure correction algorithms originally developed for fully staggered meshes can yield a velocity-pressure decoupled solution for collocated meshes. The mechanism that causes velocity-pressure decoupling is identified. It is shown that the use of a partial differential equation for the incremental pressure eliminates such a mechanism and yields a velocity-pressure coupled solution. Example flows considered are a three dimensional lid-driven cavity flow and a laminar flow through a 90 deg bend square duct. Numerical results obtained using the collocated mesh are in good agreement with the measured data and other numerical results.

Partially Melted UHP Eclogite in the Sulu Orogenic Belt, China and its rheological significance to deep continental subduction: Micro- to Macro-scale Evidence

NASA Astrophysics Data System (ADS)

Wang, Lu; Kusky, Timothy; Polat, Ali; Wang, Songjie; Jiang, Xingfu; Zong, Keqing; Wang, Junpeng; Deng, Hao; Fu, Jianmin

2015-04-01

Partially Melted UHP Eclogite in the Sulu Orogenic Belt, China and its rheological significance to deep continental subduction: Micro- to Macro-scale Evidence Numerous studies have described partial melting processes in low-high pressure meta-sedimentary rocks, some of which may generate melts that coalesce to form plutons. However, migmatized ultrahigh pressure (UHP) eclogite has never been clearly described from the microscale to macroscale, though experimental studies prove dehydration partial melting of eclogite at high pressure condition1 and low degrees of partially melted eclogite have been reported from the Qaidam UHP orogenic belt in NW China2,3 or inferred from multiphase solid (MS) inclusions within eclogite4 in the Sulu UHP belt. We present field-based documentation of decompression partial melting of UHP eclogite from Yangkou and General's Hill, Sulu Orogen. Migmatized eclogite shows successive stages of anatexis, initially starting from intragranular and grain boundary melt droplets, which grow into a 3D interconnected intergranular network, then segregate and accumulate in pressure shadow areas, and finally merge to form melt channels and dikes that transport melts to upper lithospheric levels. In-situ phengite breakdown-induced partial melting is directly identified by MS inclusions of Kfs+ barium-bearing Kfs + Pl in garnet, connected by 4-10 μm wide veinlets consisting of Bt + Kfs + Pl next to the phengite. Intergranular veinlets of plagioclase + K-feldspar first form isolated beads of melt along grain boundaries and triple junctions of quartz, and with higher degrees of melting, eventually form interconnected 3D networks along grain boundaries in the leucosome, allowing melt to escape from the intergranular realm and collect in low-stress areas. U-Pb (zircon) dating and petrological analyses on residue and leucocratic rocks shows that partial melting occurred at 228-219 Ma, shortly after peak UHP metamorphism (~230 Ma), and at depths of 30-90 km. Whole-rock trace element analyses show that the leucocratic rocks, residue and peak metamorphic stage eclogite (no decompression partial melting) show well matched mass balance relationships. Melts derived from eclogite partial melting lubricated the subducted eclogite slices and facilitated their buoyant rise from mantle depths to crustal levels. Partial melting of deeply subducted eclogite is an important process in determining the rheological structure and mechanical behavior of subducted lithosphere and its rapid exhumation, controlling flow of deep lithospheric material, and for generation of melts from the upper mantle, potentially contributing to arc magmatism and growth of continental crust. Deeply subducted, partially melted eclogite from General's Hill show that eclogites can develop regularly spaced melt channels, a meter or two thick, that would act as significant seismic anomalies5. This may provide direct evidence for the nature of enigmatic 'bright zones' presented in some deep-crustal seismic reflection profiles which have been interpreted to represent areas of melt, high fluid content or unusual rock compositions6. Hermann, J. & Green, D. H. (2001). Earth Planet. Sci. Lett. 188, 149-168. Song, S.G., et al. (2014). Geochim. Cosmochim. Acta 130 42-62. Zhang, G.B., et al. (2014). Lithos, doi: 10.1016/j.lithos.2014.12.009 Gao, X. Y., et al. (2012). J. Metamorph. Geol. 30, 193-212. Wang, L., et al. (2014). Nature Communications. 5:5604 doi: 10.1038/ncomms6604. Brown, L. et al. (1996). Science 274, 1688-1690.

User's manual for a computer program for the emulation/simulation of a space station Environmental Control and Life Support System (ESCM)

NASA Technical Reports Server (NTRS)

Yanosy, James L.

1988-01-01

This manual describes how to use the Emulation Simulation Computer Model (ESCM). Based on G189A, ESCM computes the transient performance of a Space Station atmospheric revitalization subsystem (ARS) with CO2 removal provided by a solid amine water desorbed subsystem called SAWD. Many performance parameters are computed some of which are cabin CO2 partial pressure, relative humidity, temperature, O2 partial pressure, and dew point. The program allows the user to simulate various possible combinations of man loading, metabolic profiles, cabin volumes and certain hypothesized failures that could occur.

CTR Fuel recovery system using regeneration of a molecular sieve drying bed

DOEpatents

Folkers, Charles L.

1981-01-01

A primary molecular sieve drying bed is regenerated by circulating a hot inert gas through the heated primary bed to desorb water held on the bed. The inert gas plus water vapor is then cooled and passed through an auxiliary molecular sieve bed which adsorbs the water originally desorbed from the primary bed. The main advantage of the regeneration technique is that the partial pressure of water can be reduced to the 10.sup.-9 atm. range. This is significant in certain CTR applications where tritiated water (T.sub.2 O, HTO) must be collected and kept at very low partial pressure.