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.

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

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.

Modeling the Effect of Modified Atmospheres on Conidial Germination of Fungi from Dairy Foods

PubMed Central

Nguyen Van Long, Nicolas; Vasseur, Valérie; Couvert, Olivier; Coroller, Louis; Burlot, Marion; Rigalma, Karim; Mounier, Jérôme

2017-01-01

Modified atmosphere packaging (MAP) is commonly applied to extend food shelf-life. Despite growth of a wide variety of fungal contaminants has been previously studied in relation to modified-atmospheres, few studies aimed at quantifying the effects of dioxygen (O2) and carbon dioxide (CO2) partial pressures on conidial germination in solid agar medium. In the present study, an original culture method was developed, allowing microscopic monitoring of conidial germination under modified-atmospheres in static conditions. An asymmetric model was utilized to describe germination kinetics of Paecilomyces niveus, Mucor lanceolatus, Penicillium brevicompactum, Penicillium expansum, and Penicillium roquefoti, using two main parameters, i.e., median germination time (τ) and maximum germination percentage (Pmax). These two parameters were subsequently modeled as a function of O2 partial pressure ranging from 0 to 21% and CO2 partial pressure ranging from 0.03 to 70% (8 tested levels for both O2 and CO2). Modified atmospheres with residual O2 or CO2 partial pressures below 1% and up to 70%, respectively, were not sufficient to totally inhibit conidial germination,. However, O2 levels < 1% or CO2 levels > 20% significantly increased τ and/or reduced Pmax, depending on the fungal species. Overall, the present method and results are of interest for predictive mycology applied to fungal spoilage of MAP food products. PMID:29163403

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.

Influence of dioxygen on the promotional effect of Bi during Pt-catalyzed oxidation of 1,6-hexanediol

DOE PAGES

Xie, Jiahan; Huang, Benjamin; Yin, Kehua; ...

2016-05-24

In this study, a series of carbon-supported, Bi-promoted Pt catalysts with various Bi/Pt atomic ratios was prepared by selectively depositing Bi on Pt nanoparticles. The catalysts were evaluated for 1,6-hexanediol oxidation activity in aqueous solvent under different dioxygen pressures. The rate of diol oxidation on the basis of Pt loading over a Bi-promoted catalyst was 3 times faster than that of an unpromoted Pt catalyst under 0.02 MPa of O 2, whereas the unpromoted catalyst was more active than the promoted catalyst under 1 MPa of O 2. After liquid-phase catalyst pretreatment and 1,6-hexanediol oxidation, migration of Bi on themore » carbon support was observed. The reaction order in O 2 was 0 over Bi-promoted Pt/C in comparison to 0.75 over unpromoted Pt/C in the range of 0.02–0.2 MPa of O 2. Under low O 2 pressure, rate measurements in D 2O instead of H 2O solvent revealed a moderate kinetic isotope effect (rate H2O/rate D2O) on 1,6-hexanediol oxidation over Pt/C (KIE = 1.4), whereas a negligible effect was observed on Bi-Pt/C (KIE = 0.9), indicating that the promotional effect of Bi could be related to the formation of surface hydroxyl groups from the reaction of dioxygen and water. No significant change in product distribution or catalyst stability was observed with Bi promotion, regardless of the dioxygen pressure.« less

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

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

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.

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.

Energy considerations in the partial space elevator

NASA Astrophysics Data System (ADS)

Woo, Pamela; Misra, Arun K.

2014-06-01

The space elevator has been proposed as an alternate method for space transportation. A partial elevator is composed of a tether of several hundreds of kilometres, held vertically in tension between two end masses, with its centre of orbit placed at the geosynchronous orbit. A spacecraft can dock at the lower end, and then use the climber on the elevator to ascend to higher altitudes. In this paper, energy calculations are performed, to determine whether a partial elevator can provide sufficient savings in operational costs, compared to the traditional rocket-powered launch. The energy required to launch a spacecraft from a Low Earth Orbit (LEO) to the geostationary orbit (GEO) is calculated for two trajectories. In the first trajectory, the spacecraft travels from LEO to GEO via a Hohmann transfer. In the second trajectory, the spacecraft travels from LEO to the lower end of the partial space elevator with a Hohmann transfer, and then uses the elevator to climb to GEO. The total energy required is compared between the two trajectories. The effects of tether length, spacecraft-to-climber mass ratio, altitude of LEO, and tether material are investigated.

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.

6. Partial view of rear elevations of shops building and ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

6. Partial view of rear elevations of shops building and Hangar 1301 with rear elevation of corridor (behind power plant) connecting the hangar and shops building. Side elevations of shops and hangar as well as upper rear story of power plant and stack are visible, looking south southwest - Dover Air Force Base, Hangar No. 1301, Dover, Kent County, DE

Laccases as palladium oxidases.

PubMed

Mekmouche, Yasmina; Schneider, Ludovic; Rousselot-Pailley, Pierre; Faure, Bruno; Simaan, A Jalila; Bochot, Constance; Réglier, Marius; Tron, Thierry

2015-02-01

The first example of a coupled catalytic system involving an enzyme and a palladium(ii) catalyst competent for the aerobic oxidation of alcohol in mild conditions is described. In the absence of dioxygen, the fungal laccase LAC3 is reduced by a palladium(0) species as evidenced by the UV/VIS and ESR spectra of the enzyme. During the oxidation of veratryl alcohol performed in water, at room temperature and atmospheric pressure, LAC3 regenerates the palladium catalyst, is reduced and catalyzes the four-electron reduction of dioxygen into water with no loss of enzyme activity. The association of a laccase with a water-soluble palladium complex results in a 7-fold increase in the catalytic efficiency of the complex. This is the first step in the design of a family of renewable palladium catalysts for aerobic oxidation.

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

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.

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.

4. View northeast of west (partial) and south elevations. ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

4. View northeast of west (partial) and south elevations. - Natick Research & Development Laboratories, Climatic Chambers Building, U.S. Army Natick Research, Development & Engineering Center (NRDEC), Natick, Middlesex County, MA

5. View northwest of south (partial) and east elevations. ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

5. View northwest of south (partial) and east elevations. - Natick Research & Development Laboratories, Climatic Chambers Building, U.S. Army Natick Research, Development & Engineering Center (NRDEC), Natick, Middlesex County, MA

133. PARTIAL PLAN AND ELEVATION OF MILL HOUSE & MAP ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

133. PARTIAL PLAN AND ELEVATION OF MILL HOUSE & MAP OF RESERVOIRS, From Annual Report of 1851, Water Department of Philadelphia - Fairmount Waterworks, East bank of Schuylkill River, Aquarium Drive, Philadelphia, Philadelphia County, PA

Partial elevation view of the Oregon Trunk Railway Freight Depot, ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

Partial elevation view of the Oregon Trunk Railway Freight Depot, view looking west at south end of east façade - Oregon Trunk Railway Freight Depot, Southwest First Street & Cascade Avenue, Redmond, Deschutes County, OR

Partial elevation view of the Oregon Trunk Railway Freight Depot, ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

Partial elevation view of the Oregon Trunk Railway Freight Depot, view looking west at north end of east façade - Oregon Trunk Railway Freight Depot, Southwest First Street & Cascade Avenue, Redmond, Deschutes County, OR

Partial elevation view of the Oregon Trunk Railway Freight Depot, ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

Partial elevation view of the Oregon Trunk Railway Freight Depot, view looking west at center of east façade - Oregon Trunk Railway Freight Depot, Southwest First Street & Cascade Avenue, Redmond, Deschutes County, OR

VIEW OF PARTIAL FRONT ELEVATION OF MARINE BARRACKS, LOOKING NORTHEAST ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

VIEW OF PARTIAL FRONT ELEVATION OF MARINE BARRACKS, LOOKING NORTHEAST (with scale stick) - Naval Computer & Telecommunications Area Master Station, Eastern Pacific, Radio Transmitter Facility Lualualei, Marine Barracks, Intersection of Tower Drive & Morse Street, Makaha, Honolulu County, HI

VIEW OF PARTIAL FRONT ELEVATION OF MARINE BARRACKS, LOOKING NORTHEAST ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

VIEW OF PARTIAL FRONT ELEVATION OF MARINE BARRACKS, LOOKING NORTHEAST (without scale stick). - Naval Computer & Telecommunications Area Master Station, Eastern Pacific, Radio Transmitter Facility Lualualei, Marine Barracks, Intersection of Tower Drive & Morse Street, Makaha, Honolulu County, HI

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.

1. VIEW LOOKING SOUTHWEST AT PARTIAL EAST ELEVATION OF FACTORY, ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

1. VIEW LOOKING SOUTHWEST AT PARTIAL EAST ELEVATION OF FACTORY, SHOWING FORMER OHIO & ERIE CANAL PRISM IN FOREGROUND THAT WAS USED AS WATER RESERVOIR (500,000 GALLON) - Jaite Paper Mill, 1200 West Highland Road, Sagamore Hills, Summit County, OH

NORTHEAST SIDE, PARTIAL FRONT FACADE. NOTE: A MORE COMPLETE ELEVATION ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

NORTHEAST SIDE, PARTIAL FRONT FACADE. NOTE: A MORE COMPLETE ELEVATION WAS NOT POSSIBLE DUE TO VEGETATION, SEE OBLIQUE SHOTS 2 AND 5. VIEW FACING SOUTHWEST. - Hickam Field, Officers' Housing Type G, 205 Seventh Street, Honolulu, Honolulu County, HI

4. VAL PARTIAL ELEVATION SHOWING LAUNCHER BRIDGE ON SUPPORTS, LAUNCHER ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

4. VAL PARTIAL ELEVATION SHOWING LAUNCHER BRIDGE ON SUPPORTS, LAUNCHER SLAB, SUPPORT CARRIAGE, CONCRETE 'A' FRAME STRUCTURE AND CAMERA TOWER LOOKING SOUTHEAST. - Variable Angle Launcher Complex, Variable Angle Launcher, CA State Highway 39 at Morris Reservior, Azusa, Los Angeles County, CA

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.

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

Oblique partial east elevation of Castle Garden Bridge, from south, ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

Oblique partial east elevation of Castle Garden Bridge, from south, showing structural configuration of Pratt truss, including typical panels, downstream end of squared cut stone masonry center pier, and squared cut stone masonry north abutment - Castle Garden Bridge, Township Route 343 over Bennetts Branch of Sinnemahoning Creek, Driftwood, Cameron County, PA

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.

Posterior corneal topographic changes after partial flap during laser in situ keratomileusis

PubMed Central

Sharma, N; Rani, A; Balasubramanya, R; Vajpayee, R B; Pandey, R M

2003-01-01

Aim: To study the posterior corneal topographic changes in eyes with partial flaps during laser assisted in situ keratomileusis (LASIK). Methods: Case records of 16 patients, who had partial flap in one eye during LASIK (group 1) and uncomplicated surgery in the other eye (group 2), were studied. Following occurrence of partial flap intraoperatively, laser ablation was abandoned in all the eyes. A 160/180 μm flap was attempted during the initial procedure using the Hansatome microkeratome (Bausch & Lomb Surgicals, Munich, Germany). LASIK surgery in all cases was performed using a 180 μm plate, at the mean interval of 4.16 (SD 1.5) months following the initial procedure. None of the eyes had intraoperative complication during LASIK. Relative posterior corneal surface elevation above the best fit sphere (BFS) before the initial procedure, before, and after LASIK were compared using the Orbscan slit scanning corneal topography/pachymetry system. Results: Posterior corneal elevation was comparable in the two groups, both preoperatively (group 1; 16.4 (4.8) μm, group 2; 16.1 (4.8) μm) and after final surgery (group 1; 57.2 (15.6) μm, group 2; 54.3 (13.1) μm). In group 1 after occurrence of partial flap, the posterior corneal elevation was 16.9 (4.4) μm, and this increase was not significant statistically (p=0.4). On multiple linear regression analysis, residual bed thickness (p<0.001) was independently the significant determinant of final posterior corneal elevation in both groups. Conclusion: The inadvertent occurrence of partial flap during LASIK procedure does not contribute to the increase in posterior corneal elevation. PMID:12543743

Elevated Serum Beta-D-Glucan with Pseudomonas, Aspergillus, and a Partially Acid-Fast Organism in Respiratory Cultures: A Case of Hickam's Dictum Over Occam's Razor.

PubMed

Khan, Salman; Hamula, Camille; Rana, Meenakshi; Sullivan, Timothy; Dunn, Dallas; Patel, Pinki; Mishkin, Aaron; Huprikar, Shirish

2017-10-01

We describe a case of a man with ectopic Cushing's syndrome, elevated serum beta-D-glucan, and respiratory cultures with Pseudomonas, Aspergillus, and a partially acid-fast organism. Our case highlights challenges in diagnosis and management of coinfection in an immunocompromised host.

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)

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.

Laccases as palladium oxidases† †Electronic supplementary information (ESI) available: Experimental procedures, synthesis of catalysts molecules, enzyme activity assay, bleaching experiments, oxygraph traces, oxidation of veratryl alcohol assay, inhibition experiments, electrophoresis. See DOI: 10.1039/c4sc02564d Click here for additional data file.

PubMed Central

Schneider, Ludovic; Rousselot-Pailley, Pierre; Faure, Bruno; Simaan, A. Jalila; Bochot, Constance; Réglier, Marius

2015-01-01

The first example of a coupled catalytic system involving an enzyme and a palladium(ii) catalyst competent for the aerobic oxidation of alcohol in mild conditions is described. In the absence of dioxygen, the fungal laccase LAC3 is reduced by a palladium(0) species as evidenced by the UV/VIS and ESR spectra of the enzyme. During the oxidation of veratryl alcohol performed in water, at room temperature and atmospheric pressure, LAC3 regenerates the palladium catalyst, is reduced and catalyzes the four-electron reduction of dioxygen into water with no loss of enzyme activity. The association of a laccase with a water-soluble palladium complex results in a 7-fold increase in the catalytic efficiency of the complex. This is the first step in the design of a family of renewable palladium catalysts for aerobic oxidation. PMID:29560210

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.

5. View West. West side and rear elevations of c. ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

5. View West. West side and rear elevations of c. 1890 first rear addition; partial north rear elevation of c. 1900 side ell addition; and north rear and west side elevation of final rear addition of c. 1940. - Vaughn Chevrolet Building, 101-109 East Main Street, Monongahela, Washington County, PA

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.

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…

Economic analysis for commingling effects of insect activity in the elevator boot area

USDA-ARS?s Scientific Manuscript database

Boot areas in commercial grain elevators and feed mills contribute to commingling of insects with grain that moves through the elevator leg. A partial budget and stochastic dominance model was developed to improve pest management decision-making and risk analysis assessment from commingling effects ...

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.

11. GIRDER PARTIAL ELEVATION AND SECTIONS, 80 FOOT THROUGH PLATE ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

11. GIRDER PARTIAL ELEVATION AND SECTIONS, 80 FOOT THROUGH PLATE GIRDER SPAN. (Also includes a Marking Diagram and a schedule of parts.) American Bridge Company, Ambridge Plant No. 5, sheet no. 1, dated April 7, 1928, order no. F5073. For U.S. Steel Products Company, Pacific Coast Depot, order no. SF578. For Southern Pacific Company, order no. 8873-P-28746. Scale 1/4 inch to one foot. - Napa River Railroad Bridge, Spanning Napa River, east of Soscol Avenue, Napa, Napa County, CA

Partial cambial mortality in high-elevation Pinus aristata (Pinaceae)

Treesearch

Andrew J. Schauer; Anna W. Schoettle; Richard L. Boyce

2001-01-01

Partial cambial mortality is a growth form that is characteristic of Pinus aristata trees. To better elucidate their cambial death pattern, tree size and aspect of cambial death data were gathered from three Pinus aristata forests in central Colorado, USA. Stripping frequency tended to be higher for larger diameter classes. Partial cambial mortality exhibits...

36. ARCHITECTURAL AND STRUCTURAL DETAILS OF ELEVATOR HOUSING, NaK HEATER ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

36. ARCHITECTURAL AND STRUCTURAL DETAILS OF ELEVATOR HOUSING, NaK HEATER STACK ROOF FLASHING, HOOD ELEVATION DETAIL. INCLUDES PARTIAL 'BILL OF MATERIAL.' INEEL DRAWING NUMBER 200-0633-00-287-106361. FLUOR NUMBER 5775-CPP-633-A-11. - Idaho National Engineering Laboratory, Old Waste Calcining Facility, Scoville, Butte County, ID

Partial rotator cuff repair and biceps tenotomy for the treatment of patients with massive cuff tears and retained overhead elevation: midterm outcomes with a minimum 5 years of follow-up.

PubMed

Cuff, Derek J; Pupello, Derek R; Santoni, Brandon G

2016-11-01

A subset of patients with massive irreparable rotator cuff tears present with retained overhead elevation and pain as their primary complaint. Our aim was to evaluate the outcomes of partial arthroscopic rotator cuff repair with biceps tenotomy and to report the failure rate of this procedure for patients with >5 years of follow-up. Thirty-four patients underwent partial rotator cuff repair and biceps tenotomy for treatment of a massive rotator cuff tear. Patients had preoperative active forward elevation >120° and no radiographic evidence of glenohumeral arthritis. Patients were followed up clinically and radiographically, and 28 patients had a minimum of 5 years of follow-up. Failure was defined as an American Shoulder and Elbow Surgeons score of <70, loss of active elevation >90°, or revision to reverse shoulder arthroplasty during the study period. Patients demonstrated improvements in average preoperative to postoperative American Shoulder and Elbow Surgeons scores (46.6 to 79.3 [P < .001]) and Simple Shoulder Test scores (5.7 to 9.1 [P < .001]) along with decrease in visual analog scale for pain scores (6.9 to 1.9 [P < .001]). No significant change in forward elevation (168° to 154° [P = .07]), external rotation (38° to 39° [P = 1.0]), or internal rotation (84% to 80% [P = 1.0]) was identified; 36% of patients had progression of the Hamada stage. The failure rate was 29%; 75% of patients were satisfied with their index procedure. Partial rotator cuff repair and biceps tenotomy for patients with massive irreparable rotator cuff tears with retained overhead elevation and pain as the primary complaint produced reasonable outcomes at midterm follow-up of at least 5 years. Copyright © 2016 Journal of Shoulder and Elbow Surgery Board of Trustees. Published by Elsevier Inc. All rights reserved.

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.

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.

Partial Section Through Stack, Water Tank, and Privy; Plan ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

Partial Section Through Stack, Water Tank, and Privy; Plan - Stack, Privies, & Changing Rooms; Elevation - Central of Georgia Railway, Savannah Repair Shops & Terminal Facilities, Bounded by West Broad, Jones, West Boundary & Hull Streets, Savannah, Chatham County, GA

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.

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.

A Psychophysical Evaluation of Spectral Enhancement

ERIC Educational Resources Information Center

DiGiovanni, Jeffrey J.; Nelson, Peggy B.; Schlauch, Robert S.

2005-01-01

Listeners with sensorineural hearing loss have well-documented elevated hearing thresholds; reduced auditory dynamic ranges; and reduced spectral (or frequency) resolution that may reduce speech intelligibility, especially in the presence of competing sounds. Amplification and amplitude compression partially compensate for elevated thresholds and…

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

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.

Elevational Ranges of Montane Birds and Deforestation in the Western Andes of Colombia.

PubMed

Ocampo-Peñuela, Natalia; Pimm, Stuart L

2015-01-01

Deforestation causes habitat loss, fragmentation, degradation, and can ultimately cause extinction of the remnant species. Tropical montane birds face these threats with the added natural vulnerability of narrower elevational ranges and higher specialization than lowland species. Recent studies assess the impact of present and future global climate change on species' ranges, but only a few of these evaluate the potentially confounding effect of lowland deforestation on species elevational distributions. In the Western Andes of Colombia, an important biodiversity hotspot, we evaluated the effects of deforestation on the elevational ranges of montane birds along altitudinal transects. Using point counts and mist-nets, we surveyed six altitudinal transects spanning 2200 to 2800 m. Three transects were forested from 2200 to 2800 m, and three were partially deforested with forest cover only above 2400 m. We compared abundance-weighted mean elevation, minimum elevation, and elevational range width. In addition to analysing the effect of deforestation on 134 species, we tested its impact within trophic guilds and habitat preference groups. Abundance-weighted mean and minimum elevations were not significantly different between forested and partially deforested transects. Range width was marginally different: as expected, ranges were larger in forested transects. Species in different trophic guilds and habitat preference categories showed different trends. These results suggest that deforestation may affect species' elevational ranges, even within the forest that remains. Climate change will likely exacerbate harmful impacts of deforestation on species' elevational distributions. Future conservation strategies need to account for this by protecting connected forest tracts across a wide range of elevations.

Elevational Ranges of Montane Birds and Deforestation in the Western Andes of Colombia

PubMed Central

2015-01-01

Deforestation causes habitat loss, fragmentation, degradation, and can ultimately cause extinction of the remnant species. Tropical montane birds face these threats with the added natural vulnerability of narrower elevational ranges and higher specialization than lowland species. Recent studies assess the impact of present and future global climate change on species’ ranges, but only a few of these evaluate the potentially confounding effect of lowland deforestation on species elevational distributions. In the Western Andes of Colombia, an important biodiversity hotspot, we evaluated the effects of deforestation on the elevational ranges of montane birds along altitudinal transects. Using point counts and mist-nets, we surveyed six altitudinal transects spanning 2200 to 2800m. Three transects were forested from 2200 to 2800m, and three were partially deforested with forest cover only above 2400m. We compared abundance-weighted mean elevation, minimum elevation, and elevational range width. In addition to analysing the effect of deforestation on 134 species, we tested its impact within trophic guilds and habitat preference groups. Abundance-weighted mean and minimum elevations were not significantly different between forested and partially deforested transects. Range width was marginally different: as expected, ranges were larger in forested transects. Species in different trophic guilds and habitat preference categories showed different trends. These results suggest that deforestation may affect species’ elevational ranges, even within the forest that remains. Climate change will likely exacerbate harmful impacts of deforestation on species’ elevational distributions. Future conservation strategies need to account for this by protecting connected forest tracts across a wide range of elevations. PMID:26641477

A new method of applying a controlled soil water stress, and its effect on the growth of cotton and soybean seedlings at ambient and elevated carbon dioxide

USDA-ARS?s Scientific Manuscript database

While numerous studies have shown that elevated carbon dioxide can delay soil water depletion by causing partial stomatal closure, few studies have compared responses of plant growth to the same soil water deficits imposed at ambient and elevated carbon dioxide. We applied a vacuum to ceramic cups ...

18. Photocopy of circa 1839 ink and wash drawing by ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

18. Photocopy of circa 1839 ink and wash drawing by Richard Upjohn in Avery Library, Columbia University ELEVATION OF ENTRANCE FRONT (above) AND PRELIMINARY OR PARTIAL FIRST FLOOR PLAN WITH TWO SMALL ELEVATION SKETCHES (below) - Kingscote, Bellevue Avenue & Bowery Street, Newport, Newport County, RI

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.

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.

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

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.

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

Lubrication system with tolerance for reduced gravity

NASA Technical Reports Server (NTRS)

Portlock, Lawrence E. (Inventor); McCune, Michael E. (Inventor); Dobek, Louis J. (Inventor)

2012-01-01

A lubrication system includes an auxiliary lubricant tank 48, a supply conduit 58 extending from a source of lubricant 26 to the auxiliary lubricant tank. A reduced-G bypass line 108 branches from the conduit and enters the auxiliary tank at a first elevation E.sub.1. The system also includes an auxiliary tank discharge conduit 116, a portion of which resides within the tank. The resident portion has an opening 122 at least partially at a second elevation E.sub.2 higher than the first elevation.

Lubrication System with Tolerance for Reduced Gravity

NASA Technical Reports Server (NTRS)

Portlock, Lawrence E. (Inventor); McCune, Michael E. (Inventor); Dobek, Louis J. (Inventor)

2013-01-01

A lubrication system includes an auxiliary lubricant tank 48, a supply conduit 58 extending from a source of lubricant 26 to the auxiliary lubricant tank. A reduced-G bypass line 108 branches from the conduit and enters the auxiliary tank at a first elevation E.sub.1. The system also includes an auxiliary tank discharge conduit 116, a portion of which resides within the tank. The resident portion has an opening 122 at least partially at a second elevation E.sub.2 higher than the first elevation.

Foreign Object Damage Behavior of a SiC/SiC Composite at Ambient and Elevated Temperatures

NASA Technical Reports Server (NTRS)

Bhatt, Ramakrishna T.; Pereira, J. Michael; Gyekenyesi, John P.; Choi, Sung R.

2004-01-01

Foreign object damage (FOD) behavior of a gas-turbine grade SiC/SiC ceramic matrix composite (CMC) was determined at 25 and 1316 C, employing impact velocities from 115 to 440 meters per second by 1.59-mm diameter stell-ball projectiles. Two different types of specimen support were used at each temperature: fully supported and partially supported. For a given temperature, the degree of post-impact strength degradation increased with increasing impact velocity, and was greater in a partially supported configuration than in a fully supported one. The elevated-temperature FOD resistance of the composite, particularly under partially supported loading at higher impact velocities greater than or equal to 350 meters per second, was significantly less than the ambient-temperature counterpart, attributed to a weakening effect of the composite. For fully supported loading, frontal contact stress played a major role in generating composite damage; whereas, for partially supported loading, both frontal contact and backside bending stresses were combined sources of damage generation. The SiC/SiC composite was able to survive higher energy impacts without complete structural failure but suffered more strength affecting damage from low energy impacts than AS800 and SN282 silicon nitrides.

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.

Postoperative elevation in creatine kinase and its impact on renal function in patients undergoing complex partial nephrectomy.

PubMed

Sidana, Abhinav; Walton-Diaz, Annerleim; Truong, Hong; Siddiqui, M Minhaj; Miao, Ning; Shih, Johanna; Mannes, Andrew; Bratslavsky, Gennady; Linehan, W Marston; Metwalli, Adam R

2016-07-01

To identify the risk factors associated with development of postoperative elevation of creatine kinase (CK) and study its effect on renal function in patients who underwent complex multifocal partial nephrectomy (PN). Patients who underwent PN at National Cancer Institute between January 2007 and December 2012 were included in the study. Elevated serum CK was defined as >2000 U/L. Kidney function was assessed using serum creatinine and estimated glomerular filtration rate (eGFR). Changes were reported as percent change from preoperative values and compared using the Wilcoxon test. Regression analysis was performed to identify the predictors of elevation in CK and decline in eGFR. From 407 total cases, 207 had adequate CK data for analysis. Median number of tumors removed was 3 (1-70). Median peak CK was 1458 (82-36,788). Forty-two percent developed CK elevation >2000 U/L. Factors associated with postoperative elevation of CK > 2000 were young age (p = 0.009), high BMI (p = 0.003) and operating room time (p < 0.001). Although CK > 2000 was associated with significantly greater decline in eGFR (37.4 vs. 20.3 %, p < 0.001) in immediate postoperative period, this change largely resolved to a much less clinically relevant (9.2 vs 3.3 %, p = 0.040) change after 3 months. On multivariate analysis, postoperative elevation in CK was not found to be an independent factor determining renal function at 3 months. In our cohort, a significant proportion of patients developed CK elevations >2000 U/L. While patients with elevated CK had more decline in eGFR in immediate postoperative period, postoperative elevations of CK did not appear to impact overall long-term renal function in patients undergoing PN.

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.

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.

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.

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

Activation energy determinations suggest that thiols reverse autooxidation of tetrahydrobiopterin by a different mechanism than ascorbate.

PubMed

Valent, Sándor; Tóth, Miklós

2006-01-01

In neutral aqueous solutions tetrahydrobiopterin is oxidized by dioxygen in a reaction that is succinctly described as autooxidation. Ascorbate and thiols moderate this reaction by reversing the oxidative process. In the present study the effect of various thiols on the apparent Arrhenius activation energy of tetrahydrobiopterin autooxidation was characterized and compared to that of ascorbate determined previously. We observed that - in sharp contrast to ascorbate - the efficiency of thiols to protect tetrahydrobiopterin decreased with the elevation of temperature from 22 to 37 degrees C. Accordingly, the apparent Arrhenius activation energies (in kJ/mol) measured in the presence of thiols were consistently greater than the value determined with tetrahydrobiopterin alone (59.6 +/- 1.4) or in the presence of ascorbate (59.9 +/- 2.8). Thus, the energy values were 88.8+/-1.1 with glutathione, 87.6 +/- 2.1 with N-acetylcysteine, 79.2 +/- 1.6 with cysteine, 75.1 +/- 2.4 with dithiotreitol and 70.3 +/- 0.9 with homocysteine. Since thiols are as potent reducing agents as ascorbate, these findings suggest that thiols and ascorbate protect tetrahydrobiopterin from oxidation acting at different steps of the oxidation process. It is likely that thiols reduce quinoidal dihydrobiopterin, whereas ascorbate scavenges the trihydrobiopterin radical to tetrahydrobiopterin. Furthermore, the results indicate that thiols are excellent tools to protect tetrahydrobiopterin from autooxidative decomposition in laboratory experiments conducted at relatively low temperatures, whereas the protective effect diminishes at 37 degrees C, i.e. under physiological conditions.

Aerodynamic characteristics of horizontal tail surfaces

NASA Technical Reports Server (NTRS)

Silverstein, Abe; Katzoff, S

1940-01-01

Collected data are presented on the aerodynamic characteristics of 17 horizontal tail surfaces including several with balanced elevators and two with end plates. Curves are given for coefficients of normal force, drag, and elevator hinge moment. A limited analysis of the results has been made. The normal-force coefficients are in better agreement with the lifting-surface theory of Prandtl and Blenk for airfoils of low aspect ratio than with the usual lifting-line theory. Only partial agreement exists between the elevator hinge-moment coefficients and those predicted by Glauert's thin-airfoil theory.

2. DETAIL VIEW OF MAIN ELEVATION OF MILL, LOOKING NORTHWEST. ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

2. DETAIL VIEW OF MAIN ELEVATION OF MILL, LOOKING NORTHWEST. NOTE ORIGINAL WINDOWS ON UPPER FLOORS. THE TOP FLOOR CONTAINED SPINNING AND TWISTER EQUIPMENT, THE SECOND FLOOR THE CARD ROOM AND ADDITIONAL SPINNING, AND THE GROUND FLOOR WEAVING, THE CLOTH ROOM, AND SHIPPING. A PARTIAL BASEMENT CONTAINED A MACHINE SHOP, SUPPLY DEPARTMENT, AND OVERFLOW COTTON STORAGE. - Stark Mill, 117 Corinth Road, Hogansville, Troup County, GA

Partially Ventilated Transom Flow Elevations-Unsteady Analysis

DTIC Science & Technology

2016-06-30

family of hulls that have a common fore-body with varying after-bodies. This project expands the investigation into unsteady transom flow elevations two...incident waves on the stream wise discontinuity in hull geometry due to varying transom configurations ranging from round bilge to deep-vee sections...transom. Turbulence Stimulation Hama strips were used for turbulence stimulation on the hull . Four strips of electrical tape with a combined

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.

Lead exposure and the 2010 achievement test scores of children in New York counties

PubMed Central

2012-01-01

Background Lead is toxic to cognitive and behavioral functioning in children even at levels well below those producing physical symptoms. Continuing efforts in the U.S. since about the 1970s to reduce lead exposure in children have dramatically reduced the incidence of elevated blood lead levels (with elevated levels defined by the current U.S. Centers for Disease Control threshold of 10 μg/dl). The current study examines how much lead toxicity continues to impair the academic achievement of children of New York State, using 2010 test data. Methods This study relies on three sets of data published for the 57 New York counties outside New York City: school achievement data from the New York State Department of Education, data on incidence of elevated blood lead levels from the New York State Department of Health, and data on income from the U.S. Census Bureau. We studied third grade and eighth grade test scores in English Language Arts and mathematics. Using the county as the unit of analysis, we computed bivariate correlations and regression coefficients, with percent of children achieving at the lowest reported level as the dependent variable and the percent of preschoolers in the county with elevated blood lead levels as the independent variable. Then we repeated those analyses using partial correlations to control for possible confounding effects of family income, and using multiple regressions with income included. Results The bivariate correlations between incidence of elevated lead and number of children in the lowest achievement group ranged between 0.38 and 0.47. The partial correlations ranged from 0.29 to 0.40. The regression coefficients, both bivariate and partial (both estimating the increase in percent of children in the lowest achievement group for every percent increase in the children with elevated blood lead levels), ranged from 0.52 to 1.31. All regression coefficients, when rounded to the nearest integer, were approximately 1. Thus, when the percent of children showing elevated lead increases by one percent, the percent of children in the lowest achievement group, according to the regression equations generated, also increases by about one percent. All associations were significant at the 0.05 level. Conclusion Despite public health advances, and despite the imprecision of measures, an association between the incidence of elevated blood lead and achievement in New York counties is still apparent, not attributable to confounding by income. Efforts to reduce lead exposure should persist with vigor. PMID:22269775

A self-photoprotection mechanism helps Stipa baicalensis adapt to future climate change

PubMed Central

Song, Xiliang; Zhou, Guangsheng; Xu, Zhenzhu; Lv, Xiaomin; Wang, Yuhui

2016-01-01

We examined the photosynthetic responses of Stipa baicalensis to relative long-term exposure (42 days) to the predicted elevated temperature and water availability changes to determine the mechanisms through which the plant would acclimate to future climate change. Two thermal regimes (ambient and +4 °C) and three irrigation levels (partial, normal and excess) were used in environmental control chambers. The gas exchange parameters, light response curves and A/Ci curves were determined. The elevated temperature and partial irrigation reduced the net photosynthetic rate due to a limitation in the photosynthetic capacity instead of the intercellular CO2 concentration. Partial irrigation decreased Rubisco activation and limited RuBP regeneration. The reduction in Vcmax increased with increasing temperature. Excess irrigation offset the negative effect of drought and led to a partial recovery of the photosynthetic capacity. Although its light use efficiency was restricted, the use of light and dark respiration by Stipa baicalensis was unchanged. We concluded that nonstomatal limitation was the primary reason for photosynthesis regulation in Stipa baicalensis under relative long-term climate change conditions. Although climate change caused reductions in the light use efficiency and photosynthetic rate, a self-photoprotection mechanism in Stipa baicalensis resulted in its high ability to maintain normal live activities. PMID:27161934

Psychiatric Comorbidity of Full and Partial Posttraumatic Stress Disorder among Older Adults in the United States: Results from Wave 2 of the National Epidemiologic Survey on Alcohol and Related Conditions

PubMed Central

Pietrzak, Robert H.; Goldstein, Risë B.; Southwick, Steven M.; Grant, Bridget F.

2011-01-01

Objectives To present findings on the prevalence, correlates, and psychiatric comorbidity of DSM-IV posttraumatic stress disorder (PTSD) and partial PTSD in a nationally representative sample of U.S. older adults. Design, Setting, and Participants Face-to-face interviews with 9,463 adults aged 60 years and older in the Wave 2 National Epidemiologic Survey on Alcohol and Related Conditions. Measurements Sociodemographic correlates, worst stressful experiences, comorbid lifetime mood, anxiety, substance use, and personality disorders, psychosocial functioning, and suicide attempts. Results Lifetime prevalences±standard errors of PTSD and partial PTSD were 4.5%±0.25 and 5.5%±0.27, respectively. Rates were higher in women (5.7%±0.37 and 6.5%±0.39) than men (3.1%±0.31 and 4.3%±0.37). Older adults with PTSD most frequently identified unexpected death of someone close, serious illness or injury to someone close, and own serious or life-threatening illness as their worst stressful events. Older adults exposed to trauma but without full or partial PTSD and respondents with partial PTSD most often identified unexpected death of someone close, serious illness or injury to someone close, and indirect experience of 9/11 as their worst events. PTSD was associated with elevated odds of lifetime mood, anxiety, drug use, and borderline and narcissistic personality disorders, and decreased psychosocial functioning. Partial PTSD was associated with elevated odds of mood, anxiety, and narcissistic and schizotypal personality disorders, and poorer psychosocial functioning relative to older adults exposed to trauma but without full or partial PTSD. Conclusions PTSD among older adults in the United States is slightly more prevalent than previously reported and associated with considerable psychiatric comorbidity and psychosocial dysfunction. Partial PTSD is associated with significant psychiatric comorbidity, particularly with mood and other anxiety disorders. PMID:22522959

Psychiatric comorbidity of full and partial posttraumatic stress disorder among older adults in the United States: results from wave 2 of the National Epidemiologic Survey on Alcohol and Related Conditions.

PubMed

Pietrzak, Robert H; Goldstein, Risë B; Southwick, Steven M; Grant, Bridget F

2012-05-01

To present findings on the prevalence, correlates, and psychiatric comorbidity of Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition posttraumatic stress disorder (PTSD) and partial PTSD in a nationally representative sample of U.S. older adults. Face-to-face interviews with 9,463 adults age 60 years and older in the Wave 2 National Epidemiologic Survey on Alcohol and Related Conditions. Sociodemographic correlates; worst stressful experiences; comorbid lifetime mood, anxiety, substance use, and personality disorders; psychosocial functioning; and suicide attempts. Lifetime prevalences ± standard errors of PTSD and partial PTSD were 4.5% ± 0.25 and 5.5% ± 0.27, respectively. Rates were higher in women (5.7% ± 0.37 and 6.5% ± 0.39) than in men (3.1% ± 0.31 and 4.3% ± 0.37). Older adults with PTSD most frequently identified unexpected death of someone close, serious illness or injury to someone close, and their own serious or life-threatening illness as their worst stressful events. Older adults exposed to trauma but without full or partial PTSD and respondents with partial PTSD most often identified unexpected death of someone close, serious illness or injury to someone close, and indirect experience of 9/11 as their worst events. PTSD was associated with elevated odds of lifetime mood, anxiety, drug use, and borderline and narcissistic personality disorders and decreased psychosocial functioning. Partial PTSD was associated with elevated odds of mood, anxiety, and narcissistic and schizotypal personality disorders and poorer psychosocial functioning relative to older adults exposed to trauma but without full or partial PTSD. PTSD among older adults in the United States is slightly more prevalent than previously reported and is associated with considerable psychiatric comorbidity and psychosocial dysfunction. Partial PTSD is associated with significant psychiatric comorbidity, particularly with mood and other anxiety disorders.

Extended lateral thoracic fasciocutaneous biosynthetic flap for reconstruction of full-thickness partial external ear defects: an experimental study.

PubMed

Kuvat, Samet Vasfi; Taşkın, Ümit; Yücebaş, Kadir; Tansuker, Hasan Deniz; Oktay, Mehmet Faruk; Kozanoğlu, Erol; Aydın, Salih

2017-01-01

External ear reconstruction is a controversial topic in reconstructive plastic surgery. Here, we prepared a pedicled biosynthetic flap for full-thickness, partial ear defects in rabbits. We operated on six adult female New Zealand rabbits weighing 3-4 kg. The dimensions of the lateral thoracic fasciocutaneous flap were 7 × 6 cm. The flap was elevated based on one of the bilaterally located internal thoracic arteries, which were dissected proximally. The pedicled flap was folded in two, and polypropylene mesh was sandwiched in the middle. The flap was adapted to a defect of 3.5 × 3 cm in diameter. In fact, the defect was created before elevation of the flap. Rabbits were followed up for 4 weeks, at the end of which they were killed and their ears were evaluated histopathologically. The survival rate of the rabbits was 100 %. All pedicled biosynthetic flaps were viable, but one showed partial (20 %) necrosis (1/6) and one was partially detached (1/6). Macroscopic (color, thickness, texture) and histological (polymorphonuclear leukocyte invasion in the skin, subcutaneous tissue, and at the junction between the polypropylene mesh and the flap) features of the flap were compared to the ipsilateral ear. A new technique was developed for partial external ear reconstruction with sufficient inner skeletal support and outer skin lining. Level of evidence Level NA.

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.

Practices and guidelines for temporary transverse HMA tapers.

DOT National Transportation Integrated Search

2010-05-01

During hot mix asphalt (HMA) construction and rehabilitation, partially completed pavements are often opened to : traffic between construction periods. This results in transverse dropoffs at the transition between pavements of : different elevations....

Up on The 606. Understanding the Use of a New Elevated Pedestrian and Bicycle Trail in Chicago, Illinois

Treesearch

Paul H. Gobster; Sonya Sachdeva; Greg Lindsey

2017-01-01

The 606 is the world's first multiuse elevated trail, extending for 2.7 mi (4.35 km) through diverse neighborhoods whose per capita of open space is one of the lowest in Chicago. The trail connects six ground-level parks and is managed for recreation, but it also serves as a cross-town transportation connector and was funded partially with transportation dollars....

Supplemental and highly-elevated tocopherol doses differentially regulate allergic inflammation: reversibility of α-tocopherol and γ-tocopherol's effects

PubMed Central

McCary, Christine A.; Abdala-Valencia, Hiam; Berdnikovs, Sergejs; Cook-Mills, Joan M.

2011-01-01

We have reported that supplemental doses of the α- and γ-tocopherol isoforms of vitamin E decrease and increase, respectively, allergic lung inflammation. We have now assessed whether these effects of tocopherols are reversible. For these studies, mice were treated with antigen and supplemental tocopherols in a first phase of treatment followed by a 4 week clearance phase and then the mice received a second phase of antigen and tocopherol treatments. The pro-inflammatory effects of supplemental levels of γ-tocopherol in phase 1 were only partially reversed by supplemental α-tocopherol in phase 2 but were completely reversed by raising α-tocopherol levels 10-fold in phase 2. When γ-tocopherol levels were increased 10-fold (highly-elevated tocopherol) so that the lung tissue γ-tocopherol levels were equal to the lung tissue levels of supplemental α-tocopherol, γ-tocopherol reduced leukocyte numbers in the lung lavage fluid. In contrast to the lung lavage fluid, highly-elevated levels of γ-tocopherol increased inflammation in the lung tissue. These regulatory effects of highly-elevated tocopherols on tissue inflammation and lung lavage fluid were reversible in a second phase of antigen challenge without tocopherols. In summary, the pro-inflammatory effects of supplemental γ-tocopherol on lung inflammation were partially reversed by supplemental levels of α-tocopherol but were completely reversed by highly-elevated-levels of α-tocopherol. Also, highly-elevated levels of γ-tocopherol were inhibitory and reversible in lung lavage but, importantly, were pro-inflammatory in lung tissue sections. These results have implications for future studies with tocopherols and provide a new context in which to review vitamin E studies in the literature. PMID:21317387

3. Photocopy of photograph (location of original unknown) Mary Mather, ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

3. Photocopy of photograph (location of original unknown) Mary Mather, photographer, ca. 1920 PARTIAL EAST ELEVATION, OBSCURED BY FOLIAGE - Bagatelle Plantation, East River Road (moved to Iberville Parish), Donaldsonville, Ascension Parish, LA

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

Dependence of flow and transport through the Williamson River Delta, Upper Klamath Lake, Oregon, on wind, river inflow, and lake elevation

USGS Publications Warehouse

Wood, Tamara M.

2012-01-01

The hydrodynamic model of Upper Klamath and Agency Lakes, Oregon, was used to run 384 realizations of a numerical tracer experiment in order to understand the relative effects of wind, lake elevation, and Williamson River inflow on flow and transport (the movement of water and passively transported constituents) through the Williamson River Delta. Significant findings from this study include: * The replacement rate of water increased in Tulana and Goose Bay with increasing lake elevation, Williamson River inflow, and wind speed. * The fraction of Williamson River inflow passing through either side of the Delta increased with lake elevation and Williamson River inflow. * The partial replacement rate of water in Goose Bay with water from the Williamson River increased with wind speed. * The partial replacement rate of water in Tulana with water from the Williamson River decreased with wind speed. * Strong wind forcing at the water surface caused more of the Williamson River inflow to pass through Goose Bay than through Tulana. * Westerly to northwesterly winds result in more of the Williamson River inflow passing through the Goose Bay side of the Delta than through the Tulana side. * Regression models developed from the tracer experiments can be used to quantify the dependencies between transport and the independent variables to obtain rough estimates of useful quantities such as residence time and steady-state solute concentrations.

Phonon anharmonicity of monoclinic zirconia and yttrium-stabilized zirconia

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

Li, Chen W.; Smith, Hillary L.; Lan, Tian

2015-04-13

Inelastic neutron scattering measurements on monoclinic zirconia (ZrO 2) and 8 mol% yttrium-stabilized zirconia were performed at temperatures from 300 to 1373 ωK. We reported temperature-dependent phonon densities of states (DOS) and Raman spectra obtained at elevated temperatures. First-principles lattice dynamics calculations with density functional theory gave total and partial phonon DOS curves and mode Grüneisen parameters. These mode Grüneisen parameters were used to predict the experimental temperature dependence of the phonon DOS with partial success. However, substantial anharmonicity was found at elevated temperatures, especially for phonon modes dominated by the motions of oxygen atoms. Yttrium-stabilized zirconia (YSZ) was somewhatmore » more anharmonic and had a broader phonon spectrum at low temperatures, owing in part to defects in its structure. YSZ also has a larger vibrational entropy than monoclinic zirconia.« less

Evaluation of human sclera after femtosecond laser ablation using two photon and confocal microscopy

NASA Astrophysics Data System (ADS)

Sun, Hui; Kurtz, Ronald; Juhasz, Tibor

2012-08-01

Glaucoma is the second-leading cause of blindness worldwide and is often associated with elevated intraocular pressure (IOP). Partial thickness intrascleral channels can be created with a femtosecond laser operating at a wavelength of 1700 nm. Such channels have the potential to increase outflow facility and reduce elevated IOP. Analysis of the dimensions and location of these channels is important in understanding their effects. We describe the application of two-photon microscopy and confocal microscopy for noninvasive imaging of the femtosecond laser created partial-thickness scleral channels in human cadaver eyes. High-resolution images, hundreds of microns deep in the sclera, were obtained to allow determination of the shape and dimension of such channels. This demonstrates that concept of integrating femtosecond laser surgery, and two-photon and confocal imaging has the future potential for image-guided high-precision surgery in transparent and translucent tissue.

Maternal serum alpha-fetoprotein and fetal triploidy.

PubMed

Pircon, R A; Towers, C V; Porto, M; Gocke, S E; Garite, T J

1989-10-01

Fetal triploidy is commonly found in early pregnancy. The majority of these pregnancies spontaneously abort in the first trimester. Occasionally, the pregnancy progresses to the second and third trimesters. We reviewed the maternal serum alpha-fetoprotein (MSAFP), amniotic fluid alpha-fetoprotein (AFP), amniotic fluid acetylcholinesterase (ACHE), fetal pathology, and placental pathology in sex second-trimester pregnancies complicated by fetal triploidy. Four of these patients had MSAFP values greater than 7.5 multiples of the median (MoM). Five of six pregnancies had MSAFP values greater than 2.25 MoM. All five of these patients had a partial mole. Four patients had amniotic fluid AFP values greater than 2.0 MoM. Two fetuses had associated neural tube defects. These were the only patients with positive amniotic fluid ACHE. None of the other patients had fetuses with anomalies that are known to be associated with an elevated MSAFP. The elevated MSAFP appeared to be related to the presence of a partial mole. Two of the five cases with an MSAFP greater than 2.25 MoM did not have sonographic evidence of a significant anomaly. Therefore, karyotyping can be of benefit in evaluating patients with elevated MSAFP.

Ocean acidification causes structural deformities in juvenile coral skeletons.

PubMed

Foster, Taryn; Falter, James L; McCulloch, Malcolm T; Clode, Peta L

2016-02-01

Rising atmospheric CO2 is causing the oceans to both warm and acidify, which could reduce the calcification rates of corals globally. Successful coral recruitment and high rates of juvenile calcification are critical to the replenishment and ultimate viability of coral reef ecosystems. Although elevated Pco2 (partial pressure of CO2) has been shown to reduce the skeletal weight of coral recruits, the structural changes caused by acidification during initial skeletal deposition are unknown. We show, using high-resolution three-dimensional x-ray microscopy, that ocean acidification (Pco2 ~900 μatm, pH ~7.7) not only causes reduced overall mineral deposition but also a deformed and porous skeletal structure in newly settled coral recruits. In contrast, elevated temperature (+3°C) had little effect on skeletal formation except to partially mitigate the effects of elevated Pco2. The striking structural deformities we observed show that new recruits are at significant risk, being unable to effectively build their skeletons in the Pco2 conditions predicted to occur for open ocean surface waters under a "business-as-usual" emissions scenario [RCP (representative concentration pathway) 8.5] by the year 2100.

Ocean acidification causes structural deformities in juvenile coral skeletons

PubMed Central

Foster, Taryn; Falter, James L.; McCulloch, Malcolm T.; Clode, Peta L.

2016-01-01

Rising atmospheric CO2 is causing the oceans to both warm and acidify, which could reduce the calcification rates of corals globally. Successful coral recruitment and high rates of juvenile calcification are critical to the replenishment and ultimate viability of coral reef ecosystems. Although elevated Pco2 (partial pressure of CO2) has been shown to reduce the skeletal weight of coral recruits, the structural changes caused by acidification during initial skeletal deposition are unknown. We show, using high-resolution three-dimensional x-ray microscopy, that ocean acidification (Pco2 ~900 μatm, pH ~7.7) not only causes reduced overall mineral deposition but also a deformed and porous skeletal structure in newly settled coral recruits. In contrast, elevated temperature (+3°C) had little effect on skeletal formation except to partially mitigate the effects of elevated Pco2. The striking structural deformities we observed show that new recruits are at significant risk, being unable to effectively build their skeletons in the Pco2 conditions predicted to occur for open ocean surface waters under a “business-as-usual” emissions scenario [RCP (representative concentration pathway) 8.5] by the year 2100. PMID:26989776

Effect of epileptic seizures on the cerebrospinal fluid--A systematic retrospective analysis.

PubMed

Tumani, Hayrettin; Jobs, Catherine; Brettschneider, Johannes; Hoppner, Anselm C; Kerling, Frank; Fauser, Susanne

2015-08-01

Analyses of the cerebrospinal fluid (CSF) are obligatory when epileptic seizures manifest for the first time in order to exclude life-threatening causes or treatable diseases such as acute infections or autoimmune encephalitis. However, there are only few systematic investigations on the effect of seizures themselves on CSF parameters and the significance of these parameters in differential diagnosis. CSF samples of 309 patients with epileptic and 10 with psychogenic seizures were retrospectively analyzed. CSF samples were collected between 1999 and 2008. Cell counts, the albumin quotient, lactate and Tau-protein levels were determined. Findings were correlated with seizure types, seizure etiology (symptomatic, cryptogenic, occasional seizure), and seizure duration. Pathological findings were only observed in patients with epileptic but not with psychogenic seizures. The lactate concentration was elevated in 14%, the albumin quotient in 34%, and the Tau protein level in 36% of CSF samples. Cell counts were only slightly elevated in 6% of patients. Different seizure types influenced all parameters except for the cell count: In status epilepticus highest, in simple partial seizures lowest values were seen. Symptomatic partial and generalized epileptic seizures had significantly higher Tau-protein levels than cryptogenic partial seizures. In patients with repetitive and occasional epileptic seizures, higher Tau-protein levels were seen than in those with psychogenic seizures. Duration of epileptic seizures was positively correlated with the albumin quotient, lactate and Tau-protein levels. High variability of investigated CSF parameters within each subgroup rendered a clear separation between epileptic and psychogenic seizures impossible. Elevated cell counts are infrequently observed in patients with epileptic seizures and should therefore not uncritically be interpreted as a postictal phenomenon. However, blood-CSF barrier disruption, increased glucose metabolism and elevation of neuronal damage markers are observed in considerable percentages of patients and depend on many factors such as etiology, seizure type and duration. Copyright © 2015 Elsevier B.V. All rights reserved.

Water resources data for Pennsylvania, water year 1994. Volume 2. Susquehanna and Potomac River basins. Water-data report (Annual), 1 October 1993-30 September 1994

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

Durlin, R.R.; Schaffstall, W.P.

1996-03-01

Volume 2 contains: (1) discharge records for 94 continuous-record streamflow-gaging stations and 39 partial-record stations; (2) elevation and contents records for 12 lakes and reservoirs; (3) water-quality records for 17 gaging stations and 125 partial-record and project stations; and (4) water-level records for 25 observation wells. Additional water data collected at various sites not involved in the systematic data-collection program are also presented.

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.

Mechanical properties of turbine blade alloys in hydrogen at elevated temperatures

NASA Technical Reports Server (NTRS)

Deluca, D. P.

1981-01-01

The mechanical properties of single crystal turbine blade alloys in a gaseous hydrogen environment were determined. These alloys are proposed for use in space propulsion systems in pure or partial high pressure hydrogen environments at elevated temperatures. Mechanical property tests included: tensile, creep, low fatigue (LCF), and crack growth. Specimens were in both transverse and longitudinal directions relative to the casting solidification direction. Testing was conducted on solid specimens exposed to externally pressurized environments of gaseous hydrogen and hydrogen-enriched steam.

Anticipating electrical breakdown in dielectric elastomer actuators

NASA Astrophysics Data System (ADS)

Muffoletto, Daniel P.; Burke, Kevin M.; Zirnheld, Jennifer L.

2013-04-01

The output strain of a dielectric elastomer actuator is directly proportional to the square of its applied electric field. However, since the likelihood of electric breakdown is elevated with an increased applied field, the maximum operating electric field of the dielectric elastomer is significantly derated in systems employing these actuators so that failure due to breakdown remains unlikely even as the material ages. In an effort to ascertain the dielectric strength so that stronger electric fields can be applied, partial discharge testing is used to assess the health of the actuator by detecting the charge that is released when localized instances of breakdown partially bridge the insulator. Pre-stretched and unstretched samples of VHB4910 tape were submerged in dielectric oil to remove external sources of partial discharges during testing, and the partial discharge patterns were recorded just before failure of the dielectric sample.

In-Source Reduction of Disulfide-Bonded Peptides Monitored by Ion Mobility Mass Spectrometry

NASA Astrophysics Data System (ADS)

Stocks, Bradley B.; Melanson, Jeremy E.

2018-02-01

Many peptides with antimicrobial activity and/or therapeutic potential contain disulfide bonds as a means to enhance stability, and their quantitation is often performed using electrospray ionization mass spectrometry (ESI-MS). Disulfides can be reduced during ESI under commonly used instrument conditions, which has the potential to hinder accurate peptide quantitation. We demonstrate that this in-source reduction (ISR) is predominantly observed for peptides infused from acidic solutions and subjected to elevated ESI voltages (3-4 kV). ISR is readily apparent in the mass spectrum of oxytocin—a small, single disulfide-containing peptide. However, subtle m/z shifts due to partial ISR of highly charged (z ≥ 3) peptides with multiple disulfide linkages may proceed unnoticed. Ion mobility (IM)-MS separates ions on the basis of charge and shape in the gas phase, and using insulin as a model system, we show that IM-MS arrival time distributions (ATDs) are particularly sensitive to partial ISR of large peptides. Isotope modeling allows for the relative quantitation of disulfide-intact and partially reduced states of the mobility-separated peptide conformers. Interestingly, hepcidin peptides ionized from acidic solutions at elevated ESI voltages undergo gas-phase compaction, ostensibly due to partial disulfide ISR. Our IM-MS results lead us to propose that residual acid is the likely cause of disparate ATDs recently measured for hepcidin from different suppliers [Anal. Bioanal. Chem. 409, 2559-2567 (2017)]. Overall, our results demonstrate the utility of IM-MS to detect partial ISR of disulfide-bonded peptides and reinforce the notion that peptide/protein measurements should be carried out using minimally activating instrument conditions. [Figure not available: see fulltext.

Surgical complications associated with robotic urologic procedures in elderly patients.

PubMed

Cusano, Antonio; Haddock, Peter; Staff, Ilene; Jackson, Max; Abarzua-Cabezas, Fernando; Dorin, Ryan; Meraney, Anoop; Wagner, Joseph; Shichman, Steven; Kesler, Stuart

2015-02-01

Urologic malignancies are often diagnosed at an older age, and are increasingly managed utilizing robotic-assisted surgical techniques. As such, we assessed and compared peri-postoperative complication rates following robotic urologic surgery in elderly and younger patients. A retrospective analysis of IRB-approved databases and electronic medical records identified patients who underwent robotic-assisted urologic surgery between December 2003-September 2013. Patients were grouped according to surgical procedure (partial nephrectomy, radical cystectomy, radical prostatectomy) and age at surgery (≤ 74 or ≥ 75 years old). Associations between age, comorbidities, Charlson comorbidity index (CCI), and patient outcomes were evaluated within each surgery type. 97.5% and 2.5% of patients were ≤ 74 or ≥ 75 years old, respectively. Cystectomies, partial nephrectomies and prostatectomies accounted for 3.5%, 9.5% and 87.1% of surgeries, respectively. Within cystectomy, nephrectomy and prostatectomy groups, 24.4%, 12.5% and 0.6% patients were ≥ 75 years old. Within each surgical type, elderly patients had significantly elevated CCI scores. Length of stay was significantly prolonged in elderly patients undergoing partial nephrectomy or prostatectomy. In elderly cystectomy, partial nephrectomy and prostatectomy patients, 36.7%, 14.3% and 5.9% suffered ≥ 1 Clavien grade 3-5 complication, respectively. Major complications were not significantly different between age groups. A qualitatively similar pattern was observed regarding Clavien grade 1-2 complications. The risks of robotic-assisted urologic surgery in elderly patients are not significantly elevated compared to younger patients.

Petrology of deep drill hole, Kilauea Volcano

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

Grose, L.T.; Keller, G.V.

1976-12-01

The first deep drill hole (1262 m TD) at the summit of an active volcano (1102 m elev) was drilled in 1973 at Kilauea volcano, Hawaii with support from NSF and USGS. The hole is located within southern margin of Kilauea caldera in northern part of a 15 km/sup 2/ triangular block bounded by east rift zone, Koae fault zone, and southwest rift zone-a summit area relatively free of faults, rifts, and extrusions. Nearest eruptions are from fissures 1.2 km away which are active in 1974 and which do not trend toward the drill hole. Core recovery totals 47 mmore » from 29 core runs at rather evenly spaced intervals to total depth. Megascopic, thin-section, and X-ray examination reveals: (1) Recovered core is essentially vesicular, intergranular, nonporphyritic to porphyritic olivine basalt with minor olivine diabase, picrite diabase, and basalt, (2) Hyaloclastite and pillow basalt are absent, (3) Below water table (614 m elev) with increasing depth, vesicularity decreases, and density, crystallinity, competence, vesicle fill, and alteration irregularly increase, (4) Alteration first occurs at water table where calcite and silica partially fill vesticles and olivine is partially serpentinized, (5) At about 570 m elev massive serpentinization of olivine and deposition of montmorillonite-nontronite occur; at about 210 m elev truscottite and tobermorite occur in vesicles; at about 35 m elev mordenite occurs in vesicles, (6) Bottom-hole cores have complete filling of vesicles with silica, minor silica replacement, and complete alteration of olivine, and (7) Plagioclase is unaltered. Chemical analyses of bottom-hole cores are similar to those of modern summit lavas. Alteration and low porosity in bottom-hole cores plus abrupt temperature increase suggest the drill hole penetrated a self-sealed ''cap rock'' to a hydrothermal convection cell and possibly a magma body.« less

Allosteric control of internal electron transfer in cytochrome cd1 nitrite reductase

PubMed Central

Farver, Ole; Kroneck, Peter M. H.; Zumft, Walter G.; Pecht, Israel

2003-01-01

Cytochrome cd1 nitrite reductase is a bifunctional multiheme enzyme catalyzing the one-electron reduction of nitrite to nitric oxide and the four-electron reduction of dioxygen to water. Kinetics and thermodynamics of the internal electron transfer process in the Pseudomonas stutzeri enzyme have been studied and found to be dominated by pronounced interactions between the c and the d1 hemes. The interactions are expressed both in dramatic changes in the internal electron-transfer rates between these sites and in marked cooperativity in their electron affinity. The results constitute a prime example of intraprotein control of the electron-transfer rates by allosteric interactions. PMID:12802018

Distant protonated pyridine groups in water-soluble iron porphyrin electrocatalysts promote selective oxygen reduction to water

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

Matson, Benjamin D.; Carver, Colin T.; Von Ruden, Amber L.

2012-11-08

Fe(III)-meso-tetra(pyridyl)porphines are selective electrocatalysts for the reduction of dioxygen to water in aqueous acidic solution. The 2-pyridyl derivatives, both the triflate and chloride salts, are more selective than the isomeric 4-pyridyl complexes. The improved selectivity of is ascribed to the inward-pointing pyridinium groups acting as intramolecular proton relays. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

Sedimentation and gravitational instability of Escherichia coli Suspension

NASA Astrophysics Data System (ADS)

Douarche, Carine; Salin, Dominique; Collaboration between Laboratory FAST; LPS Collaboration

2016-11-01

The successive run and tumble of Escherichia coli bacteria provides an active matter suspension of rod-like particles with a large swimming diffusion. As opposed to inactive elongated particles, this diffusion prevents clustering and instability in the gravity field. We measure the time dependent E . coli concentration profile during their sedimentation. After some hours, due to the dioxygen consumption, a motile / non-motile front forms leading to a Rayleigh-Taylor type gravitational instability. Analyzing both sedimentation and instability in the framework of active particle suspensions, we can measure the relevant bacteria hydrodynamic characteristics such as its single particle sedimentation velocity and its hindrance volume.

Degradation of naphthalene-2,6- and naphthalene-1,6-disulfonic acid by a Moraxella sp

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

Wittich, R.M.; Tast, H.G.; Knackmuss, H.J.

1988-07-01

A naphthalene-2,6-disulfonic acid (2,6NDS)-degrading Moraxella strain was isolated from an industrial sewage plant. This culture could also be adapted to naphthalene-1,6-disulfonic acid as growth substrate. Regioselective 1,2-dioxygenation effected desulfonation and catabolism to 5-sulfosalicylic acid (5SS), which also could be used a the sole carbon source. 5SS-grown cells exhibited high gentisate 1,2-dioxygenase activity. Neither 5SS- nor gentisate-grown cells oxidized 2,6NDS; therefore, 2,6NDS or an early metabolite must serve as an inducer of the initial catabolic enzymes(s).

Selective Oxidative Esterification from Two Different Alcohols via Photoredox Catalysis.

PubMed

Yi, Hong; Hu, Xia; Bian, Changliang; Lei, Aiwen

2017-01-10

Esters functionalities are important building blocks that are extensively used in the chemical industry and academic laboratories. Direct oxidative esterification from easy-available alcohols to esters would be a much more appealing approach, especially using O 2 as terminal oxidant. Inputting external energy by photocatalysis for dioxygen activation, a mild and simple method for ester synthesis from two different alcohols has been achieved in this work. This reaction is performed under neutral conditions using O 2 as the terminal oxidant. A variety of primary alcohols, especially long chain alcohols and secondary alcohols are tolerated in this system. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygen reactivity of the biferrous site in the de novo designed four helix bundle peptide DFsc: nature of the "intermediate" and reaction mechanism.

PubMed

Calhoun, Jennifer R; Bell, Caleb B; Smith, Thomas J; Thamann, Thomas J; DeGrado, William F; Solomon, Edward I

2008-07-23

The DFsc and DFscE11D de novo designed protein scaffolds support biomimetic diiron cofactor sites that react with dioxygen forming a 520 nm "intermediate" species with an apparent pseudo-first-order formation rate constant of 2.2 and 4.8 s-1, respectively. Resonance Raman spectroscopy shows that this absorption feature is due to a phenolate-to-ferric charge transfer transition arising from a single tyrosine residue coordinating terminally to one of the ferric ions in the site. Phenol coordination could provide a proton to promote rapid loss of a putative peroxo species.

Prolonged partial upper airway obstruction during sleep – an underdiagnosed phenotype of sleep-disordered breathing

PubMed Central

Anttalainen, Ulla; Tenhunen, Mirja; Rimpilä, Ville; Polo, Olli; Rauhala, Esa; Himanen, Sari-Leena; Saaresranta, Tarja

2016-01-01

Obstructive sleep apnea syndrome (OSAS) is a well-recognized disorder conventionally diagnosed with an elevated apnea–hypopnea index. Prolonged partial upper airway obstruction is a common phenotype of sleep-disordered breathing (SDB), which however is still largely underreported. The major reasons for this are that cyclic breathing pattern coupled with arousals and arterial oxyhemoglobin saturation are easy to detect and considered more important than prolonged episodes of increased respiratory effort with increased levels of carbon dioxide in the absence of cycling breathing pattern and repetitive arousals. There is also a growing body of evidence that prolonged partial obstruction is a clinically significant form of SDB, which is associated with symptoms and co-morbidities which may partially differ from those associated with OSAS. Partial upper airway obstruction is most prevalent in women, and it is treatable with the nasal continuous positive pressure device with good adherence to therapy. This review describes the characteristics of prolonged partial upper airway obstruction during sleep in terms of diagnostics, pathophysiology, clinical presentation, and comorbidity to improve recognition of this phenotype and its timely and appropriate treatment. PMID:27608271

Factitious hyperinsulinism leading to pancreatectomy: severe forms of Munchausen syndrome by proxy.

PubMed

Giurgea, Irina; Ulinski, Tim; Touati, Guy; Sempoux, Christine; Mochel, Fanny; Brunelle, Francis; Saudubray, Jean-Marie; Fekete, Claire; de Lonlay, Pascale

2005-07-01

Clinical history and inappropriate insulin secretion during hypoglycemic episodes permit the diagnosis of hyperinsulinism. We report 2 cases of factitious hyperinsulinism leading to partial pancreatectomy. Case 1 was an 8-year-old girl who presented with severe hypoglycemia and elevated insulin and C-peptide levels. Catheterization of pancreatic veins was performed to localize the excess insulin secretion. Insulinoma was suspected, and partial pancreatectomy was performed. Ten days after surgery, severe hypoglycemia recurred with severely elevated plasma insulin levels (x100) but very low C-peptide plasma levels, suggesting factitious hyperinsulinemia. Hypoglycemic episodes before surgery were provoked by oral sulfonamides; postoperative episodes were caused by parenteral insulin. Falsified prescriptions for sulfonamides and insulin by the mother, a nurse, were found. Case 2 was a 6-month-old girl who presented with seizures and hypoglycemia but had a symptom-free interval of many months afterward. At 2 years of age, repeated hypoglycemic seizures and elevated insulin plasma levels suggested congenital hyperinsulinism. C-peptide plasma level, measured once, was normal, but blood sampling was performed 15 minutes after a hypoglycemic episode. Partial pancreatectomy was performed. Two weeks after surgery, hypoglycemic seizures recurred, and the patient was admitted for pancreatic vein catheterization. This investigation was performed during hypoglycemia and revealed high insulin levels and undetectable C-peptide levels, suggesting factitious hypoglycemia. Insulin/C-peptide ratio analysis is crucial to assess factitious hypoglycemia, although sulfonamide-induced hypoglycemia is not thereby detected. One percent (2 of 250) of all cases of hyperinsulinemic hypoglycemia in our unit have been identified as Munchausen syndrome by proxy. Atypical disease history should raise the question of factitious hypoglycemia.

Pharmacological evaluation of the anxiolytic-like effects of EMD 386088, a partial 5-HT6 receptor agonist, in the rat elevated plus-maze and Vogel conflict tests.

PubMed

Jastrzębska-Więsek, Magdalena; Siwek, Agata; Partyka, Anna; Kubacka, Monika; Mogilski, Szczepan; Wasik, Anna; Kołaczkowski, Marcin; Wesołowska, Anna

2014-10-01

The 5-HT6 is one of the most recent additions to the 5-HT receptor family. Its pharmacological profile and anatomical distribution is suggestive of a putative role in mood disorders. Most of preclinical evidence suggests an anxiolytic-like action of 5-HT6 receptor antagonists. Evaluation the anxiolytic-like effects of EMD 386088, a partial 5-HT6receptor agonist, and its putative mechanism of action in rats. EMD 386088, administered intraperitoneally at a dose of 2.5 mg/kg evoked specific anxiolytic-like activity in the automated version of the conflict drinking Vogel and the elevated plus-maze tests visible by increasing all parameters indicating a potential anti-anxiety effect. Its activity was blocked by the selective 5-HT6 receptor antagonist SB 271046, but not by the selective GABAA/benzodiazepine receptor antagonist flumazenil. EMD 386088 did not intensify an anxiolytic-like effect produced by diazepam in the elevated plus-maze test. These findings suggest that EMD 386088, a 5-HT6 receptor agonist, produces anxiolytic-like activity after systemic administration which may result from direct stimulation of 5-HT6 receptors. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

Neutralization by Metal Ions of the Toxicity of Sodium Selenide

PubMed Central

Dauplais, Marc; Lazard, Myriam; Blanquet, Sylvain; Plateau, Pierre

2013-01-01

Inert metal-selenide colloids are found in animals. They are believed to afford cross-protection against the toxicities of both metals and selenocompounds. Here, the toxicities of metal salt and sodium selenide mixtures were systematically studied using the death rate of Saccharomyces cerevisiae cells as an indicator. In parallel, the abilities of these mixtures to produce colloids were assessed. Studied metal cations could be classified in three groups: (i) metal ions that protect cells against selenium toxicity and form insoluble colloids with selenide (Ag+, Cd2+, Cu2+, Hg2+, Pb2+ and Zn2+), (ii) metal ions which protect cells by producing insoluble metal-selenide complexes and by catalyzing hydrogen selenide oxidation in the presence of dioxygen (Co2+ and Ni2+) and, finally, (iii) metal ions which do not afford protection and do not interact (Ca2+, Mg2+, Mn2+) or weakly interact (Fe2+) with selenide under the assayed conditions. When occurring, the insoluble complexes formed from divalent metal ions and selenide contained equimolar amounts of metal and selenium atoms. With the monovalent silver ion, the complex contained two silver atoms per selenium atom. Next, because selenides are compounds prone to oxidation, the stabilities of the above colloids were evaluated under oxidizing conditions. 5,5'-dithiobis-(2-nitrobenzoic acid) (DTNB), the reduction of which can be optically followed, was used to promote selenide oxidation. Complexes with cadmium, copper, lead, mercury or silver resisted dissolution by DTNB treatment over several hours. With nickel and cobalt, partial oxidation by DTNB occurred. On the other hand, when starting from ZnSe or FeSe complexes, full decompositions were obtained within a few tens of minutes. The above properties possibly explain why ZnSe and FeSe nanoparticles were not detected in animals exposed to selenocompounds. PMID:23342137

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.

Maxillary overlay removable partial dentures for the restoration of worn teeth.

PubMed

Fonseca, Júlio; Nicolau, Pedro; Daher, Tony

2011-04-01

Prolonged tooth maintenance by a more aged population considerably increases the probability of dentists having to treat patients with high levels of tooth wear. Pathological tooth wear, caused primarily by parafunction, seems to be a growing problem that affects a large number of adult patients. The clinical report presents a case of a partially edentulous patient with an elevated degree of wear in the upper jaw caused by attrition and erosion, rehabilitated with a maxillary overlay removable partial denture (ORPD) consisting of a chrome-cobalt (Cr-Co) framework with anterior acrylic resin veneers, posterior cast overlays, and acrylic resin denture bases. Removable partial prosthesis is a treatment alternative when teeth are found to be severely worn or when the patient needs a simple and economical option. Because economics is a conditional factor of the treatment, the clinician should present different treatment alternatives to the patient, in which the overlay prosthesis can be considered.

Increased clutter level in echocardiography due to specular reflection

NASA Astrophysics Data System (ADS)

Fatemi, Ali; Torp, Hans; Aakhus, Svend; Rodriguez-Molares, Alfonso

2017-03-01

State-of-the-art echocardiography allows to correctly diagnose most of cardiovascular diseases. An unknown source of clutter, however, hinders the visualization of the heart in some cases. We believe this clutter is caused by the ultrasound beam being partially reflected by the ribs into the elevation direction, so that structures outside the imaging plane are displayed on top of the heart image as clutter noise. We conducted in vitro experiments in a water tank using a synthetic ventricle and pig ribs. By partially blocking the probe with the ribs in the elevation direction, objects outside the imaging plane were rendered in the B-mode image, which confirms that the ribs can behave as specular reflectors. In addition, we succeeded in reproducing clutter noise using a piece of polystyrene to simulate the reflections from the lungs. This indicates that the origin of the clutter noise in echocardiograms can be reverberation coming from the lungs via specular reflection at the ribs.

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

Karwacki, C.J.; Buchanan, J.H.; Mahle, J.J.

Experimental data are reported for the desorption of bis-2-chloroethyl sulfide, (a sulfur mustard or HD) and its decomposition products from activated coconut shell carbon (CSC). The results show that under equilibrium conditions changes in the HD partial pressure are affected primarily by its loading and temperature of the adsorbent. The partial pressure of adsorbed HD is found to increase by about a decade for each 25 C increase in temperature for CSC containing 0.01--0.1 g/g HD. Adsorption equilibria of HD appear to be little affected by coadsorbed water. Although complicated by its decomposition, the distribution of adsorbed HD (of knownmore » amount) appears to occupy pores of similar energy whether dry or in the presence of adsorbed water. On dry CSC adsorbed HD appears stable, while in the presence of water its decomposition is marked by hydrolysis at low temperature and thermal decomposition at elevated temperatures. The principal volatile products desorbed are 1,4-thioxane, 2-chloroethyl vinyl sulfide and 1,4-dithiane, with the latter favoring elevated temperatures.« less

Warming and pCO2 effects on Florida stone crab larvae

NASA Astrophysics Data System (ADS)

Gravinese, Philip M.; Enochs, Ian C.; Manzello, Derek P.; van Woesik, Robert

2018-05-01

Greenhouse gas emissions are increasing ocean temperatures and the partial pressure of CO2 (pCO2), resulting in more acidic waters. It is presently unknown how elevated temperature and pCO2 will influence the early life history stages of the majority of marine coastal species. We investigated the combined effect of elevated temperature (30 °C control and 32 °C treatment) and elevated pCO2 (450 μatm control and 1100 μatm treatment) on the (i) growth, (ii) survival, (iii) condition, and (iv) morphology of larvae of the commercially important Florida stone crab, Menippe mercenaria. At elevated temperature, larvae exhibited a significantly shorter molt stage, and elevated pCO2 caused stage-V larvae to delay metamorphosis to post-larvae. On average, elevated pCO2 resulted in a 37% decrease in survivorship relative to the control; however the effect of elevated temperature reduced larval survivorship by 71%. Exposure to both elevated temperature and pCO2 reduced larval survivorship by 80% relative to the control. Despite this, no significant differences were detected in the condition or morphology of stone crab larvae when subjected to elevated temperature and pCO2 treatments. Although elevated pCO2 could result in a reduction in larval supply, future increases in seawater temperatures are even more likely to threaten the future sustainability of the stone-crab fishery.

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.

The identity of the active site of oxalate decarboxylase and the importance of the stability of active-site lid conformations1

PubMed Central

Just, Victoria J.; Burrell, Matthew R.; Bowater, Laura; McRobbie, Iain; Stevenson, Clare E. M.; Lawson, David M.; Bornemann, Stephen

2007-01-01

Oxalate decarboxylase (EC 4.1.1.2) catalyses the conversion of oxalate into carbon dioxide and formate. It requires manganese and, uniquely, dioxygen for catalysis. It forms a homohexamer and each subunit contains two similar, but distinct, manganese sites termed sites 1 and 2. There is kinetic evidence that only site 1 is catalytically active and that site 2 is purely structural. However, the kinetics of enzymes with mutations in site 2 are often ambiguous and all mutant kinetics have been interpreted without structural information. Nine new site-directed mutants have been generated and four mutant crystal structures have now been solved. Most mutants targeted (i) the flexibility (T165P), (ii) favoured conformation (S161A, S164A, D297A or H299A) or (iii) presence (Δ162–163 or Δ162–164) of a lid associated with site 1. The kinetics of these mutants were consistent with only site 1 being catalytically active. This was particularly striking with D297A and H299A because they disrupted hydrogen bonds between the lid and a neighbouring subunit only when in the open conformation and were distant from site 2. These observations also provided the first evidence that the flexibility and stability of lid conformations are important in catalysis. The deletion of the lid to mimic the plant oxalate oxidase led to a loss of decarboxylase activity, but only a slight elevation in the oxalate oxidase side reaction, implying other changes are required to afford a reaction specificity switch. The four mutant crystal structures (R92A, E162A, Δ162–163 and S161A) strongly support the hypothesis that site 2 is purely structural. PMID:17680775

TOXICITY AND BIOACCUMULATION OF PFOS IN A PARTIAL LIFE CYCLE TEST WITH THE NORTHERN LEOPARD FROG

EPA Science Inventory

A number of recent monitoring studies have demonstrated elevated concentrations of perfluorooctane sulfonate (PFOS) in humans and wildlife throughout the world. Although no longer actively manufactured, the global distribution and relative persistence of PFOS indicates a need to...

Method for fluorination of actinide fluorides and oxyfluorides thereof using O.sub.2 F.sub.2

DOEpatents

Eller, Phillip G.; Malm, John G.; Penneman, Robert A.

1988-01-01

Method for fluorination of actinides and fluorides and oxyfluorides thereof using O.sub.2 F.sub.2 which generates actinide hexafluorides, and for removal of actinides and compounds thereof from surfaces upon which they appear as unwanted deposits. The fluorinating agent, O.sub.2 F.sub.2, has been observed to readily 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 thereby not destroyed by high temperature reactions with the walls of the reaction vessel. Dioxygen difluoride is easily prepared, stored and transferred to the desired place of reaction.

Method for recovery of actinides from actinide-bearing scrap and waste nuclear material using O/sub 2/F/sub 2/

DOEpatents

Asprey, L.B.; Eller, P.G.

1984-09-12

Method for recovery of actinides from nuclear waste material containing sintered and other oxides thereof and from scrap materials containing the metal actinides 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 detroyed by high temperature reactions with the walls of the reaction vessel. Dioxygen difluoride is readily prepared, stored and transferred to the place of reaction.

Method for fluorination of actinide fluorides and oxyfluorides thereof using O[sub 2]F[sub 2

DOEpatents

Eller, P.G.; Malm, J.G.; Penneman, R.A.

1988-11-08

Method is described for fluorination of actinides and fluorides and oxyfluorides thereof using O[sub 2]F[sub 2] which generates actinide hexafluorides, and for removal of actinides and compounds thereof from surfaces upon which they appear as unwanted deposits. The fluorinating agent, O[sub 2]F[sub 2], has been observed to readily 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 thereby not destroyed by high temperature reactions with the walls of the reaction vessel. Dioxygen difluoride is easily prepared, stored and transferred to the desired place of reaction.

O2 and CO binding to tetraaza-tripodal-capped iron(II) porphyrins.

PubMed

Ruzié, Christian; Even, Pascale; Ricard, David; Roisnel, Thierry; Boitrel, Bernard

2006-02-06

A series of tris(2-aminoethylamine) (tren) capped iron(II) porphyrins has been synthesized and characterized and their affinities for dioxygen and carbon monoxide measured. The X-ray structure of the basic scaffold with nickel inserted in the porphyrin is also reported. All the ligands differ by the nature of the group(s) attached to the secondary amine functions of the cap. These various substitutions were introduced to probe if a hydrogen bond with these secondary amine groups acting as the donor could rationalize the high affinity of these myoglobin models. This work clearly indicates that the cage structure of the tren predominates over all the other appended groups with the exception of p-nitrophenol.

PARTIAL LIFE-CYCLE TOXICITY AND BIOCONCENTRATION MODELLING OF PERFLUOROOCTANE SULFONATE (PFOS) IN THE NORTHERN LEOPARD FROG (RANA PIPIENS)

EPA Science Inventory

A number of recent monitoring studies have demonstrated elevated concentrations of perfluorooctane sulfonate (PFOS) in humans and wildlife throughout the world. Although no longer manufactured in the U.S., the global distribution and relative persistence of PFOS indicates a need ...

80. AVALON DAM Photographic copy of construction drawing c1908 ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

80. AVALON DAM - Photographic copy of construction drawing c1908 (from aperture card located at Bureau of Reclamation, Salt Lake City). UNTITLED DRAWING OF AUTOMATIC FLOOD GATES. PARTIAL PLAN AND ELEVATION - Carlsbad Irrigation District, Avalon Dam, On Pecos River, 4 miles North of Carlsbad, Carlsbad, Eddy County, NM

Developing GIS-based eastern equine encephalitis vector-host models in Tuskegee, Alabama.

PubMed

Jacob, Benjamin G; Burkett-Cadena, Nathan D; Luvall, Jeffrey C; Parcak, Sarah H; McClure, Christopher J W; Estep, Laura K; Hill, Geoffrey E; Cupp, Eddie W; Novak, Robert J; Unnasch, Thomas R

2010-02-24

A site near Tuskegee, Alabama was examined for vector-host activities of eastern equine encephalomyelitis virus (EEEV). Land cover maps of the study site were created in ArcInfo 9.2 from QuickBird data encompassing visible and near-infrared (NIR) band information (0.45 to 0.72 microm) acquired July 15, 2008. Georeferenced mosquito and bird sampling sites, and their associated land cover attributes from the study site, were overlaid onto the satellite data. SAS 9.1.4 was used to explore univariate statistics and to generate regression models using the field and remote-sampled mosquito and bird data. Regression models indicated that Culex erracticus and Northern Cardinals were the most abundant mosquito and bird species, respectively. Spatial linear prediction models were then generated in Geostatistical Analyst Extension of ArcGIS 9.2. Additionally, a model of the study site was generated, based on a Digital Elevation Model (DEM), using ArcScene extension of ArcGIS 9.2. For total mosquito count data, a first-order trend ordinary kriging process was fitted to the semivariogram at a partial sill of 5.041 km, nugget of 6.325 km, lag size of 7.076 km, and range of 31.43 km, using 12 lags. For total adult Cx. erracticus count, a first-order trend ordinary kriging process was fitted to the semivariogram at a partial sill of 5.764 km, nugget of 6.114 km, lag size of 7.472 km, and range of 32.62 km, using 12 lags. For the total bird count data, a first-order trend ordinary kriging process was fitted to the semivariogram at a partial sill of 4.998 km, nugget of 5.413 km, lag size of 7.549 km and range of 35.27 km, using 12 lags. For the Northern Cardinal count data, a first-order trend ordinary kriging process was fitted to the semivariogram at a partial sill of 6.387 km, nugget of 5.935 km, lag size of 8.549 km and a range of 41.38 km, using 12 lags. Results of the DEM analyses indicated a statistically significant inverse linear relationship between total sampled mosquito data and elevation (R2 = -.4262; p < .0001), with a standard deviation (SD) of 10.46, and total sampled bird data and elevation (R2 = -.5111; p < .0001), with a SD of 22.97. DEM statistics also indicated a significant inverse linear relationship between total sampled Cx. erracticus data and elevation (R2 = -.4711; p < .0001), with a SD of 11.16, and the total sampled Northern Cardinal data and elevation (R2 = -.5831; p < .0001), SD of 11.42. These data demonstrate that GIS/remote sensing models and spatial statistics can capture space-varying functional relationships between field-sampled mosquito and bird parameters for determining risk for EEEV transmission.

[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.

Prevalence and Axis I Comorbidity of Full and Partial Posttraumatic Stress Disorder in the United States: Results from Wave 2 of the National Epidemiologic Survey on Alcohol and Related Conditions

PubMed Central

Pietrzak, Robert H.; Goldstein, Risë B.; Southwick, Steven M.; Grant, Bridget F.

2010-01-01

The present study used data from the Wave 2 National Epidemiologic Survey on Alcohol and Related Conditions (n=34,653) to examine lifetime Axis I psychiatric comorbidity of posttraumatic stress disorder (PTSD) in a nationally representative sample of U.S. adults. Lifetime prevalences±standard errors of PTSD and partial PTSD were 6.4%±0.18 and 6.6%±0.18, respectively. Rates of PTSD and partial PTSD were higher among women (8.6%±0.26 and 8.6%±0.26) than men (4.1%±0.19 and 4.5%±0.21). Respondents with both PTSD and partial PTSD most commonly reported unexpected death of someone close, serious illness or injury to someone close, and sexual assault as their worst stressful experiences. PTSD and partial PTSD were associated with elevated lifetime rates of mood, anxiety, and substance use disorders, and suicide attempts. Respondents with partial PTSD generally had intermediate odds of comorbid Axis I disorders and psychosocial impairment relative to trauma controls and full PTSD. PMID:21168991

Femtosecond laser subsurface scleral treatment in cadaver human sclera and evaluation using two-photon and confocal microscopy

NASA Astrophysics Data System (ADS)

Sun, Hui; Fan, Zhongwei; Yan, Ying; Lian, Fuqiang; Kurtz, Ron; Juhasz, Tibor

2016-03-01

Glaucoma is the second-leading cause of blindness worldwide and is often associated with elevated intraocular pressure (IOP). Partial-thickness drainage channels can be created with femtosecond laser in the translucent sclera for the potential treatment of glaucoma. We demonstrate the creation of partial-thickness subsurface drainage channels with the femtosecond laser in the cadaver human eyeballs and describe the application of two-photon microscopy and confocal microscopy for noninvasive imaging of the femtosecond laser created partial-thickness scleral channels in cadaver human eyes. A femtosecond laser operating at a wavelength of 1700 nm was scanned along a rectangular raster pattern to create the partial thickness subsurface drainage channels in the sclera of cadaver human eyes. Analysis of the dimensions and location of these channels is important in understanding their effects. We describe the application of two-photon microscopy and confocal microscopy for noninvasive imaging of the femtosecond laser created partial-thickness scleral channels in cadaver human eyes. High-resolution images, hundreds of microns deep in the sclera, were obtained to allow determination of the shape and dimension of such partial thickness subsurface scleral channels. Our studies suggest that the confocal and two-photon microscopy can be used to investigate femtosecond-laser created partial-thickness drainage channels in the sclera of cadaver human eyes.

Finding Mount Everest and handling voids.

PubMed

Storch, Tobias

2011-01-01

Evolutionary algorithms (EAs) are randomized search heuristics that solve problems successfully in many cases. Their behavior is often described in terms of strategies to find a high location on Earth's surface. Unfortunately, many digital elevation models describing it contain void elements. These are elements not assigned an elevation. Therefore, we design and analyze simple EAs with different strategies to handle such partially defined functions. They are experimentally investigated on a dataset describing the elevation of Earth's surface. The largest value found by an EA within a certain runtime is measured, and the median over a few runs is computed and compared for the different EAs. For the dataset, the distribution of void elements seems to be neither random nor adversarial. They are so-called semirandomly distributed. To deepen our understanding of the behavior of the different EAs, they are theoretically considered on well-known pseudo-Boolean functions transferred to partially defined ones. These modifications are also performed in a semirandom way. The typical runtime until an optimum is found by an EA is analyzed, namely bounded from above and below, and compared for the different EAs. We figure out that for the random model it is a good strategy to assume that a void element has a worse function value than all previous elements. Whereas for the adversary model it is a good strategy to assume that a void element has the best function value of all previous elements.

Construction of a new, objective prognostic score for terminally ill cancer patients: a multicenter study.

PubMed

Suh, Sang-Yeon; Choi, Youn Seon; Shim, Jae Yong; Kim, Young Sung; Yeom, Chang Hwan; Kim, Daeyoung; Park, Shin Ae; Kim, Sooa; Seo, Ji Yeon; Kim, Su Hyun; Kim, Daegyeun; Choi, Sung-Eun; Ahn, Hong-Yup

2010-02-01

The goal of this study was to develop a new, objective prognostic score (OPS) for terminally ill cancer patients based on an integrated model that includes novel objective prognostic factors. A multicenter study of 209 terminally ill cancer patients from six training hospitals in Korea were prospectively followed until death. The Cox proportional hazard model was used to adjust for the influence of clinical and laboratory variables on survival time. The OPS was calculated from the sum of partial scores obtained from seven significant predictors determined by the final model. The partial score was based on the hazard ratio of each predictor. The accuracy of the OPS was evaluated. The overall median survival was 26 days. On the multivariate analysis, reduced oral intake, resting dyspnea, low performance status, leukocytosis, elevated bilirubin, elevated creatinine, and elevated lactate dehydrogenase (LDH) were identified as poor prognostic factors. The range of OPS was from 0.0 to 7.0. For the above cutoff point of 3.0, the 3-week prediction sensitivity was 74.7%, the specificity was 76.5%, and the overall accuracy was 75.5%. We developed the new OPS, without clinician's survival estimates but including a new prognostic factor (LDH). This new instrument demonstrated accurate prediction of the 3-week survival. The OPS had acceptable accuracy in this study population (training set). Further validation is required on an independent population (testing set).

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.

Dioxygen Activation and O–O Bond Formation Reactions by Manganese Corroles

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

Guo, Mian; Lee, Yong-Min; Gupta, Ranjana

Activation of dioxygen (O 2) in enzymatic and biomimetic reactions has been intensively investigated over the past several decades. More recently, O–O bond formation, which is the reverse of the O 2-activation reaction, has been the focus of current research. Herein, we report the O 2-activation and O–O bond formation reactions by manganese corrole complexes. In the O 2-activation reaction, Mn(V)-oxo and Mn(IV)-peroxo intermediates were formed when Mn(III) corroles were exposed to O 2 in the presence of base (e.g., OH –) and hydrogen atom (H atom) donor (e.g., THF or cyclic olefins); the O 2-activation reaction did not occurmore » in the absence of base and H atom donor. Moreover, formation of the Mn(V)-oxo and Mn(IV)-peroxo species was dependent on the amounts of base present in the reaction solution. The role of the base was proposed to lower the oxidation potential of the Mn(III) corroles, thereby facilitating the binding of O 2 and forming a Mn(IV)-superoxo species. The putative Mn(IV)-superoxo species was then converted to the corresponding Mn(IV)-hydroperoxo species by abstracting a H atom from H atom donor, followed by the O–O bond cleavage of the putative Mn(IV)-hydroperoxo species to form a Mn(V)-oxo species. We have also shown that addition of hydroxide ion to the Mn(V)-oxo species afforded the Mn(IV)-peroxo species via O–O bond formation and the resulting Mn(IV)-peroxo species reverted to the Mn(V)-oxo species upon addition of proton, indicating that the O–O bond formation and cleavage reactions between the Mn(V)-oxo and Mn(IV)-peroxo complexes are reversible. The present paper reports the first example of using the same manganese complex in both O 2-activation and O–O bond formation reactions.« less

Structure of a Berberine Bridge Enzyme-Like Enzyme with an Active Site Specific to the Plant Family Brassicaceae.

PubMed

Daniel, Bastian; Wallner, Silvia; Steiner, Barbara; Oberdorfer, Gustav; Kumar, Prashant; van der Graaff, Eric; Roitsch, Thomas; Sensen, Christoph W; Gruber, Karl; Macheroux, Peter

2016-01-01

Berberine bridge enzyme-like (BBE-like) proteins form a multigene family (pfam 08031), which is present in plants, fungi and bacteria. They adopt the vanillyl alcohol-oxidase fold and predominantly show bi-covalent tethering of the FAD cofactor to a cysteine and histidine residue, respectively. The Arabidopsis thaliana genome was recently shown to contain genes coding for 28 BBE-like proteins, while featuring four distinct active site compositions. We determined the structure of a member of the AtBBE-like protein family (termed AtBBE-like 28), which has an active site composition that has not been structurally and biochemically characterized thus far. The most salient and distinguishing features of the active site found in AtBBE-like 28 are a mono-covalent linkage of a histidine to the 8α-position of the flavin-isoalloxazine ring and the lack of a second covalent linkage to the 6-position, owing to the replacement of a cysteine with a histidine. In addition, the structure reveals the interaction of a glutamic acid (Glu426) with an aspartic acid (Asp369) at the active site, which appear to share a proton. This arrangement leads to the delocalization of a negative charge at the active site that may be exploited for catalysis. The structure also indicates a shift of the position of the isoalloxazine ring in comparison to other members of the BBE-like family. The dioxygen surrogate chloride was found near the C(4a) position of the isoalloxazine ring in the oxygen pocket, pointing to a rapid reoxidation of reduced enzyme by dioxygen. A T-DNA insertional mutant line for AtBBE-like 28 results in a phenotype, that is characterized by reduced biomass and lower salt stress tolerance. Multiple sequence analysis showed that the active site composition found in AtBBE-like 28 is only present in the Brassicaceae, suggesting that it plays a specific role in the metabolism of this plant family.

Reduction of protein radicals by GSH and ascorbate: potential biological significance.

PubMed

Gebicki, Janusz M; Nauser, Thomas; Domazou, Anastasia; Steinmann, Daniel; Bounds, Patricia L; Koppenol, Willem H

2010-11-01

The oxidation of proteins and other macromolecules by radical species under conditions of oxidative stress can be modulated by antioxidant compounds. Decreased levels of the antioxidants glutathione and ascorbate have been documented in oxidative stress-related diseases. A radical generated on the surface of a protein can: (1) be immediately and fully repaired by direct reaction with an antioxidant; (2) react with dioxygen to form the corresponding peroxyl radical; or (3) undergo intramolecular long range electron transfer to relocate the free electron to another amino acid residue. In pulse radiolysis studies, in vitro production of the initial radical on a protein is conveniently made at a tryptophan residue, and electron transfer often leads ultimately to residence of the unpaired electron on a tyrosine residue. We review here the kinetics data for reactions of the antioxidants glutathione, selenocysteine, and ascorbate with tryptophanyl and tyrosyl radicals as free amino acids in model compounds and proteins. Glutathione repairs a tryptophanyl radical in lysozyme with a rate constant of (1.05±0.05)×10(5) M(-1) s(-1), while ascorbate repairs tryptophanyl and tyrosyl radicals ca. 3 orders of magnitude faster. The in vitro reaction of glutathione with these radicals is too slow to prevent formation of peroxyl radicals, which become reduced by glutathione to hydroperoxides; the resulting glutathione thiyl radical is capable of further radical generation by hydrogen abstraction. Although physiologically not significant, selenoglutathione reduces tyrosyl radicals as fast as ascorbate. The reaction of protein radicals formed on insulin, β-lactoglobulin, pepsin, chymotrypsin and bovine serum albumin with ascorbate is relatively rapid, competes with the reaction with dioxygen, and the relatively innocuous ascorbyl radical is formed. On the basis of these kinetics data, we suggest that reductive repair of protein radicals may contribute to the well-documented depletion of ascorbate in living organisms subjected to oxidative stress.

Latex Clearing Protein (Lcp) of Streptomyces sp. Strain K30 Is a b-Type Cytochrome and Differs from Rubber Oxygenase A (RoxA) in Its Biophysical Properties

PubMed Central

Birke, Jakob; Röther, Wolf

2015-01-01

Specific polyisoprene-cleaving activities of 1.5 U/mg and 4.6 U/mg were determined for purified Strep-tagged latex clearing protein (Lcp) of Streptomyces sp. strain K30 at 23°C and 37°C, respectively. Metal analysis revealed the presence of approximately one atom of iron per Lcp molecule. Copper, which had been identified in Lcp1VH2 of Gordonia polyisoprenivorans previously, was below the detection limit in LcpK30. Heme was identified as a cofactor in purified LcpK30 by (i) detection of characteristic α-, β-, and γ (Soret)-bands at 562 nm, 532 nm, and 430 nm in the visible spectrum after chemical reduction, (ii) detection of an acetone-extractable porphyrin molecule, (iii) determination of a heme b-type-specific absorption maximum (556 nm) after chemical conversion of the heme group to a bipyridyl-heme complex, and (iv) detection of a b-heme-specific m/z value of 616.2 via mass spectrometry. Spectroscopic analysis showed that purified Lcp as isolated contains an oxidized heme-Fe3+ that is free of bound dioxygen. This is in contrast to the rubber oxygenase RoxA, a c-type heme-containing polyisoprene-cleaving enzyme present in Gram-negative rubber degraders, in which the covalently bound heme firmly binds a dioxygen molecule. LcpK30 also differed from RoxA in the lengths of the rubber degradation cleavage products and in having a higher melting point of 61.5°C (RoxA, 54.3°C). In summary, RoxA and Lcp both are equipped with a heme cofactor and catalyze an oxidative C-C cleavage reaction but differ in the heme subgroup type and in several biochemical and biophysical properties. These findings suggest differences in the catalytic reaction mechanisms. PMID:25819959

Proton transport facilitating water-oxidation: the role of second sphere ligands surrounding the catalytic metal cluster.

PubMed

Bao, Han; Dilbeck, Preston L; Burnap, Robert L

2013-10-01

The ability of PSII to extract electrons from water, with molecular oxygen as a by-product, is a remarkable biochemical and evolutionary innovation. From an evolutionary perspective, the invention of PSII approximately 2.7 Ga led to the accelerated accumulation of biomass in the biosphere and the accumulation of oxygen in the atmosphere, a combination that allowed for the evolution of a much more complex and extensive biosphere than would otherwise have been possible. From the biochemical and enzymatic perspective, PSII is remarkable because of the thermodynamic and kinetic obstacles that needed to have been overcome to oxidize water as the ultimate photosynthetic electron donor. This article focuses on how proton release is an integral part of how these kinetic and thermodynamic obstacles have been overcome: the sequential removal of protons from the active site of H2O-oxidation facilitates the multistep oxidation of the substrate water at the Mn4CaOx, the catalytic heart of the H2O-oxidation reaction. As noted previously, the facilitated deprotonation of the Mn4CaOx cluster exerts a redox-leveling function preventing the accumulation of excess positive charge on the cluster, which might otherwise hinder the already energetically difficult oxidation of water. Using recent results, including the characteristics of site-directed mutants, the role of the second sphere of amino acid ligands and the associated network of water molecules surrounding the Mn4CaOx is discussed in relation to proton transport in other systems. In addition to the redox-leveling function, a trapping function is assigned to the proton release step occurring immediately prior to the dioxygen chemistry. This trapping appears to involve a yet-to-be clarified gating mechanism that facilitates to coordinated release of a proton from the neighborhood of the active site thereby insuring that the backward charge-recombination reaction does not out-compete the forward reaction of dioxygen chemistry during this final step of H2O-oxidation.

The kinetic role of carboxylate residues in the proximity of the trinuclear centre in the O2 reactivity of CotA-laccase.

PubMed

Brissos, Vânia; Chen, Zhenjia; Martins, Lígia O

2012-05-28

Multicopper oxidases catalyze the four-electron reduction of dioxygen to water without the release of any reactive oxygen intermediate species. The role of carboxylate residue Asp116 located at the exit channel for water molecules of CotA-laccase has been investigated by site-saturation mutagenesis. A total of 300 clones was picked and screened for activity. Five variant enzymes, D116E, D116A, D116N, D116T and D116L, were selected for further characterisation. Spectroscopic analysis revealed only small perturbations in the geometry of the catalytic Cu sites of variants. However, a severe drop in turnover numbers (k(cat)) and downshifts by approximately 1-2 units of the optimal pH were observed for the oxidation of substrates, as compared with the wild type. The kinetics of formation and decay of peroxide intermediate (PI) was studied in type 1 depleted (T1D) CotA-laccase and in T1D-D116 or T1D-E498 mutants, previously shown to be involved in the mechanism of dioxygen reduction. It is noteworthy that CotA shows 10 times lower rates of PI formation and 10(3) higher PI decay rates as compared with other studied multicopper oxidases. The generation of PI is pH independent and mostly unaffected by the D116 or E498 mutations. In contrast, the decay of PI is markedly compromised by the replacement of D116 or E498 with non-carboxylate residues. The E498 residue appears to be the main protonable species for acceleration of PI decay at low pH. The D116 residue seems to be essential in the modulation of E498 protonation and in assisting protons to hydroxyl groups bound to the T2 Cu.

Substrate-Triggered Addition of Dioxygen to the Diferrous Cofactor of Aldehyde-Deformylating Oxygenase to form a Diferric-Peroxide Intermediate†

PubMed Central

Nørgaard, Hanne; Warui, Douglas M.; Rajakovich, Lauren J.; Chang, Wei-chen; Booker, Squire J.; Krebs, Carsten; Bollinger, J. Martin

2013-01-01

Cyanobacterial aldehyde-deformylating oxygenases (ADOs) belong to the ferritin-like diiron-carboxylate superfamily of dioxygen-activating proteins. They catalyze conversion of saturated or mono-unsaturated Cn fatty aldehydes to formate and the corresponding Cn-1 alkanes or alkenes, respectively. This unusual, apparently redox-neutral transformation actually requires four electrons per turnover to reduce the O2 co-substrate to the oxidation state of water and incorporates one O-atom from O2 into the formate co-product. We show here that the complex of the diiron(II/II) form of ADO from Nostoc punctiforme (Np) with an aldehyde substrate reacts with O2 to form a colored intermediate with spectroscopic properties suggestive of a Fe2III/III complex with a bound peroxide. Its Mössbauer spectra reveal that the intermediate possesses an antiferromagnetically (AF) coupled Fe2III/III center with resolved sub-sites. The intermediate is long-lived in the absence of a reducing system, decaying slowly (t1/2 ~ 400 s at 5 °C) to produce a very modest yield of formate (< 0.15 enzyme equivalents), but reacts rapidly with the fully reduced form of 1-methoxy-5-methylphenazine (MeOPMS) to yield product, albeit at only ~ 50% of the maximum theoretical yield (owing to competition from one or more unproductive pathway). The results represent the most definitive evidence to date that ADO can use a diiron cofactor (rather than a homo- or hetero-dinuclear cluster involving another transition metal) and provide support for a mechanism involving attack on the carbonyl of the bound substrate by the reduced O2 moiety to form a Fe2III/III-peroxyhemiacetal complex, which undergoes reductive O-O-bond cleavage, leading to C1–C2 radical fragmentation and formation of the alk(a/e)ne and formate products. PMID:23987523

Substrate-triggered addition of dioxygen to the diferrous cofactor of aldehyde-deformylating oxygenase to form a diferric-peroxide intermediate.

PubMed

Pandelia, Maria E; Li, Ning; Nørgaard, Hanne; Warui, Douglas M; Rajakovich, Lauren J; Chang, Wei-Chen; Booker, Squire J; Krebs, Carsten; Bollinger, J Martin

2013-10-23

Cyanobacterial aldehyde-deformylating oxygenases (ADOs) belong to the ferritin-like diiron-carboxylate superfamily of dioxygen-activating proteins. They catalyze conversion of saturated or monounsaturated C(n) fatty aldehydes to formate and the corresponding C(n-1) alkanes or alkenes, respectively. This unusual, apparently redox-neutral transformation actually requires four electrons per turnover to reduce the O2 cosubstrate to the oxidation state of water and incorporates one O-atom from O2 into the formate coproduct. We show here that the complex of the diiron(II/II) form of ADO from Nostoc punctiforme (Np) with an aldehyde substrate reacts with O2 to form a colored intermediate with spectroscopic properties suggestive of a Fe2(III/III) complex with a bound peroxide. Its Mössbauer spectra reveal that the intermediate possesses an antiferromagnetically (AF) coupled Fe2(III/III) center with resolved subsites. The intermediate is long-lived in the absence of a reducing system, decaying slowly (t(1/2) ~ 400 s at 5 °C) to produce a very modest yield of formate (<0.15 enzyme equivalents), but reacts rapidly with the fully reduced form of 1-methoxy-5-methylphenazinium methylsulfate ((MeO)PMS) to yield product, albeit at only ~50% of the maximum theoretical yield (owing to competition from one or more unproductive pathway). The results represent the most definitive evidence to date that ADO can use a diiron cofactor (rather than a homo- or heterodinuclear cluster involving another transition metal) and provide support for a mechanism involving attack on the carbonyl of the bound substrate by the reduced O2 moiety to form a Fe2(III/III)-peroxyhemiacetal complex, which undergoes reductive O-O-bond cleavage, leading to C1-C2 radical fragmentation and formation of the alk(a/e)ne and formate products.

PpoC from Aspergillus nidulans is a fusion protein with only one active haem.

PubMed

Brodhun, Florian; Schneider, Stefan; Göbel, Cornelia; Hornung, Ellen; Feussner, Ivo

2010-01-15

In Aspergillus nidulans Ppos [psi (precocious sexual inducer)-producing oxygenases] are required for the production of so-called psi factors, compounds that control the balance between the sexual and asexual life cycle of the fungus. The genome of A. nidulans harbours three different ppo genes: ppoA, ppoB and ppoC. For all three enzymes two different haem-containing domains are predicted: a fatty acid haem peroxidase/dioxygenase domain in the N-terminal region and a P450 haem-thiolate domain in the C-terminal region. Whereas PpoA was shown to use both haem domains for its bifunctional catalytic activity (linoleic acid 8-dioxygenation and 8-hydroperoxide isomerization), we found that PpoC apparently only harbours a functional haem peroxidase/dioxygenase domain. Consequently, we observed that PpoC catalyses mainly the dioxygenation of linoleic acid (18:2Delta9Z,12Z), yielding 10-HPODE (10-hydroperoxyoctadecadienoic acid). No isomerase activity was detected. Additionally, 10-HPODE was converted at lower rates into 10-KODE (10-keto-octadecadienoic acid) and 10-HODE (10-hydroxyoctadecadienoic acid). In parallel, decomposition of 10-HPODE into 10-ODA (10-octadecynoic acid) and volatile C-8 alcohols that are, among other things, responsible for the characteristic mushroom flavour. Besides these principle differences we also found that PpoA and PpoC can convert 8-HPODE and 10-HPODE into the respective epoxy alcohols: 12,13-epoxy-8-HOME (where HOME is hydroxyoctadecenoic acid) and 12,13-epoxy-10-HOME. By using site-directed mutagenesis we demonstrated that both enzymes share a similar mechanism for the oxidation of 18:2Delta9Z,12Z; they both use a conserved tyrosine residue for catalysis and the directed oxygenation at the C-8 and C-10 is most likely controlled by conserved valine/leucine residues in the dioxygenase domain.

Old iron, young copper: from Mars to Venus.

PubMed

Crichton, R R; Pierre, J L

2001-06-01

Iron and copper are metals which play an important role in the living world. From a brief consideration of their chemistry and biochemistry we conclude that the early chemistry of life used water soluble ferrous iron while copper was in the water-insoluble Cu(I) state as highly insoluble sulphides. The advent of oxygen was a catastrophic event for most living organisms, and can be considered to be the first general irreversible pollution of the earth. In contrast to the oxidation of iron and its loss of bioavailability as insoluble Fe(III), the oxidation of insoluble Cu(I) led to soluble Cu(II). A new iron biochemistry became possible after the advent of oxygen, with the development of chelators of Fe(III), which rendered iron once again accessible, and with the control of the potential toxicity of iron by its storage in a water soluble, non-toxic, bio-available storage protein (ferritin). Biology also discovered that whereas enzymes involved in anaerobic metabolism were designed to operate in the lower portion of the redox spectrum, the arrival of dioxygen created the need for a new redox active metal which could attain higher redox potentials. Copper, now bioavailable, was ideally suited to exploit the oxidizing power of dioxygen. The arrival of copper also coincided with the development of multicellular organisms which had extracellular cross-linked matrices capable of resisting attack by oxygen free radicals. After the initial 'iron age' subsequent evolution moved, not towards a 'copper age', but rather to an 'iron-copper' age. In the second part of the review, this symbiosis of iron and copper is examined in yeast. We then briefly consider iron and copper metabolism in mammals, before looking at iron-copper interactions in mammals, particularly man, and conclude with the reflection that, as in Greek and Roman mythology, a better understanding of the potentially positive interactions between Mars (iron) and Venus (copper) can only be to the advantage of our species.

Dioxygen Activation and O–O Bond Formation Reactions by Manganese Corroles

DOE PAGES

Guo, Mian; Lee, Yong-Min; Gupta, Ranjana; ...

2017-10-22

Activation of dioxygen (O 2) in enzymatic and biomimetic reactions has been intensively investigated over the past several decades. More recently, O–O bond formation, which is the reverse of the O 2-activation reaction, has been the focus of current research. Herein, we report the O 2-activation and O–O bond formation reactions by manganese corrole complexes. In the O 2-activation reaction, Mn(V)-oxo and Mn(IV)-peroxo intermediates were formed when Mn(III) corroles were exposed to O 2 in the presence of base (e.g., OH –) and hydrogen atom (H atom) donor (e.g., THF or cyclic olefins); the O 2-activation reaction did not occurmore » in the absence of base and H atom donor. Moreover, formation of the Mn(V)-oxo and Mn(IV)-peroxo species was dependent on the amounts of base present in the reaction solution. The role of the base was proposed to lower the oxidation potential of the Mn(III) corroles, thereby facilitating the binding of O 2 and forming a Mn(IV)-superoxo species. The putative Mn(IV)-superoxo species was then converted to the corresponding Mn(IV)-hydroperoxo species by abstracting a H atom from H atom donor, followed by the O–O bond cleavage of the putative Mn(IV)-hydroperoxo species to form a Mn(V)-oxo species. We have also shown that addition of hydroxide ion to the Mn(V)-oxo species afforded the Mn(IV)-peroxo species via O–O bond formation and the resulting Mn(IV)-peroxo species reverted to the Mn(V)-oxo species upon addition of proton, indicating that the O–O bond formation and cleavage reactions between the Mn(V)-oxo and Mn(IV)-peroxo complexes are reversible. The present paper reports the first example of using the same manganese complex in both O 2-activation and O–O bond formation reactions.« less

Autocatalytic formation of an iron(IV)-oxo complex via scandium ion-promoted radical chain autoxidation of an iron(II) complex with dioxygen and tetraphenylborate.

PubMed

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

2014-06-04

A non-heme iron(IV)-oxo complex, [(TMC)Fe(IV)(O)](2+) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), was formed by oxidation of an iron(II) complex ([(TMC)Fe(II)](2+)) with dioxygen (O2) and tetraphenylborate (BPh4(-)) in the presence of scandium triflate (Sc(OTf)3) in acetonitrile at 298 K via autocatalytic radical chain reactions rather than by a direct O2 activation pathway. The autocatalytic radical chain reaction is initiated by scandium ion-promoted electron transfer from BPh4(-) to [(TMC)Fe(IV)(O)](2+) to produce phenyl radical (Ph(•)). The chain propagation step is composed of the addition of O2 to Ph(•) and the reduction of the resulting phenylperoxyl radical (PhOO(•)) by scandium ion-promoted electron transfer from BPh4(-) to PhOO(•) to produce phenyl hydroperoxide (PhOOH), accompanied by regeneration of phenyl radical. PhOOH reacts with [(TMC)Fe(II)](2+) to yield phenol (PhOH) and [(TMC)Fe(IV)(O)](2+). Biphenyl (Ph-Ph) was formed via the radical chain autoxidation of BPh3 by O2. The induction period of the autocatalytic radical chain reactions was shortened by addition of a catalytic amount of [(TMC)Fe(IV)(O)](2+), whereas addition of a catalytic amount of ferrocene that can reduce [(TMC)Fe(IV)(O)](2+) resulted in elongation of the induction period. Radical chain autoxidation of BPh4(-) by O2 also occurred in the presence of Sc(OTf)3 without [(TMC)Fe(IV)(O)](2+), initiating the autocatalytic oxidation of [(TMC)Fe(II)](2+) with O2 and BPh4(-) to yield [(TMC)Fe(IV)(O)](2+). Thus, the general view for formation of non-heme iron(IV)-oxo complexes via O2-binding iron species (e.g., Fe(III)(O2(•-))) without contribution of autocatalytic radical chain reactions should be viewed with caution.

Oxidations of alkenes and lignin model compounds in aqueous dispersions

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

Zhu, Weiming.

1991-01-01

The objective was to develop methods to oxidize water-immiscible alkenes and lignin model compounds with polymer colloid supported transition metal catalysts. The oxidations of organic compounds were carried out in aqueous phase with several water-soluble oxidants and dioxygen. Cationic polymer latexes were prepared by the emulsion copolymerization of vinylbenzyl chloride, divinylbenzene, and vinyl octadecyl ether, or styrene, or n-decyl methacrylate, and the subsequent quaternization of copolymers with trimethylamine. The latex particles were 44 nm to 71 nm in diameter. The latex bound Mn porphyrin catalysts were formed with MnTSPP [TSPP = meso-tetrakis(2,6-dichloro-3-sulfonatophenyl)porphyrin], which catalyzed the oxidation of cyclohexene, cycloocetene, allylbenzene,more » and 1-octene by sodium hypochlorite (NaOCl) and potassium peroxymonosulfate (KHSO[sub 5]). The latex bound porphyrin catalysts showed higher activity than MnTSPP in solution. Oxidations of 3,4-dimethoxybenzyl alcohol (DMBA), 4-hydroxy-3-methoxytoluene (HMT), and 3,4-dimethoxytoluene (DMT) were performed with either dioxygen or hydrogen peroxide and CoPcTS (PcTS = tetrasulfonatophthalocyanine), FePcTS, CuPcTS, NiPcTS, FeTCPP [TCPP = meso-tetrakis(4-carboxyphenyl)porphyrin], and MnTSPP. CoPcTS catalyzed the autoxidation of DMBA and HMT at 70-85[degrees]C and pH [ge] 8. All catalysts were active for the oxidation of DMBA, HMT, and DMT with H[sub 2]O[sub 2]. Aqueous solutions of KHSO[sub 5] oxidized water-immiscible alkenes at room temperature in the absence of organic solvent. The acidic pH [le] 1.7 solutions of commercial 2KHSO[sub 5][center dot]K[sub 2]SO[sub 4] in water produced diols from all reactive alkenes except cyclooctene. Adjustment of initial pH to [ge]6.7 with NaHCO[sub 3] enabled selective epoxidations.« less

Catalytic two-electron reduction of dioxygen by ferrocene derivatives with manganese(V) corroles.

PubMed

Jung, Jieun; Liu, Shuo; Ohkubo, Kei; Abu-Omar, Mahdi M; Fukuzumi, Shunichi

2015-05-04

Electron transfer from octamethylferrocene (Me8Fc) to the manganese(V) imidocorrole complex (tpfc)Mn(V)(NAr) [tpfc = 5,10,15-tris(pentafluorophenyl)corrole; Ar = 2,6-Cl2C6H3] proceeds efficiently to give an octamethylferrocenium ion (Me8Fc(+)) and [(tpfc)Mn(IV)(NAr)](-) in acetonitrile (MeCN) at 298 K. Upon the addition of trifluoroacetic acid (TFA), further reduction of [(tpfc)Mn(IV)(NAr)](-) by Me8Fc gives (tpfc)Mn(III) and ArNH2 in deaerated MeCN. TFA also results in hydrolysis of (tpfc)Mn(V)(NAr) with residual water to produce a protonated manganese(V) oxocorrole complex ([(tpfc)Mn(V)(OH)](+)) in deaerated MeCN. [(tpfc)Mn(V)(OH)](+) is rapidly reduced by 2 equiv of Me8Fc in the presence of TFA to give (tpfc)Mn(III) in deaerated MeCN. In the presence of dioxygen (O2), (tpfc)Mn(III) catalyzes the two-electron reduction of O2 by Me8Fc with TFA in MeCN to produce H2O2 and Me8Fc(+). The rate of formation of Me8Fc(+) in the catalytic reduction of O2 follows zeroth-order kinetics with respect to the concentrations of Me8Fc and TFA, whereas the rate increases linearly with increasing concentrations of (tpfc)Mn(V)(NAr) and O2. These kinetic dependencies are consistent with the rate-determining step being electron transfer from (tpfc)Mn(III) to O2, followed by further proton-coupled electron transfer from Me8Fc to produce H2O2 and [(tpfc)Mn(IV)](+). Rapid electron transfer from Me8Fc to [(tpfc)Mn(IV)](+) regenerates (tpfc)Mn(III), completing the catalytic cycle. Thus, catalytic two-electron reduction of O2 by Me8Fc with (tpfc)Mn(V)(NAr) as a catalyst precursor proceeds via a Mn(III)/Mn(IV) redox cycle.

Preparation and characterization of ceramic sensors for use at elevated temperatures

NASA Astrophysics Data System (ADS)

You, Tao

Ceramic ITO strain sensors were prepared by reactive sputtering in various nitrogen/oxygen/argon partial pressures. The thickness of the active ITO strain elements played a significant role in the high temperature stability and piezoresistive properties, specifically, these results indicated that both gauge factor and drift rate were affected by the thickness of ITO films comprising the active strain elements. The influence of nitrogen in the reactive sputtered ITO films on the microstructure and the high temperature piezoresistive properties was also investigated. Scanning electron microscopy (SEM) revealed a partially sintered microstructure consisting of a contiguous network of sub-micron ITO particles with well-defined necks and isolated nanoporosity. Sintering and densification of the ITO particles containing these nitrogen rich grain boundaries was retarded and a contiguous network of nano-sized ITO particles was established. Aluminum doped indium tin oxide thin film exhibited an enhanced high temperature stability compared with undoped ITO thin film. The effect of aluminum doped ITO was investigated under various preparation and testing environments. Electron spectroscopy for chemical analysis (ESCA) studies indicated that interfacial reactions between ITO and aluminum increased the stability of ITO at elevated temperatures. These binding energies of indium-indium are significantly higher than those associated with stoichiometric indium oxide. A robust ceramic temperature sensor was fabricated by two different ITO elements, each with substantially different charge carrier concentrations. Thermal cycling of ITO thin films in a varied of partial oxygen pressures conditions showed that temperature coefficient of resistance (TCR) was nearly independent of oxygen partial pressure. A thermoelectric power of 6.0muV/°C and a linear voltage-temperature response were measured for an ITO thin film ceramic thermocouple over the temperature range 25--1250°C.

The Model of Transformational Change for Moral Action: A Conceptual Framework to Elevate Student Conduct Practice in Higher Education

ERIC Educational Resources Information Center

Neumeister, James R.

2017-01-01

Higher education faces heightened scrutiny regarding student misconduct, but collegiate disciplinary processes often have minimal impact on students. Their ineffectiveness is partially attributable to the absence of a conceptual framework that guides conduct administration by linking theory, practice, and outcomes. This article presents a…

Soil carbon dioxide partial pressure and dissolved inorganic carbonate chemistry under elevated carbon dioxide and ozone

Treesearch

N.J. Karberg; K.S. Pregitzer; J.S. King; A.L. Friend; J.R. Wood

2004-01-01

Global emissions of atmospheric CO2 and tropospheric O3 are rising and expected to impact large areas of the Earth's forests. While CO2 stimulates net primary production, O3 reduces photosynthesis, altering plant C allocation and reducing ecosystem C storage. The effects...

Regulation of ATP-binding cassette transporters and cholesterol efflux by glucose in primary human monocytes and murine bone marrow-derived macrophages

USDA-ARS?s Scientific Manuscript database

Individuals with type 2 diabetes mellitus are at increased risk of developing atherosclerosis. This may be partially attributable to suppression of macrophage ATP-binding cassette (ABC) transporter mediated cholesterol efflux by sustained elevated blood glucose concentrations. Two models were used...

Sucralose, an activator of the glucose-sensing receptor, increases ATP by calcium-dependent and -independent mechanisms.

PubMed

Li, Longfei; Ohtsu, Yoshiaki; Nakagawa, Yuko; Masuda, Katsuyoshi; Kojima, Itaru

2016-08-31

Sucralose is an artificial sweetener and activates the glucose-sensing receptor expressed in pancreatic β-cells. Although sucralose does not enter β-cells nor acts as a substrate for glucokinase, it induces a marked elevation of intracellular ATP ([ATP]c). The present study was conducted to identify the signaling pathway responsible for the elevation of [ATP]c induced by sucralose. Previous studies have shown that sucralose elevates cyclic AMP (cAMP), activates phospholipase C (PLC) and stimulates Ca(2+) entry by a Na(+)-dependent mechanism in MIN6 cells. The addition of forskolin induced a marked elevation of cAMP, whereas it did not affect [ATP]c. Carbachol, an activator of PLC, did not increase [ATP]c. In addition, activation of protein kinase C by dioctanoylglycerol did not affect [ATP]c. In contrast, nifedipine, an inhibitor of the voltage-dependent Ca(2+) channel, significantly reduced [ATP]c response to sucralose. Removal of extracellular Na(+) nearly completely blocked sucralose-induced elevation of [ATP]c. Stimulation of Na(+) entry by adding a Na(+) ionophore monensin elevated [ATP]c. The monensin-induced elevation of [ATP]c was only partially inhibited by nifedipine and loading of BAPTA, both of which completely abolished elevation of [Ca(2+)]c. These results suggest that Na(+) entry is critical for the sucralose-induced elevation of [ATP]c. Both calcium-dependent and -independent mechanisms are involved in the action of sucralose.

A comparison of soil climate and biological activity along an elevation gradient in the eastern Mojave Desert

USGS Publications Warehouse

Amundson, R.G.; Chadwick, O.A.; Sowers, J.M.

1989-01-01

Soil temperature, moisture, and CO2 were monitored at four sites along an elevation transect in the eastern Mojave Desert from January to October, 1987. Climate appeared to be the major factor controlling CO2 partial pressures, primarily through its influence of rates of biological reactions, vegetation densities, and organic matter production. With increasing elevation, and increasing actual evapotranspiration, the organic C, plant density, and the CO2 content of the soils increased. Between January and May, soil CO2 concentrations at a given site were closely related to variations in soil temperature. In July and October, temperatures had little effect on CO2, presumably due to low soil moisture levels. Up to 75% of litter placed in the field in March was lost by October whereas, for the 3 lower elevations, less than 10% of the litter placed in the field in April was lost through decomposition processes. ?? 1989 Springer-Verlag.

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.

The operation of 0.35 μm partially depleted SOI CMOS technology in extreme environments

NASA Astrophysics Data System (ADS)

Li, Ying; Niu, Guofu; Cressler, John D.; Patel, Jagdish; Liu, S. T.; Reed, Robert A.; Mojarradi, Mohammad M.; Blalock, Benjamin J.

2003-06-01

We evaluate the usefulness of partially depleted SOI CMOS devices fabricated in a 0.35 μm technology on UNIBOND material for electronics applications requiring robust operation under extreme environment conditions consisting of low and/or high temperature, and under substantial radiation exposure. The threshold voltage, effective mobility, and the impact ionization parameters were determined across temperature for both the nFETs and the pFETs. The radiation response was characterized using threshold voltage shifts of both the front-gate and back-gate transistors. These results suggest that this 0.35 μm partially depleted SOI CMOS technology is suitable for operation across a wide range of extreme environment conditions consisting of: cryogenic temperatures down to 86 K, elevated temperatures up to 573 K, and under radiation exposure to 1.3 Mrad(Si) total dose.

The role of elevated serum procalcitonin in neuroendocrine neoplasms of digestive system.

PubMed

Chen, Luohai; Zhang, Yu; Lin, Yuan; Deng, Langhui; Feng, Shiting; Chen, Minhu; Chen, Jie

2017-12-01

Elevated serum procalcitonin (PCT) was reported in patients with certain type of neuroendocrine neoplasms (NENs). The aim of this study was to assess the role of elevated serum PCT in NENs from digestive system. Serum PCT and serum CgA level were measured in 155 patients with NENs from digestive system. Elevated serum PCT was found in 63 patients (40.6%). Grade 3 disease was a significant factor associated with elevated serum PCT (OR, 9.24; 95%CI, 3.04-28.08; P<0.001). Serum PCT level was significantly decreased after treatment both in patients with stable disease (P=0.003) and patients with partial remission (P=0.001). In these patients, serum PCT level significantly increased again at the time of progression disease (P=0.001). Elevated serum PCT was a significant factor of worse survival (HR, 2.86; 95%CI, 1.36-6.03; P=0.006). Compared with patients with normal serum PCT and CgA level, patients with either PCT or CgA elevated and patients with both PCT and CgA elevated had progressively worse survival. Additionally, PCT expression in tumor cells was found in 24.0% of patients but did not correlate with other clinicopathological factors, including serum PCT. Serum PCT is elevated in part of patients with NENs of digestive system, especially in patients with grade 3 disease. Serum PCT level can help evaluate treatment response and its elevation indicates poor prognosis. Combination of serum PCT and CgA can improve outcome prediction. Copyright © 2017 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.

Effects of elevated root zone CO2 and air temperature on photosynthetic gas exchange, nitrate uptake, and total reduced nitrogen content in aeroponically grown lettuce plants.

PubMed

He, Jie; Austin, Paul T; Lee, Sing Kong

2010-09-01

Effects of elevated root zone (RZ) CO(2) and air temperature on photosynthesis, productivity, nitrate (NO(3)(-)), and total reduced nitrogen (N) content in aeroponically grown lettuce plants were studied. Three weeks after transplanting, four different RZ [CO(2)] concentrations [ambient (360 ppm) and elevated concentrations of 2000, 10,000, and 50,000 ppm] were imposed on plants grown at two air temperature regimes of 28 degrees C/22 degrees C (day/night) and 36 degrees C/30 degrees C. Photosynthetic CO(2) assimilation (A) and stomatal conductance (g(s)) increased with increasing photosynthetically active radiation (PAR). When grown at 28 degrees C/22 degrees C, all plants accumulated more biomass than at 36 degrees C/30 degrees C. When measured under a PAR >or=600 micromol m(-2) s(-1), elevated RZ [CO(2)] resulted in significantly higher A, lower g(s), and higher midday leaf relative water content in all plants. Under elevated RZ [CO(2)], the increase of biomass was greater in roots than in shoots, causing a lower shoot/root ratio. The percentage increase in growth under elevated RZ [CO(2)] was greater at 36 degrees C/30 degrees C although the total biomass was higher at 28 degrees C/22 degrees C. NO(3)(-) and total reduced N concentrations of shoot and root were significantly higher in all plants under elevated RZ [CO(2)] than under ambient RZ [CO(2)] of 360 ppm at both temperature regimes. At each RZ [CO(2)], NO(3)(-) and total reduced N concentration of shoots were greater at 28 degrees C/22 degrees C than at 36 degrees C/30 degrees C. At all RZ [CO(2)], roots of plants at 36 degrees C/30 degrees C had significantly higher NO(3)(-) and total reduced N concentrations than at 28 degrees C/22 degrees C. Since increased RZ [CO(2)] caused partial stomatal closure, maximal A and maximal g(s) were negatively correlated, with a unique relationship for each air temperature. However, across all RZ [CO(2)] and temperature treatments, there was a close correlation between maximal A and total shoot reduced N concentration of plants under different RZ [CO(2)], indicating that increased A under elevated RZ [CO(2)] could partially be due to the higher shoot total reduced N.

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

Characterization, catalyzed water oxidation and anticancer activities of a NIR BODIPY-Mn polymer

NASA Astrophysics Data System (ADS)

Lan, Ya-Quan; Xiao, Ke-Jing; Wu, Yun-Jie; Chen, Qiu-Yun

2017-04-01

To obtain near-IR absorbing biomaterials as fluorescence cellular imaging and anticancer agents for hypoxic cancer cell, a nano NIR fluorescence Mn(III/IV) polymer (PMnD) was spectroscopically characterized. The PMnD shows strong emission at 661 nm when excited with 643 nm. Furthermore, PMnD can catalyze water oxidation to generate dioxygen when irradiated by red LED light (10 W). In particular, the PMnD can enter into HepG-2 cells and mitochondria. Both anticancer activity and the inhibition of the expression of HIF-1α for PMnD were concentration dependent. Our results demonstrate that PMnD can be developed as mitochondria targeted imaging agents and new inhibitors for HIF-1 in hypoxic cancer cells.

Engineering laccases: in search for novel catalysts.

PubMed

Robert, Viviane; Mekmouche, Yasmina; Pailley, Pierre R; Tron, Thierry

2011-04-01

Laccases (p-diphenol oxidase, EC 1.10.3.2) are blue multicopper oxidases that catalyze the reduction of dioxygen to water, with a concomitant oxidation of small organic substrates. Since the description at the end of the nineteenth century of a factor catalyzing the rapid hardening of the latex of the Japanese lacquer trees (Rhus sp.) exposed to air laccases from different origins (plants, fungi bacteria) have been continuously discovered and extensively studied. Nowadays, molecular evolution and other powerful protein modification techniques offer possibilities to develop tailored laccases for a wide array of applications including drug synthesis, biosensors or biofuel cells. Here, we give an overview on strategies and results of our laboratory in the design of new biocatalysts based on laccases.

Engineering Laccases: In Search for Novel Catalysts

PubMed Central

Robert, Viviane; Mekmouche, Yasmina; Pailley, Pierre R; Tron, Thierry

2011-01-01

Laccases (p-diphenol oxidase, EC 1.10.3.2) are blue multicopper oxidases that catalyze the reduction of dioxygen to water, with a concomitant oxidation of small organic substrates. Since the description at the end of the nineteenth century of a factor catalyzing the rapid hardening of the latex of the Japanese lacquer trees (Rhus sp.) exposed to air laccases from different origins (plants, fungi bacteria) have been continuously discovered and extensively studied. Nowadays, molecular evolution and other powerful protein modification techniques offer possibilities to develop tailored laccases for a wide array of applications including drug synthesis, biosensors or biofuel cells. Here, we give an overview on strategies and results of our laboratory in the design of new biocatalysts based on laccases. PMID:21966250

A peroxynitrite complex of copper: formation from a copper-nitrosyl complex, transformation to nitrite and exogenous phenol oxidative coupling or nitration.

PubMed

Park, Ga Young; Deepalatha, Subramanian; Puiu, Simona C; Lee, Dong-Heon; Mondal, Biplab; Narducci Sarjeant, Amy A; del Rio, Diego; Pau, Monita Y M; Solomon, Edward I; Karlin, Kenneth D

2009-11-01

Reaction of nitrogen monoxide with a copper(I) complex possessing a tridentate alkylamine ligand gives a Cu(I)-(*NO) adduct, which when exposed to dioxygen generates a peroxynitrite (O=NOO(-))-Cu(II) species. This undergoes thermal transformation to produce a copper(II) nitrito (NO(2) (-)) complex and 0.5 mol equiv O(2). In the presence of a substituted phenol, the peroxynitrite complex effects oxidative coupling, whereas addition of chloride ion to dissociate the peroxynitrite moiety instead leads to phenol ortho nitration. Discussions include the structures (including electronic description) of the copper-nitrosyl and copper-peroxynitrite complexes and the formation of the latter, based on density functional theory calculations and accompanying spectroscopic data.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

How did life survive Earth's great oxygenation?

PubMed

Fischer, Woodward W; Hemp, James; Valentine, Joan Selverstone

2016-04-01

Life on Earth originated and evolved in anoxic environments. Around 2.4 billion-years-ago, ancestors of Cyanobacteria invented oxygenic photosynthesis, producing substantial amounts of O2 as a byproduct of phototrophic water oxidation. The sudden appearance of O2 would have led to significant oxidative stress due to incompatibilities with core cellular biochemical processes. Here we examine this problem through the lens of Cyanobacteria-the first taxa to observe significant fluxes of intracellular dioxygen. These early oxygenic organisms likely adapted to the oxidative stress by co-opting preexisting systems (exaptation) with fortuitous antioxidant properties. Over time more advanced antioxidant systems evolved, allowing Cyanobacteria to adapt to an aerobic lifestyle and become the most important environmental engineers in Earth history. Copyright © 2016 Elsevier Ltd. All rights reserved.

Water resources data for Pennsylvania, water year 1995. Volume 2. Susquehanna and Potomac River basins. Water-data report (Annual), 1 October 1994-30 September 1995

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

Durlin, R.R.; Schaffstall, W.P.

1997-02-01

This report, Volume, 2, includes record from the Susquehanna and Potomac River Basins. Specifically, it contains: (1) discharge records for 90 continuous-record streamflow-gaging stations and 41 partial-record stations; (2) elevation and contents record for 12 lakes and reservoirs; (3) water-quality records for 13 streamflow-gaging stations and 189 partial-record and project stations; and (4) water-level records for 25 network observation wells. Site locations are shown in figures throughout the report. Additional water data collected at various sites not involved in the systematic data-collection program are also presented.

Elevational Distribution and Conservation Biogeography of Phanaeine Dung Beetles (Coleoptera: Scarabaeinae) in Bolivia

PubMed Central

Herzog, Sebastian K.; Hamel-Leigue, A. Caroli; Larsen, Trond H.; Mann, Darren J.; Soria-Auza, Rodrigo W.; Gill, Bruce D.; Edmonds, W. D.; Spector, Sacha

2013-01-01

Insect macroecology and conservation biogeography studies are disproportionately scarce, especially in the Neotropics. Dung beetles are an ideal focal taxon for biodiversity research and conservation. Using distribution and body size data on the ecologically important Phanaeini, the best-known Neotropical dung beetle tribe, we determined elevational patterns of species richness, endemism, body size, and elevational range in Bolivia, specifically testing Bergmann’s and Rapoport’s rule. Richness of all 39 species and of 15 ecoregional endemics showed a hump-shaped pattern peaking at 400 m, but overall declined strongly with elevation up to 4000 m. The relationship between endemic and total species richness appeared to be curvilinear, providing only partial support for the null hypothesis that species-rich areas are more likely to be centers of endemism by chance alone. An elevational increase in the proportion of ecoregional endemics suggests that deterministic factors also appear to influence endemism in the Andes. When controlling for the effect of area using different species-area relationships, the statistically significant richness peak became more pronounced and shifted upslope to 750 m. Larger species did not have higher elevational mid-points, and mean body size decreased significantly with elevation, contradicting Bergmann’s rule. Rapoport’s rule was supported: species with higher elevational mid-points had broader elevational ranges, and mean elevational range increased significantly with elevation. The elevational decrease of phanaeine richness is in accordance with studies that demonstrated the combined influence of temperature and water availability on species diversity, but also is consistent with niche conservatism. For invertebrates, confirmation of Rapoport’s and refutation of Bergmann’s rule appear to be scale-invariant general patterns. Analyses of biogeographic patterns across elevational gradients can provide important insights for identifying conservation priorities. Phanaeines with narrow elevational ranges on isolated low-elevation mountains in eastern Bolivia are at greatest climate-change related extinction risk from range-shift gaps and mountaintop extinctions. PMID:23717678

Elevational distribution and conservation biogeography of phanaeine dung beetles (Coleoptera: Scarabaeinae) in Bolivia.

PubMed

Herzog, Sebastian K; Hamel-Leigue, A Caroli; Larsen, Trond H; Mann, Darren J; Soria-Auza, Rodrigo W; Gill, Bruce D; Edmonds, W D; Spector, Sacha

2013-01-01

Insect macroecology and conservation biogeography studies are disproportionately scarce, especially in the Neotropics. Dung beetles are an ideal focal taxon for biodiversity research and conservation. Using distribution and body size data on the ecologically important Phanaeini, the best-known Neotropical dung beetle tribe, we determined elevational patterns of species richness, endemism, body size, and elevational range in Bolivia, specifically testing Bergmann's and Rapoport's rule. Richness of all 39 species and of 15 ecoregional endemics showed a hump-shaped pattern peaking at 400 m, but overall declined strongly with elevation up to 4000 m. The relationship between endemic and total species richness appeared to be curvilinear, providing only partial support for the null hypothesis that species-rich areas are more likely to be centers of endemism by chance alone. An elevational increase in the proportion of ecoregional endemics suggests that deterministic factors also appear to influence endemism in the Andes. When controlling for the effect of area using different species-area relationships, the statistically significant richness peak became more pronounced and shifted upslope to 750 m. Larger species did not have higher elevational mid-points, and mean body size decreased significantly with elevation, contradicting Bergmann's rule. Rapoport's rule was supported: species with higher elevational mid-points had broader elevational ranges, and mean elevational range increased significantly with elevation. The elevational decrease of phanaeine richness is in accordance with studies that demonstrated the combined influence of temperature and water availability on species diversity, but also is consistent with niche conservatism. For invertebrates, confirmation of Rapoport's and refutation of Bergmann's rule appear to be scale-invariant general patterns. Analyses of biogeographic patterns across elevational gradients can provide important insights for identifying conservation priorities. Phanaeines with narrow elevational ranges on isolated low-elevation mountains in eastern Bolivia are at greatest climate-change related extinction risk from range-shift gaps and mountaintop extinctions.

Correction for Eddy Current-Induced Echo-Shifting Effect in Partial-Fourier Diffusion Tensor Imaging.

PubMed

Truong, Trong-Kha; Song, Allen W; Chen, Nan-Kuei

2015-01-01

In most diffusion tensor imaging (DTI) studies, images are acquired with either a partial-Fourier or a parallel partial-Fourier echo-planar imaging (EPI) sequence, in order to shorten the echo time and increase the signal-to-noise ratio (SNR). However, eddy currents induced by the diffusion-sensitizing gradients can often lead to a shift of the echo in k-space, resulting in three distinct types of artifacts in partial-Fourier DTI. Here, we present an improved DTI acquisition and reconstruction scheme, capable of generating high-quality and high-SNR DTI data without eddy current-induced artifacts. This new scheme consists of three components, respectively, addressing the three distinct types of artifacts. First, a k-space energy-anchored DTI sequence is designed to recover eddy current-induced signal loss (i.e., Type 1 artifact). Second, a multischeme partial-Fourier reconstruction is used to eliminate artificial signal elevation (i.e., Type 2 artifact) associated with the conventional partial-Fourier reconstruction. Third, a signal intensity correction is applied to remove artificial signal modulations due to eddy current-induced erroneous T2(∗) -weighting (i.e., Type 3 artifact). These systematic improvements will greatly increase the consistency and accuracy of DTI measurements, expanding the utility of DTI in translational applications where quantitative robustness is much needed.

Correction for Eddy Current-Induced Echo-Shifting Effect in Partial-Fourier Diffusion Tensor Imaging

PubMed Central

Truong, Trong-Kha; Song, Allen W.; Chen, Nan-kuei

2015-01-01

In most diffusion tensor imaging (DTI) studies, images are acquired with either a partial-Fourier or a parallel partial-Fourier echo-planar imaging (EPI) sequence, in order to shorten the echo time and increase the signal-to-noise ratio (SNR). However, eddy currents induced by the diffusion-sensitizing gradients can often lead to a shift of the echo in k-space, resulting in three distinct types of artifacts in partial-Fourier DTI. Here, we present an improved DTI acquisition and reconstruction scheme, capable of generating high-quality and high-SNR DTI data without eddy current-induced artifacts. This new scheme consists of three components, respectively, addressing the three distinct types of artifacts. First, a k-space energy-anchored DTI sequence is designed to recover eddy current-induced signal loss (i.e., Type 1 artifact). Second, a multischeme partial-Fourier reconstruction is used to eliminate artificial signal elevation (i.e., Type 2 artifact) associated with the conventional partial-Fourier reconstruction. Third, a signal intensity correction is applied to remove artificial signal modulations due to eddy current-induced erroneous T 2 ∗-weighting (i.e., Type 3 artifact). These systematic improvements will greatly increase the consistency and accuracy of DTI measurements, expanding the utility of DTI in translational applications where quantitative robustness is much needed. PMID:26413505

Relations between open-field, elevated plus-maze, and emergence tests in C57BL/6J and BALB/c mice injected with GABA- and 5HT-anxiolytic agents.

PubMed

Lalonde, Robert; Strazielle, Catherine

2010-06-01

Two 5HT(1A) receptor agonists and chlordiazepoxide were examined in open-field, elevated plus maze, and emergence tests. At doses with no effect in the open-field, chlordiazepoxide increased open and open/total arm visits as well as open arm duration in the elevated plus maze, whereas 5HT(1A) receptor agonists showed an anxiolytic response on a single measure. The anxiolytic action of chlordiazepoxide was limited to the less active BALB/c strain. Unlike the 5HT(1A) receptor agonists, chlordiazepoxide was also anxiolytic in the emergence test, once again only in BALB/c and not C57BL/6J mice. Significant correlations were found between emergence latencies and specific indicators of anxiety in the elevated plus-maze in chlordiazepoxide-treated but not in mice treated with buspirone and 8-OH-DPAT. These results indicate that elevated plus-maze and emergence tests depend on benzodiazepine receptors. In contrast, 5HT(1A) receptor agonists were ineffective in the emergence test and no correlation was found between emergence latencies and specific indicators of anxiety in the elevated plus-maze. Though superficially similar, the emergence test seems to tap into a partially separate facet of anxiety.

Plant growth in elevated CO2 alters mitochondrial number and chloroplast fine structure

PubMed Central

Griffin, Kevin L.; Anderson, O. Roger; Gastrich, Mary D.; Lewis, James D.; Lin, Guanghui; Schuster, William; Seemann, Jeffrey R.; Tissue, David T.; Turnbull, Matthew H.; Whitehead, David

2001-01-01

With increasing interest in the effects of elevated atmospheric CO2 on plant growth and the global carbon balance, there is a need for greater understanding of how plants respond to variations in atmospheric partial pressure of CO2. Our research shows that elevated CO2 produces significant fine structural changes in major cellular organelles that appear to be an important component of the metabolic responses of plants to this global change. Nine species (representing seven plant families) in several experimental facilities with different CO2-dosing technologies were examined. Growth in elevated CO2 increased numbers of mitochondria per unit cell area by 1.3–2.4 times the number in control plants grown in lower CO2 and produced a statistically significant increase in the amount of chloroplast stroma (nonappressed) thylakoid membranes compared with those in lower CO2 treatments. There was no observable change in size of the mitochondria. However, in contrast to the CO2 effect on mitochondrial number, elevated CO2 promoted a decrease in the rate of mass-based dark respiration. These changes may reflect a major shift in plant metabolism and energy balance that may help to explain enhanced plant productivity in response to elevated atmospheric CO2 concentrations. PMID:11226263

Chronic mesenteric volvulus in a dog

PubMed Central

Spevakow, Andrea B.; Nibblett, Belle Marie D.; Carr, Anthony P.; Linn, Kathleen A.

2010-01-01

A chronic, partial mesenteric volvulus was found on laparotomy of an adult Bernese mountain dog with a 4-month history of intermittent vomiting, diarrhea, and weight loss. The dog had elevated cholestatic and hepatocellular leakage enzymes, increased bile acids, azotemia, isosthenuria, and a hypokalemic, hypochloremic, metabolic alkalosis. The dog recovered fully following reduction of the volvulus. PMID:20357947

25. "CAST IRON HOWE TRUSS CARRYING PENNA STATE HIGHWAY ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

25. "CAST IRON HOWE TRUSS - CARRYING PENNA STATE HIGHWAY ROUTE #83 OVER READING CO. TRACKS - SOUTH OF READING, PENNA, Dwg. #6 - Sht. #1", dated November 20, 1956, shows partial side elevation of bridge truss, beginning at end post - Reading-Halls Station Bridge, U.S. Route 220, spanning railroad near Halls Station, Muncy, Lycoming County, PA

Thermal regimes and snowpack relations of periglacial talus slopes, Sierra Nevada, California, USA.

Treesearch

Constance I Millar; Robert D. Westfall; Diane L. Delany

2014-01-01

Thermal regimes of eight periglacial talus slopes, at contrasting elevations, aspects, and substrates, in the Sierra Nevada, California, had complex microclimatic patterns partially decoupled from external conditions. Over three years, warm seasons showed mean talus matrix temperatures and daily variances lower than surfaces and cooler than free-air; talus surface and...

Relation of Early Menarche to Depression, Eating Disorders, Substance Abuse, and Comorbid Psychopathology among Adolescent Girls.

ERIC Educational Resources Information Center

Stice, Eric; Presnell, Katherine; Bearman, Sarah Kate

2001-01-01

Used interview data from a community study to test whether early menarche partially accounts for increased depression, eating pathology, substance abuse, and comorbid psychopathology among adolescent girls. Found that menarche prior to 11.6 years related to elevated depression and substance abuse. Findings support assertion that early menarche is…

Heritability of HR and BP Response To Exercise Training in the HERITAGE Family Study.

ERIC Educational Resources Information Center

Rice, Treva; Gagnon, Jacques; Leon, Arthur S.; Skinner, James S.; Wilmore, Jack H.; Bouchard, Claude; Rao, D. C.

2002-01-01

Assessed the heritability of response to exercise training in resting blood pressure (BP) and heart rate (HR) among sedentary Caucasians comprising 98 families who completed an exercise training program. Results indicated that the trainability of systolic BP and HR in families with elevated BP was partially determined by genetic factors. Diastolic…

Alterations in metabolic pathways and networks in Alzheimer's disease

PubMed Central

Kaddurah-Daouk, R; Zhu, H; Sharma, S; Bogdanov, M; Rozen, S G; Matson, W; Oki, N O; Motsinger-Reif, A A; Churchill, E; Lei, Z; Appleby, D; Kling, M A; Trojanowski, J Q; Doraiswamy, P M; Arnold, S E

2013-01-01

The pathogenic mechanisms of Alzheimer's disease (AD) remain largely unknown and clinical trials have not demonstrated significant benefit. Biochemical characterization of AD and its prodromal phase may provide new diagnostic and therapeutic insights. We used targeted metabolomics platform to profile cerebrospinal fluid (CSF) from AD (n=40), mild cognitive impairment (MCI, n=36) and control (n=38) subjects; univariate and multivariate analyses to define between-group differences; and partial least square-discriminant analysis models to classify diagnostic groups using CSF metabolomic profiles. A partial correlation network was built to link metabolic markers, protein markers and disease severity. AD subjects had elevated methionine (MET), 5-hydroxyindoleacetic acid (5-HIAA), vanillylmandelic acid, xanthosine and glutathione versus controls. MCI subjects had elevated 5-HIAA, MET, hypoxanthine and other metabolites versus controls. Metabolite ratios revealed changes within tryptophan, MET and purine pathways. Initial pathway analyses identified steps in several pathways that appear altered in AD and MCI. A partial correlation network showed total tau most directly related to norepinephrine and purine pathways; amyloid-β (Ab42) was related directly to an unidentified metabolite and indirectly to 5-HIAA and MET. These findings indicate that MCI and AD are associated with an overlapping pattern of perturbations in tryptophan, tyrosine, MET and purine pathways, and suggest that profound biochemical alterations are linked to abnormal Ab42 and tau metabolism. Metabolomics provides powerful tools to map interlinked biochemical pathway perturbations and study AD as a disease of network failure. PMID:23571809

Male patients with partial androgen insensitivity syndrome: a longitudinal follow-up of growth, reproductive hormones and the development of gynaecomastia.

PubMed

Hellmann, Philip; Christiansen, Peter; Johannsen, Trine Holm; Main, Katharina M; Duno, Morten; Juul, Anders

2012-05-01

To describe the natural history of phenotype, growth and gonadal function in patients with partial androgen insensitivity syndrome. Tertiary paediatric endocrine centre. Retrospective evaluation of 14 male patients with partial androgen insensitivity syndrome (PAIS) with verified androgen receptor (AR) mutations. The authors recorded phenotypic characteristics at birth and external masculinisation score (EMS), registered longitudinal growth, circulating levels of testosterone, estradiol, luteinising hormone (LH), follicle-stimulating hormone (FSH), inhibin-B and sex hormone binding globulin (SHBG), in addition to phenotype at postpubertal follow up. The EMS ranged from 5 to 12 in PAIS at birth. Six patients were born with hypospadias and all patients developed gynaecomastia in puberty. Eight of the patients received testosterone treatment. At follow-up penile size was impaired irrespective of EMS at birth, but responded to pubertal androgen therapy in some of the patients. Serum levels of testosterone, estradiol, SHBG and LH, but not FSH and inhibin B, were markedly elevated in puberty. Final height was 181.3 cm (165.7-190.5 cm) corresponding to an SD score of 0.7 (-2.1 to +2.1 SD, n=10). Gynaecomastia and impaired phallic growth are frequently observed in adults with PAIS, but may be ameliorated by androgen therapy. The authors suggest that male patients presenting with gynaecomastia in puberty, and elevated circulating levels of testosterone, estradiol and LH in puberty, but normal FSH, should be suspected of having PAIS and undergo genetic testing for AR mutations.

Alterations in metabolic pathways and networks in Alzheimer's disease.

PubMed

Kaddurah-Daouk, R; Zhu, H; Sharma, S; Bogdanov, M; Rozen, S G; Matson, W; Oki, N O; Motsinger-Reif, A A; Churchill, E; Lei, Z; Appleby, D; Kling, M A; Trojanowski, J Q; Doraiswamy, P M; Arnold, S E

2013-04-09

The pathogenic mechanisms of Alzheimer's disease (AD) remain largely unknown and clinical trials have not demonstrated significant benefit. Biochemical characterization of AD and its prodromal phase may provide new diagnostic and therapeutic insights. We used targeted metabolomics platform to profile cerebrospinal fluid (CSF) from AD (n=40), mild cognitive impairment (MCI, n=36) and control (n=38) subjects; univariate and multivariate analyses to define between-group differences; and partial least square-discriminant analysis models to classify diagnostic groups using CSF metabolomic profiles. A partial correlation network was built to link metabolic markers, protein markers and disease severity. AD subjects had elevated methionine (MET), 5-hydroxyindoleacetic acid (5-HIAA), vanillylmandelic acid, xanthosine and glutathione versus controls. MCI subjects had elevated 5-HIAA, MET, hypoxanthine and other metabolites versus controls. Metabolite ratios revealed changes within tryptophan, MET and purine pathways. Initial pathway analyses identified steps in several pathways that appear altered in AD and MCI. A partial correlation network showed total tau most directly related to norepinephrine and purine pathways; amyloid-β (Ab42) was related directly to an unidentified metabolite and indirectly to 5-HIAA and MET. These findings indicate that MCI and AD are associated with an overlapping pattern of perturbations in tryptophan, tyrosine, MET and purine pathways, and suggest that profound biochemical alterations are linked to abnormal Ab42 and tau metabolism. Metabolomics provides powerful tools to map interlinked biochemical pathway perturbations and study AD as a disease of network failure.

Phonotactic flight of the parasitoid fly Emblemasoma auditrix (Diptera: Sarcophagidae).

PubMed

Tron, Nanina; Lakes-Harlan, Reinhard

2017-01-01

The parasitoid fly Emblemasoma auditrix locates its hosts using acoustic cues from sound producing males of the cicada Okanagana rimosa. Here, we experimentally analysed the flight path of the phonotaxis from a landmark to the target, a hidden loudspeaker in the field. During flight, the fly showed only small lateral deviations. The vertical flight direction angles were initially negative (directed downwards relative to starting position), grew positive (directed upwards) in the second half of the flight, and finally flattened (directed horizontally or slightly upwards), typically resulting in a landing above the loudspeaker. This phonotactic flight pattern was largely independent from sound pressure level or target distance, but depended on the elevation of the sound source. The flight velocity was partially influenced by sound pressure level and distance, but also by elevation. The more elevated the target, the lower was the speed. The accuracy of flight increased with elevation of the target as well as the landing precision. The minimal vertical angle difference eliciting differences in behaviour was 10°. By changing the elevation of the acoustic target after take-off, we showed that the fly is able to orientate acoustically while flying.

Process development of two high strength tantalum base alloys (ASTAR-1211C and ASTAR-1511C)

NASA Technical Reports Server (NTRS)

Ammon, R. L.

1974-01-01

Two tantalum base alloys, Ta-12W-1.0Re-0.7Hf-0.025C(ASTAR-1211C) and Ta-15W-1.0Re-0.7Hf-0.025C(ASTAR-1511C), were cast as 12.5 cm (5 inch) diameter ingots and processed to swaged rod, sheet, forged plate, and tubing. Swaged rod was evaluated with respect to low temperature ductility, elevated temperature tensile properties, and elevated temperature creep behavior. A standard swaging process and final annealing schedule were determined. Elevated temperature tensile properties, low temperature impact properties, low temperature DBTT behavior, and extended elevated temperature creep properties were determined. A process for producing ASTAR-1211C and ASTAR-1511C sheet were developed. The DBTT properties of GTA and EB weld sheet given post-weld anneal and thermal aging treatments were determined using bend and tensile specimens. High and low temperature mechanical properties of forging ASTAR-1211C and ASTAR-1511C plate were determined as well as elevated temperature creep properties. Attempts to produce ASTAR-1211C tubing were partially successful while attempts to make ASTAR-1511C tubing were completely unsuccessful.

A Systematic Review of Global Drivers of Ant Elevational Diversity

PubMed Central

Szewczyk, Tim; McCain, Christy M.

2016-01-01

Ant diversity shows a variety of patterns across elevational gradients, though the patterns and drivers have not been evaluated comprehensively. In this systematic review and reanalysis, we use published data on ant elevational diversity to detail the observed patterns and to test the predictions and interactions of four major diversity hypotheses: thermal energy, the mid-domain effect, area, and the elevational climate model. Of sixty-seven published datasets from the literature, only those with standardized, comprehensive sampling were used. Datasets included both local and regional ant diversity and spanned 80° in latitude across six biogeographical provinces. We used a combination of simulations, linear regressions, and non-parametric statistics to test multiple quantitative predictions of each hypothesis. We used an environmentally and geometrically constrained model as well as multiple regression to test their interactions. Ant diversity showed three distinct patterns across elevations: most common were hump-shaped mid-elevation peaks in diversity, followed by low-elevation plateaus and monotonic decreases in the number of ant species. The elevational climate model, which proposes that temperature and precipitation jointly drive diversity, and area were partially supported as independent drivers. Thermal energy and the mid-domain effect were not supported as primary drivers of ant diversity globally. The interaction models supported the influence of multiple drivers, though not a consistent set. In contrast to many vertebrate taxa, global ant elevational diversity patterns appear more complex, with the best environmental model contingent on precipitation levels. Differences in ecology and natural history among taxa may be crucial to the processes influencing broad-scale diversity patterns. PMID:27175999

Cognitive defusion versus thought distraction: a clinical rationale, training, and experiential exercise in altering psychological impacts of negative self-referential thoughts.

PubMed

Masuda, Akihiko; Feinstein, Amanda B; Wendell, Johanna W; Sheehan, Shawn T

2010-11-01

Using two modes of intervention delivery, the present study compared the effects of a cognitive defusion strategy with a thought distraction strategy on the emotional discomfort and believability of negative self-referential thoughts. One mode of intervention delivery consisted of a clinical rationale and training (i.e., Partial condition). The other mode contained a condition-specific experiential exercise with the negative self-referential thought in addition to the clinical rationale and training (i.e., Full condition). Nonclinical undergraduates were randomly assigned to one of five protocols: Partial-Defusion, Full-Defusion, Partial-Distraction, Full-Distraction, and a distraction-based experimental control task. The Full-Defusion condition reduced the emotional discomfort and believability of negative self-referential thoughts significantly more than other comparison conditions. The positive results of the Full-Defusion condition were also found among participants with elevated depressive symptoms.

Mass tree mortality leads to mangrove peat collapse at Bay Islands, Honduras after Hurricane Mitch

USGS Publications Warehouse

Cahoon, D.R.; Hensel, P.; Rybczyk, J.; McKee, K.L.; Proffitt, C.E.; Perez, B.C.

2003-01-01

We measured sediment elevation and accretion dynamics in mangrove forests on the islands of Guanaja and Roatan, Honduras, impacted by Hurricane Mitch in 1998 to determine if collapse of underlying peat was occurring as a result of mass tree mortality. Little is known about the balance between production and decomposition of soil organic matter in the maintenance of sediment elevation of mangrove forests with biogenic soils. Sediment elevation change measured with the rod surface elevation table from 18 months to 33 months after the storm differed significantly among low, medium and high wind impact sites. Mangrove forests suffering minimal to partial mortality gained elevation at a rate (5 mm yeara??1) greater than vertical accretion (2 mm yeara??1) measured from artificial soil marker horizons, suggesting that root production contributed to sediment elevation. Basin forests that suffered mass tree mortality experienced peat collapse of about 11 mm yeara??1 as a result of decomposition of dead root material and sediment compaction. Low soil shear strength and lack of root growth accompanied elevation decreases. Model simulations using the Relative Elevation Model indicate that peat collapse in the high impact basin mangrove forest would be 37 mm yeara??1 for the 2 years immediately after the storm, as root material decomposed. In the absence of renewed root growth, the model predicts that peat collapse will continue for at least 8 more years at a rate (7 mm yeara??1) similar to that measured (11 mm yeara??1). Mass tree mortality caused rapid elevation loss. Few trees survived and recovery of the high impact forest will thus depend primarily on seedling recruitment. Because seedling establishment is controlled in large part by sediment elevation in relation to tide height, continued peat collapse could further impair recovery rates.

GPR40 partial agonists and AgoPAMs: Differentiating effects on glucose and hormonal secretions in the rodent

PubMed Central

Pachanski, Michele J.; Kirkland, Melissa E.; Kosinski, Daniel T.; Mane, Joel; Cheewatrakoolpong, Boonlert; Xue, Jiyan; Szeto, Daphne; Forrest, Gail; Miller, Corin; Bunzel, Michelle; Plummer, Christopher W.; Chobanian, Harry R.; Miller, Michael W.; Souza, Sarah; Thomas-Fowlkes, Brande S.; Ogawa, Aimie M.; Weinglass, Adam B.; Di Salvo, Jerry; Li, Xiaoyan; Feng, Yue; Tatosian, Daniel A.; Howard, Andrew D.; Colletti, Steven L.

2017-01-01

GPR40 agonists are effective antidiabetic agents believed to lower glucose through direct effects on the beta cell to increase glucose stimulated insulin secretion. However, not all GPR40 agonists are the same. Partial agonists lower glucose through direct effects on the pancreas, whereas GPR40 AgoPAMs may incorporate additional therapeutic effects through increases in insulinotrophic incretins secreted by the gut. Here we describe how GPR40 AgoPAMs stimulate both insulin and incretin secretion in vivo over time in diabetic GK rats. We also describe effects of AgoPAMs in vivo to lower glucose and body weight beyond what is seen with partial GPR40 agonists in both the acute and chronic setting. Further comparisons of the glucose lowering profile of AgoPAMs suggest these compounds may possess greater glucose control even in the presence of elevated glucagon secretion, an unexpected feature observed with both acute and chronic treatment with AgoPAMs. Together these studies highlight the complexity of GPR40 pharmacology and the potential additional benefits AgoPAMs may possess above partial agonists for the diabetic patient. PMID:29053717

A non-pregnant woman with elevated beta-HCG: A case of para-neoplastic syndrome in ovarian cancer.

PubMed

Goldstein, Jennifer; Pandey, Prasamsa; Fleming, Nicole; Westin, Shannon; Piha-Paul, Sarina

2016-08-01

There is a broad range of possible diagnoses for an elevated beta human chorionic gonadotropin (β-hCG) in the absence of intrauterine or ectopic pregnancy. When women of child bearing potential undergo evaluation for clinical trial, it is often unclear what course of evaluation to take when a pregnancy test is positive. We describe the clinical course of a patient with widely metastatic mucinous ovarian carcinoma with metastasis to the peritoneum, lymph nodes and liver. The patient was found to have a mildly elevated β-hCG during initial evaluation for clinical trial. Extensive work up for ectopic pregnancy, trophoblastic disease, and phantom β-hCG were negative. The patient's β-hCG levels continued to rise until initiation of therapy. She was treated on a phase I protocol with restaging scans revealing a partial response. The β-hCG was retested and declined in conjunction with her response, consistent with paraneoplastic β-hCG. Here, we propose a decision making algorithm to evaluate a patient with an elevated β-hCG undergoing assessment for clinical trial.

11. Photocopy of architectural drawing (from National Archives Architectural and ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

11. Photocopy of architectural drawing (from National Archives Architectural and Cartographic Branch Alexandria, Va.) 'Non-Com-Officers Qrs.' Quartermaster General's Office Standard Plan 82, sheet 1. Lithograph on linen architectural drawing. April 1893 3 ELEVATIONS, 3 PLANS AND A PARTIAL SECTION - Fort Myer, Non-Commissioned Officers Quarters, Washington Avenue between Johnson Lane & Custer Road, Arlington, Arlington County, VA

Environment and forest regeneration in the Illinois Valley area of southwestern Oregon.

Treesearch

Don Minore; Joseph N. Graham; Edward W. Murray

1984-01-01

Multiple regression analyses were used to relate environmental factors to forest regeneration on clearcut and partial cut areas managed by the Bureau of Land Management in the Illinois Valley area southwest of Grants Pass, Oregon. Difficulty of regenerating clearcuttings at elevations between 3,000 and 4,900 feet (914 and 1 494 m) increased with increases in soil...

PROCEEDINGS OF INTERNATIONAL SYMPOSIUM ON RECENT ADVANCES IN THE ASSESSMENT OF THE HEALTH EFFECTS OF ENVIRONMENTAL POLLUTION, HELD AT PARIS (FRANCE) ON 24-28 JUNE 1974. VOLUME III

EPA Science Inventory

;Partial contents: The incidence of elevated blood lead values in an asymptomatic pediatric population residing in a major American industrial state; Method for the identification of environmental noise levels requisite to protect public health and welfare; Improved methods of sa...

Pheochromocytoma of urinary bladder - a case report.

PubMed

Sharma, Shaleen; Gokhro, Sunil; Sharma, K K; Sadasukhi, T C

2007-08-01

Pheochromocytomas are catecholamine producing neuroendocrine tumours. Bladder involvement with pheochromocytoma is rare that usually presents with hypertension, hematuria and syncope often related to voiding. Clinical manifestation may be inconsistent and high index of suspicion is required for accurate diagnosis. We report a case, who presented with gross intermittent hematuria and mild elevation of pulserate and bloodpressure. Patient was adequately treated with partial cystectomy.

Steady flow rate to a partially penetrating well with seepage face in an unconfined aquifer

NASA Astrophysics Data System (ADS)

Behrooz-Koohenjani, Siavash; Samani, Nozar; Kompani-Zare, Mazda

2011-06-01

The flow rate to fully screened, partially penetrating wells in an unconfined aquifer is numerically simulated using MODFLOW 2000, taking into account the flow from the seepage face and decrease in saturated thickness of the aquifer towards the well. A simple three-step method is developed to find the top of the seepage face and hence the seepage-face length. The method is verified by comparing it with the results of previous predictive methods. The results show that the component of flow through the seepage face can supply a major portion of the total pumping rate. Variations in flow rate as a function of the penetration degree, elevation of the water level in the well and the distance to the far constant head boundary are investigated and expressed in terms of dimensionless curves and equations. These curves and equations can be used to design the degree of penetration for which the allowable steady pumping rate is attained for a given elevation of water level in the well. The designed degree of penetration or flow rate will assure the sustainability of the aquifer storage, and can be used as a management criterion for issuing drilling well permits by groundwater protection authorities.

Water resources data for Pennsylvania, water year 1992. Volume 2. Susquehanna and Potomac river basins. Water-data report (Annual), 1 October 1991-30 September 1992

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

Durlin, R.R.; Schaffstall, W.P.

1993-08-01

Water resources data for the 1992 water year for Pennsylvania consist of records of discharge and water quality of streams; contents and elevations of lakes and reservoirs; and water levels and water quality of ground-water wells. The report, Volume 2, includes records from the Susquehanna and Potomac River basins. Specifically, it contains discharge records for 85 continuous-record streamflow-gaging stations and 38 partial-record stations; elevation and contents records for 13 lakes and reservoirs; water-quality records for 12 streamflow-gaging stations and 48 ungaged streamsites; and water-level records for 25 observation wells.

Simulating certain aspects of hypogravity: Effects on the mandibular incisors of suspended rats (PULEH model)

NASA Technical Reports Server (NTRS)

Simmons, D. J.; Winter, F.; Morey-Holton, E. R.

1984-01-01

The effect of a hypogravity simulating model on the rate of mandibular incisor formation, dentinogenesis and, amelogenesis in laboratory rats was studied. The model is the partial unloading by elevating the hindquarters. In this system, rat hindquarters are elevated 30 to 40 deg from the cage floors to completely unload the hindlimbs, but the animals are free to move about using their forelimbs. This model replicates the fluid sift changes which occur during the weightlessness of spaceflight and produces an osteopenia in the weight bearing skeletons. The histogenesis and/or mineralization rates of the mandibular incisor during the first 19d of PULEH in young growing rats are recorded.

Parquet: Regions of areal plastic dislocations (on Venus)

NASA Technical Reports Server (NTRS)

Sukhanov, A. L.

1986-01-01

The extensive flat elevations of the Northern Hemisphere of Venus are covered with frequently intersecting lines of dislocations, resembling the outline of a giant parquet. In the internal sections of these regions we find grabens and regions of extension, and on the periphery lobe-shaped flow structures. The parquet was formed after the beginning of the formation of the lava plains, but covered by the youngest lava. These structures apparently arose partly because of the dragging of blocks of crust by the asthenospheric flows, and partly in the gravitational sliding of such heated blocks in the partial melting of their base. It is possible that these elevations occupy on Venus the place of the Earth's rift systems.

Asymptomatic elevation of liver enzymes due to levetiracetam: a case report.

PubMed

Sethi, Nitin K; Sethi, Prahlad K; Torgovnick, Josh; Arsura, Edward; Cukierwar, Frances

2013-01-01

Levetiracetam is a commonly used broad-spectrum anticonvulsant efficacious in both partial and generalized seizures. It has an extremely favorable side effect profile with few drug-drug interactions, low potential for hematological and hepatic toxicity, and thus has rapidly become the preferred drug in patients with traumatic brain injuries who need seizure prophylaxis. We report, here, a patient who was started on levetiracetam for seizure prophylaxis after developing large bifrontal-parietal traumatic subdural hematomas (SDH) following a fall from a horse necessitating bifrontal craniotomies for evacuation. The patient developed an asymptomatic elevation of the liver enzymes. The liver enzymes trended back to normal after levetiracetam was stopped, and topiramate was initiated in its place.

O₂migration rates in [NiFe] hydrogenases. A joint approach combining free-energy calculations and kinetic modeling.

PubMed

Topin, Jérémie; Diharce, Julien; Fiorucci, Sébastien; Antonczak, Serge; Golebiowski, Jérôme

2014-01-23

Hydrogenases are promising candidates for the catalytic production of green energy by means of biological ways. The major impediment to such a production is rooted in their inhibition under aerobic conditions. In this work, we model dioxygen migration rates in mutants of a hydrogenase of Desulfovibrio fructusovorans. The approach relies on the calculation of the whole potential of mean force for O2 migration within the wild-type as well as in V74M, V74F, and V74Q mutant channels. The three free-energy barriers along the entire migration pathway are converted into chemical rates through modeling based on Transition State Theory. The use of such a model recovers the trend of O2 migration rates among the series.

Anharmonic frequencies of CX2Y2 (X, Y = O, N, F, H, D) isomers and related systems obtained from vibrational multiconfiguration self-consistent field theory.

PubMed

Pfeiffer, Florian; Rauhut, Guntram

2011-10-13

Accurate anharmonic frequencies are provided for molecules of current research, i.e., diazirines, diazomethane, the corresponding fluorinated and deuterated compounds, their dioxygen analogs, and others. Vibrational-state energies were obtained from state-specific vibrational multiconfiguration self-consistent field theory (VMCSCF) based on multilevel potential energy surfaces (PES) generated from explicitly correlated coupled cluster, CCSD(T)-F12a, and double-hybrid density functional calculations, B2PLYP. To accelerate the vibrational structure calculations, a configuration selection scheme as well as a polynomial representation of the PES have been exploited. Because experimental data are scarce for these systems, many calculated frequencies of this study are predictions and may guide experiments to come.

Crystallization and preliminary X-ray diffraction studies of a novel ferredoxin involved in the dioxygenation of carbazole by Novosphingobium sp. KA1

PubMed Central

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

2008-01-01

Novosphingobium sp. KA1 uses carbazole 1,9a-dioxygenase (CARDO) as the first dioxygenase in its carbazole-degradation pathway. The CARDO of KA1 contains a terminal oxygenase component and two electron-transfer components: ferredoxin and ferredoxin reductase. In contrast to the CARDO systems of other species, the ferredoxin component of KA1 is a putidaredoxin-type protein. This novel ferredoxin was crystallized at 293 K by the hanging-drop vapour-diffusion method using PEG MME 550 as the precipitant under anaerobic conditions. The crystals belong to space group C2221 and diffraction data were collected to a resolution of 1.9 Å (the diffraction limit was 1.6 Å). PMID:18607094

Functional role of long-lived flowers in preventing pollen limitation in a high elevation outcrossing species

PubMed Central

Pacheco, Diego Andrés; Dudley, Leah S

2017-01-01

Abstract Low pollinator visitation in harsh environments may lead to pollen limitation which can threaten population persistence. Consequently, avoidance of pollen limitation is expected in outcrossing species subjected to habitually low pollinator service. The elevational decline in visitation rates on many high mountains provides an outstanding opportunity for addressing this question. According to a recent meta-analysis, levels of pollen limitation in alpine and lowland species do not differ. If parallel trends are manifested among populations of alpine species with wide elevational ranges, how do their uppermost populations contend with lower visitation? We investigated visitation rates and pollen limitation in high Andean Rhodolirium montanum. We test the hypothesis that lower visitation rates at high elevations are compensated for by the possession of long-lived flowers. Visitation rates decreased markedly over elevation as temperature decreased. Pollen limitation was absent at the low elevation site but did occur at the high elevation site. While initiation of stigmatic pollen deposition at high elevations was not delayed, rates of pollen arrival were lower, and cessation of pollination, as reflected by realized flower longevity, occurred later in the flower lifespan. Comparison of the elevational visitation decline and levels of pollen limitation indicates that flower longevity partially compensates for the lower visitation rates at high elevation. The functional role of flower longevity, however, was strongly masked by qualitative pollen limitation arising from higher abortion levels attributable to transference of genetically low-quality pollen in large clones. Stronger clonal growth at high elevations could counterbalance the negative fitness consequences of residual pollen limitation due to low visitation rates and/or difficult establishment under colder conditions. Visitation rates on the lower part of the elevational range greatly exceeded community rates recorded several decades ago when the planet was cooler. Current pollen limitation for some species in some habitats might underestimate historical levels. PMID:29225762

Climate change (elevated CO₂, elevated temperature and moderate drought) triggers the antioxidant enzymes' response of grapevine cv. Tempranillo, avoiding oxidative damage.

PubMed

Salazar-Parra, Carolina; Aguirreolea, Jone; Sánchez-Díaz, Manuel; Irigoyen, Juan José; Morales, Fermín

2012-02-01

Photosynthetic carbon fixation (A(N) ) and photosynthetic electron transport rate (ETR) are affected by different environmental stress factors, such as those associated with climate change. Under stress conditions, it can be generated an electron excess that cannot be consumed, which can react with O₂, producing reactive oxygen species. This work was aimed to evaluate the influence of climate change (elevated CO₂, elevated temperature and moderate drought) on the antioxidant status of grapevine (Vitis vinifera) cv. Tempranillo leaves, from veraison to ripeness. The lowest ratios between electrons generated (ETR) and consumed (A(N) + respiration + photorespiration) were observed in plants treated with elevated CO₂ and elevated temperature. In partially irrigated plants under current ambient conditions, electrons not consumed seemed to be diverted to alternative ways. Oxidative damage to chlorophylls and carotenoids was not observed. However, these plants had increases in thiobarbituric acid reacting substances, an indication of lipid peroxidation. These increases matched well with an early rise of H₂O₂ and antioxidant enzyme activities, superoxide dismutase (EC 1.15.1.1), ascorbate peroxidase (EC 1.11.1.11) and catalase (EC 1.11.1.6). Enzymatic activities were maintained high until ripeness. In conclusion, plants grown under current ambient conditions and moderate drought were less efficient to cope with oxidative damage than well-irrigated plants, and more interestingly, plants grown under moderate drought but treated with elevated CO₂ and elevated temperature were not affected by oxidative damage, mainly because of higher rates of electrons consumed in photosynthetic carbon fixation. Copyright © Physiologia Plantarum 2011.

Predicting redox-sensitive contaminant concentrations in groundwater using random forest classification

NASA Astrophysics Data System (ADS)

Tesoriero, Anthony J.; Gronberg, Jo Ann; Juckem, Paul F.; Miller, Matthew P.; Austin, Brian P.

2017-08-01

Machine learning techniques were applied to a large (n > 10,000) compliance monitoring database to predict the occurrence of several redox-active constituents in groundwater across a large watershed. Specifically, random forest classification was used to determine the probabilities of detecting elevated concentrations of nitrate, iron, and arsenic in the Fox, Wolf, Peshtigo, and surrounding watersheds in northeastern Wisconsin. Random forest classification is well suited to describe the nonlinear relationships observed among several explanatory variables and the predicted probabilities of elevated concentrations of nitrate, iron, and arsenic. Maps of the probability of elevated nitrate, iron, and arsenic can be used to assess groundwater vulnerability and the vulnerability of streams to contaminants derived from groundwater. Processes responsible for elevated concentrations are elucidated using partial dependence plots. For example, an increase in the probability of elevated iron and arsenic occurred when well depths coincided with the glacial/bedrock interface, suggesting a bedrock source for these constituents. Furthermore, groundwater in contact with Ordovician bedrock has a higher likelihood of elevated iron concentrations, which supports the hypothesis that groundwater liberates iron from a sulfide-bearing secondary cement horizon of Ordovician age. Application of machine learning techniques to existing compliance monitoring data offers an opportunity to broadly assess aquifer and stream vulnerability at regional and national scales and to better understand geochemical processes responsible for observed conditions.

Warming reduces carbon losses from grassland exposed to elevated atmospheric carbon dioxide.

PubMed

Pendall, Elise; Heisler-White, Jana L; Williams, David G; Dijkstra, Feike A; Carrillo, Yolima; Morgan, Jack A; Lecain, Daniel R

2013-01-01

The flux of carbon dioxide (CO2) between terrestrial ecosystems and the atmosphere may ameliorate or exacerbate climate change, depending on the relative responses of ecosystem photosynthesis and respiration to warming temperatures, rising atmospheric CO2, and altered precipitation. The combined effect of these global change factors is especially uncertain because of their potential for interactions and indirectly mediated conditions such as soil moisture. Here, we present observations of CO2 fluxes from a multi-factor experiment in semi-arid grassland that suggests a potentially strong climate - carbon cycle feedback under combined elevated [CO2] and warming. Elevated [CO2] alone, and in combination with warming, enhanced ecosystem respiration to a greater extent than photosynthesis, resulting in net C loss over four years. The effect of warming was to reduce respiration especially during years of below-average precipitation, by partially offsetting the effect of elevated [CO2] on soil moisture and C cycling. Carbon losses were explained partly by stimulated decomposition of soil organic matter with elevated [CO2]. The climate - carbon cycle feedback observed in this semiarid grassland was mediated by soil water content, which was reduced by warming and increased by elevated [CO2]. Ecosystem models should incorporate direct and indirect effects of climate change on soil water content in order to accurately predict terrestrial feedbacks and long-term storage of C in soil.

Predicting redox-sensitive contaminant concentrations in groundwater using random forest classification

USGS Publications Warehouse

Tesoriero, Anthony J.; Gronberg, Jo Ann M.; Juckem, Paul F.; Miller, Matthew P.; Austin, Brian P.

2017-01-01

Machine learning techniques were applied to a large (n > 10,000) compliance monitoring database to predict the occurrence of several redox-active constituents in groundwater across a large watershed. Specifically, random forest classification was used to determine the probabilities of detecting elevated concentrations of nitrate, iron, and arsenic in the Fox, Wolf, Peshtigo, and surrounding watersheds in northeastern Wisconsin. Random forest classification is well suited to describe the nonlinear relationships observed among several explanatory variables and the predicted probabilities of elevated concentrations of nitrate, iron, and arsenic. Maps of the probability of elevated nitrate, iron, and arsenic can be used to assess groundwater vulnerability and the vulnerability of streams to contaminants derived from groundwater. Processes responsible for elevated concentrations are elucidated using partial dependence plots. For example, an increase in the probability of elevated iron and arsenic occurred when well depths coincided with the glacial/bedrock interface, suggesting a bedrock source for these constituents. Furthermore, groundwater in contact with Ordovician bedrock has a higher likelihood of elevated iron concentrations, which supports the hypothesis that groundwater liberates iron from a sulfide-bearing secondary cement horizon of Ordovician age. Application of machine learning techniques to existing compliance monitoring data offers an opportunity to broadly assess aquifer and stream vulnerability at regional and national scales and to better understand geochemical processes responsible for observed conditions.

Warming Reduces Carbon Losses from Grassland Exposed to Elevated Atmospheric Carbon Dioxide

PubMed Central

Pendall, Elise; Heisler-White, Jana L.; Williams, David G.; Dijkstra, Feike A.; Carrillo, Yolima; Morgan, Jack A.; LeCain, Daniel R.

2013-01-01

The flux of carbon dioxide (CO2) between terrestrial ecosystems and the atmosphere may ameliorate or exacerbate climate change, depending on the relative responses of ecosystem photosynthesis and respiration to warming temperatures, rising atmospheric CO2, and altered precipitation. The combined effect of these global change factors is especially uncertain because of their potential for interactions and indirectly mediated conditions such as soil moisture. Here, we present observations of CO2 fluxes from a multi-factor experiment in semi-arid grassland that suggests a potentially strong climate – carbon cycle feedback under combined elevated [CO2] and warming. Elevated [CO2] alone, and in combination with warming, enhanced ecosystem respiration to a greater extent than photosynthesis, resulting in net C loss over four years. The effect of warming was to reduce respiration especially during years of below-average precipitation, by partially offsetting the effect of elevated [CO2] on soil moisture and C cycling. Carbon losses were explained partly by stimulated decomposition of soil organic matter with elevated [CO2]. The climate – carbon cycle feedback observed in this semiarid grassland was mediated by soil water content, which was reduced by warming and increased by elevated [CO2]. Ecosystem models should incorporate direct and indirect effects of climate change on soil water content in order to accurately predict terrestrial feedbacks and long-term storage of C in soil. PMID:23977180

An environmental stress model correctly predicts unimodal trends in overall species richness and diversity along intertidal elevation gradients

NASA Astrophysics Data System (ADS)

Zwerschke, Nadescha; Bollen, Merle; Molis, Markus; Scrosati, Ricardo A.

2013-12-01

Environmental stress is a major factor structuring communities. An environmental stress model (ESM) predicts that overall species richness and diversity should follow a unimodal trend along the full stress gradient along which assemblages from a regional biota can occur (not to be confused with the intermediate disturbance hypothesis, which makes predictions only for basal species along an intermediate-to-high stress range). Past studies could only provide partial support for ESM predictions because of the limited stress range surveyed or a low sampling resolution. In this study, we measured overall species richness and diversity (considering all seaweeds and invertebrates) along the intertidal elevation gradient on two wave-sheltered rocky shores from Helgoland Island, on the NE Atlantic coast. In intertidal habitats, tides cause a pronounced gradient of increasing stress from low to high elevations. We surveyed up to nine contiguous elevation zones between the lowest intertidal elevation (low stress) and the high intertidal boundary (high stress). Nonlinear regression analyses revealed that overall species richness and diversity followed unimodal trends across elevations on the two studied shores. Therefore, our study suggests that the ESM might constitute a useful tool to predict local richness and diversity as a function of environmental stress. Performing tests on other systems (marine as well as terrestrial) should help to refine the model.

Growth habit and leaf economics determine gas exchange responses to high elevation in an evergreen tree, a deciduous shrub and a herbaceous annual

PubMed Central

Shi, Zuomin; Haworth, Matthew; Feng, Qiuhong; Cheng, Ruimei; Centritto, Mauro

2015-01-01

Plant growth at high elevations necessitates physiological and morphological plasticity to enable photosynthesis (A) under conditions of reduced temperature, increased radiation and the lower partial pressure of atmospheric gases, in particular carbon dioxide (pCO2). Previous studies have observed a wide range of responses to elevation in plant species depending on their adaptation to temperature, elevational range and growth habit. Here, we investigated the effect of an increase in elevation from 2500 to 3500 m above sea level (a.s.l.) on three montane species with contrasting growth habits and leaf economic strategies. While all of the species showed identical increases in foliar δ13C, dark respiration and nitrogen concentration with elevation, contrasting leaf gas exchange and photosynthetic responses were observed between species with different leaf economic strategies. The deciduous shrub Salix atopantha and annual herb Rumex dentatus exhibited increased stomatal (Gs) and mesophyll (Gm) conductance and enhanced photosynthetic capacity at the higher elevation. However, evergreen Quercus spinosa displayed reduced conductance to CO2 that coincided with lower levels of photosynthetic carbon fixation at 3500 m a.s.l. The lower Gs and Gm values of evergreen species at higher elevations currently constrains their rates of A. Future rises in the atmospheric concentration of CO2 ([CO2]) will likely predominantly affect evergreen species with lower specific leaf areas (SLAs) and levels of Gm rather than deciduous species with higher SLA and Gm values. We argue that climate change may affect plant species that compose high-elevation ecosystems differently depending on phenotypic plasticity and adaptive traits affecting leaf economics, as rising [CO2] is likely to benefit evergreen species with thick sclerophyllous leaves. PMID:26433706

Carbon balance, partitioning and photosynthetic acclimation in fruit-bearing grapevine (Vitis vinifera L. cv. Tempranillo) grown under simulated climate change (elevated CO2, elevated temperature and moderate drought) scenarios in temperature gradient greenhouses.

PubMed

Salazar-Parra, Carolina; Aranjuelo, Iker; Pascual, Inmaculada; Erice, Gorka; Sanz-Sáez, Álvaro; Aguirreolea, Jone; Sánchez-Díaz, Manuel; Irigoyen, Juan José; Araus, José Luis; Morales, Fermín

2015-02-01

Although plant performance under elevated CO2 has been extensively studied in the past little is known about photosynthetic performance changing simultaneously CO2, water availability and temperature conditions. Moreover, despite of its relevancy in crop responsiveness to elevated CO2 conditions, plant level C balance is a topic that, comparatively, has received little attention. In order to test responsiveness of grapevine photosynthetic apparatus to predicted climate change conditions, grapevine (Vitis vinifera L. cv. Tempranillo) fruit-bearing cuttings were exposed to different CO2 (elevated, 700ppm vs. ambient, ca. 400ppm), temperature (ambient vs. elevated, ambient +4°C) and irrigation levels (partial vs. full irrigation). Carbon balance was followed monitoring net photosynthesis (AN, C gain), respiration (RD) and photorespiration (RL) (C losses). Modification of environment (13)C isotopic composition (δ(13)C) under elevated CO2 (from -10.30 to -24.93‰) enabled the further characterization of C partitioning into roots, cuttings, shoots, petioles, leaves, rachides and berries. Irrespective of irrigation level and temperature, exposure to elevated CO2 induced photosynthetic acclimation of plants. C/N imbalance reflected the inability of plants grown at 700ppm CO2 to develop strong C sinks. Partitioning of labeled C to storage organs (main stem and roots) did not avoid accumulation of labeled photoassimilates in leaves, affecting negatively Rubisco carboxylation activity. The study also revealed that, after 20 days of treatment, no oxidative damage to chlorophylls or carotenoids was observed, suggesting a protective role of CO2 either at current or elevated temperatures against the adverse effect of water stress. Copyright © 2014 Elsevier GmbH. All rights reserved.

Stair-Step Pattern of Soil Bacterial Diversity Mainly Driven by pH and Vegetation Types Along the Elevational Gradients of Gongga Mountain, China

PubMed Central

Li, Jiabao; Shen, Zehao; Li, Chaonan; Kou, Yongping; Wang, Yansu; Tu, Bo; Zhang, Shiheng; Li, Xiangzhen

2018-01-01

Ecological understandings of soil bacterial community succession and assembly mechanism along elevational gradients in mountains remain not well understood. Here, by employing the high-throughput sequencing technique, we systematically examined soil bacterial diversity patterns, the driving factors, and community assembly mechanisms along the elevational gradients of 1800–4100 m on Gongga Mountain in China. Soil bacterial diversity showed an extraordinary stair-step pattern along the elevational gradients. There was an abrupt decrease of bacterial diversity between 2600 and 2800 m, while no significant change at either lower (1800–2600 m) or higher (2800–4100 m) elevations, which coincided with the variation in soil pH. In addition, the community structure differed significantly between the lower and higher elevations, which could be primarily attributed to shifts in soil pH and vegetation types. Although there was no direct effect of MAP and MAT on bacterial community structure, our partial least squares path modeling analysis indicated that bacterial communities were indirectly influenced by climate via the effect on vegetation and the derived effect on soil properties. As for bacterial community assembly mechanisms, the null model analysis suggested that environmental filtering played an overwhelming role in the assembly of bacterial communities in this region. In addition, variation partition analysis indicated that, at lower elevations, environmental attributes explained much larger fraction of the β-deviation than spatial attributes, while spatial attributes increased their contributions at higher elevations. Our results highlight the importance of environmental filtering, as well as elevation-related spatial attributes in structuring soil bacterial communities in mountain ecosystems. PMID:29636740

Interfacial RhO{sub x}/CeO{sub 2} sites as locations for low temperature N{sub 2}O dissociation

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

Cunningham, J.; Hickey, J.N.; Soria, J.

Temperatures required for extensive N{sub 2}O dissociation to N{sub 2}, or to N{sub 2} plus O{sub 2}, over 0.5% RhO{sub x}/CeO{sub 2} materials, and over polycrystalline Rh{sub 2}O{sub 3} or CeO{sub 2}, are compared for preoxidised and for prereduced samples on the basis of conversions achieved in pulsed-reactant, continuous-flow and recirculatory microcatalytic reactors. Influences of sample prereduction or preoxidation upon those measurements and upon results from parallel ESR and FTIR studies of N{sub 2}O interactions with such materials are presented and compared. Over partially reduced 0.5% RhO{sub x}/CeO{sub 2} materials complete dissociation of N{sub 2}O pulses to N{sub 2} plusmore » O{sub 2} is obtained at temperatures 50-100{degrees} lower than those required for extensive dissociation over prereduced Rh{sub 2}O{sub 3}. Furthermore, N{sub 2} was the sole product from the latter. Higher ongoing N{sub 2}O conversions to N{sub 2} plus O{sub 2} at 623 K over 0.5% Rh/CeO{sub 2} in pulsed-reactant than in continuous-flow mode point to regeneration of active sites under helium flushing between pulses. The TPD profile for dioxygen release from Rhodia containing samples at temperatures 350-550 K is presented. ESR measurements reveal complementary effects of outgassings at temperatures, T{sub v}, {ge} 573 K upon the availability at RhO{sub x}/CeO{sub 2} surfaces of electron-excess sites reactive towards N{sub 2}O. Differences from observations over Rh{sub 2}O{sub 3} and CeO{sub 2} can be understood by attributing the low-temperature activity of RhO{sub x}/CeO{sub 2} to electron excess sites at microinterfaces between the dispersed Rhodia component and the Ceria support.« less

Selective, tunable O 2 binding in cobalt(II)–triazolate/pyrazolate metal–organic frameworks

DOE PAGES

Xiao, Dianne J.; Gonzalez, Miguel I.; Darago, Lucy E.; ...

2016-05-16

Here, the air-free reaction of CoCl 2 with 1,3,5-tri(1H- 1,2,3-triazol-5-yl)benzene (H 3BTTri) in N,N-dimethylformamide (DMF) and methanol leads to the formation of Co- BTTri (Co 3[(Co 4Cl) 3(BTTri) 8] 2·DMF), a sodalite-type metal-organic framework. Desolvation of this material generates coordinatively unsaturated low-spin cobalt(II) centers that exhibit a strong preference for binding O 2 over N 2, with isosteric heats of adsorption (Q st) of -34(1) and -12(1) kJ/ mol, respectively. The low-spin (S = 1/2) electronic configuration of the metal centers in the desolvated framework is supported by structural, magnetic susceptibility, and computational studies. A single-crystal X-ray structure determination revealsmore » that O 2 binds end-on to each framework cobalt center in a 1:1 ratio with a Co-O 2 bond distance of 1.973(6) Å. Replacement of one of the triazolate linkers with a more electron-donating pyrazolate group leads to the isostructural framework Co-BDTriP (Co 3[(Co 4Cl) 3(BDTriP) 8] 2·DMF; H 3BDTriP = 5,5'-(5-(1H-pyrazol-4-yl)-1,3-phenylene)bis(1H-1,2,3-triazole)), which demonstrates markedly higher yet still fully reversible O 2 affinities (Q st = -47(1) kJ/mol at low loadings). Electronic structure calculations suggest that the O 2 adducts in Co-BTTri are best described as cobalt(II)-dioxygen species with partial electron transfer, while the stronger binding sites in Co-BDTriP form cobalt(III)-superoxo moieties. The stability, selectivity, and high O 2 adsorption capacity of these materials render them promising new adsorbents for air separation processes.« less

4-Sulphobenzoate 3,4-dioxygenase. Purification and properties of a desulphonative two-component enzyme system from Comamonas testosteroni T-2.

PubMed Central

Locher, H H; Leisinger, T; Cook, A M

1991-01-01

Cell-free extracts of Comamonas testosteroni T-2 grown in toluene-p-sulphonate/salts medium catalyse the conversion of p-sulphobenzoate (PSB) into protocatechuate and sulphite by an NADH-requiring and Fe2(+)-activated dioxygenase. Anion-exchange chromatography of extracts yielded red (A) and yellow (B) protein fractions, both of which were necessary for dioxygenative activity. Further purification of each fraction by hydrophobic interaction chromatography and gel filtration led to two homogeneous protein components (A and B), which together converted 1 mol each of PSB, O2 and NADH into 1 mol each of protocatechuate, sulphite and, presumably, NAD+. The system was named 4-sulphobenzoate 3,4-dioxygenase (PSB dioxygenase system). Monomeric component B (Mr 36,000) was determined to be a reductase that contained 1 mol of FMN and about 2 mol each of iron and inorganic sulphur per mol. This component transferred electrons from NADH to the oxygenase component (A) or to, e.g., cytochrome c. Homodimeric component A (subunit Mr 50,000) of the PSB dioxygenase system contained one [2Fe-2S] centre per subunit and its u.v.-visible-absorption spectrum corresponded to a Rieske-type iron-sulphur centre. The requirement for activation by iron was interpreted as partial loss of mononuclear iron during purification of component A. Component A could be reduced by dithionite or by NADH plus catalytic amounts of component B. The PSB dioxygenase system displayed a narrow substrate range: none of 18 sulphonated or non-sulphonated analogues of PSB showed significant substrate-dependent O2 uptake. The physical properties of the PSB dioxygenase system resemble those of other bacterial multi-component dioxygenase, especially phthalate dioxygenase. However, it differs from most characterized systems in its overall reaction; the product is a vicinal diphenol, and not a dihydrodiol. Images Fig. 3. PMID:2012609

Differential effects of total and partial sleep deprivation on salivary factors in Wistar rats.

PubMed

Lasisi, Dr T J; Shittu, S T; Meludu, C C; Salami, A A

2017-01-01

Aim of this study was to investigate the effects of sleep deprivation on salivary factors in rats. Animals were randomly assigned into three groups of 6 animals each as control, total sleep deprivation (TSD) and partial sleep deprivation (PSD) groups. The multiple platform method was used to induce partial and total sleep deprivation for 7days. On the 8th day, stimulated saliva samples were collected for the analysis of salivary lag time, flow rate, salivary amylase activity, immunoglobulin A secretion rate and corticosterone levels using ELISA and standard kinetic enzyme assay. Data were analyzed using ANOVA with Dunnett T3 post hoc tests. Salivary flow rate reduced significantly in the TSD group compared with the PSD group as well as the control group (p=0.01). The secretion rate of salivary IgA was significantly reduced in the TSD group compared with the control group (p=0.04). Salivary amylase activity was significantly elevated in the TSD group compared with the PSD group as well as control group (p<0.001). However, there were no significant changes in the salivary lag time and levels of corticosterone among the groups. These findings suggest that total sleep deprivation is associated with reduced salivary flow rate and secretion rate of IgA as well as elevated levels of salivary amylase activity in rats. However, sleep recovery of four hours in the PSD group produced ameliorative effects on the impaired functions of salivary glands. Copyright © 2016 Elsevier Ltd. All rights reserved.

Physical Health Conditions Associated with Posttraumatic Stress Disorder in U.S. Older Adults: Results from Wave 2 of the National Epidemiologic Survey on Alcohol and Related Conditions

PubMed Central

Pietrzak, Robert H.; Goldstein, Risë B.; Southwick, Steven M.; Grant, Bridget F.

2011-01-01

Background/Objectives Trauma exposure and posttraumatic stress disorder (PTSD) may increase risk for medical conditions in older adults. We present findings on past-year medical conditions associated with lifetime trauma exposure, and full and partial PTSD, in a nationally representative sample of U.S. older adults. Design, Setting, Participants, and Measurements Face-to-face diagnostic interviews were conducted with 9,463 adults aged 60 and older in the Wave 2 National Epidemiologic Survey on Alcohol and Related Conditions. Logistic regression analyses adjusting for sociodemographics and psychiatric comorbidity evaluated associations between PTSD status and past-year medical disorders; linear regression models evaluated associations with past-month physical functioning. Results After adjustment for sociodemographic characteristics and comorbid lifetime mood, anxiety, substance use, attention-deficit/hyperactivity, and personality disorders, respondents with lifetime PTSD were more likely than trauma controls to report being diagnosed by a healthcare professional with hypertension, angina pectoris, tachycardia, other heart disease, stomach ulcer, gastritis, and arthritis (odds ratios [ORs]=1.3–1.8); they also scored lower on a measure of physical functioning than controls and respondents with partial PTSD. Respondents with lifetime partial PTSD were more likely than controls to report past-year diagnoses of gastritis (OR=1.7), angina pectoris (OR=1.5), and arthritis (OR=1.4), and reported worse physical functioning. Number of lifetime traumatic event types was associated with most of the medical conditions assessed; adjustment for these events reduced the magnitudes of and rendered non-significant most associations between PTSD status and medical conditions. Conclusion Older adults with lifetime PTSD have elevated rates of several physical health conditions, many of which are chronic disorders of aging, and poorer physical functioning. Older adults with lifetime partial PTSD have elevated rates of gastritis, angina pectoris, and arthritis, and poorer physical functioning. PMID:22283516

Anxiolytic efficacy of repeated oral capsaicin in rats with partial aberration of oral sensory relay to brain.

PubMed

Choi, Young-Jun; Kim, Jin Young; Jin, Wei-Peng; Kim, Yoon-Tae; Lee, Jong-Ho; Jahng, Jeong Won

2015-07-01

This study was conducted to examine if taste over load with oral capsaicin improves the adverse behavioural effects induced by partial aberration of oral sensory relays to brain with bilateral transections of the lingual and chorda tympani nerves. Male Sprague-Dawley rats received daily 1 ml of 0.02% capsaicin or water drop by drop into the oral cavity following the bilateral transections of the lingual and chorda tympani nerves. Rats were subjected to ambulatory activity, elevated plus maze and forced swim tests after 11th, 14th and 17th daily administration of capsaicin or water, respectively. The basal and stress-induced plasma corticosterone levels were examined after the end of behavioural tests. Ambulatory counts, distance travelled, centre zone activities and rearing were increased, and rostral grooming decreased, during the activity test in capsaicin treated rats. Behavioural scores of capsaicin rats during elevated plus maze test did not differ from control rats. Immobility during the swim test was decreased in capsaicin rats with near significance (P = 0.0547). Repeated oral capsaicin increased both the basal level and stress-induced elevation of plasma corticosterone in rats with bilateral transections of the lingual and chorda tympani nerves. It is concluded that repeated oral administration of capsaicin reduces anxiety-like behaviours in rats that received bilateral transections of the lingual and chorda tympani nerves, and that the increased corticosterone response, possibly modulating the hippocampal neural plasticity, may be implicated in the anxiolytic efficacy of oral capsaicin. Copyright © 2015 Elsevier Ltd. All rights reserved.

JP-8 jet fuel exposure rapidly induces high levels of IL-10 and PGE2 secretion and is correlated with loss of immune function.

PubMed

Harris, David T; Sakiestewa, Debbie; Titone, Dominic; Witten, Mark

2007-05-01

The US Air Force has implemented the widespread use of JP-8 jet fuel in its operations, although a thorough understanding of its potential effects upon exposed personnel is unclear. Previous work has demonstrated that JP-8 exposure is immunosuppressive. In the present study, the potential mechanisms for the effects of JP-8 exposure on the immune system were investigated. Exposure of mice to JP-8 for 1 h/day resulted in immediate secretion of two immunosuppressive agents; namely, interleukin-10 (IL-10) and prostaglandin E2 (PGE2). JP-8 exposure rapidly induced a persistently high level of serum IL-10 and PGE2 at an exposure concentration of 1000 mg/m3. IL-10 levels peaked at 2 h post-JP-8 exposure and then stabilized at significantly elevated serum levels, while PGE2 levels peaked after 2-3 days of exposure and then stabilized. Elevated IL-10 and PGE2 levels may at least partially explain the effects of JP-8 exposure on immune function. Elevated IL-10 and PGE2 levels, however, cannot explain all of the effects due to JP-8 exposure (e.g., decreased organ weights and decreased viable immune cells), as treatment with a PGE2 inhibitor did not completely reverse the immunosuppressive effects of jet fuel exposure. Thus, low concentration JP-8 jet fuel exposures have significant effects on the immune system, which can be partially explained by the secretion of immunosuppressive modulators, which are cumulative over time.

Do American dippers obtain a survival benefit from altitudinal migration?

PubMed

Green, David J; Whitehorne, Ivy B J; Middleton, Holly A; Morrissey, Christy A

2015-01-01

Studies of partial migrants provide an opportunity to assess the cost and benefits of migration. Previous work has demonstrated that sedentary American dippers (residents) have higher annual productivity than altitudinal migrants that move to higher elevations to breed. Here we use a ten-year (30 period) mark-recapture dataset to evaluate whether migrants offset their lower productivity with higher survival during the migration-breeding period when they occupy different habitat, or early and late-winter periods when they coexist with residents. Mark-recapture models provide no evidence that apparent monthly survival of migrants is higher than that of residents at any time of the year. The best-supported model suggests that monthly survival is higher in the migration-breeding period than winter periods. Another well-supported model suggested that residency conferred a survival benefit, and annual apparent survival (calculated from model weighted monthly apparent survival estimates using the Delta method) of residents (0.511 ± 0.038SE) was slightly higher than that of migrants (0.487 ± 0.032). Winter survival of American dippers was influenced by environmental conditions; monthly apparent survival increased as maximum daily flow rates increased and declined as winter temperatures became colder. However, we found no evidence that environmental conditions altered differences in winter survival of residents and migrants. Since migratory American dippers have lower productivity and slightly lower survival than residents our data suggests that partial migration is likely an outcome of competition for limited nest sites at low elevations, with less competitive individuals being forced to migrate to higher elevations in order to breed.

Effects of episodic low aragonite saturation and elevated temperature on the physiology of Stylophora pistillata

NASA Astrophysics Data System (ADS)

Lürig, M.; Kunzmann, A.

2015-05-01

As global climate change is predicted to gradually alter the oceans' carbonate system and water temperature, knowledge about the effects an altered marine environment has on the physiology of reef building (hermatypic) coral species is more widely established. However, although it is recognized that seawater temperature and the carbonate system of a coral reef can change rapidly and with great amplitude, little is known about how the interaction of these natural fluctuations with long term effects of climate change may affect the metabolism and productivity of hermatypic corals. To investigate this, we acclimated the hermatypic coral Stylophora pistillata to a "worst case" scenario for carbon dioxide emissions (aragonite saturation state [ΩARAG] = 1.6), and tested how exposure to short term (24 h) elevated temperature (+ 3 °C) and further lowered ΩARAG (-1 unit) affected its photosynthesis and respiration. While episodic exposure to very low ΩARAG had only little effect on S. pistillata's physiology, short term heat stress caused a shift from net oxygen production to consumption and partial coral bleaching. Higher gross coral respiration, and lowered photosynthetic activity under episodically elevated temperature may have been the result of photoinhibition and partial coral bleaching. These findings suggest that fluctuating environmental conditions in combination with a low ΩARAG background signal may impair basic metabolic processes in calcifying corals. In a future high-CO2 world short term stress could be relevant for reef ecosystem processes, and may affect the resilience of coral reefs to other external influences and effects of climate change.

Effect of Elevated Reperfusion Pressure on "No Reflow" Area and Infarct Size in a Porcine Model of Ischemia-Reperfusion.

PubMed

Pantsios, Chris; Kapelios, Chris; Vakrou, Styliani; Diakos, Nikolaos; Pozios, Iraklis; Kontogiannis, Chris; Nanas, John; Malliaras, Konstantinos

2016-07-01

The "no reflow" phenomenon (microvascular obstruction despite restoration of epicardial blood flow) develops postreperfusion in acute myocardial infarction and is associated with poor prognosis. We hypothesized that increased reperfusion pressure may attenuate the no reflow phenomenon, as it could provide adequate flow to overcome the high resistance of the microvasculature within the no reflow zone. Thus, we investigated the effect of modestly elevated blood pressure during reperfusion on the extent of no reflow area and infarct size in a porcine model of ischemia-reperfusion. Eighteen farm pigs underwent acute myocardial infarction by occlusion of the anterior descending coronary artery for 1 hour, followed by 2 hours of reperfusion. Just prior to reperfusion, animals were randomized into 2 groups: in group 1 (control group, n = 9), no intervention was performed. In group 2 (n = 9), aortic pressure was increased by ∼20% (compared to ischemia) by partial clamping of the ascending aorta during reperfusion. Following 2 hours of reperfusion, animals were euthanized to measure area at risk, infarct size, and area of no reflow. Partial clamping of the ascending aorta resulted in modest elevation of blood pressure during reperfusion. The area at risk did not differ between the 2 groups. The no reflow area was significantly increased in group 2 compared to control animals (50% ± 13% vs 37% ± 9% of the area at risk; P = .04). The infarcted area was significantly increased in group 2 compared to control animals (75% ± 17% vs 52% ± 23% of the area at risk; P = .03). Significant positive correlations were observed between systolic aortic pressure and no reflow area, between systolic aortic pressure and infarcted area and between infarcted area and no reflow area during reperfusion. Modestly elevated blood pressure during reperfusion is associated with an increase in no reflow area and in infarct size in a clinically relevant porcine model of ischemia-reperfusion. © The Author(s) 2015.

Bladed Terrain on Pluto: Possible origins and evolution

NASA Astrophysics Data System (ADS)

Moore, Jeffrey M.; Howard, Alan D.; Umurhan, Orkan M.; White, Oliver L.; Schenk, Paul M.; Beyer, Ross A.; McKinnon, William B.; Spencer, John R.; Singer, Kelsi N.; Grundy, William M.; Earle, Alissa M.; Schmitt, Bernard; Protopapa, Silvia; Nimmo, Francis; Cruikshank, Dale P.; Hinson, David P.; Young, Leslie A.; Stern, S. Alan; Weaver, Harold A.; Olkin, Cathy B.; Ennico, Kimberly; Collins, Geoffrey; Bertrand, Tanguy; Forget, François; Scipioni, Francesca; New Horizons Science Team

2018-01-01

Bladed Terrain on Pluto consists of deposits of massive CH4, which are observed to occur within latitudes 30° of the equator and are found almost exclusively at the highest elevations (> 2 km above the mean radius). Our analysis indicates that these deposits of CH4 preferentially precipitate at low latitudes where net annual solar energy input is lowest. CH4 and N2 will both precipitate at low elevations. However, since there is much more N2 in the atmosphere than CH4, the N2 ice will dominate at these low elevations. At high elevations the atmosphere is too warm for N2 to precipitate so only CH4 can do so. We conclude that following the time of massive CH4 emplacement; there have been sufficient excursions in Pluto's climate to partially erode these deposits via sublimation into the blades we see today. Blades composed of massive CH4 ice implies that the mechanical behavior of CH4 can support at least several hundred meters of relief at Pluto surface conditions. Bladed Terrain deposits may be widespread in the low latitudes of the poorly seen sub-Charon hemisphere, based on spectral observations. If these locations are indeed Bladed Terrain deposits, they may mark heretofore unrecognized regions of high elevation.

Maintenance of C sinks sustains enhanced C assimilation during long-term exposure to elevated [CO2] in Mojave Desert shrubs.

PubMed

Aranjuelo, Iker; Ebbets, Allison L; Evans, R Dave; Tissue, David T; Nogués, Salvador; van Gestel, Natasja; Payton, Paxton; Ebbert, Volker; Adams, Williams W; Nowak, Robert S; Smith, Stanley D

2011-10-01

During the first few years of elevated atmospheric [CO(2)] treatment at the Nevada Desert FACE Facility, photosynthetic downregulation was observed in desert shrubs grown under elevated [CO(2)], especially under relatively wet environmental conditions. Nonetheless, those plants maintained increased A (sat) (photosynthetic performance at saturating light and treatment [CO(2)]) under wet conditions, but to a much lesser extent under dry conditions. To determine if plants continued to downregulate during long-term exposure to elevated [CO(2)], responses of photosynthesis to elevated [CO(2)] were examined in two dominant Mojave Desert shrubs, the evergreen Larrea tridentata and the drought-deciduous Ambrosia dumosa, during the eighth full growing season of elevated [CO(2)] treatment at the NDFF. A comprehensive suite of physiological processes were collected. Furthermore, we used C labeling of air to assess carbon allocation and partitioning as measures of C sink activity. Results show that elevated [CO(2)] enhanced photosynthetic performance and plant water status in Larrea, especially during periods of environmental stress, but not in Ambrosia. δ(13)C analyses indicate that Larrea under elevated [CO(2)] allocated a greater proportion of newly assimilated C to C sinks than Ambrosia. Maintenance by Larrea of C sinks during the dry season partially explained the reduced [CO(2)] effect on leaf carbohydrate content during summer, which in turn lessened carbohydrate build-up and feedback inhibition of photosynthesis. δ(13)C results also showed that in a year when plant growth reached the highest rates in 5 years, 4% (Larrea) and 7% (Ambrosia) of C in newly emerging organs were remobilized from C that was assimilated and stored for at least 2 years prior to the current study. Thus, after 8 years of continuous exposure to elevated [CO(2)], both desert perennials maintained their photosynthetic capacities under elevated [CO(2)]. We conclude that C storage, remobilization, and partitioning influence the responsiveness of these desert shrubs during long-term exposure to elevated [CO(2)].

Cooling systems for ultra-high temperature turbines.

PubMed

Yoshida, T

2001-05-01

This paper describes an introduction of research and development activities on steam cooling in gas turbines at elevated temperature of 1500 C and 1700 C level, partially including those on water cooling. Descriptions of a new cooling system that employs heat pipes are also made. From the view point of heat transfer, its promising applicability is shown with experimental data and engine performance numerical evaluation.

Gobi Desert, China as seen from STS-59

NASA Technical Reports Server (NTRS)

1994-01-01

View to the south by southwest across the southern Gobi Desert (China) across the Chi-Lien-Shan or Quilienshan or Nanshan (Mountains) in Gansu Province to Lake Quinghai or Ch'ing-Hai (orthography varies with political conditions and scholarship) in Quinghai Province. The lake has a surface elevation of 10,450 feet, partially filling one of the easternmost closed drainage basins of Central Asia.

Ice fishing by wintering Bald Eagles in Arizona

Treesearch

Teryl G. Grubb; Roy G. Lopez

1997-01-01

Northern Arizona winters vary within and between years with occasional heavy snows (up to 0.6 m) and extreme cold (overnight lows -18 to -29°C) interspersed with dry periods, mild temperatures (daytime highs reaching 10°C), and general loss of snow cover at all but highest elevations. Lakes in the area may freeze and thaw partially or totally several times during a...

Method of fabricating a (1223) Tl-Ba-Ca-Cu-O superconductor

DOEpatents

Tkaczyk, John Eric; Lay, Kenneth Wilbur; He, Qing

1997-01-01

A method is disclosed for fabricating a polycrystalline <223> thallium-containing superconductor having high critical current at elevated temperatures and in the presence of a magnetic field. A powder precursor containing compounds other than thallium is compressed on a substrate. Thallium is incorporated in the densified powder precursor at a high temperature in the presence of a partial pressure of a thallium-containing vapor.

Modeling RP-1 Fuel Advanced Distillation Data using Comprehensive Two-Dimensional Gas Chromatography Coupled with Time-of-Flight Mass Spectrometry and Partial Least Squares Analysis

DTIC Science & Technology

2014-05-07

of a variety of complex liquid samples including, but not limited to, crude oil [12], gasoline [16], biodiesel fuel [17, 19], jet fuel [5, 10, 11...doi: 10.1021/ie302399v 19. Bruno TJ, Wolk A, Naydich A (2009) Stabilization of Biodiesel Fuel at Elevated Temperature with Hydrogen Donors

Centrifuge Testing of a Partially-Confined FC-72 Spray

DTIC Science & Technology

2006-11-01

induced body forces. Heat transfer associated with closed - loop spray cooling will be affected by acceleration body forces, the extent of which is not...impingement cooling, spray cooling, heat pipes , loop heat pipes , carbon foam impregnated with phase-change materials, and combinations of the above...reduced gravity and elevated gravity experiments to help prove viability of pulsating heat pipes (PHPs) for space applications. The PHPs, filled

Increased thrombin generation in a mouse model of cancer cachexia is partially interleukin-6 dependent.

PubMed

Reddel, C J; Allen, J D; Ehteda, A; Taylor, R; Chen, V M Y; Curnow, J L; Kritharides, L; Robertson, G

2017-03-01

Essentials Cancer cachexia and cancer-associated thrombosis have not previously been mechanistically linked. We assessed thrombin generation and coagulation parameters in cachectic C26 tumor-bearing mice. C26 mice are hypercoagulable, partially corrected by blocking tumor derived interleukin-6. Coagulability and anti-inflammatory interventions may be clinically important in cancer cachexia. Background Cancer cachexia and cancer-associated thrombosis are potentially fatal outcomes of advanced cancer, which have not previously been mechanistically linked. The colon 26 (C26) carcinoma is a well-established mouse model of complications of advanced cancer cachexia, partially dependent on high levels of interleukin-6 (IL-6) produced by the tumor. Objectives To assess if cancer cachexia altered the coagulation state and if this was attributable to tumor IL-6 production. Methods In male BALB/c*DBA2 (F1 hybrid) mice with a C26 tumor we used modified calibrated automated thrombogram and fibrin generation (based on overall hemostatic potential) assays to assess the functional coagulation state, and also examined fibrinogen, erythrocyte sedimentation rate (ESR), platelet count, tissue factor pathway inhibitor (TFPI) and hepatic expression of coagulation factors by microarray. C26 mice were compared with non-cachectic NC26, pair-fed and sham control mice. IL-6 expression in C26 cells was knocked down by lentiviral shRNA constructs. Results C26 mice with significant weight loss and highly elevated IL-6 had elevated thrombin generation, fibrinogen, ESR, platelets and TFPI compared with all control groups. Fibrin generation was elevated compared with pair-fed and sham controls but not compared with NC26 tumor mice. Hepatic expression of coagulation factors and fibrinolytic inhibitors was increased. Silencing IL-6 in the tumor significantly, but incompletely, attenuated the increased thrombin generation, fibrinogen and TFPI. Conclusions Cachectic C26 tumor-bearing mice are in a hypercoagulable state, which is partly attributable to IL-6 release by the tumor. The findings support the importance of the coagulation state in cancer cachexia and the clinical utility of anti-inflammatory interventions. © 2017 International Society on Thrombosis and Haemostasis.

Systematic Perturbation of the Trinuclear Copper Cluster in the Multicopper Oxidases: The Role of Active Site Asymmetry in its Reduction of O2 to H2O

PubMed Central

Augustine, Anthony J.; Kjaergaard, Christian; Qayyum, Munzarin; Ziegler, Lynn; Kosman, Daniel J.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.

2010-01-01

The multicopper oxidase Fet3p catalyzes the four-electron reduction of dioxygen to water, coupled to the one-electron oxidation of four equivalents of substrate. To carry out this process the enzyme utilizes four Cu atoms: a type 1, a type 2, and a coupled binuclear, type 3 site. Substrates are oxidized at the T1 Cu, which rapidly transfers electrons, 13 Å away, to a trinuclear copper cluster composed of the T2 and T3 sites where dioxygen is reduced to water in two sequential 2e− steps. This study focuses on two variants of Fet3p, H126Q and H483Q, that perturb the two T3 Cu's, T3α and T3β, respectively. The variants have been isolated in both holo and type 1 depleted (T1D) forms, T1DT3αQ and T1DT3βQ, and their trinuclear copper clusters have been characterized in their oxidized and reduced states. While the variants are only mildly perturbed relative to T1D in the resting oxidized state, in contrast to T1D they are both found to have lost a ligand in their reduced states. Importantly, T1DT3αQ reacts with O2 but T1DT3βQ does not. Thus loss of a ligand at T3β, but not at T3α, turns off O2 reactivity, indicating that T3β and T2 are required for the 2e− reduction of O2 to form the peroxide intermediate (PI), whereas T3α remains reduced. This is supported by the spectroscopic features of PI in T1DT3αQ, which are identical to T1D PI. This selective redox activity of one edge of the trinuclear cluster demonstrates its asymmetry in O2 reactivity. The structural origin of this asymmetry between the T3α and T3β is discussed as is its contribution to reactivity. PMID:20377263

Density functional study for the bridged dinuclear center based on a high-resolution X-ray crystal structure of ba3 cytochrome c oxidase from Thermus thermophilus.

PubMed

Du, Wen-Ge Han; Noodleman, Louis

2013-12-16

Strong electron density for a peroxide type dioxygen species bridging the Fea3 and CuB dinuclear center (DNC) was observed in the high-resolution (1.8 Å) X-ray crystal structures (PDB entries 3S8G and 3S8F) of ba3 cytochrome c oxidase (CcO) from Thermus thermophilus. The crystals represent the as-isolated X-ray photoreduced CcO structures. The bridging peroxide was proposed to arise from the recombination of two radiation-produced HO(•) radicals formed either very near to or even in the space between the two metals of the DNC. It is unclear whether this peroxide species is in the O2(2-), O2(•)(-), HO2(-), or the H2O2 form and what is the detailed electronic structure and binding geometry including the DNC. In order to answer what form of this dioxygen species was observed in the DNC of the 1.8 Å X-ray CcO crystal structure (3S8G), we have applied broken-symmetry density functional theory (BS-DFT) geometric and energetic calculations (using OLYP potential) on large DNC cluster models with different Fea3-CuB oxidation and spin states and with O2(2-), O2(•)(-), HO2(-), or H2O2 in the bridging position. By comparing the DFT optimized geometries with the X-ray crystal structure (3S8G), we propose that the bridging peroxide is HO2(-). The X-ray crystal structure is likely to represent the superposition of the Fea3(2+)-(HO2(-))-CuB(+) DNC's in different states (Fe(2+) in low spin (LS), intermediate spin (IS), or high spin (HS)) with the majority species having the proton of the HO2(-) residing on the oxygen atom (O1) which is closer to the Fea3(2+) site in the Fea3(2+)-(HO-O)(-)-CuB(+) conformation. Our calculations show that the side chain of Tyr237 is likely trapped in the deprotonated Tyr237(-) anion form in the 3S8G X-ray crystal structure.

Self-assembly of supramolecular triarylamine nanowires in mesoporous silica and biocompatible electrodes thereof

NASA Astrophysics Data System (ADS)

Licsandru, Erol-Dan; Schneider, Susanne; Tingry, Sophie; Ellis, Thomas; Moulin, Emilie; Maaloum, Mounir; Lehn, Jean-Marie; Barboiu, Mihail; Giuseppone, Nicolas

2016-03-01

Biocompatible silica-based mesoporous materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. The formation of hybrid electroactive silica nanostructures is thus expected to be of great interest for the design of biocompatible conducting materials such as bioelectrodes. Here we show that we can grow supramolecular stacks of triarylamine molecules in the confined space of oriented mesopores of a silica nanolayer covering a gold electrode. This addressable bottom-up construction is triggered from solution simply by light irradiation. The resulting self-assembled nanowires act as highly conducting electronic pathways crossing the silica layer. They allow very efficient charge transfer from the redox species in solution to the gold surface. We demonstrate the potential of these hybrid constitutional materials by implementing them as biocathodes and by measuring laccase activity that reduces dioxygen to produce water.Biocompatible silica-based mesoporous materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. The formation of hybrid electroactive silica nanostructures is thus expected to be of great interest for the design of biocompatible conducting materials such as bioelectrodes. Here we show that we can grow supramolecular stacks of triarylamine molecules in the confined space of oriented mesopores of a silica nanolayer covering a gold electrode. This addressable bottom-up construction is triggered from solution simply by light irradiation. The resulting self-assembled nanowires act as highly conducting electronic pathways crossing the silica layer. They allow very efficient charge transfer from the redox species in solution to the gold surface. We demonstrate the potential of these hybrid constitutional materials by implementing them as biocathodes and by measuring laccase activity that reduces dioxygen to produce water. Electronic supplementary information (ESI) available: Synthetic protocols, XPS measurements, contact angle measurements, additional cyclic voltammograms and electrochemical impedance spectroscopy. See DOI: 10.1039/c5nr06977g

Saturation kinetics in phenolic O-H bond oxidation by a mononuclear Mn(III)-OH complex derived from dioxygen.

PubMed

Wijeratne, Gayan B; Corzine, Briana; Day, Victor W; Jackson, Timothy A

2014-07-21

The mononuclear hydroxomanganese(III) complex, [Mn(III)(OH)(dpaq)](+), which is supported by the amide-containing N5 ligand dpaq (dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate) was generated by treatment of the manganese(II) species, [Mn(II)(dpaq)](OTf), with dioxygen in acetonitrile solution at 25 °C. This oxygenation reaction proceeds with essentially quantitative yield (greater than 98% isolated yield) and represents a rare example of an O2-mediated oxidation of a manganese(II) complex to generate a single product. The X-ray diffraction structure of [Mn(III)(OH)(dpaq)](+) reveals a short Mn-OH distance of 1.806(13) Å, with the hydroxo moiety trans to the amide function of the dpaq ligand. No shielding of the hydroxo group is observed in the solid-state structure. Nonetheless, [Mn(III)(OH)(dpaq)](+) is remarkably stable, decreasing in concentration by only 10% when stored in MeCN at 25 °C for 1 week. The [Mn(III)(OH)(dpaq)](+) complex participates in proton-coupled electron transfer reactions with substrates with relatively weak O-H and C-H bonds. For example, [Mn(III)(OH)(dpaq)](+) oxidizes TEMPOH (TEMPOH = 2,2'-6,6'-tetramethylpiperidine-1-ol), which has a bond dissociation free energy (BDFE) of 66.5 kcal/mol, in MeCN at 25 °C. The hydrogen/deuterium kinetic isotope effect of 1.8 observed for this reaction implies a concerted proton-electron transfer pathway. The [Mn(III)(OH)(dpaq)](+) complex also oxidizes xanthene (C-H BDFE of 73.3 kcal/mol in dimethylsulfoxide) and phenols, such as 2,4,6-tri-t-butylphenol, with BDFEs of less than 79 kcal/mol. Saturation kinetics were observed for phenol oxidation, implying an initial equilibrium prior to the rate-determining step. On the basis of a collective body of evidence, the equilibrium step is attributed to the formation of a hydrogen-bonding complex between [Mn(III)(OH)(dpaq)](+) and the phenol substrates.

Mechanistic insights into iron redox transformations in the presence of natural organic matter: Impact of pH and light

NASA Astrophysics Data System (ADS)

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

2015-09-01

The various pathways contributing to the formation and decay of Fe(II) in the presence of Suwanee River Fulvic Acid (SRFA) in acidic solutions are investigated here both in the presence and absence of light and over the pH range of 3-5. Our results show that ligand to metal charge transfer (LMCT) is the dominant pathway for photochemical Fe(III) reduction and resultant Fe(II) formation over the pH range examined. In comparison, under non-irradiated conditions, Fe(III) reduction occurs, for the most part, as a result of the presence of hydroquinone-like moieties in SRFA. Irradiation of SRFA also results in the generation of both long-lived and short-lived Fe(II) oxidants with the long-lived Fe(II) oxidant similar to semiquinone-like radicals with these radicals formed via superoxide-mediated oxidation of the hydroquinone-like moieties present in SRFA. Dioxygen plays an important role in production of the long-lived Fe(II) oxidant since generation of superoxide occurs via reduction of dioxygen. The short-lived Fe(II) oxidant is similar to peroxyl radicals which are generated via hydroxylation of organic moieties. The overall rate of generation of both the short- and long-lived Fe(II) oxidants is dependent on pH with the generation rates of these oxidants increasing with increase in pH. Based on our experimental data, we have developed a kinetic model that satisfactorily describes all Fe transformations observed in SRFA solutions over the pH range 3-5 under non-irradiated, previously irradiated and continuously irradiated conditions. Fe species undergo continual cycling between Fe(II) and Fe(III) oxidation states with Fe(II)-Fe(III) turnover frequencies in the presence of 10 mg.L-1 SRFA of 17.3, 27.4 and 33.2 h-1 at pH 3, 3.5 and 4 on continuous photolysis compared to turnover frequencies of 1.9, 2.5 and 2.9 h-1 at pH 3, 3.5 and 4 in the dark.

Proton-coupled electron-transfer reduction of dioxygen catalyzed by a saddle-distorted cobalt phthalocyanine.

PubMed

Honda, Tatsuhiko; Kojima, Takahiko; Fukuzumi, Shunichi

2012-03-07

Proton-coupled electron-transfer reduction of dioxygen (O(2)) to afford hydrogen peroxide (H(2)O(2)) was investigated by using ferrocene derivatives as reductants and saddle-distorted (α-octaphenylphthalocyaninato)cobalt(II) (Co(II)(Ph(8)Pc)) as a catalyst under acidic conditions. The selective two-electron reduction of O(2) by dimethylferrocene (Me(2)Fc) and decamethylferrocene (Me(10)Fc) occurs to yield H(2)O(2) and the corresponding ferrocenium ions (Me(2)Fc(+) and Me(10)Fc(+), respectively). Mechanisms of the catalytic reduction of O(2) are discussed on the basis of detailed kinetics studies on the overall catalytic reactions as well as on each redox reaction in the catalytic cycle. The active species to react with O(2) in the catalytic reaction is switched from Co(II)(Ph(8)Pc) to protonated Co(I)(Ph(8)PcH), depending on the reducing ability of ferrocene derivatives employed. The protonation of Co(II)(Ph(8)Pc) inhibits the direct reduction of O(2); however, the proton-coupled electron transfer from Me(10)Fc to Co(II)(Ph(8)Pc) and the protonated [Co(II)(Ph(8)PcH)](+) occurs to produce Co(I)(Ph(8)PcH) and [Co(I)(Ph(8)PcH(2))](+), respectively, which react immediately with O(2). The rate-determining step is a proton-coupled electron-transfer reduction of O(2) by Co(II)(Ph(8)Pc) in the Co(II)(Ph(8)Pc)-catalyzed cycle with Me(2)Fc, whereas it is changed to the electron-transfer reduction of [Co(II)(Ph(8)PcH)](+) by Me(10)Fc in the Co(I)(Ph(8)PcH)-catalyzed cycle with Me(10)Fc. A single crystal of monoprotonated [Co(III)(Ph(8)Pc)](+), [Co(III)Cl(2)(Ph(8)PcH)], produced by the proton-coupled electron-transfer reduction of O(2) by Co(II)(Ph(8)Pc) with HCl, was obtained, and the crystal structure was determined in comparison with that of Co(II)(Ph(8)Pc). © 2012 American Chemical Society

August Median Streamflow on Ungaged Streams in Eastern Aroostook County, Maine

USGS Publications Warehouse

Lombard, Pamela J.; Tasker, Gary D.; Nielsen, Martha G.

2003-01-01

Methods for estimating August median streamflow were developed for ungaged, unregulated streams in the eastern part of Aroostook County, Maine, with drainage areas from 0.38 to 43 square miles and mean basin elevations from 437 to 1,024 feet. Few long-term, continuous-record streamflow-gaging stations with small drainage areas were available from which to develop the equations; therefore, 24 partial-record gaging stations were established in this investigation. A mathematical technique for estimating a standard low-flow statistic, August median streamflow, at partial-record stations was applied by relating base-flow measurements at these stations to concurrent daily flows at nearby long-term, continuous-record streamflow- gaging stations (index stations). Generalized least-squares regression analysis (GLS) was used to relate estimates of August median streamflow at gaging stations to basin characteristics at these same stations to develop equations that can be applied to estimate August median streamflow on ungaged streams. GLS accounts for varying periods of record at the gaging stations and the cross correlation of concurrent streamflows among gaging stations. Twenty-three partial-record stations and one continuous-record station were used for the final regression equations. The basin characteristics of drainage area and mean basin elevation are used in the calculated regression equation for ungaged streams to estimate August median flow. The equation has an average standard error of prediction from -38 to 62 percent. A one-variable equation uses only drainage area to estimate August median streamflow when less accuracy is acceptable. This equation has an average standard error of prediction from -40 to 67 percent. Model error is larger than sampling error for both equations, indicating that additional basin characteristics could be important to improved estimates of low-flow statistics. Weighted estimates of August median streamflow, which can be used when making estimates at partial-record or continuous-record gaging stations, range from 0.03 to 11.7 cubic feet per second or from 0.1 to 0.4 cubic feet per second per square mile. Estimates of August median streamflow on ungaged streams in the eastern part of Aroostook County, within the range of acceptable explanatory variables, range from 0.03 to 30 cubic feet per second or 0.1 to 0.7 cubic feet per second per square mile. Estimates of August median streamflow per square mile of drainage area generally increase as mean elevation and drainage area increase.

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.

Nonoperative treatment of distal biceps brachii musculotendinous partial rupture: a report of two cases.

PubMed

López-Zabala, I; Fernández-Valencia, J A

2013-01-01

Musculotendinous ruptures of the distal biceps brachii are extremely rare injuries whose clinical presentation is similar to distal biceps avulsion. We describe two cases of patients who suffered a distal biceps brachii musculotendinous partial rupture. The first patient was playing soccer as goalkeeper and experienced sudden pain while throwing the ball overhead with his left arm. The second patient experienced sudden pain while weightlifting with his right arm. The mechanism of injury was the same in the two cases, as both involved glenohumeral elevation with elbow extension and forearm supination. Neither of these two patients underwent surgical repair or rehabilitation, and both had perfect scores of 100 on the Mayo Clinic Performance Index for the Elbow at one-year followup.

Acute postoperative obstruction of extracardiac conduit due to separation of thin fibrous peel.

PubMed

Agarwal, K C; Edwards, W D; Puga, F J; Mair, D D

1982-03-01

Late postoperative obstruction of extracardiac conduits may occur in some patients and may result from one of several mechanisms. Severe intraoperative or early postoperative obstruction of such conduits is very rare. Herein we describe a case of acute, severe, early postoperative obstruction of an extracardiac conduit; this followed partial excision and replacement of a Hancock conduit in which late postoperative calcific valvular stenosis had occurred. Unexpectedly elevated right ventricular pressure should suggest the possibility of acute conduit obstruction. In cases with partial conduit replacement, the remaining segment should be carefully inspected for the presence of a peel; if a peel is present, it should be removed from the conduit even if it is considered thin and nonobstructive.

Effect of 1% Inspired CO2 During Head-Down Tilt on Ocular Structures, Cerebral Blood Flow, and Visual Acuity in Healthy Human Subjects

NASA Technical Reports Server (NTRS)

Laurie, S. S.; Hu, X.; Lee, S. M. C.; Martin, D. S.; Phillips, T. R.; Ploutz-Snyder, R.; Smith, S. M.; Stenger, M. B.; Taibbi, G.; Zwart, S. R.;

Surface studies of thermionic cathodes and the mechanism of operation of an impregnated tungsten cathode

NASA Technical Reports Server (NTRS)

Forman, R.

1976-01-01

The surface properties of conventional impregnated cathodes were investigated by the use of Auger spectroscopy and work function measurements, and these were compared with a synthesized barium or barium oxide coated tungsten surface. The barium and barium oxide coated surfaces were prepared by evaporating barium onto a tungsten surface that can be heated to elevated temperatures. Multilayer or monolayer coverages can be investigated using this technique. The results of this study show that the surface of an impregnated tungsten cathode is identical to that observed for a synthesized monolayer or partial monolayer of barium on partially oxidized tungsten, using the criteria of identical Auger patterns and work functions. Desorption measurements of barium from a tungsten surface were also made. These results in conjunction with Auger and work function data were interpreted to show that throughout most of its life an impregnated cathode operating in the range of 1100 C has a partial monolayer rather than a monolayer of barium on its surface.

Elevated depressive symptoms enhance reflexive but not reflective auditory category learning.

PubMed

Maddox, W Todd; Chandrasekaran, Bharath; Smayda, Kirsten; Yi, Han-Gyol; Koslov, Seth; Beevers, Christopher G

2014-09-01

In vision an extensive literature supports the existence of competitive dual-processing systems of category learning that are grounded in neuroscience and are partially-dissociable. The reflective system is prefrontally-mediated and uses working memory and executive attention to develop and test rules for classifying in an explicit fashion. The reflexive system is striatally-mediated and operates by implicitly associating perception with actions that lead to reinforcement. Although categorization is fundamental to auditory processing, little is known about the learning systems that mediate auditory categorization and even less is known about the effects of individual difference in the relative efficiency of the two learning systems. Previous studies have shown that individuals with elevated depressive symptoms show deficits in reflective processing. We exploit this finding to test critical predictions of the dual-learning systems model in audition. Specifically, we examine the extent to which the two systems are dissociable and competitive. We predicted that elevated depressive symptoms would lead to reflective-optimal learning deficits but reflexive-optimal learning advantages. Because natural speech category learning is reflexive in nature, we made the prediction that elevated depressive symptoms would lead to superior speech learning. In support of our predictions, individuals with elevated depressive symptoms showed a deficit in reflective-optimal auditory category learning, but an advantage in reflexive-optimal auditory category learning. In addition, individuals with elevated depressive symptoms showed an advantage in learning a non-native speech category structure. Computational modeling suggested that the elevated depressive symptom advantage was due to faster, more accurate, and more frequent use of reflexive category learning strategies in individuals with elevated depressive symptoms. The implications of this work for dual-process approach to auditory learning and depression are discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Elevated Depressive Symptoms Enhance Reflexive but not Reflective Auditory Category Learning

PubMed Central

Maddox, W. Todd; Chandrasekaran, Bharath; Smayda, Kirsten; Yi, Han-Gyol; Koslov, Seth; Beevers, Christopher G.

2014-01-01

In vision an extensive literature supports the existence of competitive dual-processing systems of category learning that are grounded in neuroscience and are partially-dissociable. The reflective system is prefrontally-mediated and uses working memory and executive attention to develop and test rules for classifying in an explicit fashion. The reflexive system is striatally-mediated and operates by implicitly associating perception with actions that lead to reinforcement. Although categorization is fundamental to auditory processing, little is known about the learning systems that mediate auditory categorization and even less is known about the effects of individual difference in the relative efficiency of the two learning systems. Previous studies have shown that individuals with elevated depressive symptoms show deficits in reflective processing. We exploit this finding to test critical predictions of the dual-learning systems model in audition. Specifically, we examine the extent to which the two systems are dissociable and competitive. We predicted that elevated depressive symptoms would lead to reflective-optimal learning deficits but reflexive-optimal learning advantages. Because natural speech category learning is reflexive in nature, we made the prediction that elevated depressive symptoms would lead to superior speech learning. In support of our predictions, individuals with elevated depressive symptoms showed a deficit in reflective-optimal auditory category learning, but an advantage in reflexive-optimal auditory category learning. In addition, individuals with elevated depressive symptoms showed an advantage in learning a non-native speech category structure. Computational modeling suggested that the elevated depressive symptom advantage was due to faster, more accurate, and more frequent use of reflexive category learning strategies in individuals with elevated depressive symptoms. The implications of this work for dual-process approach to auditory learning and depression are discussed. PMID:25041936

California dragonfly and damselfly (Odonata) database: temporal and spatial distribution of species records collected over the past century

PubMed Central

Ball-Damerow, Joan E.; Oboyski, Peter T.; Resh, Vincent H.

2015-01-01

Abstract The recently completed Odonata database for California consists of specimen records from the major entomology collections of the state, large Odonata collections outside of the state, previous literature, historical and recent field surveys, and from enthusiast group observations. The database includes 32,025 total records and 19,000 unique records for 106 species of dragonflies and damselflies, with records spanning 1879–2013. Records have been geographically referenced using the point-radius method to assign coordinates and an uncertainty radius to specimen locations. In addition to describing techniques used in data acquisition, georeferencing, and quality control, we present assessments of the temporal, spatial, and taxonomic distribution of records. We use this information to identify biases in the data, and to determine changes in species prevalence, latitudinal ranges, and elevation ranges when comparing records before 1976 and after 1979. The average latitude of where records occurred increased by 78 km over these time periods. While average elevation did not change significantly, the average minimum elevation across species declined by 108 m. Odonata distribution may be generally shifting northwards as temperature warms and to lower minimum elevations in response to increased summer water availability in low-elevation agricultural regions. The unexpected decline in elevation may also be partially the result of bias in recent collections towards centers of human population, which tend to occur at lower elevations. This study emphasizes the need to address temporal, spatial, and taxonomic biases in museum and observational records in order to produce reliable conclusions from such data. PMID:25709531

Effects of Mild Hypercapnia During Head-Down Bed Rest on Ocular Structures, Cerebral Blood Flow, aud Visual Acuity in Healthy Human Subjects

NASA Technical Reports Server (NTRS)

Laurie, S. S.; Taibbi, G.; Lee, S. M. C.; Martin, D. S.; Zanello, S.; Ploutz-Snyder, R.; Hu, X.; Stenger, M. B.; Vizzeri, G.

2014-01-01

The cephalad fluid shift induced by microgravity has been hypothesized to cause an elevation in intracranial pressure (ICP) and contribute to the development of the Visual Impairment/Intracranial Pressure (VIIP) syndrome, as experienced by some astronauts during long-duration space flight. Elevated ambient partial pressure of carbon dioxide (PCO2) on ISS may also raise ICP and contribute to VIIP development. We seek to determine if the combination of mild CO2 exposure, similar to that occurring on the International Space Station, with the cephalad fluid shift induced by head-down tilt, will induce ophthalmic and cerebral blood flow changes similar to those described in the VIIP syndrome. We hypothesize that mild hypercapnia in the head-down tilt position will increase choroidal blood volume and cerebral blood flow, raise intraocular pressure (IOP), and transiently reduce visual acuity as compared to the seated or the head-down tilt position without elevated CO2, respectively.

Early in vivo changes in calcium ions, oxidative stress markers, and ion channel immunoreactivity following partial injury to the optic nerve.

PubMed

Wells, Jonathan; Kilburn, Matthew R; Shaw, Jeremy A; Bartlett, Carole A; Harvey, Alan R; Dunlop, Sarah A; Fitzgerald, Melinda

2012-03-01

CNS injury is often localized but can be followed by more widespread secondary degenerative events that usually result in greater functional loss. Using a partial transection model in rat optic nerve (ON). we recently demonstrated in vivo increases in the oxidative stress-associated enzyme MnSOD 5 min after injury. However, mechanisms by which early oxidative stress spreads remain unclear. In the present study, we assessed ion distributions, additional oxidative stress indicators, and ion channel immunoreactivity in ON in the first 24 hr after partial transection. Using nanoscale secondary ion mass spectroscopy (NanoSIMS), we demonstrate changes in the distribution pattern of Ca ions following partial ON transection. Regions of elevated Ca ions in normal ON in vivo rapidly decrease following partial ON transection, but there is an increasingly punctate distribution at 5 min and 24 hr after injury. We also show rapid decreases in catalase activity and later increases in immunoreactivity of the advanced glycation end product carboxymethyl lysine in astrocytes. Increased oxidative stress in astrocytes is accompanied by significantly increased immunoreactivity of the AMPA receptor subunit GluR1 and aquaporin 4 (AQP4). Taken together, the results indicate that Ca ion changes and oxidative stress are early events following partial ON injury that are associated with changes in GluR1 AMPA receptor subunits and altered ionic balance resulting from increased AQP4. Copyright © 2011 Wiley Periodicals, Inc.

Childhood maltreatment, psychological resources, and depressive symptoms in women with breast cancer.

PubMed

Kuhlman, Kate Ryan; Boyle, Chloe C; Irwin, Michael R; Ganz, Patricia A; Crespi, Catherine M; Asher, Arash; Petersen, Laura; Bower, Julienne E

2017-10-01

Childhood maltreatment is associated with elevated risk for depression across the human lifespan. Identifying the pathways through which childhood maltreatment relates to depressive symptoms may elucidate intervention targets that have the potential to reduce the lifelong negative health sequelae of maltreatment exposure. In this cross-sectional study, 271 women with early-stage breast cancer were assessed after their diagnosis but before the start of adjuvant treatment (chemotherapy, radiation, endocrine therapy). Participants completed measures of childhood maltreatment exposure, psychological resources (optimism, mastery, self-esteem, mindfulness), and depressive symptoms. Using multiple mediation analyses, we examined which psychological resources uniquely mediated the relationship between childhood maltreatment and depressive symptoms. Exposure to maltreatment during childhood was robustly associated with lower psychological resources and elevated depressive symptoms. Further, lower optimism and mindfulness mediated the association between childhood maltreatment and elevated depressive symptoms. These results support existing theory that childhood maltreatment is associated with lower psychological resources, which partially explains elevated depressive symptoms in a sample of women facing breast cancer diagnosis and treatment. These findings warrant replication in populations facing other major life events and highlight the need for additional studies examining childhood maltreatment as a moderator of treatment outcomes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Flooding of Ganymede's bright terrains by low-viscosity water-ice lavas.

PubMed

Schenk, P M; McKinnon, W B; Gwynn, D; Moore, J M

2001-03-01

Large regions of the jovian moon Ganymede have been resurfaced, but the means has been unclear. Suggestions have ranged from volcanic eruptions of liquid water or solid ice to tectonic deformation, but definitive high-resolution morphological evidence has been lacking. Here we report digital elevation models of parts of the surface of Ganymede, derived from stereo pairs combining data from the Voyager and Galileo spacecraft, which reveal bright, smooth terrains that lie at roughly constant elevations 100 to 1,000 metres below the surrounding rougher terrains. These topographic data, together with new images that show fine-scale embayment and burial of older features, indicate that the smooth terrains were formed by flooding of shallow structural troughs by low-viscosity water-ice lavas. The oldest and most deformed areas (the 'reticulate' terrains) in general have the highest relative elevations, whereas units of the most common resurfaced type--the grooved terrain--lie at elevations between those of the smooth and reticulate terrains. Bright terrain, which accounts for some two-thirds of the surface, probably results from a continuum of processes, including crustal rifting, shallow flooding and groove formation. Volcanism plays an integral role in these processes, and is consistent with partial melting of Ganymede's interior.

The globins of cyanobacteria and algae.

PubMed

Johnson, Eric A; Lecomte, Juliette T J

2013-01-01

Approximately, 20 years ago, a haemoglobin gene was identified within the genome of the cyanobacterium Nostoc commune. Haemoglobins have now been confirmed in multiple species of photosynthetic microbes beyond N. commune, and the diversity of these proteins has recently come under increased scrutiny. This chapter summarizes the state of knowledge concerning the phylogeny, physiology and chemistry of globins in cyanobacteria and green algae. Sequence information is by far the best developed and the most rapidly expanding aspect of the field. Structural and ligand-binding properties have been described for just a few proteins. Physiological data are available for even fewer. Although activities such as nitric oxide dioxygenation and oxygen scavenging are strong candidates for cellular function, dedicated studies will be required to complete the story on this intriguing and ancient group of proteins. © 2013 Elsevier Ltd. All rights reserved.

Dioxygen Binding, Activation, and Reduction to H2O by Cu Enzymes.

PubMed

Solomon, Edward I

2016-07-05

Oxygen intermediates in copper enzymes exhibit unique spectroscopic features that reflect novel geometric and electronic structures that are key to reactivity. This perspective will describe: (1) the bonding origin of the unique spectroscopic features of the coupled binuclear copper enzymes and how this overcomes the spin forbiddenness of O2 binding and activates monooxygenase activity, (2) how the difference in exchange coupling in the non-coupled binuclear Cu enzymes controls the reaction mechanism, and (3) how the trinuclear Cu cluster present in the multicopper oxidases leads to a major structure/function difference in enabling the irreversible reductive cleavage of the O-O bond with little overpotential and generating a fully oxidized intermediate, different from the resting enzyme studied by crystallography, that is key in enabling fast PCET in the reductive half of the catalytic cycle.

7. Photographic copy (reduced to 4 x 5 from 8 ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

7. Photographic copy (reduced to 4 x 5 from 8 X 10 black and white paper reproduction in 1941 appraisal by E.E. Malloy at the Engineering Office, Oakland Army Base, California). Photograph taken between June 1940 and January 1941 by unknown photographer. PARTIAL SOUTH ELEVATION OF VEHICLE MAINTENANCE SHOP (BLDG. 99). - Oakland Army Base, Vehicle Maintenance Shop, Attu Street & Corregidor Avenue, Oakland, Alameda County, CA

Phylogenetic analysis of Common Garter Snake (Thamnophis sirtalis) stomach contents detects cryptic range of a secretive salamander (Ensatina eschscholtzii oregonensis) Herpetological Conservation and Biology 5(3):395–402

Treesearch

Sean B. Reilly; Andrew D Gottsho; Justin M. Garwood; Bryan Jennings

2010-01-01

Given the current global amphibian decline, it is crucial to obtain accurate and current information regarding species distributions. Secretive amphibians such as plethodontid salamanders can be difficult to detect in many cases, especially in remote, high elevation areas. We used molecular phylogenetic analyses to identify three partially digested salamanders palped...

Identification of the molecular genetic basis of the low palmitic acid seed oil trait in soybean mutant line RG3 and association analysis of molecular markers with elevated seed stearic acid and reduced seed palmitic acid

USDA-ARS?s Scientific Manuscript database

The fatty acid composition of vegetable oil is becoming increasingly critical for the ultimate functionality and utilization in foods and industrial products. Partial chemical hydrogenation of soybean oil increases oxidative stability and shelf life but also results in the introduction of trans fats...

Method of fabricating a (1223) Tl-Ba-Ca-Cu-O superconductor

DOEpatents

Tkaczyk, J.E.; Lay, K.W.; He, Q.

1997-07-08

A method is disclosed for fabricating a polycrystalline <223> thallium-containing superconductor having high critical current at elevated temperatures and in the presence of a magnetic field. A powder precursor containing compounds other than thallium is compressed on a substrate. Thallium is incorporated in the densified powder precursor at a high temperature in the presence of a partial pressure of a thallium-containing vapor. 2 figs.

Reproducible MRI Measurement of Adipose Tissue Volumes in Genetic and Dietary Rodent Obesity Models

PubMed Central

Johnson, David H.; Flask, Chris A.; Ernsberger, Paul R.; Wong, Wilbur C. K.; Wilson, David L.

2010-01-01

Purpose To develop ratio MRI [lipid/(lipid+water)] methods for assessing lipid depots and compare measurement variability to biological differences in lean controls (spontaneously hypertensive rats, SHRs), dietary obese (SHR-DO), and genetic/dietary obese (SHROBs) animals. Materials and Methods Images with and without CHESS water-suppression were processed using a semi-automatic method accounting for relaxometry, chemical shift, receive coil sensitivity, and partial volume. Results Partial volume correction improved results by 10–15%. Over six operators, volume variation was reduced to 1.9 ml from 30.6 ml for single-image-analysis with intensity inhomogeneity. For three acquisitions on the same animal, volume reproducibility was <1%. SHROBs had 6X visceral and 8X subcutaneous adipose tissue than SHRs. SHR-DOs had enlarged visceral depots (3X SHRs). SHROB had significantly more subcutaneous adipose tissue, indicating a strong genetic component to this fat depot. Liver ratios in SHR-DO and SHROB were higher than SHR, indicating elevated fat content. Among SHROBs, evidence suggested a phenotype SHROB* having elevated liver ratios and visceral adipose tissue volumes. Conclusion Effects of diet and genetics on obesity were significantly larger than variations due to image acquisition and analysis, indicating that these methods can be used to assess accumulation/depletion of lipid depots in animal models of obesity. PMID:18821617

Leukemia cell infiltration causes defective erythropoiesis partially through MIP-1α/CCL3.

PubMed

Wang, Y; Gao, A; Zhao, H; Lu, P; Cheng, H; Dong, F; Gong, Y; Ma, S; Zheng, Y; Zhang, H; Zhang, Y; Xu, J; Zhu, X; Yuan, W; Zhang, X; Hao, S; Cheng, T

2016-09-01

Leukemia often results in severe anemia, which may significantly contribute to patient mortality and morbidity. However, the mechanisms underlying defective erythropoiesis in leukemia have not been fully elucidated. In this study, we demonstrated that insufficient erythropoiesis in an immunocompetent acute myeloid leukemia (AML) murine model was due to reduced proliferation of megakaryocyte erythroid progenitors and increased apoptosis of erythroblasts. Colony-forming cell assays indicated that the leukemic bone marrow (BM) plasma inhibited erythroid colony formation, whereas they had no inhibitory effect on other types of colonies. Cytokine array analysis demonstrated that the chemokine CCL3 was elevated in the plasma of AML mice and patients. CCL3 inhibited erythroid differentiation of hematopoietic stem cells, common myeloid progenitors and especially megakaryocytic-erythroid progenitors. Administration of the CCR1 antagonist partially recovered the yield of erythroid colonies in the presence of CCL3 or leukemic BM plasma. Mechanistically, we observed an increase of p38 phosphorylation and subsequent downregulation of GATA1 after CCL3 treatment. Furthermore, knockdown of CCL3 attenuated leukemic progression and alleviated anemia. Therefore, our results demonstrate that elevated CCL3 in the leukemic environment suppresses erythropoiesis via CCR1-p38 activation, suggesting a novel mechanism for the erythroid defects observed in leukemia.

In-situ restoration of one-stage partial nitritation-anammox process deteriorated by nitrate build-up via elevated substrate levels

PubMed Central

Wang, Xiaolong; Gao, Dawen

2016-01-01

The one-stage partial nitritation and anammox process (PN/A) has been a promising microbial process to remove ammonia from wastewater especially with low carbon/nitrogen ratio. The main breakdown was the deterioration caused by overgrowth of nitrite oxidizing bacteria (NOB) resulting effluent nitrate build-up in the PN/A process. This study presented an in-situ restoring strategy for suppressing NOB activity in a one-stage granular PN/A system deteriorated over 2 months, using elevated concentrations of substrates (ammonia and nitrite) under limited dissolved oxygen level. The results showed that the NOB activity was successfully suppressed after 56 days of restoration, and finally the ratio of produced nitrate/consumed ammonium was reduced from 36.8% to 7%. On day 66 the nitrogen removal rate obtained as 1.2 kg N/(m3·d). The high FA level (5–40 mg/L) and low dissolved oxygen (<0.13 mg/L) were responsible for NOB suppression. From quantitative PCR (qPCR) analysis, after this restoration, anammox bacteria had a widely growth, and AOB stay stable, but Nitrospira increase and Nitrobacter declined. High amount of NOB was still persistent in the granules, which was not easy to wash-out and threaten the deammonification performance. PMID:27881860

Study on optimal fat content in total parenteral nutrition in partially hepatectomized rats.

PubMed

Abe, S; Sakabe, S; Hirata, M; Kamuro, H; Asahara, N; Watanabe, M

1997-04-01

In order to investigate the optimal fat content for total parenteral nutrition (TPN) solutions, male Wistar rats were subjected to 70% hepatectomy and then placed, for five days, on one of five TPN regimens in which fat represented 0%, 10%, 20%, 30% and 40%, respectively, of the total calorie content. As serum triglyceride levels in the fat-treated groups were lower than those in the non-treated normal rats, it was concluded that the administered fat was sufficiently hydrolyzed. The greater the fat content, the higher the regeneration rate of the remnant liver. Significant differences were found between the 0%-fat group and 20%-plus fat groups. Hepatic triglyceride level was significantly lower in the 20%-fat group. Hepatic protein level was significantly elevated in all fat-treated groups. Serum phospholipids and total cholesterol due to the lecithin contained in fat emulsion were significantly elevated in the 30 and 40%-fat groups, indicating that fat content of 30 and 40% was excessive. The results suggest that TPN containing fat is superior to fat-free TPN for liver regeneration after partial hepatectomy, and that optimal fat content is estimated to be about 20% of total calorie content in the case of this fat emulsion.

Metabolic effects of physiological levels of caffeine in myotubes.

PubMed

Schnuck, Jamie K; Gould, Lacey M; Parry, Hailey A; Johnson, Michele A; Gannon, Nicholas P; Sunderland, Kyle L; Vaughan, Roger A

2018-02-01

Caffeine has been shown to stimulate multiple major regulators of cell energetics including AMP-activated protein kinase (AMPK) and Ca 2+ /calmodulin-dependent protein kinase II (CaMKII). Additionally, caffeine induces peroxisome proliferator-activated receptor gamma coactivator 1-alpha (PGC-1α) and mitochondrial biogenesis. While caffeine enhances oxidative metabolism, experimental concentrations often exceed physiologically attainable concentrations through diet. This work measured the effects of low-level caffeine on cellular metabolism and gene expression in myotubes, as well as the dependence of caffeine's effects on the nuclear receptor peroxisome proliferator-activated receptor beta/delta (PPARβ/δ). C2C12 myotubes were treated with various doses of caffeine for up to 24 h. Gene and protein expression were measured via qRT-PCR and Western blot, respectively. Cellular metabolism was determined via oxygen consumption and extracellular acidification rate. Caffeine significantly induced regulators of mitochondrial biogenesis and oxidative metabolism. Mitochondrial staining was suppressed in PPARβ/δ-inhibited cells which was rescued by concurrent caffeine treatment. Caffeine-treated cells also displayed elevated peak oxidative metabolism which was partially abolished following PPARβ/δ inhibition. Similar to past observations, glucose uptake and GLUT4 content were elevated in caffeine-treated cells, however, glycolytic metabolism was unaltered following caffeine treatment. Physiological levels of caffeine appear to enhance cell metabolism through mechanisms partially dependent on PPARβ/δ.

Isolation and partial characterization of mutants with elevated lipid content in Chlorella sorokiniana and Scenedesmus obliquus.

PubMed

Vigeolas, Hélène; Duby, Francéline; Kaymak, Esra; Niessen, Guillaume; Motte, Patrick; Franck, Fabrice; Remacle, Claire

2012-11-30

This paper describes the isolation and partial biomass characterization of high triacylglycerol (TAG) mutants of Chlorella sorokiniana and Scenedesmus obliquus, two algal species considered as potential source of biodiesel. Following UV mutagenesis, 2000 Chlorella and 2800 Scenedesmus colonies were screened with a method based on Nile Red fluorescence. Several mutants with high Nile Red fluorescence were selected by this high-throughput method in both species. Growth and biomass parameters of the strongest mutants were analyzed in detail. All of the four Chlorella mutants showed no significant changes in growth rate, cell weight, cell size, protein and chlorophyll contents on a per cell basis. Whereas all contained elevated total lipid and TAG content per unit of dry weight, two of them were also affected for starch metabolism, suggesting a change in biomass/storage carbohydrate composition. Two Scenedesmus mutants showed a 1.5 and 2-fold increased cell weight and larger cells compared to the wild type, which led to a general increase of biomass including total lipid and TAG content on a per cell basis. Such mutants could subsequently be used as commercial oleaginous algae and serve as an alternative to conventional petrol. Copyright © 2012 Elsevier B.V. All rights reserved.

Effects of perceived stress and uplifts on inflammation and coagulability.

PubMed

Jain, Shamini; Mills, Paul J; von Känel, Roland; Hong, Suzi; Dimsdale, Joel E

2007-01-01

We investigated whether depressed mood and chronic hassles and uplifts predicted levels of hemostasis markers D-Dimer and type-1 plasminogen activator inhibitor (PAI-1), as well as the proinflammatory markers interleukin-6 (IL-6) and soluble intercellular adhesion molecule-1 (sICAM-1) in 108 healthy individuals. One hundred eight African-American and Euro-American men and women were studied (58 men, 50 women; mean age = 36.5 +/- 8 years). D-Dimer, PAI-1, IL-6, and sICAM-1 plasma levels were analyzed from fasting venous blood samples. Data were analyzed via hierarchical linear regression and followed with partial correlation analysis. Regression analyses combined with partial correlation analyses suggested that increases in hassle frequency predicted elevated levels of sICAM-1 (p= .034), and increases in hassle severity predicted elevated levels of D-Dimer (p= .017). Increases in uplift intensity predicted lower levels of PAI-1 (p= .004) as well as showed a trend for decreased IL-6 (p= .069). Depressed mood did not significantly predict any dependent variable. These results were independent of sociodemographic, biological, and other related mood variables. The findings suggest that for even relatively healthy persons, increased perceptions of hassles are independently associated with greater inflammation and hypercoagulability, whereas increased perceptions of uplifts are independently associated with decreased hypercoagulability.

Partial loss of Smad7 function impairs bone remodeling, osteogenesis and enhances osteoclastogenesis in mice.

PubMed

Li, Nan; Lee, Wayne Yuk-Wai; Lin, Si-En; Ni, Ming; Zhang, Ting; Huang, Xiao-Ru; Lan, Hui-Yao; Li, Gang

2014-10-01

Smad7 is well demonstrated as a negative regulator of TGF-β signaling. Its alteration in expression often results in diseases such as cancer and fibrosis. However, the exact role of Smad7 in regulating bone remodeling during mammalian development has not been properly delineated. In this study we performed experiments to clarify the involvement of Smad7 in regulating osteogenesis and osteoclastogenesis both invivo and invitro. Genetically engineered Smad7(ΔE1) (KO) mice were used, whereby partial functional of Smad7 is lost by deleting exon I of the Smad7 gene and the truncated proteins cause a hypomorphic allele. Analysis with μCT imagery and bone histomorphometry showed that the KO mice had lower TbN, TbTh, higher TbSp in the metaphysic region of the femurs at 6, 12, 24weeks from birth, as well as decreased MAR and increased osteoclast surface compared with the WT mice. In vitro BM-MSC multi-lineage differentiation evaluation showed that the KO group had reduced osteogenic potential, fewer mineralized nodules, lower ALP activity, and reduced gene expression of Col1A1, Runx2 and OCN. The adipogenic potential was elevated in the KO group with more formation of lipid droplets, and increased gene expression of Adipsin and C/EBPα. The osteoclastogenic potential of KO mice BMMs was elevate, with emergence of more osteoclasts, larger resorptive areas, and increased gene expression of TRAP and CTR. Our results indicate that partial loss of Smad7 function in mice leads to compromised bone formation and enhanced bone resorption. Thus, Smad7 is acknowledged as a novel key regulator between osteogenesis and osteoclastogenesis. Copyright © 2014 Elsevier Inc. All rights reserved.

The effect of the perfluorocarbon emulsion Oxycyte on platelet count and function in the treatment of decompression sickness in a swine model.

PubMed

Cronin, William A; Senese, Angela L; Arnaud, Francoise G; Regis, David P; Auker, Charles R; Mahon, Richard T

2016-09-01

Decompression from elevated ambient pressure is associated with platelet activation and decreased platelet counts. Standard treatment for decompression sickness (DCS) is hyperbaric oxygen therapy. Intravenous perfluorocarbon (PFC) emulsion is a nonrecompressive therapy being examined that improves mortality in animal models of DCS. However, PFC emulsions are associated with a decreased platelet count. We used a swine model of DCS to study the effect of PFC therapy on platelet count, function, and hemostasis. Castrated male swine (n = 50) were fitted with a vascular port, recovered, randomized, and compressed to 180 feet of sea water (fsw) for 31 min followed by decompression at 30 fsw/min. Animals were observed for DCS, administered 100% oxygen, and treated with either emulsified PFC Oxycyte (DCS-PFC) or isotonic saline (DCS-NS). Controls underwent the same procedures, but were not compressed (Sham-PFC and Sham-NS). Measurements of platelet count, thromboelastometry, and coagulation were obtained 1 h before compression and 1, 24, 48, 96, 168 and 192 h after treatment. No significant changes in normalized platelet counts were observed. Prothrombin time was elevated in DCS-PFC from 48 to 192 h compared with DCS-NS, and from 96 to 192 h compared with Sham-PFC. Normalized activated partial thromboplastin time was also elevated in DCS-PFC from 168 to 192 h compared with Sham-PFC. No bleeding events were noted. DCS treated with PFC (Oxycyte) does not impact platelet numbers, whole blood clotting by thromboelastometry, or clinical bleeding. Late changes in prothrombin time and activated partial thromboplastin time associated with PFC use in both DCS therapy and controls warrant further investigation.

Jumonji Domain Containing Protein 6: A Novel Oxygen Sensor in the Human Placenta.

PubMed

Alahari, Sruthi; Post, Martin; Caniggia, Isabella

2015-08-01

Persistent low oxygen is implicated in the pathogenesis of placental-associated pathologies such as preeclampsia, a serious disorder of pregnancy. Emerging evidence implicates a novel family of Jumonji C catalytic domain proteins as mediators of hypoxic gene expression. Here, we investigated the regulatory relationship between Jumonji C domain containing protein 6 (JMJD6) and hypoxia-inducible factor (HIF)1A in the human placenta at physiological and pathological conditions. JMJD6 expression inversely correlated with changes in oxygen tension during early placental development, ie, high at 7-9 weeks when-partial pressure of O2 is low and declining afterwards when-partial pressure of O2 increases. Moreover, JMJD6 protein was significantly elevated in early-onset preeclamptic placentae, localizing to the syncytiotrophoblast layer and syncytial knots. Exposure of primary isolated trophoblast cells, human villous explants, and JEG3 choriocarcinoma cells to low oxygen (3%) and sodium nitroprusside (inducer of oxidative stress) also resulted in elevated JMJD6 levels, which was abrogated by HIF1A knockdown. In normoxia, knockdown of JMJD6 in JEG3 cells stabilized HIF1A with a concomitant decrease in von Hippel-Lindau (VHL) tumor suppressor protein, a negative regulator of HIF1A stability. In contrast, overexpression of JMJD6 enhanced VHL expression and destabilized HIF1A. JMJD6 regulation of VHL stability did not involve the ubiquitin-proteasome system but likely occurred through lysyl hydroxylation and small ubiquitin-like modifier 1-dependent small ubiquitin-like modifierylation. In summary, our data signify a novel role for JMJD6 as an oxygen sensor in the human placenta, and alterations in the JMJD6-VHL-HIF1A feedback loop may indirectly contribute to elevated HIF1A found in preeclampsia.

Effect of different seated positions on lung volume and oxygenation in acute respiratory distress syndrome.

PubMed

Dellamonica, J; Lerolle, N; Sargentini, C; Hubert, S; Beduneau, G; Di Marco, F; Mercat, A; Diehl, J L; Richard, J C M; Bernardin, G; Brochard, L

2013-06-01

Lung volume available for ventilation is markedly decreased during acute respiratory distress syndrome. Body positioning may contribute to increase lung volume and partial verticalization is simple to perform. This study evaluated whether verticalization had parallel effects on oxygenation and end expiratory lung volume (EELV). Prospective multicenter study in 40 mechanically ventilated patients with ALI/ARDS in five university hospital MICUs. We evaluated four 45-min successive trunk position epochs (supine slightly elevated at 15°; semi recumbent with trunk elevated at 45°; seated with trunk elevated at 60° and legs down at 45°; back to supine). Arterial blood gases, EELV measured using the nitrogen washin/washout, and static compliance were measured. Responders were defined by a PaO₂/FiO₂ increase >20 % between supine and seated position. Results are median [25th-75th percentiles]. With median PEEP = 10 cmH₂O, verticalization increased lung volume but only responders (13 patients, 32 %) had a significant increase in EELV/PBW (predicted body weight) compared to baseline. This increase persisted at least partially when patients were positioned back to supine. Responders had a lower EELV/PBW supine [14 mL/kg (13-15) vs. 18 mL/kg (15-27) (p = 0.005)] and a lower compliance [30 mL/cmH₂O (22-38) vs. 42 (30-46) (p = 0.01)] than non-responders. Strain decreased with verticalization for responders. EELV/PBW increase and PaO₂/FiO₂ increase were not correlated. Verticalization is easily achieved and improves oxygenation in approximately 32 % of the patients together with an increase in EELV. Nonetheless, effect of verticalization on EELV/PBW is not predictable by PaO₂/FiO₂ increase, its monitoring may be helpful for strain optimization.

Emotional Reactivity, Behavior Problems, and Social Adjustment at School Entry in a High-risk Sample

PubMed Central

Kalvin, Carla B.; Bierman, Karen L.; Gatzke-Kopp, Lisa M.

2016-01-01

Prior research suggests that heightened emotional reactivity to emotionally distressing stimuli may be associated with elevated internalizing and externalizing behaviors, and contribute to impaired social functioning. These links were explored in a sample of 169 economically-disadvantaged kindergarteners (66 % male; 68 % African American, 22 % Hispanic, 10 % Caucasian) oversampled for elevated aggression. Physiological measures of emotional reactivity (respiratory sinus arrhythmia [RSA], heart rate [HR], and cardiac pre-ejection period [PEP]) were collected, and teachers and peers provided ratings of externalizing and internalizing behavior, prosocial competence, and peer rejection. RSA withdrawal, HR reactivity, and PEP shortening (indicating increased arousal) were correlated with reduced prosocial competence, and RSA withdrawal and HR reactivity were correlated with elevated internalizing problems. HR reactivity was also correlated with elevated externalizing problems and peer rejection. Linear regressions controlling for age, sex, race, verbal proficiency, and resting physiology showed that HR reactivity explained unique variance in both teacher-rated prosocial competence and peer rejection, and contributed indirectly to these outcomes through pathways mediated by internalizing and externalizing problems. A trend also emerged for the unique contribution of PEP reactivity to peer-rated prosocial competence. These findings support the contribution of emotional reactivity to behavior problems and social adjustment among children living in disadvantaged urban contexts, and further suggest that elevated reactivity may confer risk for social difficulties in ways that overlap only partially with internalizing and externalizing behavior problems. PMID:26943804

Association of Fibroblast Growth Factor 23 With Atrial Fibrillation in Chronic Kidney Disease, From the Chronic Renal Insufficiency Cohort Study

PubMed Central

Mehta, Rupal; Cai, Xuan; Lee, Jungwha; Scialla, Julia J.; Bansal, Nisha; Sondheimer, James H.; Chen, Jing; Hamm, L. Lee; Ricardo, Ana C.; Navaneethan, Sankar D.; Deo, Rajat; Rahman, Mahboob; Feldman, Harold I.; Go, Alan S.; Isakova, Tamara; Wolf, Myles

2016-01-01

Importance Levels of fibroblast growth factor 23 (FGF23) are elevated in chronic kidney disease (CKD) and strongly associated with left ventricular hypertrophy, heart failure, and death. Whether FGF23 is an independent risk factor for atrial fibrillation in CKD is unknown. Objective To investigate the association of FGF23 with atrial fibrillation in CKD. Design, Setting, and Participants Prospective cohort study of 3876 individuals with mild to severe CKD who enrolled in the Chronic Renal Insufficiency Cohort Study between June 19, 2003, and September 3, 2008, and were followed up through March 31, 2013. Exposures Baseline plasma FGF23 levels. Main Outcomes and Measures Prevalent and incident atrial fibrillation. Results The study cohort comprised 3876 participants. Their mean (SD) age was 57.7 (11.0) years, and 44.8% (1736 of 3876) were female. Elevated FGF23 levels were independently associated with increased odds of prevalent atrial fibrillation (n = 660) after adjustment for cardiovascular and CKD-specific factors (odds ratio of highest vs lowest FGF23 quartile, 2.30; 95% CI, 1.69-3.13; P < .001 for linear trend across quartiles). During a median follow-up of 7.6 years (interquartile range, 6.3-8.6 years), 247 of the 3216 participants who were at risk developed incident atrial fibrillation (11.9 events per 1000 person-years). In fully adjusted models, elevated FGF23 was independently associated with increased risk of incident atrial fibrillation after adjustment for demographic, cardiovascular, and CKD-specific factors, and other markers of mineral metabolism (hazard ratio of highest vs lowest FGF23 quartile, 1.59; 95% CI, 1.00-2.53; P = .02 for linear trend across quartiles). The results were unchanged when further adjusted for ejection fraction, but individual adjustments for left ventricular mass index, left atrial area, and interim heart failure events partially attenuated the association of elevated FGF23 with incident atrial fibrillation. Conclusions and Relevance Elevated FGF23 is independently associated with prevalent and incident atrial fibrillation in patients with mild to severe CKD. The effect may be partially mediated through a diastolic dysfunction pathway that includes left ventricular hypertrophy, atrial enlargement, and heart failure events. PMID:27434583

Phospho-eIF2α level is important for determining abilities of BACE1 reduction to rescue cholinergic neurodegeneration and memory defects in 5XFAD mice.

PubMed

Devi, Latha; Ohno, Masuo

2010-09-23

β-Site APP-cleaving enzyme 1 (BACE1) initiates amyloid-β (Aβ) generation and thus represents a prime therapeutic target in treating Alzheimer's disease (AD). Notably, increasing evidence indicates that BACE1 levels become elevated in AD brains as disease progresses; however, it remains unclear how the BACE1 upregulation may affect efficacies of therapeutic interventions including BACE1-inhibiting approaches. Here, we crossed heterozygous BACE1 knockout mice with AD transgenic mice (5XFAD model) and compared the abilities of partial BACE1 reduction to rescue AD-like phenotypes at earlier (6-month-old) and advanced (15-18-month-old) stages of disease, which expressed normal (∼100%) and elevated (∼200%) levels of BACE1, respectively. BACE1(+/-) deletion rescued memory deficits as tested by the spontaneous alternation Y-maze task in 5XFAD mice at the earlier stage and prevented their septohippocampal cholinergic deficits associated with significant neuronal loss. Importantly, BACE1(+/-) deletion was no longer able to rescue memory deficits or cholinergic neurodegeneration in 5XFAD mice at the advanced stage. Moreover, BACE1(+/-) deletion significantly reduced levels of Aβ42 and the β-secretase-cleaved C-terminal fragment (C99) in 6-month-old 5XFAD mouse brains, while these neurotoxic β-cleavage products dramatically elevated with age and were not affected by BACE1(+/-) deletion in 15-18-month-old 5XFAD brains. Interestingly, although BACE1(+/-) deletion lowered BACE1 expression by ∼50% in 5XFAD mice irrespective of age in concordance with the reduction in gene copy number, BACE1 equivalent to wild-type controls remained in BACE1(+/-)·5XFAD mice at the advanced age. In accord, phosphorylation of the translation initiation factor eIF2α, an important mediator of BACE1 elevation, was dramatically increased (∼9-fold) in 15-18-month-old 5XFAD mice and remained highly upregulated (∼6-fold) in age-matched BACE1(+/-)·5XFAD mice. Together, our results indicate that partial reduction of BACE1 is not sufficient to block the phospho-eIF2α-dependent BACE1 elevation during the progression of AD, thus limiting its abilities to reduce cerebral Aβ/C99 levels and rescue memory deficits and cholinergic neurodegeneration.

Restorative Effects of Uridine Plus Docosahexaenoic Acid in a Rat Model of Parkinson’s Disease

PubMed Central

Cansev, Mehmet; Ulus, Ismail H.; Wang, Lei; Maher, Timothy J.; Wurtman, Richard J.

2008-01-01

Summary Administering uridine-5’-monophosphate (UMP) and docosahexaenoic acid (DHA) increases synaptic membranes (as characterized by pre-and post-synaptic proteins) and dendritic spines in rodents. We examined their effects on rotational behavior and dopaminergic markers in rats with partial unilateral 6-hydroxydopamine (6-OHDA)-induced striatal lesions. Rats receiving UMP, DHA, both, or neither, daily, and intrastriatal 6-OHDA 3 days after treatment onset, were tested for d-amphetamine-induced rotational behavior and dopaminergic markers after 24 and 28 days, respectively. UMP/DHA treatment reduced ipsilateral rotations by 57% and significantly elevated striatal dopamine, tyrosine hydroxylase (TH) activity, TH protein and Synapsin-1 on the lesioned side. Hence, giving uridine and DHA may partially restore dopaminergic neurotransmission in this model of Parkinson’s Disease. PMID:18761383

Restorative effects of uridine plus docosahexaenoic acid in a rat model of Parkinson's disease.

PubMed

Cansev, Mehmet; Ulus, Ismail H; Wang, Lei; Maher, Timothy J; Wurtman, Richard J

2008-11-01

Administering uridine-5'-monophosphate (UMP) and docosahexaenoic acid (DHA) increases synaptic membranes (as characterized by pre- and post-synaptic proteins) and dendritic spines in rodents. We examined their effects on rotational behavior and dopaminergic markers in rats with partial unilateral 6-hydroxydopamine (6-OHDA)-induced striatal lesions. Rats receiving UMP, DHA, both, or neither, daily, and intrastriatal 6-OHDA 3 days after treatment onset, were tested for d-amphetamine-induced rotational behavior and dopaminergic markers after 24 and 28 days, respectively. UMP/DHA treatment reduced ipsilateral rotations by 57% and significantly elevated striatal dopamine, tyrosine hydroxylase (TH) activity, TH protein and synapsin-1 on the lesioned side. Hence, giving uridine and DHA may partially restore dopaminergic neurotransmission in this model of Parkinson's disease.

Partial exposure of frog heart to high-potassium solution: an easily reproducible model mimicking ST segment changes.

PubMed

Kon, Nobuaki; Abe, Nozomu; Miyazaki, Masahiro; Mushiake, Hajime; Kazama, Itsuro

2018-04-18

By simply inducing burn injuries on the bullfrog heart, we previously reported a simple model of abnormal ST segment changes observed in human ischemic heart disease. In the present study, instead of inducing burn injuries, we partially exposed the surface of the frog heart to high-potassium (K + ) solution to create a concentration gradient of the extracellular K + within the myocardium. Dual recordings of ECG and the cardiac action potential demonstrated significant elevation of the ST segment and the resting membrane potential, indicating its usefulness as a simple model of heart injury. Additionally, from our results, Na + /K + -ATPase activity was thought to be primarily responsible for generating the K + concentration gradient and inducing the ST segment changes in ECG.

Growth in elevated CO(2) can both increase and decrease photochemistry and photoinhibition of photosynthesis in a predictable manner. Dactylis glomerata grown in two levels of nitrogen nutrition.

PubMed

Hymus, G J; Baker, N R; Long, S P

2001-11-01

Biochemically based models of C(3) photosynthesis can be used to predict that when photosynthesis is limited by the amount of Rubisco, increasing atmospheric CO(2) partial pressure (pCO(2)) will increase light-saturated linear electron flow through photosystem II (J(t)). This is because the stimulation of electron flow to the photosynthetic carbon reduction cycle (J(c)) will be greater than the competitive suppression of electron flow to the photorespiratory carbon oxidation cycle (J(o)). Where elevated pCO(2) increases J(t), then the ratio of absorbed energy dissipated photochemically to that dissipated non-photochemically will rise. These predictions were tested on Dactylis glomerata grown in fully controlled environments, at either ambient (35 Pa) or elevated (65 Pa) pCO(2), and at two levels of nitrogen nutrition. As was predicted, for D. glomerata grown in high nitrogen, J(t) was significantly higher in plants grown and measured at elevated pCO(2) than for plants grown and measured at ambient pCO(2). This was due to a significant increase in J(c) exceeding any suppression of J(o). This increase in photochemistry at elevated pCO(2) protected against photoinhibition at high light. For plants grown at low nitrogen, J(t) was significantly lower in plants grown and measured at elevated pCO(2) than for plants grown and measured at ambient pCO(2). Elevated pCO(2) again suppressed J(o); however growth in elevated pCO(2) resulted in an acclimatory decrease in leaf Rubisco content that removed any stimulation of J(c). Consistent with decreased photochemistry, for leaves grown at low nitrogen, the recovery from a 3-h photoinhibitory treatment was slower at elevated pCO(2).

Fish allergy causing angioedema and secondary angle-closure glaucoma.

PubMed

Calder, Donovan; Calder, Jennifer

2013-03-06

A 56-year-old woman with a history of primary angle-closure glaucoma presented with acute generalised swelling, and facial angioedema following a fish meal. She complained of nausea, vomiting, headache, pain in both eyes and acute loss of vision. Her visual acuity was reduced and intraocular pressures (IOP) were elevated. Gonioscopy revealed complete angle closure in the left eye and complete to partial closure in the right eye. Through existing peripheral iridotomies the anterior capsules were seen pressed up against the iris of both eyes. A diagnosis of angle-closure glaucoma was made, medications were started to reduce the elevated intraocular pressure and systemic antihistamine to counter the allergic reaction. She was hospitalised for further management. A follow-up at 2 years revealed her visual acuities and IOP had remained normal.

Water resources data, Kansas, water year 2004

USGS Publications Warehouse

Putnam, J.E.; Schneider, D.R.

2005-01-01

Water-resources data for the 2004 water year for Kansas consist of records of stage, discharge, and water quality of streams; elevation and contents of lakes and reservoirs; and water levels of ground-water wells. This report contains records for water discharge at 155 complete-record gaging stations; elevation and contents at 17 lakes and reservoirs; water-quality records at 2 precipitation stations, water-level data at 14 observation wells; and records of specific conductance, pH, water temperature, dissolved oxygen, and turbidity at 16 gaging stations and 2 lakes with water-quality monitors. Also included are discharge data for 29 high-flow partial-record stations. These data represent that part of the National Water Information System collected by the U.S. Geological Survey in cooperation with local, State, and Federal agencies in Kansas.

Procapra picticaudata (Artiodactyla: Bovidae)

USGS Publications Warehouse

Leslie, David M.

2010-01-01

Procapra picticaudata Hodgson, 1846, is commonly called the Tibetan gazelle, goa (= Tibetan), or zang yuan ling (= Chinese) and is monotypic. It is a high-elevation specialist endemic to the Tibetan Plateau where it prefers alpine meadow and alpine steppe but uses other lower-elevation plains and valleys. It is partial to good grasslands with high diversity of forbs. There have been no systematic estimates of total numbers of P. picticaudata. Populations are currently widespread but have been reduced from historic levels and are vulnerable because of poaching in remote areas and competition with livestock of pastoralists. P. picticaudata is uncommon in zoos and private collections. It is a threatened Class II species in China and considered “Near Threatened" by the International Union for Conservation of Nature and Natural Resources.

Acute metabolic and physiologic response of goats to narcosis

NASA Technical Reports Server (NTRS)

Schatte, C. L.; Bennett, P. B.

1973-01-01

Assessment of the metabolic consequences of exposure to elevated partial pressures of nitrogen and helium under normobaric and hyperbaric conditions in goats. The results include the finding that hyperbaric nitrogen causes and increase in metabolic rate and a general decrease in blood constituent levels which is interpreted as reflecting a shift toward fatty acid metabolism at the expense of carbohydrates. A similar but more pronounced pattern was observed with hyperbaric helium.

Gobi Desert, China as seen from STS-59

NASA Image and Video Library

1994-04-14

STS059-220-041 (9-20 April 1994) --- View to the south by southwest across the southern Gobi Desert (China) across the Chi-Lien-Shan or Quilienshan or Nanshan (Mountains) in Gansu Province to Lake Quinghai or Ch'ing-Hai (orthography varies with political conditions and scholarship) in Quinghai Province. The lake has a surface elevation of 10,450 feet, partially filling one of the easternmost closed drainage basins of Central Asia. Hasselblad photograph.

11. photographer unknown 3 September 1984 AERIAL VIEW OF BONNEVILLE ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

11. photographer unknown 3 September 1984 AERIAL VIEW OF BONNEVILLE PROJECT TAKEN AT 6000-FOOT ELEVATION. POWERHOUSE #1 AND NAVIGATION LOCK ARE IN UPPER/CENTER PART OF PHOTO, AND THE DAM/SPILLWAY IS IN LEFT/CENTER; THE SECOND POWERHOUSE IS PARTIALLY VISIBLE IN LOWER LEFT CORNER. COLUMBIA RIVER FLOWS FROM LEFT-TO-RIGHT. - Bonneville Project, Columbia River, 1 mile Northeast of Exit 40, off Interstate 84, Bonneville, Multnomah County, OR

Environmental Assessment for Selected Capital Improvement Plan (CIP) Projects

DTIC Science & Technology

2009-01-01

the USACE Wetlands Delineation Manual as ”those areas that are inundated or saturated by surface or ground water at a frequency and duration... potential for a conventional water supply (Air Force 2000a). Due to its proximity to the Back River and the Chesapeake Bay, and its low ground elevation...coincide, even partially, in time would tend to offer a higher potential for cumulative effects . To identify cumulative effects , this EA addresses three

Heavy Metal Contaminated Soil Treatment: Conceptual Development

DTIC Science & Technology

1987-02-01

utilized, particularly for trivalent chromium . ’Breakthrough did eventually occur, due to the coating of the crushed limestone, with only partial...characterizations indicated that several Army installations had elevated total metal concentrations in their soils and Chromium , Cadmium and Lead were the most...2,2000 F) were effective in reducing chromium levels below 1 mg/L in both boiling water and weak acid (pH 5; H2 SO 4) extractions. These extractions were

The Mechanism of Blood Function and Production After Injury.

DTIC Science & Technology

1980-02-01

radioactive 59Fe labeled red cell dilution method described by Garcia7 . Red cell 2,3 diphosphoglycerate levels were measured using a commercial kit...and protein depleted rats was also associated with elevated 2,3 diphosphoglycerate levels (p<.05)(Table IV) suggesting partial compensation for anemic...Brewer, G.J.: The relationship between red cell 2,3 diphosphoglycerate and levels of hemoglobin in the human. Proc.Soc. Exp.Biol.Med. 150(1): 215-9

Spatial and temporal functional changes in alpine summit vegetation are driven by increases in shrubs and graminoids.

PubMed

Venn, Susanna; Pickering, Catherine; Green, Ken

2014-01-01

Classical approaches to investigating temporal and spatial changes in community composition offer only partial insight into the ecology that drives species distribution, community patterns and processes, whereas a functional approach can help to determine many of the underlying mechanisms that drive such patterns. Here, we aim to bring these two approaches together to understand such drivers, using an elevation gradient of sites, a repeat species survey and species functional traits. We used data from a repeat vegetation survey on five alpine summits and measured plant height, leaf area, leaf dry matter content and specific leaf area (SLA) for every species recorded in the surveys. We combined species abundances with trait values to produce a community trait-weighted mean (CTWM) for each trait, and then combined survey results with the CTWMs. Across the gradient of summits, more favourable conditions for plant growth (warmer, longer growing season) occurred at the lower elevations. Vegetation composition changes between 2004 and 2011 (according to non-metric multi-dimensional scaling ordination) were strongly affected by the high and increasing abundance of species with high SLA at high elevations. Species life-form categories strongly affected compositional changes and functional composition, with increasing dominance of tall shrubs and graminoids at the lower-elevation summits, and an overall increase in graminoids across the gradient. The CTWM for plant height and leaf dry matter content significantly decreased with elevation, whereas for leaf area and SLA it significantly increased. The significant relationships between CTWM and elevation may suggest specific ecological processes, namely plant competition and local productivity, influencing vegetation preferentially across the elevation gradient, with the dominance of shrubs and graminoids driving the patterns in the CTWMs.

Spatial and temporal functional changes in alpine summit vegetation are driven by increases in shrubs and graminoids

PubMed Central

Venn, Susanna; Pickering, Catherine; Green, Ken

2014-01-01

Classical approaches to investigating temporal and spatial changes in community composition offer only partial insight into the ecology that drives species distribution, community patterns and processes, whereas a functional approach can help to determine many of the underlying mechanisms that drive such patterns. Here, we aim to bring these two approaches together to understand such drivers, using an elevation gradient of sites, a repeat species survey and species functional traits. We used data from a repeat vegetation survey on five alpine summits and measured plant height, leaf area, leaf dry matter content and specific leaf area (SLA) for every species recorded in the surveys. We combined species abundances with trait values to produce a community trait-weighted mean (CTWM) for each trait, and then combined survey results with the CTWMs. Across the gradient of summits, more favourable conditions for plant growth (warmer, longer growing season) occurred at the lower elevations. Vegetation composition changes between 2004 and 2011 (according to non-metric multi-dimensional scaling ordination) were strongly affected by the high and increasing abundance of species with high SLA at high elevations. Species life-form categories strongly affected compositional changes and functional composition, with increasing dominance of tall shrubs and graminoids at the lower-elevation summits, and an overall increase in graminoids across the gradient. The CTWM for plant height and leaf dry matter content significantly decreased with elevation, whereas for leaf area and SLA it significantly increased. The significant relationships between CTWM and elevation may suggest specific ecological processes, namely plant competition and local productivity, influencing vegetation preferentially across the elevation gradient, with the dominance of shrubs and graminoids driving the patterns in the CTWMs. PMID:24790129

Improving yield potential in crops under elevated CO2: Integrating the photosynthetic and nitrogen utilization efficiencies

PubMed Central

Kant, Surya; Seneweera, Saman; Rodin, Joakim; Materne, Michael; Burch, David; Rothstein, Steven J.; Spangenberg, German

2012-01-01

Increasing crop productivity to meet burgeoning human food demand is challenging under changing environmental conditions. Since industrial revolution atmospheric CO2 levels have linearly increased. Developing crop varieties with increased utilization of CO2 for photosynthesis is an urgent requirement to cope with the irreversible rise of atmospheric CO2 and achieve higher food production. The primary effects of elevated CO2 levels in most crop plants, particularly C3 plants, include increased biomass accumulation, although initial stimulation of net photosynthesis rate is only temporal and plants fail to sustain the maximal stimulation, a phenomenon known as photosynthesis acclimation. Despite this acclimation, grain yield is known to marginally increase under elevated CO2. The yield potential of C3 crops is limited by their capacity to exploit sufficient carbon. The “C fertilization” through elevated CO2 levels could potentially be used for substantial yield increase. Rubisco is the rate-limiting enzyme in photosynthesis and its activity is largely affected by atmospheric CO2 and nitrogen availability. In addition, maintenance of the C/N ratio is pivotal for various growth and development processes in plants governing yield and seed quality. For maximizing the benefits of elevated CO2, raising plant nitrogen pools will be necessary as part of maintaining an optimal C/N balance. In this review, we discuss potential causes for the stagnation in yield increases under elevated CO2 levels and explore possibilities to overcome this limitation by improved photosynthetic capacity and enhanced nitrogen use efficiency. Opportunities of engineering nitrogen uptake, assimilatory, and responsive genes are also discussed that could ensure optimal nitrogen allocation toward expanding source and sink tissues. This might avert photosynthetic acclimation partially or completely and drive for improved crop production under elevated CO2 levels. PMID:22833749

Improving yield potential in crops under elevated CO(2): Integrating the photosynthetic and nitrogen utilization efficiencies.

PubMed

Kant, Surya; Seneweera, Saman; Rodin, Joakim; Materne, Michael; Burch, David; Rothstein, Steven J; Spangenberg, German

2012-01-01

Increasing crop productivity to meet burgeoning human food demand is challenging under changing environmental conditions. Since industrial revolution atmospheric CO(2) levels have linearly increased. Developing crop varieties with increased utilization of CO(2) for photosynthesis is an urgent requirement to cope with the irreversible rise of atmospheric CO(2) and achieve higher food production. The primary effects of elevated CO(2) levels in most crop plants, particularly C(3) plants, include increased biomass accumulation, although initial stimulation of net photosynthesis rate is only temporal and plants fail to sustain the maximal stimulation, a phenomenon known as photosynthesis acclimation. Despite this acclimation, grain yield is known to marginally increase under elevated CO(2). The yield potential of C(3) crops is limited by their capacity to exploit sufficient carbon. The "C fertilization" through elevated CO(2) levels could potentially be used for substantial yield increase. Rubisco is the rate-limiting enzyme in photosynthesis and its activity is largely affected by atmospheric CO(2) and nitrogen availability. In addition, maintenance of the C/N ratio is pivotal for various growth and development processes in plants governing yield and seed quality. For maximizing the benefits of elevated CO(2), raising plant nitrogen pools will be necessary as part of maintaining an optimal C/N balance. In this review, we discuss potential causes for the stagnation in yield increases under elevated CO(2) levels and explore possibilities to overcome this limitation by improved photosynthetic capacity and enhanced nitrogen use efficiency. Opportunities of engineering nitrogen uptake, assimilatory, and responsive genes are also discussed that could ensure optimal nitrogen allocation toward expanding source and sink tissues. This might avert photosynthetic acclimation partially or completely and drive for improved crop production under elevated CO(2) levels.

Elevated temperature drives kelp microbiome dysbiosis, while elevated carbon dioxide induces water microbiome disruption

PubMed Central

Morris, Megan M.; Brown, Matt; Doane, Michael; Edwards, Matthew S.; Michael, Todd P.; Dinsdale, Elizabeth A.

2018-01-01

Global climate change includes rising temperatures and increased pCO2 concentrations in the ocean, with potential deleterious impacts on marine organisms. In this case study we conducted a four-week climate change incubation experiment, and tested the independent and combined effects of increased temperature and partial pressure of carbon dioxide (pCO2), on the microbiomes of a foundation species, the giant kelp Macrocystis pyrifera, and the surrounding water column. The water and kelp microbiome responded differently to each of the climate stressors. In the water microbiome, each condition caused an increase in a distinct microbial order, whereas the kelp microbiome exhibited a reduction in the dominant kelp-associated order, Alteromondales. The water column microbiomes were most disrupted by elevated pCO2, with a 7.3 fold increase in Rhizobiales. The kelp microbiome was most influenced by elevated temperature and elevated temperature in combination with elevated pCO2. Kelp growth was negatively associated with elevated temperature, and the kelp microbiome showed a 5.3 fold increase Flavobacteriales and a 2.2 fold increase alginate degrading enzymes and sulfated polysaccharides. In contrast, kelp growth was positively associated with the combination of high temperature and high pCO2 ‘future conditions’, with a 12.5 fold increase in Planctomycetales and 4.8 fold increase in Rhodobacteriales. Therefore, the water and kelp microbiomes acted as distinct communities, where the kelp was stabilizing the microbiome under changing pCO2 conditions, but lost control at high temperature. Under future conditions, a new equilibrium between the kelp and the microbiome was potentially reached, where the kelp grew rapidly and the commensal microbes responded to an increase in mucus production. PMID:29474389

Community structure and elevational diversity patterns of soil Acidobacteria.

PubMed

Zhang, Yuguang; Cong, Jing; Lu, Hui; Li, Guangliang; Qu, Yuanyuan; Su, Xiujiang; Zhou, Jizhong; Li, Diqiang

2014-08-01

Acidobacteria is one of the most dominant and abundant phyla in soil, and was believed to have a wide range of metabolic and genetic functions. Relatively little is known about its community structure and elevational diversity patterns. We selected four elevation gradients from 1000 to 2800 m with typical vegetation types of the northern slope of Shennongjia Mountain in central China. The vegetation types were evergreen broadleaved forest, deciduous broadleaved forest, coniferous forest and sub-alpine shrubs. We analyzed the soil acidobacterial community composition, elevational patterns and the relationship between Acidobacteria subdivisions and soil enzyme activities by using the 16S rRNA meta-sequencing technique and multivariate statistical analysis. The result found that 19 known subdivisions as well as an unclassified phylotype were presented in these forest sites, and Subdivision 6 has the highest number of detectable operational taxonomic units (OTUs). A significant single peak distribution pattern (P<0.05) between the OTU number and the elevation was observed. The Jaccard and Bray-Curtis index analysis showed that the soil Acidobacteria compositional similarity significantly decreased (P<0.01) with the increase in elevation distance. Mantel test analysis showed the most of the soil Acidobacteria subdivisions had the significant relationship (P<0.01) with different soil enzymes. Therefore, soil Acidobacteria may be involved in different ecosystem functions in global elemental cycles. Partial Mantel tests and CCA analysis showed that soil pH, soil temperature and plant diversity may be the key factors in shaping the soil Acidobacterial community structure. Copyright © 2014. Published by Elsevier B.V.

Seedling ecology and restoration of blackbrush (Coleogyne ramosissima) in the Mojave Desert, United States

USGS Publications Warehouse

Jones, Lisa C.; Schwinning, Susanne; Esque, Todd C.

2014-01-01

Increases in fire frequency are disrupting many ecological communities not historically subjected to fire. In the southwestern United States, the blackbrush (Coleogyne ramosissima) community is among the most threatened, often replaced by invasive annual grasses after fire. This long-lived shrub is vulnerable because it recruits sporadically, partially due to mast seeding and the absence of a seed bank. The goal of this study was to evaluate if shrub restoration can be enhanced by identifying and ameliorating recruitment limitations. Specifically, we tested the effect of encapsulating seeds in predation-deterring “seed balls.” We also tested the effects of nurse plants and mammalian exclusion cages on seedling emergence, growth, and survivorship. These experiments were conducted in a full-factorial design across three sites differing in elevation. Over 2 years, 13% of all planted seeds emerged and the effect of seed balls was overwhelmingly negative because of low emergence. Nurse plants had overall positive effects at Low Elevation, but negative effects at Mid- and High Elevation. Emergence and survival were highest in caged plots everywhere, and effect sizes increased with elevation. Interactions between the cage and the nurse plant treatments indicated that nurse plants tended to attract mammalian predators, lowering emergence and seedling survivorship, particularly at higher elevations. Findings conform to the stress-gradient hypothesis in that interactions among seedlings and mature plants shifted from facilitation to competition as environmental stress decreased with increasing elevation, suggesting that they are transferable to ecologically similar communities elsewhere. Knowledge of site-specific recruitment limitations can help minimize ineffective restoration efforts.

Co-administration of α-lipoic acid and cyclosporine aggravates colon ulceration of acetic acid-induced ulcerative colitis via facilitation of NO/COX-2/miR-210 cascade

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

El-Gowelli, Hanan M., E-mail: dr_Hanan_el_gowali@hotmail.com; Saad, Evan I.; Abdel-Galil, Abdel-Galil A.

In this work, α-lipoic acid and cyclosporine demonstrated significant protection against acetic acid-induced ulcerative colitis in rats. We proposed that α-lipoic acid and cyclosporine co-administration might modulate their individual effects. Induction of ulcerative colitis in rats was performed by intra-rectal acetic acid (5% v/v) administration for 3 consecutive days. Effects of individual or combined used of α-lipoic acid (35 mg/kg ip) or cyclosporine (5 mg/kg sc) for 6 days starting 2 days prior to acetic acid were assessed. Acetic acid caused colon ulceration, bloody diarrhea and weight loss. Histologically, there was mucosal atrophy and inflammatory cells infiltration in submucosa, associatedmore » with depletion of colon reduced glutathione, superoxide dismutase and catalase activities and elevated colon malondialdehyde, serum C-reactive protein (C-RP) and tumor necrosis factor-α (TNF-α). Colon gene expression of cyclooxygenase-2 and miR-210 was also elevated. These devastating effects of acetic acid were abolished upon concurrent administration of α-lipoic acid. Alternatively, cyclosporine caused partial protection against acetic acid-induced ulcerative colitis. Cyclosporine did not restore colon reduced glutathione, catalase activity, serum C-RP or TNF-α. Unexpectedly, co-administration of α-lipoic acid and cyclosporine aggravated colon ulceration. Concomitant use of α-lipoic acid and cyclosporine significantly increased nitric oxide production, cyclooxygenase-2 and miR-210 gene expression compared to all other studied groups. The current findings suggest that facilitation of nitric oxide/cyclooxygenase-2/miR-210 cascade constitutes, at least partially, the cellular mechanism by which concurrent use of α-lipoic acid and cyclosporine aggravates colon damage. Collectively, the present work highlights the probable risk of using α-lipoic acid/cyclosporine combination in ulcerative colitis patients. - Highlights: • Lipoic acid is more effective than cyclosporine in protection against colitis. • Lipoic acid elevates colon antioxidant defensive mechanism and reduces inflammation. • Co-administration of lipoic acid and cyclosporine aggravates colon damage. • NO/COX-2/miR-210 elevations mediate cyclosporine–lipoic acid interaction.« less

Full fusion of proximal thoracic curve helps to prevent postoperative cervical tilt in Lenke type 2 adolescent idiopathic scoliosis patients with right-elevated shoulder.

PubMed

Jiang, Jun; Qian, Bang-Ping; Qiu, Yong; Wang, Bin; Yu, Yang; Zhu, Ze-Zhang

2017-08-23

To date, no study had reported the phenomenon of deteriorated postoperative cervical tilt in Lenke type 2 adolescent idiopathic scoliosis patients. The purpose of this study is to evaluate the cervical tilt in Lenke type 2 adolescent idiopathic scoliosis patients with right-elevated shoulder treated by either full fusion or partial/non fusion of the proximal thoracic curve. A total of 30 Lenke type 2 AIS patients with preoperative right-elevated shoulder underwent posterior spinal instrumentation from 2009 to 2011 were included in this study. All the subjects were divided into 2 groups according to the selection of upper instrumented vertebra. There were 14 cases proximally fused to T1 or T2 (Group A) and 16 cases proximally fused to T3 or below (Group B). Both standing anteroposterior and sagittal X-ray films of the spine obtained preoperatively, one week after the operation, and at a minimum of two-year follow-up were analyzed with respect to the following parameters: cervical tilt, T1 tilt, proximal thoracic Cobb angle, main thoracic Cobb angle, apical vertebral translation of proximal thoracic curve, apical vertebral translation of main thoracic curve, radiographic shoulder height, cervical lordosis, proximal thoracic kyphosis and main thoracic kyphosis. Most (83.3%) of the patients in these two groups gained satisfactory shoulder balance after surgery. However, the cervical tilt significantly improved in group A (p < 0.001) but deteriorated in group B (p < 0.001). In group A, the decrease of cervical tilt significantly positively correlated with that of T1 tilt (p < 0.001). In group B, the increase of cervical tilt significantly positively correlated with both the increase of T1 tilt (p < 0.001) and the increase of apical vertebral translation of proximal thoracic curve (p < 0.05). Lenke type 2 AIS patients with right-elevated shoulder gain improved shoulder but deteriorated cervical tilt after partial/non fusion of proximal thoracic curve. Full fusion of proximal thoracic curve helps to prevent the residual cervical tilt in these patients.

Determination of partial molar volumes from free energy perturbation theory†

PubMed Central

Vilseck, Jonah Z.; Tirado-Rives, Julian

2016-01-01

Partial molar volume is an important thermodynamic property that gives insights into molecular size and intermolecular interactions in solution. Theoretical frameworks for determining the partial molar volume (V°) of a solvated molecule generally apply Scaled Particle Theory or Kirkwood–Buff theory. With the current abilities to perform long molecular dynamics and Monte Carlo simulations, more direct methods are gaining popularity, such as computing V° directly as the difference in computed volume from two simulations, one with a solute present and another without. Thermodynamically, V° can also be determined as the pressure derivative of the free energy of solvation in the limit of infinite dilution. Both approaches are considered herein with the use of free energy perturbation (FEP) calculations to compute the necessary free energies of solvation at elevated pressures. Absolute and relative partial molar volumes are computed for benzene and benzene derivatives using the OPLS-AA force field. The mean unsigned error for all molecules is 2.8 cm3 mol−1. The present methodology should find use in many contexts such as the development and testing of force fields for use in computer simulations of organic and biomolecular systems, as a complement to related experimental studies, and to develop a deeper understanding of solute–solvent interactions. PMID:25589343

Determination of partial molar volumes from free energy perturbation theory.

PubMed

Vilseck, Jonah Z; Tirado-Rives, Julian; Jorgensen, William L

2015-04-07

Partial molar volume is an important thermodynamic property that gives insights into molecular size and intermolecular interactions in solution. Theoretical frameworks for determining the partial molar volume (V°) of a solvated molecule generally apply Scaled Particle Theory or Kirkwood-Buff theory. With the current abilities to perform long molecular dynamics and Monte Carlo simulations, more direct methods are gaining popularity, such as computing V° directly as the difference in computed volume from two simulations, one with a solute present and another without. Thermodynamically, V° can also be determined as the pressure derivative of the free energy of solvation in the limit of infinite dilution. Both approaches are considered herein with the use of free energy perturbation (FEP) calculations to compute the necessary free energies of solvation at elevated pressures. Absolute and relative partial molar volumes are computed for benzene and benzene derivatives using the OPLS-AA force field. The mean unsigned error for all molecules is 2.8 cm(3) mol(-1). The present methodology should find use in many contexts such as the development and testing of force fields for use in computer simulations of organic and biomolecular systems, as a complement to related experimental studies, and to develop a deeper understanding of solute-solvent interactions.

Defining Recovery from an Eating Disorder: Conceptualization, Validation, and Examination of Psychosocial Functioning and Psychiatric Comorbidity

PubMed Central

Bardone-Cone, Anna M.; Harney, Megan B.; Maldonado, Christine R.; Lawson, Melissa A.; Robinson, D. Paul; Smith, Roma; Tosh, Aneesh

2009-01-01

Conceptually, eating disorder recovery should include physical, behavioral, and psychological components, but such a comprehensive approach has not been consistently employed. Guided by theory and recent recovery research, we identified a “fully recovered” group (n=20) based on physical (body mass index), behavioral (absence of eating disorder behaviors), and psychological (Eating Disorder Examination-Questionnaire) indices, and compared them with groups of partially recovered (n=15), active eating disorder (n=53), and healthy controls (n=67). The fully recovered group was indistinguishable from controls on all eating disorder-related measures used, while the partially recovered group was less disordered than the active eating disorder group on some measures, but not on body image. Regarding psychosocial functioning, both the fully and partially recovered groups had psychosocial functioning similar to the controls, but there was a pattern of more of the partially recovered group reporting eating disorder aspects interfering with functioning. Regarding other psychopathology, the fully recovered group was no more likely than the controls to experience current Axis I pathology, but they did have elevated rates of current anxiety disorder. Results suggest that a stringent definition of recovery from an eating disorder is meaningful. Clinical implications and future directions regarding defining eating disorder recovery are discussed. PMID:19945094

Oxidation of manganese in an ancient aquifer, Kimberley formation, Gale crater, Mars

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

Lanza, Nina L.; Wiens, Roger C.; Arvidson, Raymond E.

We report that the Curiosity rover observed high Mn abundances (>25 wt % MnO) in fracture-filling materials that crosscut sandstones in the Kimberley region of Gale crater, Mars. The correlation between Mn and trace metal abundances plus the lack of correlation between Mn and elements such as S, Cl, and C, reveals that these deposits are Mn oxides rather than evaporites or other salts. On Earth, environments that concentrate Mn and deposit Mn minerals require water and highly oxidizing conditions; hence, these findings suggest that similar processes occurred on Mars. In conclusion, based on the strong association between Mn-oxide depositionmore » and evolving atmospheric dioxygen levels on Earth, the presence of these Mn phases on Mars suggests that there was more abundant molecular oxygen within the atmosphere and some groundwaters of ancient Mars than in the present day.« less

Modeling tyrosinase activity. Effect of ligand topology on aromatic ring hydroxylation: an overview.

PubMed

De, Anindita; Mandal, Sukanta; Mukherjee, Rabindranath

2008-01-01

Synthetic modeling of tyrosinase (o-phenol ring hydroxylation) has emerged as a novel class of successful biomimetic studies. It is a well-established fact that the reaction of dioxygen with copper(I) complexes of m-xylyl-based ligands generate putative copper-oxygen intermediate species such as side-on peroxo {CuII2(mu-O2)}2+ [in some cases bis-oxo {CuIII2(mu-O)2}2+ in equilibrium with isomeric side-on peroxo], due to oxygen activation. Electrophilic attack of such species brings about monooxygenase activity by incorporating one of the oxygens to m-xylyl ring of the ligand and the other oxygen is reduced to hydroxide ion. The goal of this review is to provide a concise overview of the present day knowledge in this field of research to emphasize the important role the designed ligands play in eliciting the desired tyrosinase-like chemistry.

Enzymatic biofuel cell based on electrodes modified with lipid liquid-crystalline cubic phases

NASA Astrophysics Data System (ADS)

Nazaruk, Ewa; Smoliński, Sławomir; Swatko-Ossor, Marta; Ginalska, Grażyna; Fiedurek, Jan; Rogalski, Jerzy; Bilewicz, Renata

Two glassy carbon electrodes modified with enzymes embedded in lyotropic liquid-crystalline cubic phase were used for the biofuel cell construction. The monoolein liquid-crystalline film allowed to avoid separators in the biofuel cell. Glucose and oxygen as fuels, and glucose oxidase and laccase as anode and cathode biocatalysts, respectively were used. The biofuel cell parameters were examined in McIlvaine buffer, pH 7 solution containing 15 mM of glucose and saturated with dioxygen. A series of mediators were tested taking into account their formal potentials, stability in the cubic phase and efficiency of mediation. Most stable was the biofuel cell based on tetrathiafulvalene (TTF) and 2,2‧-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) as anode and cathode mediators, respectively. The open-circuit voltage was equal to 450 ± 40 mV. The power densities and current densities were measured for all the systems studied.

Biological nitric oxide signalling: chemistry and terminology

PubMed Central

Heinrich, Tassiele A; da Silva, Roberto S; Miranda, Katrina M; Switzer, Christopher H; Wink, David A; Fukuto, Jon M

2013-01-01

Biological nitrogen oxide signalling and stress is an area of extreme clinical, pharmacological, toxicological, biochemical and chemical research interest. The utility of nitric oxide and derived species as signalling agents is due to their novel and vast chemical interactions with a variety of biological targets. Herein, the chemistry associated with the interaction of the biologically relevant nitrogen oxide species with fundamental biochemical targets is discussed. Specifically, the chemical interactions of nitrogen oxides with nucleophiles (e.g. thiols), metals (e.g. hemeproteins) and paramagnetic species (e.g. dioxygen and superoxide) are addressed. Importantly, the terms associated with the mechanisms by which NO (and derived species) react with their respective biological targets have been defined by numerous past chemical studies. Thus, in order to assist researchers in referring to chemical processes associated with nitrogen oxide biology, the vernacular associated with these chemical interactions is addressed. PMID:23617570

Twinning in fcc lattice creates low-coordinated catalytically active sites in porous gold

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

Krajčí, Marian; Kameoka, Satoshi; Tsai, An-Pang

We describe a new mechanism for creation of catalytically active sites in porous gold. Samples of porous gold prepared by de-alloying Al{sub 2}Au exhibit a clear correlation between the catalytic reactivity towards CO oxidation and structural defects in the fcc lattice of Au. We have found that on the stepped (211) surfaces quite common twin boundary defects in the bulk structure of porous gold can form long close-packed rows of atoms with the coordination number CN = 6. DFT calculations confirm that on these low-coordinated Au sites dioxygen chemisorbs and CO oxidation can proceed via the Langmuir–Hinshelwood mechanism with themore » activation energy of 37 kJ/mol or via the CO–OO intermediate with the energy barrier of 19 kJ/mol. The existence of the twins in porous gold is stabilized by the surface energy.« less

a Migration Well Model for the Binding of Ligands to Heme Proteins.

NASA Astrophysics Data System (ADS)

Beece, Daniel Kenneth

The binding of carbon monoxide and dioxygen to heme proteins can be viewed as occurring in distinct stages: diffusion in the solvent, migration through the matrix, and occupation of the pocket before the final binding step. A model is presented which can explain the dominant kinetic behavior of several different heme protein-ligand systems. The model assumes that a ligand molecule in the solvent sequentially encounters discrete energy barriers on the way to the binding site. The rate to surmount each barrier is distributed, except for the pseudofirst order rate corresponding to the step into the protein from the solvent. The migration through the matrix is equivalent to a small number of distinct jumps. Quantitative analysis of the data permit estimates of the barrier heights, preexponentials and solvent coupling factors for each rate. A migration coefficient and a matrix occupation factor are defined.

Small Molecule Signaling Agents: The Integrated Chemistry and Biochemistry of Nitrogen Oxides, Oxides of Carbon, Dioxygen, Hydrogen Sulfide, and Their Derived Species

PubMed Central

Fukuto, Jon M.; Carrington, Samantha J.; Tantillo, Dean J.; Harrison, Jason G.; Ignarro, Louis J.; Freeman, Bruce A.; Chen, Andrew; Wink, David A.

2014-01-01

Several small molecule species formally known primarily as toxic gases have, over the past 20 years, been shown to be endogenously generated signaling molecules. The biological signaling associated with the small molecules NO, CO, H2S (and the nonendogenously generated O2), and their derived species have become a topic of extreme interest. It has become increasingly clear that these small molecule signaling agents form an integrated signaling web that affects/regulates numerous physiological processes. The chemical interactions between these species and each other or biological targets is an important factor in their roles as signaling agents. Thus, a fundamental understanding of the chemistry of these molecules is essential to understanding their biological/physiological utility. This review focuses on this chemistry and attempts to establish the chemical basis for their signaling functions. PMID:22263838

H2 conversion in the presence of O2 as performed by the membrane-bound [NiFe]-hydrogenase of Ralstonia eutropha.

PubMed

Lenz, Oliver; Ludwig, Marcus; Schubert, Torsten; Bürstel, Ingmar; Ganskow, Stefanie; Goris, Tobias; Schwarze, Alexander; Friedrich, Bärbel

2010-04-26

[NiFe]-hydrogenases catalyze the oxidation of H(2) to protons and electrons. This reversible reaction is based on a complex interplay of metal cofactors including the Ni-Fe active site and several [Fe-S] clusters. H(2) catalysis of most [NiFe]-hydrogenases is sensitive to dioxygen. However, some bacteria contain hydrogenases that activate H(2) even in the presence of O(2). There is now compelling evidence that O(2) affects hydrogenase on three levels: 1) H(2) catalysis, 2) hydrogenase maturation, and 3) H(2)-mediated signal transduction. Herein, we summarize the genetic, biochemical, electrochemical, and spectroscopic properties related to the O(2) tolerance of hydrogenases resident in the facultative chemolithoautotroph Ralstonia eutropha H16. A focus is given to the membrane-bound [NiFe]-hydogenase, which currently represents the best-characterized member of O(2)-tolerant hydrogenases.

Novel hybrid materials based on the vanadium oxide nanobelts

NASA Astrophysics Data System (ADS)

Zabrodina, G. S.; Makarov, S. G.; Kremlev, K. V.; Yunin, P. A.; Gusev, S. A.; Kaverin, B. S.; Kaverina, L. B.; Ketkov, S. Yu.

2016-04-01

Novel hybrid materials based on zinc phthalocyanine and nanostructured vanadium oxides have attracted extensive attention for the development of academic research and innovative industrial applications such as flexible electronics, optical sensors and heterogeneous catalysts. Vanadium oxides nanobelts were synthesized via a hydrothermal treatment V2O5·nH2O gel with surfactants (TBAB, CTAB) used as structure-directing agents, where CTAB - cetyltrimethylammonium bromide, TBAB - tetrabutylammonium bromide. Hybrid materials were prepared decoration of (CTA)0.33V2O5 flexible nanobelts with cationic zinc phthalocyanine by the ion-exchange route. Investigations of the thermal stability, morphologies and structures of the (CTA)0.33V2O5, (TBA)0.16V2O5 nanobelts and zinc phthalocyanine exchange product were carried out. The hybrid materials based on the nanostructured vanadium oxide and zinc phthalocyanine were tested as photocatalysts for oxidation of citronellol and 2-mercaptoethanol by dioxygen.

Elaboration of copper-oxygen mediated C-H activation chemistry in consideration of future fuel and feedstock generation.

PubMed

Lee, Jung Yoon; Karlin, Kenneth D

2015-04-01

To contribute solutions to current energy concerns, improvements in the efficiency of dioxygen mediated C-H bond cleavage chemistry, for example, selective oxidation of methane to methanol, could minimize losses in natural gas usage or produce feedstocks for fuels. Oxidative C-H activation is also a component of polysaccharide degradation, potentially affording alternative biofuels from abundant biomass. Thus, an understanding of active-site chemistry in copper monooxygenases, those activating strong C-H bonds is briefly reviewed. Then, recent advances in the synthesis-generation and study of various copper-oxygen intermediates are highlighted. Of special interest are cupric-superoxide, Cu-hydroperoxo and Cu-oxy complexes. Such investigations can contribute to an enhanced future application of C-H oxidation or oxygenation processes using air, as concerning societal energy goals. Copyright © 2015 Elsevier Ltd. All rights reserved.

Rate theories and puzzles of hemeprotein kinetics.

PubMed

Frauenfelder, H; Wolynes, P G

1985-07-26

The binding of dioxygen and carbon monoxide to heme proteins such as myoglobin and hemoglobin has been studied with flash photolysis. At temperatures below 200 K, binding occurs from within the heme pocket and, contrary to expectation, with nearly equal rates for both ligands. This observation has led to a reexamination of the theory of the association reaction taking into account friction, protein structure, and the nature of electronic transitions. The rate coefficients for the limiting cases of large and small friction are found with simple arguments that use characteristic lengths and times. The arguments indicate how transition state theory as well as calculations based on nonadiabatic perturbation theory, which is called the Golden Rule, may fail. For ligand-binding reactions the data suggest the existence of intermediate states not directly observed so far. The general considerations may also apply to other biomolecular processes such as electron transport.

Guaianolides from two subspecies of Amphoricarpos neumayeri from Montenegro.

PubMed

Djordjević, Iris; Vajs, Vlatka; Bulatović, Vanja; Menković, Nebojsa; Tesević, Vele; Macura, Slobodan; Janaćković, Pedja; Milosavljević, Slobodan

2004-08-01

Quantitative (1)H NMR measurements revealed delta(11(13)) sesquiterpene gamma-lactones as the main constituents ( >or= 1% per weight of dried plant material) in the crude extracts of the aerial parts of Amphoricarpos neumayeri ssp. neumayeri and ssp. murbeckii from mountains Orjen and Visitor (Montenegro), respectively. Preparative silica gel chromatography afforded thirteen guai-11(13)-en-12,6alpha-olides, named amphoricarpolides (1-13), with the same relative (1alphaH,4betaH,5alphaH,7betaH) configuration of the basic skeleton. The common structural feature of lactones 2-13 was 3beta,15-dioxygenation pattern. The only exception was 1 (3-deoxyamphoricarpolide), containing a single oxygen substituent (15-OH). Eight of them exhibited an additional oxygen substituent, 9beta-OH (5 and 6), 2alpha-OH (8-12), or 2alpha-OAc (13). Compound 7 was epoxydated at 10alpha(14)-position, whereas the remaining lactones contained a 10(14) double bond.

Significance of Brain Tissue Oxygenation and the Arachidonic Acid Cascade in Stroke

PubMed Central

Rink, Cameron

2011-01-01

Abstract The significance of the hypoxia component of stroke injury is highlighted by hypermetabolic brain tissue enriched with arachidonic acid (AA), a 22:6n-3 polyunsaturated fatty acid. In an ischemic stroke environment in which cerebral blood flow is arrested, oxygen-starved brain tissue initiates the rapid cleavage of AA from the membrane phospholipid bilayer. Once free, AA undergoes both enzyme-independent and enzyme-mediated oxidative metabolism, resulting in the formation of number of biologically active metabolites which themselves contribute to pathological stroke outcomes. This review is intended to examine two divergent roles of molecular dioxygen in brain tissue as (1) a substrate for life-sustaining homeostatic metabolism of glucose and (2) a substrate for pathogenic metabolism of AA under conditions of stroke. Recent developments in research concerning supplemental oxygen therapy as an intervention to correct the hypoxic component of stroke injury are discussed. Antioxid. Redox Signal. 14, 1889–1903. PMID:20673202

Oxygen and Oxygen Toxicity: The Birth of Concepts

PubMed Central

Zhu, Hong; Traore, Kassim; Santo, Arben; Trush, Michael A.; Li, Y. Robert

2018-01-01

Molecular dioxygen (O2) is an essential element of aerobic life, yet incomplete reduction or excitation of O2 during aerobic metabolisms generates diverse oxygen-containing reactive species, commonly known as reactive oxygen species (ROS). On the one hand, ROS pose a serious threat to aerobic organisms via inducing oxidative damage to cellular constituents. On the other hand, these reactive species, when their generation is under homeostatic control, also play important physiological roles (e.g., constituting an important component of immunity and participating in redox signaling). This article defines oxygen and the key facts about oxygen, and discusses the relationship between oxygen and the emergence of early animals on Earth. The article then describes the discovery of oxygen by three historical figures and examines the birth of the concepts of oxygen toxicity and the underlying free radical mechanisms. The article ends with a brief introduction to the emerging field of ROS-mediated redox signaling and physiological responses. PMID:29707642

Oxidation of manganese in an ancient aquifer, Kimberley formation, Gale crater, Mars

DOE PAGES

Lanza, Nina L.; Wiens, Roger C.; Arvidson, Raymond E.; ...

2016-07-28

We report that the Curiosity rover observed high Mn abundances (>25 wt % MnO) in fracture-filling materials that crosscut sandstones in the Kimberley region of Gale crater, Mars. The correlation between Mn and trace metal abundances plus the lack of correlation between Mn and elements such as S, Cl, and C, reveals that these deposits are Mn oxides rather than evaporites or other salts. On Earth, environments that concentrate Mn and deposit Mn minerals require water and highly oxidizing conditions; hence, these findings suggest that similar processes occurred on Mars. In conclusion, based on the strong association between Mn-oxide depositionmore » and evolving atmospheric dioxygen levels on Earth, the presence of these Mn phases on Mars suggests that there was more abundant molecular oxygen within the atmosphere and some groundwaters of ancient Mars than in the present day.« less

Oxygen activation at mononuclear nonheme iron centers: a superoxo perspective.

PubMed

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

2010-04-19

Dioxygen (O(2)) 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 O(2) 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, [(Tp(iPr2))Fe(II)(O(2)CC(O)CH(3))], 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 that the iron(III) superoxo species can play in the course of O(2) activation at a nonheme iron center.

Efficient oxidation of alcohols to carbonyl compounds with molecular oxygen catalyzed by N-hydroxyphthalimide combined with a Co species

PubMed

Iwahama; Yoshino; Keitoku; Sakaguchi; Ishii

2000-10-06

Highly efficient catalytic oxidation of alcohols with molecular oxygen by N-hydroxyphthalimide (NHPI) combined with a Co species was developed. The oxidation of 2-octanol in the presence of catalytic amounts of NHPI and Co(OAc)2 under atmospheric dioxygen in AcOEt at 70 degrees C gave 2-octanone in 93% yield. The oxidation was significantly enhanced by adding a small amount of benzoic acid to proceed smoothly even at room temperature. Primary alcohols were oxidized by NHPI in the absence of any metal catalyst to form the corresponding carboxylic acids in good yields. In the oxidation of terminal vic-diols such as 1,2-butanediol, carbon-carbon bond cleavage was induced to give one carbon less carboxylic acids such as propionic acid, while internal vic-diols were selectively oxidized to 1,2-diketones.

Hybrid biobattery based on arylated carbon nanotubes and laccase.

PubMed

Stolarczyk, Krzysztof; Sepelowska, Małgorzata; Lyp, Dominika; Zelechowska, Kamila; Biernat, Jan F; Rogalski, Jerzy; Farmer, Kevin D; Roberts, Ken N; Bilewicz, Renata

2012-10-01

Single-walled carbon nanotubes (SWCNT) were covalently modified with anthracene and anthraquinone and used for the construction of cathodes for biocatalytic reduction of dioxygen. The nanotubes with aromatic groups casted onto the electrode increased the working surface of the electrode and enabled efficient direct electron transfer (DET) between the enzyme and the electrode. The aryl groups enter the hydrophobic pocket of the T1 center of laccase responsible for exchanging electrons with the substrate. Glassy carbon electrode covered with arylated SWCNT and coated with a layer of neutralized Nafion containing laccase was found to be a very efficient cathode in the hybrid battery. Zn wire covered with a Nafion film served as the anode. The cell parameters were determined: power density was 2 mW/cm(2) and the open circuit potential was 1.5 V. Copyright © 2011 Elsevier B.V. All rights reserved.

Sedimentation and gravitational instability of Escherichia coli Suspension

NASA Astrophysics Data System (ADS)

Salin, Dominique; Douarche, Carine

2017-11-01

The successive runs and tumbles of Escherichia coli bacteria provide an active matter suspension of rod-like particles with a large swimming, Brownian like, diffusion. As opposed to inactive elongated particles, this diffusion prevents clustering of the particles and hence instability in the gravity field. We measure the time dependent E . coli concentration profile during their sedimentation. After some hours, due to the dioxygen consumption, a motile / non-motile front forms leading to a Rayleigh-Taylor type gravitational instability. Analysing both sedimentation and instability in the framework of active particle suspensions, we can measure the relevant bacteria hydrodynamic characteristics such as its single particle sedimentation velocity and its hindrance volume. Comparing these quantities to the ones of equivalent passive particles (ellipsoid, rod) we tentatively infer the effective shape and size of the bacteria involved in its buoyancy induced advection and diffusion. Laboratoire FAST University Paris Saclay France.

Importance of measuring lactate levels in children with sepsis.

PubMed

Anil, Nisha

2017-10-10

Sepsis is a major public health problem as well as one of the leading causes of preventable death in children because of failure to recognise the early signs and symptoms and to resuscitate rapidly. Blood lactate levels are used to assess the severity of sepsis and the effectiveness of resuscitation. Lactate levels are easily obtainable and should be checked in all patients admitted with suspected sepsis within six hours of presentation. The test should be repeated four and eight-hours post-diagnosis of sepsis. For the diagnosis of sepsis, patients' clinical symptoms, along with the combined analysis of partial pressure of oxygen, carbon dioxide and lactate levels, should be used. A multitude of factors can cause elevated lactate levels and so clinicians should use elevated levels cautiously by considering all other aetiologies. This article, which focuses on practice in Australia but makes reference to the UK, discusses the importance of measuring lactate levels in sepsis, the pathophysiology of lactate production, causes of elevated lactate levels, lactate measurement, nursing management of patients with elevated lactate levels, limitations of using lactate as a biomarker for diagnosing sepsis and implications for practice. ©2012 RCN Publishing Company Ltd. All rights reserved. Not to be copied, transmitted or recorded in any way, in whole or part, without prior permission of the publishers.

Glutathione S-transferases as antioxidant defence agents confer pyrethroid resistance in Nilaparvata lugens.

PubMed Central

Vontas, J G; Small, G J; Hemingway, J

2001-01-01

Selection of a laboratory colony of the brown planthopper Nilaparvata lugens with the pyrethroids permethrin and lambda-cyhalothrin increased its resistance to both insecticides. Biochemical analysis and synergistic studies with metabolic inhibitors indicated that elevated glutathione S-transferases (GSTs) with a predominant peroxidase activity conferred resistance to both pyrethroids, whereas esterases conferred part of the resistance to permethrin. Purified esterases hydrolysed permethrin at a slow rate, but incubation of either pyrethroid or their primary metabolites with partially purified GSTs had no effect on the metabolic profile. Although GSTs were sensitive to inhibition by both pyrethroids, they did not serve as binding proteins, as previously hypothesized [Grant and Matsumura (1988) Insect Biochem. 18, 615-622]. We demonstrate that pyrethroids, in addition to their neurotoxic effect, induce oxidative stress and lipid peroxidation in insects. Pyrethroid exposure induced lipid peroxides, protein oxidation and depleted reduced glutathione. Elevated GSTs in the resistant strains attenuated the pyrethroid-induced lipid peroxidation and reduced mortality, whereas their in vivo inhibition eliminated their protective role. We therefore hypothesize that the main role of elevated GSTs in conferring resistance in N. lugens is through protecting tissues from oxidative damage. Our study extends the GSTs' range of efficacy to pyrethroid insecticides and possibly explains the role of elevated GSTs in other pyrethroid-resistant insects. PMID:11415437

Postoperative elevation of CA15-3 due to pernicious anemia in a patient without evidence of breast cancer recurrence.

PubMed

Adachi, Yayoi; Kikumori, Toyone; Miyajima, Noriyuki; Inaishi, Takahiro; Onishi, Eiji; Shibata, Masahiro; Nakanishi, Kenichi; Takeuchi, Dai; Hayashi, Hironori; Kodera, Yasuhiro

2015-12-01

Cancer antigen 15-3 (CA15-3) is considered as a marker for breast cancer recurrence. However, we encountered a case where the patient showed postoperative elevation of the CA15-3 level due to pernicious anemia without evidence of breast cancer recurrence. The patient was a 60-year-old postmenopausal woman. She had undergone partial mastectomy and sentinel lymph node biopsy (SLNB) for her T1 left breast cancer. SLNB had indicated no lymph node metastases. The tumor was positive for hormone receptors and negative for human epidermal growth factor receptor 2. Therefore, an aromatase inhibitor and external beam irradiation had been administered as adjuvant therapy. However, the CA15-3 level was found to be elevated at 6 months postoperatively. Although imaging studies did not indicate breast cancer recurrence, CA15-3 levels continued to increase. Based on the findings of blood tests and gastroendoscopy, a diagnosis of pernicious anemia due to vitamin B12 deficiency was finally confirmed at 2 years and 6 months postoperatively. The CA15-3 level returned to normal after vitamin B12 administration. The possibility of pernicious anemia should be considered in cases of postoperative elevated CA15-3 levels with no evidence of recurrence in patients with early breast cancer.

Perfectionism Group Treatment for Eating Disorders in an Inpatient, Partial Hospitalization, and Outpatient Setting.

PubMed

Levinson, Cheri A; Brosof, Leigh C; Vanzhula, Irina A; Bumberry, Laura; Zerwas, Stephanie; Bulik, Cynthia M

2017-11-01

Perfectionism is elevated in individuals with eating disorders and is posited to be a risk factor, maintaining factor, and treatment barrier. However, there has been little literature testing the feasibility and effectiveness of perfectionism interventions in individuals specifically with eating disorders in an open group format. In the current study, we tested the feasibility of (a) a short cognitive behavioural therapy for perfectionism intervention delivered in an inpatient, partial hospitalization, and outpatient for eating disorders setting (combined N = 28; inpatient n = 15; partial hospital n = 9; outpatient n = 4), as well as (b) a training for disseminating the treatment in these settings (N = 9). Overall, we found that it was feasible to implement a perfectionism group in each treatment setting, with both an open and closed group format. This research adds additional support for the implementation of perfectionism group treatment for eating disorders and provides information on the feasibility of implementing such interventions across multiple settings. Copyright © 2017 John Wiley & Sons, Ltd and Eating Disorders Association. Copyright © 2017 John Wiley & Sons, Ltd and Eating Disorders Association.

Social Anxiety and Heavy Situational Drinking: Coping and Conformity Motives as Multiple Mediators

PubMed Central

Terlecki, Meredith A.; Buckner, Julia D.

2014-01-01

Individuals with clinically elevated social anxiety are at greater risk for alcohol use disorder, and the relation between social anxiety and drinking problems is at least partially accounted for by drinking more in negative emotional (e.g., feeling sad or angry) and personal/intimate (e.g., before sexual intercourse) situations. Identification of cognitive/motivational factors related to drinking in these high-risk situations could inform the development of treatment and prevention interventions for these high-risk drinkers. The current study examined the mediating effect of drinking motives on the relationship between social anxiety and drinking these high-risk situations amongst undergraduates (N = 232). Clinically elevated social anxiety was associated with greater coping and conformity motives. Both coping and conformity motives mediated the relation between social anxiety and heavier alcohol consumption in negative emotional and personal/intimate contexts. Multiple mediation analyses indicated that these motives work additively to mediate the social anxiety-drinking situations relationship, such that that heavy situational drinking amongst undergraduates with clinically elevated social anxiety can be jointly attributed to desire to cope with negative affect and to avoid social scrutiny. PMID:25233446

Pressurized pyrolysis of rice husk in an inert gas sweeping fixed-bed reactor with a focus on bio-oil deoxygenation.

PubMed

Qian, Yangyang; Zhang, Jie; Wang, Jie

2014-12-01

The pyrolysis of rice husk was conducted in a fixed-bed reactor with a sweeping nitrogen gas to investigate the effects of pressure on the pyrolytic behaviors. The release rates of main gases during the pyrolysis, the distributions of four products (char, bio-oil, water and gas), the elemental compositions of char, bio-oil and gas, and the typical compounds in bio-oil were determined. It was found that the elevation of pressure from 0.1MPa to 5.0MPa facilitated the dehydration and decarboxylation of bio-oil, and the bio-oils obtained under the elevated pressures had significantly less oxygen and higher calorific value than those obtained under atmospheric pressure. The former bio-oils embraced more acetic acid, phenols and guaiacols. The elevation of pressure increased the formation of CH4 partially via the gas-phase reactions. An attempt is made in this study to clarify "the pure pressure effect" and "the combined effect with residence time". Copyright © 2014 Elsevier Ltd. All rights reserved.

Elevated temperature mechanical properties and residual tensile properties of two cast superalloys and several nickel-base oxide dispersion strengthened alloys

NASA Technical Reports Server (NTRS)

Whittenberger, J. D.

1981-01-01

The elevated temperature tensile, stress-rupture and creep properties and residual tensile properties after creep straining have been determined for two cast superalloys and several wrought Ni-16Cr-4Al-yttria oxide dispersion strengthened (ODS) alloys. The creep behavior of the ODS alloys is similar to that of previously studied ODS nickel alloys. In general, the longitudinal direction is stronger than the long transverse direction, and creep is at least partially due to a diffusional creep mechanism as dispersoid-free zones were observed after creep-rupture testing. The tensile properties of the nickel-base superalloy B-1900 and cobalt-base superalloy MAR-M509 are not degraded by prior elevated temperature creep straining (at least up to 1 pct) between 1144 and 1366 K. On the other hand, the room temperature tensile properties of ODS nickel-base alloys can be reduced by prior creep strains of 0.5 pct or less between 1144 and 1477 K, with the long transverse direction being more susceptible to degradation than the longitudinal direction.

Building physiological toughness: Some aversive events during extinction may attenuate return of fear.

PubMed

Culver, Najwa C; Stevens, Stephan; Fanselow, Michael S; Craske, Michelle G

2018-03-01

Although exposure therapy is an effective treatment for anxiety disorders, fear sometimes returns following successful therapy. Recent literature in animal models indicates that incorporating some aversive events into extinction training may offset these return of fear effects. The effect of occasional reinforced extinction trials was investigated in a sample of thirty-nine participants using a fear conditioning and extinction paradigm. Participants either underwent traditional extinction procedures during which the conditional stimulus which had been paired with the unconditional stimulus (US) during acquisition training (CS+) was presented alone with no presentations of the US or partially reinforced extinction during which there were several unpredicted CS+/US pairings. As measured by skin conductance responses, physiological fear responding remained elevated during extinction for participants who experienced partially reinforced extinction; however, these participants demonstrated protection from rapid reacquisition effects. Results from the subjective US-expectancy ratings did not provide evidence of protection against rapid reacquisition in the partially reinforced extinction group; however, there was evidence of protection from spontaneous recovery effects. Lastly, as measured by valence ratings, it was unclear whether partially reinforced extinction provided protection from fear recovery effects. Although participants who experienced partially reinforced extinction demonstrated protection from rapid reacquisition as measured by skin conductance responses, they also demonstrated significantly higher levels of physiological fear responding during extinction which made the results of the spontaneous recovery test more difficult to interpret. Occasional CS-US pairings during extinction may protect against return of fear effects. Clinical implications are discussed. Published by Elsevier Ltd.

Metal-organic complexes in geochemical processes: Estimation of standard partial molal thermodynamic properties of aqueous complexes between metal cations and monovalent organic acid ligands at high pressures and temperatures

NASA Astrophysics Data System (ADS)

Shock, Everetr L.; Koretsky, Carla M.

1995-04-01

Regression of standard state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state allows evaluation of standard partial molal entropies ( overlineSo) of aqueous metal-organic complexes involving monovalent organic acid ligands. These values of overlineSo provide the basis for correlations that can be used, together with correlation algorithms among standard partial molal properties of aqueous complexes and equation-of-state parameters, to estimate thermodynamic properties including equilibrium constants for complexes between aqueous metals and several monovalent organic acid ligands at the elevated pressures and temperatures of many geochemical processes which involve aqueous solutions. Data, parameters, and estimates are given for 270 formate, propanoate, n-butanoate, n-pentanoate, glycolate, lactate, glycinate, and alanate complexes, and a consistent algorithm is provided for making other estimates. Standard partial molal entropies of association ( Δ -Sro) for metal-monovalent organic acid ligand complexes fall into at least two groups dependent upon the type of functional groups present in the ligand. It is shown that isothermal correlations among equilibrium constants for complex formation are consistent with one another and with similar correlations for inorganic metal-ligand complexes. Additional correlations allow estimates of standard partial molal Gibbs free energies of association at 25°C and 1 bar which can be used in cases where no experimentally derived values are available.

Gleeble Testing of Tungsten Samples

DTIC Science & Technology

2013-02-01

as a diffusion barrier to prevent the tungsten samples from fusing to the tungsten carbide inserts at elevated temperatures. After the anvils were...anvils with removable tungsten carbide inserts. The inserts were 19.05 mm (0.75 in) in diameter and 25.4 mm (1 in) long; they were purchased from...rhenium are shown in tables 6 and 7 and figure 7. The sample tested at 1300 °C, T4, partially embedded into the tungsten carbide (WC) inserts during

Elevation of GM2 ganglioside during ethanol-induced apoptotic neurodegeneration in the developing mouse brain

PubMed Central

Saito, Mitsuo; Chakraborty, Goutam; Shah, Relish; Mao, Rui-Fen; Kumar, Asok; Yang, Dun-Sheng; Dobrenis, Kostantin; Saito, Mariko

2012-01-01

GM2 ganglioside in the brain increased during ethanol-induced acute apoptotic neurodegeneration in 7-day-old mice. A small but a significant increase observed 2 h after ethanol exposure was followed by a marked increase around 24 h. Subcellular fractionation of the brain 24 h after ethanol treatment indicated that GM2 increased in synaptic and non-synaptic mitochondrial fractions as well as in a lysosome-enriched fraction characteristic to the ethanol-exposed brain. Immunohistochemical staining of GM2 in the ethanol-treated brain showed strong punctate staining mainly in activated microglia, in which it partially overlapped with staining for LAMP1, a late endosomal/lysosomal marker. Also, there was weaker neuronal staining, which partially co-localized with complex IV, a mitochondrial marker, and was augmented in cleaved caspase-3-positive neurons. In contrast, the control brain showed only faint and diffuse GM2 staining in neurons. Incubation of isolated brain mitochondria with GM2 in vitro induced cytochrome c release in a manner similar to that of GD3 ganglioside. Because ethanol is known to trigger mitochondria-mediated apoptosis with cytochrome c release and caspase-3 activation in the 7-day–old mouse brain, the GM2 elevation in mitochondria may be relevant to neuroapoptosis. Subsequently, activated microglia accumulated GM2, indicating a close relationship between GM2 and ethanol-induced neurodegeneration. PMID:22372857

Tandospirone, a 5-HT1A partial agonist, ameliorates aberrant lactate production in the prefrontal cortex of rats exposed to blockade of N-methy-D-aspartate receptors; Toward the therapeutics of cognitive impairment of schizophrenia.

PubMed

Uehara, Takashi; Matsuoka, Tadasu; Sumiyoshi, Tomiki

2014-01-01

Augmentation therapy with serotonin-1A (5-HT1A) receptor partial agonists has been suggested to improve cognitive impairment in patients with schizophrenia. Decreased activity of prefrontal cortex may provide a basis for cognitive deficits of the disease. Lactate plays a significant role in the supply of energy to the brain, and glutamatergic neurotransmission contributes to lactate production. The purposes of this study were to examine the effect of repeated administration (once a daily for 4 days) of tandospirone (0.05 or 5 mg/kg) on brain energy metabolism, as represented by extracellular lactate concentration (eLAC) in the medial prefrontal cortex (mPFC) of a rat model of schizophrenia. Four-day treatment with MK-801, an NMDA-R antagonist, prolonged eLAC elevation induced by foot-shock stress (FS). Co-administration with the high-dose tandospirone suppressed prolonged FS-induced eLAC elevation in rats receiving MK-801, whereas tandospirone by itself did not affected eLAC increment. These results suggest that stimulation of 5-HT1A receptors ameliorates abnormalities of energy metabolism in the mPFC due to blockade of NMDA receptors. These findings provide a possible mechanism, based on brain energy metabolism, by which 5-HT1A agonism improve cognitive impairment of schizophrenia and related disorders.

Infragravity waves on fringing reefs in the tropical Pacific: Dynamic setup

NASA Astrophysics Data System (ADS)

Becker, J. M.; Merrifield, M. A.; Yoon, H.

2016-05-01

Cross-shore pressure and current observations from four fringing reefs of lengths ranging from 135 to 420 m reveal energetic low-frequency (˜0.001-0.05 Hz) motions. The spatial structure and temporal amplitudes of an empirical orthogonal function analysis of the pressure measurements suggest the dominant low-frequency variability is modal. Incoming and outgoing linear flux estimates also support partially standing modes on the reef flat during energetic events. A cross-covariance analysis suggests that breakpoint forcing excites these partially standing modes, similar to previous findings at other steep reefs. The dynamics of Symonds et al. (1982) with damping are applied to a step reef, with forcing obtained by extending a point break model of Vetter et al. (2010) for breaking wave setup to the low-frequency band using the shoaled envelope of the incident free surface elevation. A one parameter, linear analytical model for the reef flat free surface elevation is presented, which describes between 75% and 97% of the variance of the observed low-frequency shoreline significant wave height for all reefs considered over a range of conditions. The linear model contains a single dimensionless parameter that is the ratio of the inertial to dissipative time scales, and the observations from this study exhibit more low-frequency variability when the dissipative time scale is greater than the inertial time scale for the steep reefs considered.

Advanced carbon-based material C{sub 60} modification using partially ionized cluster and energetic beams

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

Du Yuancheng; Ren Zhongmin; Ning Zhifeng

1997-06-20

Two processes have been undertaken using Partially ionized cluster deposition (PICBD) and energetic ion bombardment beams deposition (IBD) respectively. C{sub 60} films deposited by PICBD at V=0 and 65 V, which result in highly textured close-packed structure in orientation (110) and being more polycrystalline respectively, the resistance of C{sub 60} films to oxygen diffusion contamination will be improved. In the case of PICBD, the ionized C{sub 60} soccer-balls molecules in the evaporation beams will be fragmented in collision with the substrate under the elevated accelerating fields Va. As a new synthetic IBD processing, two low energy (400 and 1000 eV)more » nitrogen ion beams have been used to bombard C{sub 60} films to synthesize the carbon nitride films.« less

Dysfunctional Attitudes Scale Perfectionism: A Predictor and Partial Mediator of Acute Treatment Outcome among Clinically Depressed Adolescents

PubMed Central

Jacobs, Rachel H.; Silva, Susan G.; Reinecke, Mark A.; Curry, John F.; Ginsburg, Golda S.; Kratochvil, Christopher J.; March, John S.

2009-01-01

The effect of perfectionism on acute treatment outcomes was explored in a randomized controlled trial of 439 clinically depressed adolescents (12–17 years of age) enrolled in the Treatment for Adolescents with Depression Study (TADS) who received cognitive behavior therapy (CBT), fluoxetine, a combination of CBT and FLX, or pill placebo. Measures included the Children’s Depression Rating Scale–Revised, the Suicidal Ideation Questionnaire–Grades 7–9, and the perfectionism subscale from the Dysfunctional Attitudes Scale (DAS). Predictor results indicate that adolescents with higher versus lower DAS perfectionism scores at baseline, regardless of treatment, continued to demonstrate elevated depression scores across the acute treatment period. In the case of suicidality, DAS perfectionism impeded improvement. Treatment outcomes were partially mediated by the change in DAS perfectionism across the 12-week period. PMID:20183664

Emotional Reactivity, Behavior Problems, and Social Adjustment at School Entry in a High-risk Sample.

PubMed

Kalvin, Carla B; Bierman, Karen L; Gatzke-Kopp, Lisa M

2016-11-01

Prior research suggests that heightened emotional reactivity to emotionally distressing stimuli may be associated with elevated internalizing and externalizing behaviors, and contribute to impaired social functioning. These links were explored in a sample of 169 economically-disadvantaged kindergarteners (66 % male; 68 % African American, 22 % Hispanic, 10 % Caucasian) oversampled for elevated aggression. Physiological measures of emotional reactivity (respiratory sinus arrhythmia [RSA], heart rate [HR], and cardiac pre-ejection period [PEP]) were collected, and teachers and peers provided ratings of externalizing and internalizing behavior, prosocial competence, and peer rejection. RSA withdrawal, HR reactivity, and PEP shortening (indicating increased arousal) were correlated with reduced prosocial competence, and RSA withdrawal and HR reactivity were correlated with elevated internalizing problems. HR reactivity was also correlated with elevated externalizing problems and peer rejection. Linear regressions controlling for age, sex, race, verbal proficiency, and resting physiology showed that HR reactivity explained unique variance in both teacher-rated prosocial competence and peer rejection, and contributed indirectly to these outcomes through pathways mediated by internalizing and externalizing problems. A trend also emerged for the unique contribution of PEP reactivity to peer-rated prosocial competence. These findings support the contribution of emotional reactivity to behavior problems and social adjustment among children living in disadvantaged urban contexts, and further suggest that elevated reactivity may confer risk for social difficulties in ways that overlap only partially with internalizing and externalizing behavior problems.

Water resources data for Pennsylvania, water year 1993. Volume 2. Susquehanna and Potomac river basins. Water-data report (Annual), 1 October 1992-30 September 1993

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

Durlin, R.R.; Schaffstall, W.P.

1994-01-01

Water resources data for the 1993 water year for Pennsylvania consist of records of discharge and water quality of streams; contents and elevations of lakes and reservoirs; and water levels and water quality of ground-water wells. The report, Volume 2, includes records from the Susquehanna and Potomac River Basins. Specifically, Volume 2 contains (1) discharge records for 97 continuous-record streamflow-gaging stations and 39 partial-record stations; (2) elevation and contents records for 13 lakes and reservoirs; and (3) water-level records for 25 observation wells. The location of these sites is shown in figures 6-8. Additional waste data collected at various sitesmore » not involved in the systematic data-collection program are also presented.« less

Water Resources Data, Kansas, Water Year 2001

USGS Publications Warehouse

Putnam, J.E.; Lacock, D.L.; Schneider, D.R.

2002-01-01

Water-resources data for the 2001 water year for Kansas consist of records of stage, discharge, and water quality of streams; elevation and contents of lakes and reservoirs; and water levels of ground-water wells. This report contains records for water discharge at 145 complete-record gaging stations; elevation and contents at 20 lakes and reservoirs; waterquality records at 2 precipitation stations, water-level data at 19 observation wells; and records of specific conductance, pH, water temperature, dissolved oxygen, and turbidity at 11 gaging stations. Also included are discharge data for 26 high-flow partial-record stations, miscellaneous onsite water-quality data collected at 140 stations, and suspended-sediment concentration for 12 stations. These data represent that part of the National Water Information System collected by the U.S. Geological Survey in cooperation with local, State, and Federal agencies in Kansas.

Water Resources Data, Kansas, Water Year 2002

USGS Publications Warehouse

Putnam, J.E.; Schneider, D.R.

2003-01-01

Water-resources data for the 2002 water year for Kansas consist of records of stage, discharge, and water quality of streams; elevation and contents of lakes and reservoirs; and water levels of ground-water wells. This report contains records for water discharge at 149 complete-record gaging stations; elevation and contents at 20 lakes and reservoirs; waterquality records at 2 precipitation stations, water-level data at 18 observation wells; and records of specific conductance, pH, water temperature, dissolved oxygen, and turbidity at 11 gaging stations. Also included are discharge data for 26 high-flow partial-record stations, miscellaneous onsite water-quality data collected at 142 stations, and suspended-sediment concentration for 12 stations. These data represent that part of the National Water Information System collected by the U.S. Geological Survey in cooperation with local, State, and Federal agencies in Kansas.

Water Resources Data, Kansas, Water Year 2000

USGS Publications Warehouse

Putnam, J.E.; Lacock, D.L.; Schneider, D.R.; Carlson, M.D.

2001-01-01

Water-resources data for the 2000 water year for Kansas consist of records of stage, discharge, and water quality of streams; elevation and contents of lakes and reservoirs; and water levels of ground-water wells. This report contains records for water discharge at 144 complete-record gaging stations; elevation and contents at 19 lakes and reservoirs; water-quality records at 2 precipitation stations, water-level data at 18 observation wells; and records of specific conductance, pH, water temperature, dissolved oxygen, and turbidity at 8 gaging stations. Also included are discharge data for 26 high-flow partial-record stations, and miscellaneous onsite water-quality data collected at 134 stations, and suspended-sediment concentration for 12 stations. These data represent that part of the National Water Information System collected by the U.S. Geological Survey in cooperation with local, State, and Federal agencies in Kansas.

Water Resources Data, Kansas, Water Year 1999

USGS Publications Warehouse

Putnam, J.E.; Lacock, D.L.; Schneider, D.R.; Carlson, M.D.

2000-01-01

Water-resources data for the 1999 water year for Kansas consist of records of stage, discharge, and water quality of streams; elevation and contents of lakes and reservoirs; and water levels of ground-water wells. This report contains records for water discharge at 143 gaging stations; elevation and contents at 19 watershed lakes and reservoirs; and water-level data at 19 observation wells; and records of specific conductance, pH, water temperature, dissolved oxygen, and turbidity at 4 stations. Also included are data for 26 high-flow and 2 low-flow partial-record stations; and 2 chemical quality of precipitation stations. Miscellaneous onsite water-quality data were collected at 132 stations. These data represent that part of the National Water Information System collected by the U.S. Geological Survey in cooperation with State, local, and Federal agencies in Kansas.

H3N2 canine influenza virus causes severe morbidity in dogs with induction of genes related to inflammation and apoptosis

PubMed Central

2013-01-01

Dogs are companion animals that live in close proximity with humans. Canine H3N2 influenza virus has been isolated from pet dogs that showed severe respiratory signs and other clinical symptoms such as fever, reduced body weight, and interstitial pneumonia. The canine H3N2 influenza virus can be highly transmissible among dogs via aerosols. When we analyzed global gene expression in the lungs of infected dogs, the genes associated with the immune response and cell death were greatly elevated. Taken together, our results suggest that canine H3N2 influenza virus can be easily transmitted among dogs, and that severe pneumonia in the infected dogs may be partially due to the elevated expression of genes related to inflammation and apoptosis. PMID:24090140

Theory of Mind and Executive Control Deficits in Typically Developing Adults and Adolescents with High Levels of Autism Traits.

PubMed

Gökçen, Elif; Frederickson, Norah; Petrides, K V

2016-06-01

Autism spectrum disorder (ASD) is characterised by profound difficulties in empathic processing and executive control. Whilst the links between these processes have been frequently investigated in populations with autism, few studies have examined them at the subclinical level. In addition, the contribution of alexithymia, a trait characterised by impaired interoceptive awareness and empathy, and elevated in those with ASD, is currently unclear. The present two-part study employed a comprehensive battery of tasks to examine these processes. Findings support the notion that executive function and theory of mind are related abilities. They also suggest that individuals with elevated levels of autism-like traits experience a partially similar pattern of social and executive function difficulties to those diagnosed with ASD, and that these impairments are not explained by co-occurring alexithymia.

XANES, EXAFS and Kbeta spectroscopic studies of the oxygen-evolving complex in Photosystem II

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

Robblee, John Henry

A key question for the understanding of photosynthetic water oxidation is whether the four oxidizing equivalents necessary to oxidize water to dioxygen are accumulated on the four Mn ions of the oxygen evolving complex (OEC), or whether some ligand-centered oxidations take place before the formation and release of dioxygen during the S 3 → [S 4] → S 0 transition. Progress in instrumentation and flash sample preparation allowed us to apply Mn Kβ X-ray emission spectroscopy (Kb XES) to this problem for the first time. The Kβ XES results, in combination with Mn X-ray absorption near-edge structure (XANES) and electronmore » paramagnetic resonance (EPR) data obtained from the same set of samples, show that the S 2 → S 3 transition, in contrast to the S 0 → S 1 and S 1 → S 2 transitions, does not involve a Mn-centered oxidation. This is rationalized by manganese μ-oxo bridge radical formation during the S 2 → S 3 transition. Using extended X-ray absorption fine structure (EXAFS) spectroscopy, the local environment of the Mn atoms in the S 0 state has been structurally characterized. These results show that the Mn-Mn distance in one of the di-μ-oxo-bridged Mn-Mn moieties increases from 2.7 Å in the S 1} state to 2.85 Å in the S 0 state. Furthermore, evidence is presented that shows three di-μ-oxo binuclear Mn 2 clusters may be present in the OEC, which is contrary to the widely held theory that two such clusters are present in the OEC. The EPR properties of the S 0 state have been investigated and a characteristic ''multiline'' signal in the S 0 state has been discovered in the presence of methanol. This provides the first direct confirmation that the native S 0 state is paramagnetic. In addition, this signal was simulated using parameters derived from three possible oxidation states of Mn in the S 0 state. The dichroic nature of X-rays from synchrotron radiation and single-crystal Mn complexes have been exploited to selectively probe Mn-ligand bonds using XANES and EXAFS spectroscopy. The results from single-crystal Mn complexes show that dramatic dichroism exists in these complexes, and are suggestive of a promising future for single-crystal studies of PS II.« less

Long-Term Behavior of Simulated Partial Lead Service Line Replacements

PubMed Central

St. Clair, Justin; Cartier, Clement; Triantafyllidou, Simoni; Clark, Brandi; Edwards, Marc

2016-01-01

Abstract In this 48-month pilot study, long-term impacts of copper:lead galvanic connections on lead release to water were assessed without confounding differences in pipe exposure prehistory or disturbances arising from cutting lead pipe. Lead release was tracked from three lead service line configurations, including (1) 100% lead, (2) traditional partial replacement with 50% copper upstream of 50% lead, and (3) 50% lead upstream of 50% copper as a function of flow rate, connection types, and sampling methodologies. Elevated lead from galvanic corrosion worsened with time, with 140% more lead release from configurations representing traditional partial replacement configurations at 14 months compared to earlier data in the first 8 months. Even when sampled consistently at moderate flow rate (8 LPM) and collecting all water passing through service lines, conditions representing traditional partial service line configurations were significantly worse (≈40%) when compared to 100% lead pipe. If sampled at a high flow rate (32 LPM) and collecting 2 L samples from service lines, 100% of samples collected from traditional partial replacement configurations exceeded thresholds posing an acute health risk versus a 0% risk for samples from 100% lead pipe. Temporary removal of lead accumulations near Pb:Cu junctions and lead deposits from other downstream plastic pipes reduced risk of partial replacements relative to that observed for 100% lead. When typical brass compression couplings were used to connect prepassivated lead pipes, lead release spiked up to 10 times higher, confirming prior concerns raised at bench and field scale regarding adverse impacts of crevices and service line disturbances on lead release. To quantify semirandom particulate lead release from service lines in future research, whole-house filters have many advantages compared to other approaches. PMID:26989344

Streamflow measurements, basin characteristics, and streamflow statistics for low-flow partial-record stations operated in Massachusetts from 1989 through 1996

USGS Publications Warehouse

Ries, Kernell G.

1999-01-01

A network of 148 low-flow partial-record stations was operated on streams in Massachusetts during the summers of 1989 through 1996. Streamflow measurements (including historical measurements), measured basin characteristics, and estimated streamflow statistics are provided in the report for each low-flow partial-record station. Also included for each station are location information, streamflow-gaging stations for which flows were correlated to those at the low-flowpartial-record station, years of operation, and remarks indicating human influences of stream-flowsat the station. Three or four streamflow measurements were made each year for three years during times of low flow to obtain nine or ten measurements for each station. Measured flows at the low-flow partial-record stations were correlated with same-day mean flows at a nearby gaging station to estimate streamflow statistics for the low-flow partial-record stations. The estimated streamflow statistics include the 99-, 98-, 97-, 95-, 93-, 90-, 85-, 80-, 75-, 70-, 65-, 60-, 55-, and 50-percent duration flows; the 7-day, 10- and 2-year low flows; and the August median flow. Characteristics of the drainage basins for the stations that theoretically relate to the response of the station to climatic variations were measured from digital map data by use of an automated geographic information system procedure. Basin characteristics measured include drainage area; total stream length; mean basin slope; area of surficial stratified drift; area of wetlands; area of water bodies; and mean, maximum, and minimum basin elevation.Station descriptions and calculated streamflow statistics are also included in the report for the 50 continuous gaging stations used in correlations with the low-flow partial-record stations.

Nitrogen-doped graphene interpenetrated 3D Ni-nanocages: efficient and stable water-to-dioxygen electrocatalysts

NASA Astrophysics Data System (ADS)

Dhavale, Vishal M.; Gaikwad, Sachin S.; George, Leena; Devi, R. Nandini; Kurungot, Sreekumar

2014-10-01

Herein, we report the synthesis of a nitrogen-doped graphene (NGr) interpenetrated 3D Ni-nanocage (Ni-NGr) electrocatalyst by a simple water-in-oil (w/o) emulsion technique for oxidation of water to dioxygen. Correlation of adsorption of NGr and subsequent interpenetration through the specific surface plane of nickel particles as well as the concomitant interaction of N and C with Ni in the nano-regime has been investigated. Apart from the benefits of the synergistic interactions between Ni, N, and C, the overall integrity of the structure and its intra-molecular connectivity within the framework help in achieving better oxygen evolution characteristics at a significantly reduced overpotential. The engineered Ni-NGr nanocage displays a substantially low overpotential of ~290 mV at a practical current density of 20 mA cm-2 in 0.1 M KOH. In comparison, NGr and Ni-particles as separate entities give overpotentials of ~570 and ~370 mV under similar conditions. Moreover, the long term stability of Ni-NGr was investigated by anodic potential cycling for 500 cycles and an 8.5% increment in the overpotential at 20 mA cm-2 was observed. Additionally, a chronoamperometric test was performed for 15 h at 20 mA cm-2, which highlights the better sustainability of Ni-NGr under the actual operating conditions. Finally, the quantitative estimation of evolved oxygen was monitored by gas chromatography and was found to be 70 mmol h-1 g-1 of oxygen, which is constant in the second cycle as well.Herein, we report the synthesis of a nitrogen-doped graphene (NGr) interpenetrated 3D Ni-nanocage (Ni-NGr) electrocatalyst by a simple water-in-oil (w/o) emulsion technique for oxidation of water to dioxygen. Correlation of adsorption of NGr and subsequent interpenetration through the specific surface plane of nickel particles as well as the concomitant interaction of N and C with Ni in the nano-regime has been investigated. Apart from the benefits of the synergistic interactions between Ni, N, and C, the overall integrity of the structure and its intra-molecular connectivity within the framework help in achieving better oxygen evolution characteristics at a significantly reduced overpotential. The engineered Ni-NGr nanocage displays a substantially low overpotential of ~290 mV at a practical current density of 20 mA cm-2 in 0.1 M KOH. In comparison, NGr and Ni-particles as separate entities give overpotentials of ~570 and ~370 mV under similar conditions. Moreover, the long term stability of Ni-NGr was investigated by anodic potential cycling for 500 cycles and an 8.5% increment in the overpotential at 20 mA cm-2 was observed. Additionally, a chronoamperometric test was performed for 15 h at 20 mA cm-2, which highlights the better sustainability of Ni-NGr under the actual operating conditions. Finally, the quantitative estimation of evolved oxygen was monitored by gas chromatography and was found to be 70 mmol h-1 g-1 of oxygen, which is constant in the second cycle as well. Electronic supplementary information (ESI) available: An experimental procedure for the synthesis of GO, Gr, Ni-particles, and Ni-Gr. TEM images of Gr, NGr, and Ni-Gr. XPS of C 1s and O 1s of Ni-NGr. C 1s, O 1s and N 1s spectra of NGr. A comparative cyclic voltammogram of NGr and Ni-NGr. A Tafel plot, RRDE, HR-TEM image of Ni-NGr and the corresponding line profile showing the lattice spacing values, anodic scan of NGr. Comparative anodic scan of Ni-particles, Ni-Gr and Ni-NGr. CV of the Pt-electrode and capacitive CV. SEM elemental mapping and the mechanism of OER. See DOI: 10.1039/c4nr03578j

Combined effects of CO2 and light on the N2-fixing cyanobacterium Trichodesmium IMS101: a mechanistic view.

PubMed

Levitan, Orly; Kranz, Sven A; Spungin, Dina; Prásil, Ondrej; Rost, Björn; Berman-Frank, Ilana

2010-09-01

The marine diazotrophic cyanobacterium Trichodesmium responds to elevated atmospheric CO(2) partial pressure (pCO(2)) with higher N(2) fixation and growth rates. To unveil the underlying mechanisms, we examined the combined influence of pCO(2) (150 and 900 microatm) and light (50 and 200 micromol photons m(-2) s(-1)) on Trichodesmium IMS101. We expand on a complementary study that demonstrated that while elevated pCO(2) enhanced N(2) fixation and growth, oxygen evolution and carbon fixation increased mainly as a response to high light. Here, we investigated changes in the photosynthetic fluorescence parameters of photosystem II, in ratios of the photosynthetic units (photosystem I:photosystem II), and in the pool sizes of key proteins involved in the fixation of carbon and nitrogen as well as their subsequent assimilation. We show that the combined elevation in pCO(2) and light controlled the operation of the CO(2)-concentrating mechanism and enhanced protein activity without increasing their pool size. Moreover, elevated pCO(2) and high light decreased the amounts of several key proteins (NifH, PsbA, and PsaC), while amounts of AtpB and RbcL did not significantly change. Reduced investment in protein biosynthesis, without notably changing photosynthetic fluxes, could free up energy that can be reallocated to increase N(2) fixation and growth at elevated pCO(2) and light. We suggest that changes in the redox state of the photosynthetic electron transport chain and posttranslational regulation of key proteins mediate the high flexibility in resources and energy allocation in Trichodesmium. This strategy should enable Trichodesmium to flourish in future surface oceans characterized by elevated pCO(2), higher temperatures, and high light.

Autonomic dysfunction assessed by EZSCAN and subclinical atherosclerosis.

PubMed

Sun, Jichao; Zhang, Yinfei; Xu, Baihui; Lv, Xiaofei; Ding, Lin; Chen, Ying; Sun, Wanwan; Lu, Jieli; Xu, Min; Bi, Yufang; Ning, Guang

2014-09-01

The present study aimed to explore the association between autonomic dysfunction and measurements of atherosclerosis in a middle-aged and elderly Chinese population. A population-based cross-sectional study was performed in Shanghai, China, from March to August 2010, with 5076 participants included in the analysis. Autonomic function was assessed by a novel EZSCAN test based on sudomotor function analysis. Carotid intima-media thickness (CIMT) was measured using B-mode ultrasonography and brachial-ankle pulse wave velocity (ba-PWV) was measured using an autonomic device. Participants were divided into three groups based on EZSCAN values: Group 1: EZSCAN 0-24; Group 2, EZSCAN 25-49; and Group 3, EZSCAN 50-100. These groups denoted autonomic dysfunction risk groups as follows: no risk, moderate risk and high risk, respectively. The prevalence of elevated CIMT and ba-PWV increased markedly with increasing EZSCAN values (elevated CIMT 7.4%, 17.5%, and 29.7%, elevated ba-PWV 3.2%, 19.7%, and 36.5%, in Groups 1, 2, and 3, respectively; both Ptrend < 0.0001). Logistic regressions revealed that EZSCAN values ≥50 were associated with a non-significantly higher risk of elevated CIMT (odds ratio [OR] = 1.43; 95% confidence interval [CI] 0.98-2.07) and a significantly higher risk of elevated ba-PWV (OR = 2.16; 95% CI 1.25-3.71) compared with EZSCAN values <25, after controlling for conventional risk factors. A higher EZSCAN value (≥50), an index of high autonomic dysfunction risk, was associated with an increased risk of elevated ba-PWV and CIMT. Such associations were partially explained by traditional atherosclerotic risk factors. © 2014 Ruijin Hospital, Shanghai Jiaotong University School of Medicine and Wiley Publishing Asia Pty Ltd.

Reproductive traits associated with species turnover of amphibians in Amazonia and its Andean slopes.

PubMed

Jiménez-Robles, Octavio; Guayasamin, Juan M; Ron, Santiago R; De la Riva, Ignacio

2017-04-01

Assembly of ecological communities is important for the conservation of ecosystems, predicting perturbation impacts, and understanding the origin and loss of biodiversity. We tested how amphibian communities are assembled by neutral and niche-based mechanisms, such as habitat filtering. Species richness, β-diversities, and reproductive traits of amphibians were evaluated at local scale in seven habitats at different elevation and disturbance levels in Wisui Biological Station, Morona-Santiago, Ecuador, on the foothills of the Cordillera del Kutukú; and at regional scale using 109 localities across evergreen forests of Amazonia and its Andean slopes (0-3,900 m a.s.l.). At local scale, species composition showed strong differences among habitats, explained mainly by turnover. Reproductive modes occurred differently across habitats (e.g., prevalence of direct developers at high elevation, where breeding in ground level water disappears). At regional scale, elevation was the most important factor explaining the changes in species richness, reproductive trait occurrences, and biotic dissimilarities. Species number in all groups decreased with elevation except for those with lotic tadpoles and terrestrial reproduction stages. Seasonality, annual precipitation, and relative humidity partially explained the occurrence of some reproductive traits. Biotic dissimilarities were also mostly caused by turnover rather than nestedness and were particularly high in montane and foothill sites. Within lowlands, geographic distance explained more variability than elevation. Habitat filtering was supported by the different occurrence of reproductive traits according to elevation, water availability, and breeding microhabitats at both scales, as well as other assembly mechanisms based in biotic interactions at local scale. Human-generated land use changes in Amazonia and its Andean slopes reduce local amphibian biodiversity by alteration of primary forests and loss of their microhabitats and the interaction network that maintains their unique amphibian assemblages with different reproductive strategies.

Process of forming catalytic surfaces for wet oxidation reactions

NASA Technical Reports Server (NTRS)

Jagow, R. B. (Inventor)

1977-01-01

A wet oxidation process was developed for oxidizing waste materials, comprising dissolved ruthenium salt in a reactant feed stream containing the waste materials. The feed stream is introduced into a reactor, and the reactor contents are then raised to an elevated temperature to effect deposition of a catalytic surface of ruthenium black on the interior walls of the reactor. The feed stream is then maintained in the reactor for a period of time sufficient to effect at least partial oxidation of the waste materials.

VIPER: Chronic Pain after Amputation: Inflammatory Mechanisms, Novel Analgesic Pathways, and Improved Patient Safety

DTIC Science & Technology

2016-10-01

inflammatory mediators. Pro-inflammatory mediators including TNF-α, TNF-β, IL-8, ICAM-1, Tie2, CRP, and SAA were elevated in patients with chronic residual limb...IL-12, TNF-β, PIGF, Tie2, SAA and ICAM-1), and inversely with concentrations of the anti-inflammatory mediator IL-13, as well as IL-2 and Eotaxin-3...catastrophizing and residual limb pain intensity were partially mediated by TNF-α, TNF- β, SAA , and ICAM-1 levels. Results suggest that chronic post

Familial acromegaly with pituitary adenoma. Report of three affected siblings.

PubMed

Abbassioun, K; Fatourehchi, V; Amirjamshidi, A; Meibodi, N A

1986-03-01

The authors report the cases of three brothers with pituitary adenomas who had classical findings of acromegaly and gigantism. Two had irreducibly elevated growth hormone (GH) values and underwent transsphenoidal microsurgical extirpation of their tumors. The third acromegalic brother had a normal GH value and evidence of panhypopituitarism; he had a small intrasellar tumor and a partially empty sella. The pattern of inheritance was probably autosomal recessive. A review of literature indicated that familial incidence of isolated acromegaly with pituitary adenomas is rare.

Phospho-eIF2α Level Is Important for Determining Abilities of BACE1 Reduction to Rescue Cholinergic Neurodegeneration and Memory Defects in 5XFAD Mice

PubMed Central

Devi, Latha; Ohno, Masuo

2010-01-01

β-Site APP-cleaving enzyme 1 (BACE1) initiates amyloid-β (Aβ) generation and thus represents a prime therapeutic target in treating Alzheimer's disease (AD). Notably, increasing evidence indicates that BACE1 levels become elevated in AD brains as disease progresses; however, it remains unclear how the BACE1 upregulation may affect efficacies of therapeutic interventions including BACE1-inhibiting approaches. Here, we crossed heterozygous BACE1 knockout mice with AD transgenic mice (5XFAD model) and compared the abilities of partial BACE1 reduction to rescue AD-like phenotypes at earlier (6-month-old) and advanced (15–18-month-old) stages of disease, which expressed normal (∼100%) and elevated (∼200%) levels of BACE1, respectively. BACE1+/− deletion rescued memory deficits as tested by the spontaneous alternation Y-maze task in 5XFAD mice at the earlier stage and prevented their septohippocampal cholinergic deficits associated with significant neuronal loss. Importantly, BACE1+/− deletion was no longer able to rescue memory deficits or cholinergic neurodegeneration in 5XFAD mice at the advanced stage. Moreover, BACE1+/− deletion significantly reduced levels of Aβ42 and the β-secretase-cleaved C-terminal fragment (C99) in 6-month-old 5XFAD mouse brains, while these neurotoxic β-cleavage products dramatically elevated with age and were not affected by BACE1+/− deletion in 15–18-month-old 5XFAD brains. Interestingly, although BACE1+/− deletion lowered BACE1 expression by ∼50% in 5XFAD mice irrespective of age in concordance with the reduction in gene copy number, BACE1 equivalent to wild-type controls remained in BACE1+/−·5XFAD mice at the advanced age. In accord, phosphorylation of the translation initiation factor eIF2α, an important mediator of BACE1 elevation, was dramatically increased (∼9-fold) in 15–18-month-old 5XFAD mice and remained highly upregulated (∼6-fold) in age-matched BACE1+/−·5XFAD mice. Together, our results indicate that partial reduction of BACE1 is not sufficient to block the phospho-eIF2α-dependent BACE1 elevation during the progression of AD, thus limiting its abilities to reduce cerebral Aβ/C99 levels and rescue memory deficits and cholinergic neurodegeneration. PMID:20886088

Is the foot elevation the optimal position for wound healing of a diabetic foot?

PubMed

Park, D J; Han, S K; Kim, W K

2010-03-01

In managing diabetic foot ulcers, foot elevation has generally been recommended to reduce oedema and prevent other sequential problems. However, foot elevation may decrease tissue oxygenation of the foot more than the dependent position since the dependent position is known to increase blood flow within the arterial system. In addition, diabetic foot ulcers, which have peripheral vascular insufficiency, generally have less oedema than other wounds. Therefore, we argue that foot elevation may not be helpful for healing of vascularly compromised diabetic foot ulcers since adequate tissue oxygenation is an essential factor in diabetic wound healing. The purpose of this study was to evaluate the influence of foot height on tissue oxygenation and to determine the optimal foot position to accelerate wound healing of diabetic foot ulcers. This study included 122 cases (73 males and 47 females; two males had bilateral disease) of diabetic foot ulcer patients aged 40-93 years. Trans-cutaneous partial oxygen tension (TcpO(2)) values of diabetic feet were measured before and after foot elevation (n=21). Elevation was achieved by placing a foot over four cushions. We also measured foot TcpO(2) values before and after lowering the feet (n=122). Feet were lowered to the patient's tibial height, approximately 30-35 cm, beside a bed handrail. Due to the large number of lowering measurements, we divided them into five sub-groups according to initial TcpO(2.) Tissue oxygenation values were compared. Foot-elevation-lowered TcpO(2) values before and after elevation were 32.5+/-22.2 and 23.8+/-23.1 mmHg (p<0.01), respectively. Foot-lowering-augmented TcpO(2) values before and after lowering were 44.6+/-23.8 and 58.0+/-25.9 mmHg (p<0.01), respectively. The lower the initial TcpO(2) level, the more the TcpO(2) level increased. The foot lowering, rather than elevation, significantly augments TcpO(2) and may stimulate healing of diabetic foot ulcers. (c) 2008 British Association of Plastic, Reconstructive and Aesthetic Surgeons. Published by Elsevier Ltd. All rights reserved.

Spectroscopic and Theoretical Study of CuI Binding to His111 in the Human Prion Protein Fragment 106–115

PubMed Central

2016-01-01

The ability of the cellular prion protein (PrPC) to bind copper in vivo points to a physiological role for PrPC in copper transport. Six copper binding sites have been identified in the nonstructured N-terminal region of human PrPC. Among these sites, the His111 site is unique in that it contains a MKHM motif that would confer interesting CuI and CuII binding properties. We have evaluated CuI coordination to the PrP(106–115) fragment of the human PrP protein, using NMR and X-ray absorption spectroscopies and electronic structure calculations. We find that Met109 and Met112 play an important role in anchoring this metal ion. CuI coordination to His111 is pH-dependent: at pH >8, 2N1O1S species are formed with one Met ligand; in the range of pH 5–8, both methionine (Met) residues bind to CuI, forming a 1N1O2S species, where N is from His111 and O is from a backbone carbonyl or a water molecule; at pH <5, only the two Met residues remain coordinated. Thus, even upon drastic changes in the chemical environment, such as those occurring during endocytosis of PrPC (decreased pH and a reducing potential), the two Met residues in the MKHM motif enable PrPC to maintain the bound CuI ions, consistent with a copper transport function for this protein. We also find that the physiologically relevant CuI-1N1O2S species activates dioxygen via an inner-sphere mechanism, likely involving the formation of a copper(II) superoxide complex. In this process, the Met residues are partially oxidized to sulfoxide; this ability to scavenge superoxide may play a role in the proposed antioxidant properties of PrPC. This study provides further insight into the CuI coordination properties of His111 in human PrPC and the molecular mechanism of oxygen activation by this site. PMID:26930130

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.

Rapid Liver Hypertrophy After Portal Vein Occlusion Correlates with the Degree of Collateralization Between Lobes-a Study in Pigs.

PubMed

Deal, Rebecca; Frederiks, Charles; Williams, Lauren; Olthof, Pim B; Dirscherl, Konstantin; Keutgen, Xavier; Chan, Edie; Deziel, Daniel; Hertl, Martin; Schadde, Erik

2018-02-01

Associating liver partition and portal vein ligation for staged hepatectomy (ALPPS) induces more rapid liver growth than portal vein ligation (PVL). Transection of parenchyma in ALPPS may prevent the formation of collaterals between lobes. The aim of this study was to determine if abrogating the formation of collaterals through parenchymal transection impacted growth rate. Twelve Yorkshire Landrace pigs were randomized to undergo ALPPS, PVL, or "partial ALPPS" by varying degrees of parenchymal transection. Hepatic volume was measured after 7 days. Portal blood flow and pressure were measured. Portal vein collaterals were examined from epoxy casts. PVL, ALPPS, and partial ALPPS led to volume increases of the RLL by 15.5% (range 3-22), 64% (range 45-76), and 32% (range 18-77), respectively, with significant differences between PVL and ALPPS/partial ALPPS (p < 0.05). In PVL and partial ALPPS, substantial new portal vein collaterals were found. The number of collaterals correlated inversely with the growth rate (p = 0.039). Portal vein pressure was elevated in all models after ligation suggesting hyperflow to the portal vein-supplied lobe (p < 0.05). These data suggest that liver hypertrophy following PVL is inversely proportional to the development of collaterals. Hypertrophy after ALPPS is likely more rapid due to reduction of collaterals through transection.

Exercise in obese female rats has beneficial effects on maternal and male and female offspring metabolism

PubMed Central

Vega, Claudia C; Reyes-Castro, Luis A; Bautista, Claudia J; Larrea, Fernando; Nathanielsz, Peter W; Zambrano, Elena

2013-01-01

BACKGROUND Maternal obesity (MO) impairs maternal and offspring health. Mechanisms and interventions to prevent adverse maternal and offspring outcomes need to be determined. Human studies are confounded by socio-economic status providing the rationale for controlled animal data on effects of maternal exercise (MEx) intervention on maternal (F0) and offspring (F1) outcomes in MO. HYPOTHESIS MO produces metabolic and endocrine dysfunction, increases maternal and offspring glucocorticoid exposure, oxidative stress and adverse offspring outcomes by postnatal day (PND) 36. MEx prevents these outcomes. METHODS F0 female rats ate either control or obesogenic diet from weaning through lactation. Half of each group wheel ran (from day ninety of life through pregnancy beginning day 120) providing four groups (n=8/group) – i) controls, ii) obese, iii) exercised controls and iv) exercised obese. After weaning, PND 21, F1 offspring ate a control diet. Metabolic parameters of F0 prepregnancy and end of lactation and F1 offspring at PND 36 were analyzed. RESULTS Exercise did not change maternal weight. Before breeding, MO elevated F0 glucose, insulin, triglycerides, cholesterol, leptin, fat and oxidative stress. Exercise completely prevented the triglyceride rise and partially glucose, insulin, cholesterol and oxidative stress increases. MO decreased fertility, recovered by exercise. At the end of lactation, exercise returned all metabolic variables except leptin to control levels. Exercise partially prevented MO elevated corticosterone. F1 Offspring weights were similar at birth. At PND 36 MO increased F1 male but not female offspring leptin, triglycerides and fat mass. In controls exercise reduced male and female offspring glucose, prevented the offspring leptin increase and partially the triglyceride rise. CONCLUSIONS MEx before and during pregnancy has beneficial effects on maternal and offspring metabolism and endocrine function occurring with no weight change in mothers and offspring indicating the importance of body composition rather than weight in evaluations of metabolic status. PMID:23949616

Course of Disinhibited Social Engagement Disorder From Early Childhood to Early Adolescence.

PubMed

Guyon-Harris, Katherine L; Humphreys, Kathryn L; Fox, Nathan A; Nelson, Charles A; Zeanah, Charles H

2018-05-01

Disinhibited social engagement disorder (DSED) is poorly understood beyond early childhood. The course of DSED signs in a sample of children who experienced severe, early deprivation from early childhood to early adolescence was examined using variable-centered (linear mixed modeling) and person-centered (growth mixture modeling) approaches. The study included 124 children with a history of institutional care from a randomized controlled trial of foster care as an alternative to institutional care and 69 community comparison children matched by age and sex. DSED signs were assessed at baseline (mean age 22 months), 30, 42, and 54 months of age, and 8 and 12 years of age using a validated caregiver report of disturbed attachment behavior. Variable-centered analyses based on intent-to-treat groups indicated that signs of DSED decreased sharply for children randomized to foster care and decreased slightly but remained high for children randomized to care as usual. Person-centered analyses showed 4 profiles (i.e., elevated, persistent modest, early decreasing, and minimal). Elevated and persistent modest courses were associated with greater placement disruptions (F 3,99  = 4.29, p = .007, partial eta-squared [η 2 ] = 0.12), older age at placement into foster care (F 3,56  = 3.41, p < .05, partial η 2  = 0.16), and more time in institutional care (F 3,115  = 11.91, p < .001, partial η 2  = 0.24) compared with decreasing and minimal courses. Early and sustained placement into families after deprivation is associated with minimal or decreasing signs of DSED across development. Shortening the amount of time children spend in institutions and preserving placements could help decrease signs of DSED into early adolescence in previously institutionalized children. Copyright © 2018 American Academy of Child and Adolescent Psychiatry. Published by Elsevier Inc. All rights reserved.

Association of breast feeding with early childhood dental caries: Japanese population-based study

PubMed Central

Yorifuji, Takashi; Yamakawa, Michiyo; Inoue, Sachiko; Saito, Keiko; Doi, Hiroyuki; Kawachi, Ichiro

2015-01-01

Objectives We investigated the association between breastfeeding duration during the first half year of life and the risk of early childhood caries from the age of 30 to 66 months in Japan. Design Observational study of a longitudinal survey. Setting A secondary data analysis of the Japanese Longitudinal Survey of Babies in the 21st Century. Participants 43 383 infants at the age of 6 months. Outcome measures Early childhood caries—defined as a child's visit to a dentist for treatment of dental caries during the past 12 months—was ascertained from the caregiver from the age of 30 months in the survey. We estimated the risk of dental caries each year according to duration of breast feeding using logistic regression analyses. We controlled for a set of biological factors (birth weight, sex, parity and maternal age at delivery) and socioeconomic factors (maternal educational attainment and smoking status, marital status at delivery, family income and region of birth and residence). Results We found that infants who had been breast fed for at least 6 or 7 months, both exclusively and partially, were at elevated risk of dental caries at the age of 30 months compared with those who had been exclusively formula fed. Adjusted ORs were 1.78 (95% CI, (1.45 to 2.17)) for the exclusively breastfed group and 1.39 (1.14 to 1.70) for the partially breastfed group. However, the associations became attenuated through the follow-up period and were no longer statistically significant beyond the age of 42 months for the partially breastfed group and beyond the age of 54 months for the exclusively breastfed group. Conclusions We found an association between breast feeding for at least 6 or 7 months and elevated risk of dental caries at age 30 months. However, the association became attenuated as children grew older. PMID:25795694

The role of clopidogrel in early and sustained arterial patency after fibrinolysis for ST-segment elevation myocardial infarction: the ECG CLARITY-TIMI 28 Study.

PubMed

Scirica, Benjamin M; Sabatine, Marc S; Morrow, David A; Gibson, C Michael; Murphy, Sabina A; Wiviott, Stephen D; Giugliano, Robert P; McCabe, Carolyn H; Cannon, Christopher P; Braunwald, Eugene

2006-07-04

This study was designed to determine the relationship between clopidogrel and early ST-segment resolution (STRes) and the interaction of the two with clinical outcomes after fibrinolysis. ST-segment resolution is an early noninvasive marker of coronary reperfusion. The CLARITY-TIMI 28 (Clopidogrel as Adjunctive Reperfusion Therapy-Thrombolysis in Myocardial Infarction 28) trial randomized 3,491 patients with ST-segment elevation myocardial infarction (STEMI) undergoing fibrinolysis to clopidogrel versus placebo. ST-segment resolution was defined as complete (>70%), partial (30% to 70%), or none (<30%). Electrocardiograms were valid for interpretation in 2,431 patients at 90 min and 2,087 at 180 min. There was no difference in the rate of complete STRes between the clopidogrel and placebo groups at 90 min (38.4% vs. 36.6% at 90 min). When patients were stratified by STRes category, treatment with clopidogrel resulted in greater benefit among those with evidence of early STRes, with greater odds of an open artery at late angiography in patients with partial (odds ratio [OR] 1.4, p = 0.04) or complete (OR 2.0, p < 0.001) STRes, but no improvement in those with no STRes at 90 min (OR 0.89, p = 0.48) (p for interaction = 0.003). Clopidogrel was also associated with a significant reduction in the odds of an in-hospital death or myocardial infarction in patients who achieved partial (OR 0.30, p = 0.003) or complete STRes at 90 min (OR 0.49, p = 0.056), whereas clinical benefit was not apparent in patients who had no STRes (OR 0.98, p = 0.95) (p for interaction = 0.027). By 30 days, the clinical benefit of clopidogrel was predominately seen in patients with complete STRes. Clopidogrel appears to improve late coronary patency and clinical outcomes by preventing reocclusion of open arteries rather than by facilitating early reperfusion.

Positron annihilation and X-ray diffraction studies on tin oxide thin films

NASA Astrophysics Data System (ADS)

Prabakar, K.; Abhaya, S.; Krishnan, R.; Kalavathi, S.; Dash, S.; Jayapandian, J.; Amarendra, G.

2009-04-01

Positron annihilation spectroscopy along with glancing incidence X-ray diffraction have been used to investigate tin oxide thin films grown on Si by pulsed laser deposition. The films were prepared at room temperature and at 670 K under oxygen partial pressure. As-grown samples are amorphous and are found to contain large concentration of open volume sites (vacancy defects). Post-deposition annealing of as-grown samples at 970 K is found to drastically reduce the number of open volume sites and the film becomes crystalline. However, film grown under elevated temperature and under partial pressure of oxygen is found to exhibit a lower S-parameter, indicating lower defect concentration. Based on the analysis of experimental positron annihilation results, the defect-sensitive S-parameter and the overlayer thickness of tin oxide thin films are deduced. S- W correlation plots exhibit distinct positron trapping defect states in three samples.

Growth of GaAs crystals from the melt in a partially confined configuration

NASA Technical Reports Server (NTRS)

Gatos, Harry C.; Lagowski, Jacek

1988-01-01

The experimental approach was directed along two main goals: (1) the implementation of an approach to melt growth in a partially confined configuration; and (2) the investigation of point defect interaction and electronic characteristics as related to thermal treatment following solidification and stoichiometry. Significant progress was made along both fronts. Crystal growth of GaAs in triangular ampuls was already carried out successfully and consistent with the model. In fact, pronounced surface tension phenomena which cannot be observed in ordinary confinement system were identified and should premit the assessment of Maragoni effects prior to space processing. Regarding thermal treatment, it was discovered that the rate of cooling from elevated temperatures is primarily responsible for a whole class of defect interactions affecting the electronic characteristics of GaAs and that stoichiometry plays a critical role in the quality of GaAs.

Habitat features and predictive habitat modeling for the Colorado chipmunk in southern New Mexico

USGS Publications Warehouse

Rivieccio, M.; Thompson, B.C.; Gould, W.R.; Boykin, K.G.

2003-01-01

Two subspecies of Colorado chipmunk (state threatened and federal species of concern) occur in southern New Mexico: Tamias quadrivittatus australis in the Organ Mountains and T. q. oscuraensis in the Oscura Mountains. We developed a GIS model of potentially suitable habitat based on vegetation and elevation features, evaluated site classifications of the GIS model, and determined vegetation and terrain features associated with chipmunk occurrence. We compared GIS model classifications with actual vegetation and elevation features measured at 37 sites. At 60 sites we measured 18 habitat variables regarding slope, aspect, tree species, shrub species, and ground cover. We used logistic regression to analyze habitat variables associated with chipmunk presence/absence. All (100%) 37 sample sites (28 predicted suitable, 9 predicted unsuitable) were classified correctly by the GIS model regarding elevation and vegetation. For 28 sites predicted suitable by the GIS model, 18 sites (64%) appeared visually suitable based on habitat variables selected from logistic regression analyses, of which 10 sites (36%) were specifically predicted as suitable habitat via logistic regression. We detected chipmunks at 70% of sites deemed suitable via the logistic regression models. Shrub cover, tree density, plant proximity, presence of logs, and presence of rock outcrop were retained in the logistic model for the Oscura Mountains; litter, shrub cover, and grass cover were retained in the logistic model for the Organ Mountains. Evaluation of predictive models illustrates the need for multi-stage analyses to best judge performance. Microhabitat analyses indicate prospective needs for different management strategies between the subspecies. Sensitivities of each population of the Colorado chipmunk to natural and prescribed fire suggest that partial burnings of areas inhabited by Colorado chipmunks in southern New Mexico may be beneficial. These partial burnings may later help avoid a fire that could substantially reduce habitat of chipmunks over a mountain range.

Tree cover at fine and coarse spatial grains interacts with shade tolerance to shape plant species distributions across the Alps

PubMed Central

Nieto-Lugilde, Diego; Lenoir, Jonathan; Abdulhak, Sylvain; Aeschimann, David; Dullinger, Stefan; Gégout, Jean-Claude; Guisan, Antoine; Pauli, Harald; Renaud, Julien; Theurillat, Jean-Paul; Thuiller, Wilfried; Van Es, Jérémie; Vittoz, Pascal; Willner, Wolfgang; Wohlgemuth, Thomas; Zimmermann, Niklaus E.; Svenning, Jens-Christian

2015-01-01

The role of competition for light among plants has long been recognised at local scales, but its importance for plant species distributions at larger spatial scales has generally been ignored. Tree cover modifies the local abiotic conditions below the canopy, notably by reducing light availability, and thus, also the performance of species that are not adapted to low-light conditions. However, this local effect may propagate to coarser spatial grains, by affecting colonisation probabilities and local extinction risks of herbs and shrubs. To assess the effect of tree cover at both the plot- and landscape-grain sizes (approximately 10-m and 1-km), we fit Generalised Linear Models (GLMs) for the plot-level distributions of 960 species of herbs and shrubs using 6,935 vegetation plots across the European Alps. We ran four models with different combinations of variables (climate, soil and tree cover) at both spatial grains for each species. We used partial regressions to evaluate the independent effects of plot- and landscape-grain tree cover on plot-level plant communities. Finally, the effects on species-specific elevational range limits were assessed by simulating a removal experiment comparing the species distributions under high and low tree cover. Accounting for tree cover improved the model performance, with the probability of the presence of shade-tolerant species increasing with increasing tree cover, whereas shade-intolerant species showed the opposite pattern. The tree cover effect occurred consistently at both the plot and landscape spatial grains, albeit most strongly at the former. Importantly, tree cover at the two grain sizes had partially independent effects on plot-level plant communities. With high tree cover, shade-intolerant species exhibited narrower elevational ranges than with low tree cover whereas shade-tolerant species showed wider elevational ranges at both limits. These findings suggest that forecasts of climate-related range shifts for herb and shrub species may be modified by tree cover dynamics. PMID:26290621

Elevated progranulin contributes to synaptic and learning deficit due to loss of fragile X mental retardation protein.

PubMed

Zhang, Kun; Li, Yu-Jiao; Guo, Yanyan; Zheng, Kai-Yin; Yang, Qi; Yang, Le; Wang, Xin-Shang; Song, Qian; Chen, Tao; Zhuo, Min; Zhao, Ming-Gao

2017-12-01

Fragile X syndrome is an inheritable form of intellectual disability caused by loss of fragile X mental retardation protein (FMRP, encoded by the FMR1 gene). Absence of FMRP caused overexpression of progranulin (PGRN, encoded by GRN), a putative tumour necrosis factor receptor ligand. In the present study, we found that progranulin mRNA and protein were upregulated in the medial prefrontal cortex of Fmr1 knock-out mice. In Fmr1 knock-out mice, elevated progranulin caused insufficient dendritic spine pruning and late-phase long-term potentiation in the medial prefrontal cortex of Fmr1 knock-out mice. Partial progranulin knock-down restored spine morphology and reversed behavioural deficits, including impaired fear memory, hyperactivity, and motor inflexibility in Fmr1 knock-out mice. Progranulin increased levels of phosphorylated glutamate ionotropic receptor GluA1 and nuclear factor kappa B in cultured wild-type neurons. Tumour necrosis factor receptor 2 antibody perfusion blocked the effects of progranulin on GluA1 phosphorylation; this result indicates that tumour necrosis factor receptor 2 is required for progranulin-mediated GluA1 phosphorylation and late-phase long-term potentiation expression. However, high basal level of progranulin in Fmr1 knock-out mice prevented further facilitation of synaptic plasticity by exogenous progranulin. Partial downregulation of progranulin or tumour necrosis factor receptor 2/nuclear factor kappa B signalling restored synaptic plasticity and memory deficits in Fmr1 knock-out mice. These findings suggest that elevated PGRN is linked to cognitive deficits of fragile X syndrome, and the progranulin/tumour necrosis factor receptor 2 signalling pathway may be a putative therapeutic target for improving cognitive deficits in fragile X syndrome. © The Author (2017). Published by Oxford University Press on behalf of the Guarantors of Brain. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

miR-330 regulates the proliferation of colorectal cancer cells by targeting Cdc42

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

Li, Yuefeng; Zhu, Xiaolan; Xu, Wenlin

2013-02-15

Highlights: ► miR-330 was inversely correlated with Cdc42 in colorectal cancer cells. ► Elevated miR-330 suppressed cell proliferation in vivo and in vitro. ► Elevated miR-330 mimicked the effect of Cdc42 knockdown. ► Restoration of Cdc42 could partially attenuate the effects of miR-330. -- Abstract: MicroRNAs are small non-coding RNA molecules that play important roles in the multistep process of colorectal carcinoma (CRC) development. However, the miRNA–mRNA regulatory network is far from being fully understood. The objective of this study was to investigate the expression and the biological roles of miR-330 in colorectal cancer cells. Cdc42, one of the bestmore » characterized members of the Rho GTPase family, was found to be up-regulated in several types of human tumors including CRC and has been implicated in cancer initiation and progression. In the present study, we identified miR-330, as a potential regulator of Cdc42, was found to be inversely correlated with Cdc42 expression in colorectal cancer cell lines. Ectopic expression of miR-330 down-regulated Cdc42 expression at both protein and mRNA level, mimicked the effect of Cdc42 knockdown in inhibiting proliferation, inducing G1 cell cycle arrest and apoptosis of the colorectal cancer cells, whereas restoration of Cdc42 could partially attenuate the effects of miR-330. In addition, elevated expression of miR-330 could suppress the immediate downstream effectors of Cdc42 and inhibit the growth of colorectal cancer cells in vivo. To sum up, our results establish a role of miR-330 in negatively regulating Cdc42 expression and colorectal cancer cell proliferation. They suggest that manipulating the expression level of Cdc42 by miR-330 has the potential to influence colorectal cancer progression.« less

Weight loss and vascular inflammatory markers in overweight women with and without polycystic ovary syndrome.

PubMed

Moran, Lisa J; Noakes, Manny; Wittert, Gary A; Clifton, Peter M; Norman, Robert J

2012-11-01

Polycystic ovary syndrome (PCOS) is associated with increased cardiovascular disease risk. The effect of weight loss on the vascular inflammatory markers plasminogen activator inhibitor-1 (PAI-1), asymmetric dimethylarginine (ADMA), soluble vascular cell adhesion molecule-1 (sVCAM-1) and intracellular adhesion molecule-1 (sICAM-1) is unknown. Overweight women with (n=14) and without (n=13) PCOS of comparable age and body mass index undertook an 8-week weight-loss programme. Women with PCOS had elevated PAI-1, sVCAM-1 and sICAM-1 before and after weight loss compared with the controls. For all women, sVCAM-1 (P=0.026) and sICAM-1 (P=0.04) decreased with weight loss. Women with PCOS have elevated inflammatory markers, which are partially reduced by weight loss. Copyright © 2012 Reproductive Healthcare Ltd. Published by Elsevier Ltd. All rights reserved.

Silent disco: dancing in synchrony leads to elevated pain thresholds and social closeness

PubMed Central

Tarr, Bronwyn; Launay, Jacques; Dunbar, Robin I.M.

2016-01-01

Moving in synchrony leads to cooperative behaviour and feelings of social closeness, and dance (involving synchronisation to others and music) may cause social bonding, possibly as a consequence of released endorphins. This study uses an experimental paradigm to determine which aspects of synchrony in dance are associated with changes in pain threshold (a proxy for endorphin release) and social bonding between strangers. Those who danced in synchrony experienced elevated pain thresholds, whereas those in the partial and asynchrony conditions experienced no analgesic effects. Similarly, those in the synchrony condition reported being more socially bonded, although they did not perform more cooperatively in an economic game. This experiment suggests that dance encourages social bonding amongst co-actors by stimulating the production of endorphins, but may not make people more altruistic. We conclude that dance may have been an important human behaviour evolved to encourage social closeness between strangers. PMID:27540276

Water Resources Data--Kansas, Water Year 2003

USGS Publications Warehouse

Putnam, J.E.; Schneider, D.R.

2004-01-01

Water-resources data for the 2003 water year for Kansas consist of records of stage, discharge, and water quality of streams; elevation and contents of lakes and reservoirs; and water levels of ground-water wells. This report contains records for water discharge at 148 complete-record gaging stations; elevation and contents at 17 lakes and reservoirs; water-quality records at 2 precipitation stations, water-level data at 12 observation wells; and records of specific conductance, pH, water temperature, dissolved oxygen, and turbidity at 11 gaging stations and 2 lakes with water-quality monitors. Also included are discharge data for 27 high-flow partial-record stations, miscellaneous onsite water-quality data collected at 138 stations, and suspended-sediment concentration for 11 stations. These data represent that part of the National Water Information System collected by the U.S. Geological Survey in cooperation with local, State, and Federal agencies in Kansas.

Effect of Elevated Temperature on Mechanical Assets of Metakaolin Base Steel Fiber Reinforced Concrete

NASA Astrophysics Data System (ADS)

Vijay Anand, M.; Ibrahim, Azmi; Patil, Anand A.; Muthu, K. U.

2017-06-01

The fact of vast usage of concrete leads to important problems regarding its design and preparation of eco-friendly to obtain an economic cost of the product on varieties of time periods. Conventional ordinary Portland concrete may not able to meet its functional requisites as it found inconsistency in high temperature. The exposing of concrete structure to elevated temperature may be in case of rocket launching space ships, nuclear power plants. In this experiment, to enhance the high temperature resistance, pozzolanic materials and steel fibres are added to preserve the strength characteristics of concrete structure. In this analysis, the pozzolanic admixture MK is used as partial replacement of cementatious materials. The volume fraction of steel fibre is varied 0.25%, 0.5%, 0.75% and 1% by preserving MK as stationary for 10% replacement of cement. The strength parameters of concrete such as compressive strength, split tensile strength and flexural strength are studied.

Desmoid type fibromatosis: A case report with an unusual etiology

PubMed Central

Jafri, Syed Faisal; Obaisi, Obada; Vergara, Gerardo G; Cates, Joe; Singh, Jaswinder; Feeback, Jennifer; Yandrapu, Harathi

2017-01-01

Desmoid type fibromatosis (DTF) is a rare, locally invasive, non-metastasizing soft tissue tumor. We report an interesting case of DTF involving the pancreatic head of a 54-year-old woman. She presented with intermittent dysphagia and significant weight loss within a 3-mo period. Laboratory findings showed mild elevation of transaminases, significant elevation of alkaline phosphatase and direct hyperbilirubinemia, indicating obstructive jaundice. Computerized tomography of the abdomen revealed a mass in the head of the pancreas, dilated common bile duct, and dilated pancreatic duct. Endoscopic retrograde cholangiopancreatography and endoscopic ultrasound showed a large hypoechoic mass in the head of the pancreas causing extrahepatic biliary obstruction and pancreatic ductal dilation. The patient underwent a successful partial pancreatico-duodenectomy and cholecystectomy. She received no additional therapy after surgery, and liver function tests were normalized within nine days after surgery. Currently, surgical resection is the recommended first line treatment. The patient will be followed for any recurrence. PMID:28979721

Evaluation of single photon and Geiger mode Lidar for the 3D Elevation Program

USGS Publications Warehouse

Stoker, Jason M.; Abdullah, Qassim; Nayegandhi, Amar; Winehouse, Jayna

2016-01-01

Data acquired by Harris Corporation’s (Melbourne, FL, USA) Geiger-mode IntelliEarth™ sensor and Sigma Space Corporation’s (Lanham-Seabrook, MD, USA) Single Photon HRQLS sensor were evaluated and compared to accepted 3D Elevation Program (3DEP) data and survey ground control to assess the suitability of these new technologies for the 3DEP. While not able to collect data currently to meet USGS lidar base specification, this is partially due to the fact that the specification was written for linear-mode systems specifically. With little effort on part of the manufacturers of the new lidar systems and the USGS Lidar specifications team, data from these systems could soon serve the 3DEP program and its users. Many of the shortcomings noted in this study have been reported to have been corrected or improved upon in the next generation sensors.

Osthole Enhances Osteogenesis in Osteoblasts by Elevating Transcription Factor Osterix via cAMP/CREB Signaling In Vitro and In Vivo.

PubMed

Zhang, Zhong-Rong; Leung, Wing Nang; Li, Gang; Kong, Siu Kai; Lu, Xiong; Wong, Yin Mei; Chan, Chun Wai

2017-06-08

Anabolic anti-osteoporotic agents are desirable for treatment and prevention of osteoporosis and fragility fractures. Osthole is a coumarin derivative extracted from the medicinal herbs Cnidium monnieri (L.) Cusson and Angelica pubescens Maxim.f. Osthole has been reported with osteogenic and anti-osteoporotic properties, whereas the underlying mechanism of its benefit still remains unclear. The objective of the present study was to investigate the osteopromotive action of osthole on mouse osteoblastic MC3T3-E1 cells and on mouse femoral fracture repair, and to explore the interaction between osthole-induced osteopromotive effect and cyclic adenosine monophosphate (cAMP) elevating effect. Osthole treatment promoted osteogenesis in osteoblasts by enhancing alkaline phosphatase (ALP) activity and mineralization. Oral gavage of osthole enhanced fracture repair and increased bone strength. Mechanistic study showed osthole triggered the cAMP/CREB pathway through the elevation of the intracellular cAMP level and activation of the phosphorylation of the cAMP response element-binding protein (CREB). Blockage of cAMP/CREB downstream signals with protein kinase A (PKA) inhibitor KT5720 partially suppressed osthole-mediated osteogenesis by inhibiting the elevation of transcription factor, osterix. In conclusion, osthole shows osteopromotive effect on osteoblasts in vitro and in vivo. Osthole-mediated osteogenesis is related to activation of the cAMP/CREB signaling pathway and downstream osterix expression.

Osthole Enhances Osteogenesis in Osteoblasts by Elevating Transcription Factor Osterix via cAMP/CREB Signaling In Vitro and In Vivo

PubMed Central

Zhang, Zhong-Rong; Leung, Wing Nang; Li, Gang; Kong, Siu Kai; Lu, Xiong; Wong, Yin Mei; Chan, Chun Wai

2017-01-01

Anabolic anti-osteoporotic agents are desirable for treatment and prevention of osteoporosis and fragility fractures. Osthole is a coumarin derivative extracted from the medicinal herbs Cnidium monnieri (L.) Cusson and Angelica pubescens Maxim.f. Osthole has been reported with osteogenic and anti-osteoporotic properties, whereas the underlying mechanism of its benefit still remains unclear. The objective of the present study was to investigate the osteopromotive action of osthole on mouse osteoblastic MC3T3-E1 cells and on mouse femoral fracture repair, and to explore the interaction between osthole-induced osteopromotive effect and cyclic adenosine monophosphate (cAMP) elevating effect. Osthole treatment promoted osteogenesis in osteoblasts by enhancing alkaline phosphatase (ALP) activity and mineralization. Oral gavage of osthole enhanced fracture repair and increased bone strength. Mechanistic study showed osthole triggered the cAMP/CREB pathway through the elevation of the intracellular cAMP level and activation of the phosphorylation of the cAMP response element-binding protein (CREB). Blockage of cAMP/CREB downstream signals with protein kinase A (PKA) inhibitor KT5720 partially suppressed osthole-mediated osteogenesis by inhibiting the elevation of transcription factor, osterix. In conclusion, osthole shows osteopromotive effect on osteoblasts in vitro and in vivo. Osthole-mediated osteogenesis is related to activation of the cAMP/CREB signaling pathway and downstream osterix expression. PMID:28629115

Mixed Species Flock, Nest Height, and Elevation Partially Explain Avian Haemoparasite Prevalence in Colombia

PubMed Central

González, Angie D.; Matta, Nubia E.; Ellis, Vincenzo A.; Miller, Eliot T.; Ricklefs, Robert E.; Gutiérrez, H. Rafael

2014-01-01

The high avian biodiversity present in the Neotropical region offers a great opportunity to explore the ecology of host-parasite relationships. We present a survey of avian haemoparasites in a megadiverse country and explore how parasite prevalences are related to physical and ecological host characteristics. Using light microscopy, we documented the presence of haemoparasites in over 2000 individuals belonging to 246 species of wild birds, from nine localities and several ecosystems of Colombia. We analysed the prevalence of six avian haemoparasite taxa in relation to elevation and the following host traits: nest height, nest type, foraging strata, primary diet, sociality, migratory behaviour, and participation in mixed species flocks. Our analyses indicate significant associations between both mixed species flocks and nest height and Haemoproteus and Leucocytozoon prevalence. The prevalence of Leucocytozoon increased with elevation, whereas the prevalence of Trypanosoma and microfilariae decreased. Plasmodium and Haemoproteus prevalence did not vary significantly with elevation; in fact, both parasites were found up to 3300m above sea level. The distribution of parasite prevalence across the phylogeny of bird species included in this study showed little host phylogenetic signal indicating that infection rates in this system are evolutionarily labile. Vector distribution as well as the biology of transmission and the maintenance of populations of avian haemoparasites deserve more detailed study in this system. PMID:24950223

Systematic biology analysis on photosynthetic carbon metabolism of maize leaf following sudden heat shock under elevated CO2.

PubMed

Qu, Mingnan; Chen, Genyun; Bunce, James A; Zhu, Xiaocen; Sicher, Richard C

2018-05-18

Plants would experience more complex environments, such as sudden heat shock (SHS) stress combined with elevated CO 2 in the future, and might adapt to this stressful condition by optimizing photosynthetic carbon metabolism (PCM). It is interesting to understand whether this acclimation process would be altered in different genotypes of maize under elevated CO 2 , and which metabolites represent key indicators reflecting the photosynthetic rates (P N ) following SHS. Although B76 had greater reduction in P N during SHS treatment, our results indicated that P N in genotype B76, displayed faster recovery after SHS treatment under elevated CO 2 than in genotype B106. Furthermore, we employed a stepwise feature extraction approach by partial linear regression model. Our findings demonstrated that 9 key metabolites over the total (35 metabolites) can largely explain the variance of P N during recovery from SHS across two maize genotypes and two CO 2 grown conditions. Of these key metabolites, malate, valine, isoleucine, glucose and starch are positively correlated with recovery pattern of P N . Malate metabolites responses to SHS were further discussed by incorporating with the activities and gene expression of three C 4 photosynthesis-related key enzymes. We highlighted the importance of malate metabolism during photosynthesis recovery from short-term SHS, and data integration analysis to better comprehend the regulatory framework of PCM in response to abiotic stress.

Anxiety Independently Contributes to Elevated Inflammation in Humans with Obesity

PubMed Central

Pierce, Gary L.; Kalil, Graziela Z.; Ajibewa, Tiwaloluwa; Holwerda, Seth W.; Persons, Jane; Moser, David J.; Fiedorowicz, Jess G.

2016-01-01

Objective Anxious and depressive states are associated with increased cardiovascular disease (CVD) risk and a proinflammatory phenotype, although the latter appears to be at least partially explained by adiposity. We hypothesized that depression and anxiety would be associated with elevated inflammation independent of adiposity in persons with obesity at high risk of CVD. Methods We explored the relation between baseline anxiety as measured by the Beck Anxiety Inventory (BAI) and depression as measured by the Beck Depression Inventory-II (BDI-II), and baseline serum c-reactive protein (CRP) in a cross-sectional sample of 100 participants [mean (SD) age 57.8 (7.7) years; 64% female] with obesity [mean (SD) body mass index, BMI 37.3 (5.5) kg/m2] enrolled in a clinical trial for pharmacological weight loss interventions. Results BAI, but not BDI-II, scores were significantly correlated with CRP (rho=0.28, p=0.005). BMI was also highly correlated with CRP (rho=0.42, p<0.0001). In multivariate models, the relation between anxiety and CRP remained significant (p=0.038), independent of BMI, age and sex. Conclusion Anxiety, but not depression, is associated with elevated inflammation in persons with obesity beyond that attributable to higher BMI. Further study is warranted to assess whether anxiety represents a potential therapeutic target to mitigate corresponding CVD risk associated with elevated inflammation in persons with obesity. PMID:28000423

Mixed species flock, nest height, and elevation partially explain avian haemoparasite prevalence in Colombia.

PubMed

González, Angie D; Matta, Nubia E; Ellis, Vincenzo A; Miller, Eliot T; Ricklefs, Robert E; Gutiérrez, H Rafael

2014-01-01

The high avian biodiversity present in the Neotropical region offers a great opportunity to explore the ecology of host-parasite relationships. We present a survey of avian haemoparasites in a megadiverse country and explore how parasite prevalences are related to physical and ecological host characteristics. Using light microscopy, we documented the presence of haemoparasites in over 2000 individuals belonging to 246 species of wild birds, from nine localities and several ecosystems of Colombia. We analysed the prevalence of six avian haemoparasite taxa in relation to elevation and the following host traits: nest height, nest type, foraging strata, primary diet, sociality, migratory behaviour, and participation in mixed species flocks. Our analyses indicate significant associations between both mixed species flocks and nest height and Haemoproteus and Leucocytozoon prevalence. The prevalence of Leucocytozoon increased with elevation, whereas the prevalence of Trypanosoma and microfilariae decreased. Plasmodium and Haemoproteus prevalence did not vary significantly with elevation; in fact, both parasites were found up to 3300 m above sea level. The distribution of parasite prevalence across the phylogeny of bird species included in this study showed little host phylogenetic signal indicating that infection rates in this system are evolutionarily labile. Vector distribution as well as the biology of transmission and the maintenance of populations of avian haemoparasites deserve more detailed study in this system.

Antiproliferative effect of elevated glucose in human microvascular endothelial cells

NASA Technical Reports Server (NTRS)

Kamal, K.; Du, W.; Mills, I.; Sumpio, B. E.

1998-01-01

Diabetic microangiopathy has been implicated as a fundamental feature of the pathological complications of diabetes including retinopathy, neuropathy, and diabetic foot ulceration. However, previous studies devoted to examining the deleterious effects of elevated glucose on the endothelium have been performed largely in primary cultured cells of macrovessel origin. Difficulty in the harvesting and maintenance of microvascular endothelial cells in culture have hindered the study of this relevant population. Therefore, the objective of this study was to characterize the effect of elevated glucose on the proliferation and involved signaling pathways of an immortalized human dermal microvascular endothelial cell line (HMEC-1) that possess similar characteristics to their in vivo counterparts. Human dermal microvascular endothelial cells (HMEC-1) were grown in the presence of normal (5 mM) or high D-glucose (20 mM) for 14 days. The proliferative response of HMEC-1 was compared under these conditions as well as the cAMP and PKC pathways by in vitro assays. Elevated glucose significantly inhibited (P < 0.05) HMEC-1 proliferation after 7, 10, and 14 days. This effect was not mimicked by 20 mM mannitol. The antiproliferative effect was more pronounced with longer exposure (1-14 days) to elevated glucose and was irreversible 4 days after a 10-day exposure. The antiproliferative effect was partially reversed in the presence of a PKA inhibitor, Rp-cAMP (10-50 microM), and/or a PKC inhibitor, Calphostin C (10 nM). HMEC-1 exposed to elevated glucose (20 mM) for 14 days caused an increase in cyclic AMP accumulation, PKA, and PKC activity but was not associated with the activation of downstream events such as CRE and AP-1 binding activity. These data support the hypothesis that HMEC-1 is a suitable model to study the deleterious effects of elevated glucose on microvascular endothelial cells. Continued studies with HMEC-1 may prove advantageous in delineation of the molecular pathophysiology associated with diabetic microangiopathy.

The Role of Sink Strength and Nitrogen Availability in the Down-Regulation of Photosynthetic Capacity in Field-Grown Nicotiana tabacum L. at Elevated CO2 Concentration.

PubMed

Ruiz-Vera, Ursula M; De Souza, Amanda P; Long, Stephen P; Ort, Donald R

2017-01-01

Down-regulation of photosynthesis is among the most common responses observed in C 3 plants grown under elevated atmospheric CO 2 concentration ([CO 2 ]). Down-regulation is often attributed to an insufficient capacity of sink organs to use or store the increased carbohydrate production that results from the stimulation of photosynthesis by elevated [CO 2 ]. Down-regulation can be accentuated by inadequate nitrogen (N) supply, which may limit sink development. While there is strong evidence for down-regulation of photosynthesis at elevated [CO 2 ] in enclosure studies most often involving potted plants, there is little evidence for this when [CO 2 ] is elevated fully under open-air field treatment conditions. To assess the importance of sink strength on the down-regulation of photosynthesis and on the potential of N to mitigate this down-regulation under agriculturally relevant field conditions, two tobacco cultivars ( Nicotiana tabacum L. cv. Petit Havana; cv. Mammoth) of strongly contrasting ability to produce the major sink of this crop, leaves, were grown under ambient and elevated [CO 2 ] and with two different N additions in a free air [CO 2 ] (FACE) facility. Photosynthetic down-regulation at elevated [CO 2 ] reached only 9% in cv. Mammoth late in the season likely reflecting sustained sink strength of the rapidly growing plant whereas down-regulation in cv. Petit Havana reached 25%. Increased N supply partially mitigated down-regulation of photosynthesis in cv. Petit Havana and this mitigation was dependent on plant developmental stage. Overall, these field results were consistent with the hypothesis that sustained sink strength, that is the ability to utilize photosynthate, and adequate N supply will allow C 3 crops in the field to maintain enhanced photosynthesis and therefore productivity as [CO 2 ] continues to rise.

Effects of Urtica dioica on oxidative stress, proliferation and apoptosis after partial hepatectomy in rats.

PubMed

Oguz, Serhat; Kanter, Mehmet; Erboga, Mustafa; Toydemir, Toygar; Sayhan, Mustafa Burak; Onur, Hatice

2015-05-01

The present study was performed to investigate the effect of Urtica dioica (UD) on liver regeneration after partial hepatectomy (PH) in rats. A total of 24 male Sprague Dawley rats were divided into three groups: sham-operated, PH and PH + UD; each group contains eight animals. The rats in UD-treated groups were given UD oils (2 ml/kg/day) once a day orally for 7 days starting 3 days prior to hepatectomy operation. At day 7 after resection, liver samples were collected. The levels of malondialdehyde (MDA), superoxide dismutase (SOD) and glutathione (GSH) were estimated in liver homogenates. Moreover, histopathological examination, mitotic index (MI), proliferating cell nuclear antigen labeling, proliferation index (PI), transferase-mediated deoxyuridine triphosphate nick end-labeling assay, apoptotic index (AI) were evaluated at day 7 after hepatectomy. As a result, UD significantly increased MI and PI, significantly decreased AI and also attenuated hepatic vacuolar degeneration and sinusoidal congestion in PH rats. UD treatment significantly decreased the elevated tissue MDA level and increased the reduced SOD activity and GSH level in the tissues. These results suggest that UD pretreatment was beneficial for rat liver regeneration after partial hepatectomy. © The Author(s) 2013.

Gamma-vinyl GABA increases nonvesicular release of GABA and glutamate in the nucleus accumbens in rats via action on anion channels and GABA transporters

PubMed Central

Peng, Xiao-Qing; Gardner, Eliot L.

2013-01-01

Rationale γ-Amino butyric acid (GABA) is a well-characterized inhibitory neurotransmitter in the central nervous system, which may also stimulate nonvesicular release of other neurotransmitters under certain conditions. We have recently reported that γ-vinyl GABA (GVG), an irreversible GABA transaminase inhibitor, elevates extracellular GABA but fails to alter dopamine release in the nucleus accumbens (NAc). Objectives Here, we investigated the mechanism(s) by which GVG elevates extracellular GABA levels and whether GVG also alters glutamate release in the NAc. Materials and methods In vivo microdialysis was used to simultaneously measure extracellular NAc GABA and glutamate before and after GVG administration in freely moving rats. Results Systemic administration of GVG or intra-NAc local perfusion of GVG significantly increased extracellular NAc GABA and glutamate. GVG-enhanced GABA was completely blocked by intra-NAc local perfusion of 5-nitro-2, 3-(phenylpropylamino)-benzoic acid (NPPB), a selective anion channel blocker and partially blocked by SKF89976A, a type 1 GABA transporter inhibitor. GVG-enhanced glutamate was completely blocked by NPPB or SKF89976A. Tetrodotoxin, a voltage-dependent Na+-channel blocker, failed to alter GVG-enhanced GABA and glutamate. Conclusions These data suggest that GVG-enhanced extracellular GABA and glutamate are mediated predominantly by the opening of anion channels and partially by the reversal of GABA transporters. Enhanced extracellular glutamate may functionally attenuate the pharmacological action of GABA and prevent enhanced GABA-induced excess inhibition. PMID:20033132

A 12-year prognosis of adult-onset asthma: Seinäjoki Adult Asthma Study.

PubMed

Tuomisto, Leena E; Ilmarinen, Pinja; Niemelä, Onni; Haanpää, Jussi; Kankaanranta, Terhi; Kankaanranta, Hannu

2016-08-01

Long-term prognosis of adult-onset asthma is poorly known. To evaluate 12-year prognosis of adult-onset asthma and the factors associated with disease prognosis. Seinäjoki Adult-onset Asthma Study (SAAS) is a 12-year real-life single-center follow-up study of new-onset asthma diagnosed at adult age and treated in primary and specialized care. Remission was defined by no symptoms and no asthma medication use for 6 months. Asthma control was evaluated according to Global Initiative for Asthma 2010. Factors associated with current asthma control were analyzed by multinomial multivariate logistic regression. A total of 203 patients (79% of the baseline population) were followed for 12 years. Remission occurred in 6 (3%) patients. In 34% asthma was controlled, in 36% it was partially controlled and in 30% uncontrolled. Uncontrolled asthma was predicted by elevated body-mass index at baseline, smoking (pack-years) and current allergic or persistent rhinitis. Elevated blood eosinophils and good lung function (FEV1) at baseline protected from uncontrolled asthma. In contrast, gender, age at the onset or baseline symptoms (Airways Questionnaire 20) were not significant predictors of uncontrolled disease. During a 12-year follow-up, remission of adult-onset asthma was rare occurring in only 3% of patients. The majority of patients (66%) presented either with uncontrolled or partially controlled asthma. This study is registered at ClinicalTrials.gov with identifier number NCT02733016. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of Estrogen and Estrus Cycle on Pharmacokinetics, Absorption and Disposition of Genistein in Female Sprague-Dawley Rats

PubMed Central

Kulkarni, Kaustubh H.; Yang, Zhen; Tao, Niu; Hu, Ming

2014-01-01

Genistein is an active soy isoflavone with anticancer activities but it is unknown why it has a higher oral bioavailability in female than in male rats. Our study determined the effects of estrus cycle on genistein’s oral bioavailability. Female rats with various levels of estrogen were orally administered with genistein or used in a four-site rat intestinal perfusion experiment. Rats in “proestrus” group (with elevated estrogen) had significantly reduced (57% decrease, p<0.05) oral bioavailability of total genistein (aglycone+conjugates) than those in “metoestrus” group (with basal level of estrogen). Female ovariectomized rats, due to lack of estrogen, showed oral bioavailability of total genistein similar to the “metoestrus” group but higher (155% increase, p<0.05) than the “proestrus” group. Based on intestinal perfusion studies, the increased bioavailability was partially attributed to the higher (>100% increase, p<0.05) hepatic disposition via glucuronidation and possibly more efficient enterohepatic recycling of genistein in the “metoestrus” group. Furthermore, chronic exogenous supplementation of estradiol in ovariectomized rats significantly reduced (77%, p<0.05) the oral bioavailability of total genistein, mostly via increased sulfation (>10 folds) in liver, to a level comparable to those in the “proestrus” group. In conclusion, the oral bioavailability of total genistein was inversely proportional to elevated estrogen levels in female rats, which is partially mediated through the regulation of hepatic enzymes responsible disposition of genistein. PMID:22757747

Elevation of GM2 ganglioside during ethanol-induced apoptotic neurodegeneration in the developing mouse brain.

PubMed

Saito, Mitsuo; Chakraborty, Goutam; Shah, Relish; Mao, Rui-Fen; Kumar, Asok; Yang, Dun-Sheng; Dobrenis, Kostantin; Saito, Mariko

2012-05-01

GM2 ganglioside in the brain increased during ethanol-induced acute apoptotic neurodegeneration in 7-day-old mice. A small but a significant increase observed 2 h after ethanol exposure was followed by a marked increase around 24 h. Subcellular fractionation of the brain 24 h after ethanol treatment indicated that GM2 increased in synaptic and non-synaptic mitochondrial fractions as well as in a lysosome-enriched fraction characteristic to the ethanol-exposed brain. Immunohistochemical staining of GM2 in the ethanol-treated brain showed strong punctate staining mainly in activated microglia, in which it partially overlapped with staining for LAMP1, a late endosomal/lysosomal marker. Also, there was weaker neuronal staining, which partially co-localized with complex IV, a mitochondrial marker, and was augmented in cleaved caspase 3-positive neurons. In contrast, the control brain showed only faint and diffuse GM2 staining in neurons. Incubation of isolated brain mitochondria with GM2 in vitro induced cytochrome c release in a manner similar to that of GD3 ganglioside. Because ethanol is known to trigger mitochondria-mediated apoptosis with cytochrome c release and caspase 3 activation in the 7-day-old mouse brain, the GM2 elevation in mitochondria may be relevant to neuroapoptosis. Subsequently, activated microglia accumulated GM2, indicating a close relationship between GM2 and ethanol-induced neurodegeneration. © 2012 The Authors. Journal of Neurochemistry © 2012 International Society for Neurochemistry.

Sodium phenylbutyrate, a drug with known capacity to reduce endoplasmic reticulum stress, partially alleviates lipid-induced insulin resistance and beta-cell dysfunction in humans.

PubMed

Xiao, Changting; Giacca, Adria; Lewis, Gary F

2011-03-01

Chronically elevated free fatty acids contribute to insulin resistance and pancreatic β-cell failure. Among numerous potential factors, the involvement of endoplasmic reticulum (ER) stress has been postulated to play a mechanistic role. Here we examined the efficacy of the chemical chaperone, sodium phenylbutyrate (PBA), a drug with known capacity to reduce ER stress in animal models and in vitro, on lipid-induced insulin resistance and β-cell dysfunction in humans. Eight overweight or obese nondiabetic men underwent four studies each, in random order, 4 to 6 weeks apart. Two studies were preceded by 2 weeks of oral PBA (7.5 g/day), followed by a 48-h i.v. infusion of intralipid/heparin or saline, and two studies were preceded by placebo treatment, followed by similar infusions. Insulin secretion rates (ISRs) and sensitivity (S(I)) were assessed after the 48-h infusions by hyperglycemic and hyperinsulinemic-euglycemic clamps, respectively. Lipid infusion reduced S(I), which was significantly ameliorated by pretreatment with PBA. Absolute ISR was not affected by any treatment; however, PBA partially ameliorated the lipid-induced reduction in the disposition index (DI = ISR × S(I)), indicating that PBA prevented lipid-induced β-cell dysfunction. These results suggest that PBA may provide benefits in humans by ameliorating the insulin resistance and β-cell dysfunction induced by prolonged elevation of free fatty acids.

Time course of the establishment of uterine seawater conditions in late-term pregnant spiny dogfish (Squalus acanthias).

PubMed

Kormanik, G A

1988-07-01

The gestation period for embryos of the spiny dogfish, Squalus acanthias (L.) lasts for nearly 2 years. During the latter part of this period the pups remain in the uterus and the fluid surrounding the embryos resembles sea water with respect to the major ions, but is low in pH (approx. 6), high in partial pressure of carbon dioxide (approx. 3 mmHg; 1 mmHg = 133.3 Pa), low in total carbon dioxide content (approx. 0.2 mmol l-1), and may have a total ammonia concentration of up to 22 mmol l-1. Thus the conditions under which the pups complete their development in utero is quite remarkable. The derivation of these conditions was examined in late-term pregnant females, from whose uterine horns the pups had been removed, by monitoring changes that occurred in instilled uterine sea water. The mother is responsible for reducing the pH, reducing the total carbon dioxide content and elevating the partial pressure of carbon dioxide to the levels observed in fresh-caught females, in less than 24 h. The ammonia concentration is also elevated, but this takes rather longer. The decreased pH is responsible for the accumulation of ammonia in the uterine sea water, and it also serves to protect the pups from the toxic effects of NH3, by converting it to the relatively non-toxic ionic form, NH4+. The reasons for the establishment of these uterine seawater conditions are still not evident.

Lyme Carditis Buried Beneath ST-Segment Elevations

PubMed Central

Umpierrez De Reguero, Adrian

2017-01-01

Lyme disease is caused by the spirochete Borrelia burgdorferi and is carried to human hosts by infected ticks. There are nearly 30,000 cases of Lyme disease reported to the CDC each year, with 3-4% of those cases reporting Lyme carditis. The most common manifestation of Lyme carditis is partial heart block following bacterial-induced inflammation of the conducting nodes. Here we report a 45-year-old gentleman that presented to the hospital with intense nonradiating chest pressure and tightness. Lab studies were remarkable for elevated troponins. EKG demonstrated normal sinus rhythm with mild ST elevations. Three weeks prior to hospital presentation, patient had gone hunting near Madison. One week prior to admission, he noticed an erythematous lesion on his right shoulder. Because of his constellation of history, arthralgias, and carditis, he was started on ceftriaxone to treat probable Lyme disease. This case illustrates the importance of thorough history taking and extensive physical examination when assessing a case of possible acute myocardial infarction. Because Lyme carditis is reversible, recognition of this syndrome in young patients, whether in the form of AV block, myocarditis, or acute myocardial ischemia, is critical to the initiation of appropriate antibiotics in order to prevent permanent heart block, or even death. PMID:28713599

Social anxiety and heavy situational drinking: coping and conformity motives as multiple mediators.

PubMed

Terlecki, Meredith A; Buckner, Julia D

2015-01-01

Individuals with clinically elevated social anxiety are at greater risk for alcohol use disorder, and the relation between social anxiety and drinking problems is at least partially accounted for by drinking more in negative emotional (e.g., feeling sad or angry) and personal/intimate (e.g., before sexual intercourse) situations. Identification of cognitive/motivational factors related to drinking in these high-risk situations could inform the development of treatment and prevention interventions for these high-risk drinkers. The current cross-sectional study examined the mediating effect of drinking motives on the relationship between social anxiety and drinking these high-risk situations among undergraduates (N=232). Clinically elevated social anxiety was associated with greater coping and conformity motives. Both coping and conformity motives mediated the relation between social anxiety and heavier alcohol consumption in negative emotional and personal/intimate contexts. Multiple mediation analyses indicated that these motives work additively to mediate the social anxiety-drinking situations relationship, such that heavy situational drinking among undergraduates with clinically elevated social anxiety can be jointly attributed to desire to cope with negative affect and to avoid social scrutiny. Copyright © 2014 Elsevier Ltd. All rights reserved.

Resonant frequencies in an elevated spherical container partially filled with water: FEM and measurement

NASA Astrophysics Data System (ADS)

Curadelli, O.; Ambrosini, D.; Mirasso, A.; Amani, M.

2010-01-01

In this paper, a numerical-experimental study of the overall dynamical response of elevated spherical tanks subjected to horizontal base motion is presented. The main objective is to gain insight in the physical response of this particular structural typology widely used in the petrochemical industry as liquefied petroleum gas (LPG) containers. In order to identify the natural frequencies of the modes that mainly contribute to the response, experimental free vibration tests on an elevated spherical tank model for different liquid levels were carried out. Next, a numerical model that takes into account the coupling between fluid and structure was developed and validated against the experimental results. A very good agreement between experimental and numerical results was obtained. The results obtained show the influence of liquid levels on natural frequencies and indicate that the sloshing has a significant effect on the dynamical characteristics of the analyzed system. In order to obtain a good representation of the overall dynamical behaviour of the system by means of a simplified lumped mass model, a minimum of three masses is suggested. Finally, appropriate names of these three masses are proposed in the present paper.

Activated Rho Kinase Mediates Diabetes-Induced Elevation of Vascular Arginase Activation and Contributes to Impaired Corpora Cavernosa Relaxation: Possible Involvement of p38 MAPK Activation

PubMed Central

Nunes, Kenia P.; Yao, Lin; Liao, James K.; Webb, R. Clinton; Caldwell, Ruth B.; Caldwell, R. William

2013-01-01

Introduction Activated RhoA/Rho kinase (ROCK) has been implicated in diabetes-induced erectile dysfunction. Earlier studies have demonstrated involvement of ROCK pathway in the activation of arginase in endothelial cells. However, signaling pathways activated by ROCK in the penis remain unclear. Aim We tested whether ROCK and p38 MAPK are involved in the elevation of arginase activity and subsequent impairment of corpora cavernosal (CC) relaxation in diabetes. Methods Eight weeks after streptozotocin-induced diabetes, vascular functional studies, arginase activity assay, and protein expression of RhoA, ROCK, phospho-p38 MAPK, p38 MAPK, phospho-MYPT-1Thr850, MYPT-1 and arginase levels were assessed in CC tissues from nondiabetic wild type (WT), diabetic (D) WT (WT + D), partial ROCK 2+/− knockout (KO), and ROCK 2+/− KO + D mice. Main Outcome Measures The expression of RhoA, ROCK 1 and 2, phosphorylation of MYPT-1Thr850 and p38 MAPK, arginase activity/expression, endothelial- and nitrergic-dependent relaxation of CC was assayed. Results Diabetes significantly reduced maximum relaxation (Emax) to both endothelium-dependent acetylcholine (WT + D: Emax; 61 ± 4% vs. WT: Emax; 75 ± 2%) and nitrergic nerve stimulation. These effects were associated with increased expression of active RhoA, ROCK 2, phospho-MYPT-1Thr850, phospho-p38 MAPK, arginase II, and activity of corporal arginase (1.6-fold) in WT diabetic CC. However, this impairment in CC of WT + D mice was absent in heterozygous ROCK 2+/− KO + D mice for acetylcholine (Emax: 80 ± 5%) and attenuated for nitrergic nerve-induced relaxation. CC of ROCK 2+/− KO + D mice showed much less ROCK activity, did not exhibit p38 MAPK activation, and had reduced arginase activity and arginase II expression. These findings indicate that ROCK 2 mediates diabetes-induced elevation of arginase activity. Additionally, pretreatment of WT diabetic CC with inhibitors of arginase (ABH) or p38 MAPK (SB203580) partially prevented impairment of ACh- and nitrergic nerve-induced relaxation and elevation of arginase activity. Conclusion ROCK 2, p38 MAPK and arginase play key roles in diabetes-induced impairment of CC relaxation. PMID:23566117

Metabolic shifts in the Antarctic fish Notothenia rossii in response to rising temperature and PCO2

PubMed Central

2012-01-01

Introduction Ongoing ocean warming and acidification increasingly affect marine ecosystems, in particular around the Antarctic Peninsula. Yet little is known about the capability of Antarctic notothenioid fish to cope with rising temperature in acidifying seawater. While the whole animal level is expected to be more sensitive towards hypercapnia and temperature, the basis of thermal tolerance is set at the cellular level, with a putative key role for mitochondria. This study therefore investigates the physiological responses of the Antarctic Notothenia rossii after long-term acclimation to increased temperatures (7°C) and elevated PCO2 (0.2 kPa CO2) at different levels of physiological organisation. Results For an integrated picture, we analysed the acclimation capacities of N. rossii by measuring routine metabolic rate (RMR), mitochondrial capacities (state III respiration) as well as intra- and extracellular acid–base status during acute thermal challenges and after long-term acclimation to changing temperature and hypercapnia. RMR was partially compensated during warm- acclimation (decreased below the rate observed after acute warming), while elevated PCO2 had no effect on cold or warm acclimated RMR. Mitochondrial state III respiration was unaffected by temperature acclimation but depressed in cold and warm hypercapnia-acclimated fish. In both cold- and warm-exposed N. rossii, hypercapnia acclimation resulted in a shift of extracellular pH (pHe) towards more alkaline values. A similar overcompensation was visible in muscle intracellular pH (pHi). pHi in liver displayed a slight acidosis after warm normo- or hypercapnia acclimation, nevertheless, long-term exposure to higher PCO2 was compensated for by intracellular bicarbonate accumulation. Conclusion The partial warm compensation in whole animal metabolic rate indicates beginning limitations in tissue oxygen supply after warm-acclimation of N. rossii. Compensatory mechanisms of the reduced mitochondrial capacities under chronic hypercapnia may include a new metabolic equilibrium to meet the elevated energy demand for acid–base regulation. New set points of acid–base regulation under hypercapnia, visible at the systemic and intracellular level, indicate that N. rossii can at least in part acclimate to ocean warming and acidification. It remains open whether the reduced capacities of mitochondrial energy metabolism are adaptive or would impair population fitness over longer timescales under chronically elevated temperature and PCO2. PMID:23075125

Does Long-Term Elevation of CO2 Concentration Increase Photosynthesis in Forest Floor Vegetation? (Indiana Strawberry in a Maryland Forest).

PubMed

Osborne, C. P.; Drake, B. G.; LaRoche, J.; Long, S. P.

1997-05-01

As the partial pressure of CO2 (pCO2) in the atmosphere rises, photorespiratory loss of carbon in C3 photosynthesis will diminish and the net efficiency of light-limited photosynthetic carbon uptake should rise. We tested this expectation for Indiana strawberry (Duchesnea indica) growing on a Maryland forest floor. Open-top chambers were used to elevate the pCO2 of a forest floor habitat to 67 Pa and were paired with control chambers providing an ambient pCO2 of 38 Pa. After 3.5 years, D. indica leaves grown and measured in the elevated pCO2 showed a significantly greater maximum quantum efficiency of net photosynthesis (by 22%) and a lower light compensation point (by 42%) than leaves grown and measured in the control chambers. The quantum efficiency to minimize photorespiration, measured in 1% O2, was the same for controls and plants grown at elevated pCO2. This showed that the maximum efficiency of light-energy transduction into assimilated carbon was not altered by acclimation and that the increase in light-limited photosynthesis at elevated pCO2 was simply a function of the decrease in photorespiration. Acclimation did decrease the ribulose-1,5-bisphosphate carboxylase/oxygenase and light-harvesting chlorophyll protein content of the leaf by more than 30%. These changes were associated with a decreased capacity for light-saturated, but not light-limited, photosynthesis. Even so, leaves of D. indica grown and measured at elevated pCO2 showed greater light-saturated photosynthetic rates than leaves grown and measured at the current atmospheric pCO2. In situ measurements under natural forest floor lighting showed large increases in leaf photosynthesis at elevated pCO2, relative to controls, in both summer and fall. The increase in efficiency of light-limited photosynthesis with elevated pCO2 allowed positive net photosynthetic carbon uptake on days and at locations on the forest floor that light fluxes were insufficient for positive net photosynthesis in the current atmospheric pCO2.

Does long-term elevation of CO{sub 2} concentration increase photosynthesis in forest floor vegetation? Indiana strawberry in a Maryland forest

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

Osborne, C.P.; Long, S.P.; Drake, B.G.

1997-05-01

As the partial pressure of CO{sub 2} (pCO{sub 2}) in the atmosphere rises, photorespiratory loss of carbon in C, photosynthesis will diminish and the net efficiency of light-limited photosynthetic carbon uptake should rise. Indiana strawberry (Duchesnea indica) growing on a Maryland forest floor was tested. Open-top chambers were used to elevate the pCO{sub 2} of a forest floor habitat to 67 Pa and were paired with control chambers with an ambient pCO{sub 2} of 38 Pa. After 3.5 years, D. indica leaves in the elevated pCO{sub 2} showed a significantly greater maximum quantum efficiency of net photosynthesis (by 22%) andmore » a lower light compensation point (by 42%) than leaves in the control chambers. The quantum efficiency to minimize photorespiration was the same for controls and plants grown at elevated pCO{sub 2}, showing the maximum efficiency of light-energy transduction into assimilated carbon was not altered by acclimation and the increase in light-limited photosynthesis at elevated pCO{sub 2} was a function of the decrease in photorespiration. Acclimation did decrease the ribulose-1,5-bisphosphate carboxylase/oxygenase and light-harvesting chlorophyll protein content of the leaf by more than 30%. These changes were associated with a decreased capacity for light-saturated, but not light-limited, photosynthesis. Leaves of D. indica grown and measured at elevated pCO{sub 2} showed greater light-saturated photosynthetic rates than leaves grown and measured at the current atmospheric pCO{sub 2}. In situ measurements under natural lighting showed large increases in leaf photosynthesis at elevated pCO{sub 2}, relative to controls, in both summer and fall. The increase in efficiency of light-limited photosynthesis with elevated pCO{sub 2} allowed positive net photosynthetic carbon uptake on days and at locations on the forest floor that light fluxes were insufficient for positive net photosynthesis in the current atmospheric pCO{sub 2}. 33 refs., 3 figs., 3 tabs.« less

Taking Snapshots of Photosynthetic Water Oxidation Using Femtosecond X-ray Diffraction and Spectroscopy

PubMed Central

Kern, Jan; Tran, Rosalie; Alonso-Mori, Roberto; Koroidov, Sergey; Echols, Nathaniel; Hattne, Johan; Ibrahim, Mohamed; Gul, Sheraz; Laksmono, Hartawan; Sierra, Raymond G.; Gildea, Richard J.; Han, Guangye; Hellmich, Julia; Lassalle-Kaiser, Benedikt; Chatterjee, Ruchira; Brewster, Aaron S.; Stan, Claudiu A.; Glöckner, Carina; Lampe, Alyssa; DiFiore, Dörte; Milathianaki, Despina; Fry, Alan R.; Seibert, M. Marvin; Koglin, Jason E.; Gallo, Erik; Uhlig, Jens; Sokaras, Dimosthenis; Weng, Tsu-Chien; Zwart, Petrus H.; Skinner, David E.; Bogan, Michael J.; Messerschmidt, Marc; Glatzel, Pieter; Williams, Garth J.; Boutet, Sébastien; Adams, Paul D.; Zouni, Athina; Messinger, Johannes; Sauter, Nicholas K.; Bergmann, Uwe; Yano, Junko; Yachandra, Vittal K.

2014-01-01

The dioxygen we breathe is formed from water by its light-induced oxidation in photosystem II. O2 formation takes place at a catalytic manganese cluster within milliseconds after the photosystem II reaction center is excited by three single-turnover flashes. Here we present combined X-ray emission spectra and diffraction data of 2 flash (2F) and 3 flash (3F) photosystem II samples, and of a transient 3F′ state (250 μs after the third flash), collected under functional conditions using an X-ray free electron laser. The spectra show that the initial O-O bond formation, coupled to Mn-reduction, does not yet occur within 250 μs after the third flash. Diffraction data of all states studied exhibit an anomalous scattering signal from Mn but show no significant structural changes at the present resolution of 4.5 Å. This study represents the initial frames in a molecular movie of the structural changes during the catalytic reaction in photosystem II. PMID:25006873

Diffusion of dioxygen in 1-alkenes and biphenyl in perfluoro- n-alkanes

NASA Astrophysics Data System (ADS)

Kowert, Bruce A.; Sobush, Kurtis T.; Dang, Nhan C.; Seele, Louis G., III; Fuqua, Chantel F.; Mapes, Courtney L.

2002-02-01

The translational diffusion constant, D, has been measured for O 2 in the even 1-alkenes 1-C 6H 12 to 1-C 16H 32 and biphenyl in n-C 6F 14 and n-C 9F 20. Deviations from the Stokes-Einstein relation were found; the use of D/ T= A/ ηp gave p=0.560±0.017 for O 2 in the 1-alkenes, the same (within experimental error) as found previously for O 2 in the n-alkanes. The charge transfer (CT) transition used to detect O 2 in the 1-alkenes is at 220 nm. The D values for biphenyl in the perfluoro- n-alkanes (PFAs) are consistent with those in the n-alkanes, where p=0.718±0.004. These results suggest that O 2 has similar solute-solvent interactions in both the 1-alkenes and n-alkanes as does biphenyl in the n-alkanes and PFAs.

Flavodiiron Protein from Trichomonas vaginalis Hydrogenosomes: the Terminal Oxygen Reductase▿

PubMed Central

Smutná, Tamara; Gonçalves, Vera L.; Saraiva, Lígia M.; Tachezy, Jan; Teixeira, Miguel; Hrdý, Ivan

2009-01-01

Trichomonas vaginalis is one of a few eukaryotes that have been found to encode several homologues of flavodiiron proteins (FDPs). Widespread among anaerobic prokaryotes, these proteins are believed to function as oxygen and/or nitric oxide reductases to provide protection against oxidative/nitrosative stresses and host immune responses. One of the T. vaginalis FDP homologues is equipped with a hydrogenosomal targeting sequence and is expressed in the hydrogenosomes, oxygen-sensitive organelles that participate in carbohydrate metabolism and assemble iron-sulfur clusters. The bacterial homologues characterized thus far have been dimers or tetramers; the trichomonad protein is a dimer of identical 45-kDa subunits, each noncovalently binding one flavin mononucleotide. The protein reduces dioxygen to water but is unable to utilize nitric oxide as a substrate, similarly to its closest homologue from another human parasite Giardia intestinalis and related archaebacterial proteins. T. vaginalis FDP is able to accept electrons derived from pyruvate or NADH via ferredoxin and is proposed to play a role in the protection of hydrogenosomes against oxygen. PMID:19011120

Taking snapshots of photosynthetic water oxidation using femtosecond X-ray diffraction and spectroscopy

NASA Astrophysics Data System (ADS)

Kern, Jan; Tran, Rosalie; Alonso-Mori, Roberto; Koroidov, Sergey; Echols, Nathaniel; Hattne, Johan; Ibrahim, Mohamed; Gul, Sheraz; Laksmono, Hartawan; Sierra, Raymond G.; Gildea, Richard J.; Han, Guangye; Hellmich, Julia; Lassalle-Kaiser, Benedikt; Chatterjee, Ruchira; Brewster, Aaron S.; Stan, Claudiu A.; Glöckner, Carina; Lampe, Alyssa; Difiore, Dörte; Milathianaki, Despina; Fry, Alan R.; Seibert, M. Marvin; Koglin, Jason E.; Gallo, Erik; Uhlig, Jens; Sokaras, Dimosthenis; Weng, Tsu-Chien; Zwart, Petrus H.; Skinner, David E.; Bogan, Michael J.; Messerschmidt, Marc; Glatzel, Pieter; Williams, Garth J.; Boutet, Sébastien; Adams, Paul D.; Zouni, Athina; Messinger, Johannes; Sauter, Nicholas K.; Bergmann, Uwe; Yano, Junko; Yachandra, Vittal K.

2014-07-01

The dioxygen we breathe is formed by light-induced oxidation of water in photosystem II. O2 formation takes place at a catalytic manganese cluster within milliseconds after the photosystem II reaction centre is excited by three single-turnover flashes. Here we present combined X-ray emission spectra and diffraction data of 2-flash (2F) and 3-flash (3F) photosystem II samples, and of a transient 3F’ state (250 μs after the third flash), collected under functional conditions using an X-ray free electron laser. The spectra show that the initial O-O bond formation, coupled to Mn reduction, does not yet occur within 250 μs after the third flash. Diffraction data of all states studied exhibit an anomalous scattering signal from Mn but show no significant structural changes at the present resolution of 4.5 Å. This study represents the initial frames in a molecular movie of the structural changes during the catalytic reaction in photosystem II.

Catalase-like activity studies of the manganese(II) adsorbed zeolites

NASA Astrophysics Data System (ADS)

ćiçek, Ekrem; Dede, Bülent

2013-12-01

Preparation of manganese(II) adsorbed on zeolite 3A, 4A, 5A. AW-300, ammonium Y zeolite, organophilic, molecular sieve and catalase-like enzyme activity of manganese(II) adsorbed zeolites are reported herein. Firstly zeolites are activated at 873 K for two hours before contact manganese(II) ions. In order to observe amount of adsorption, filtration process applied for the solution. The pure zeolites and manganese(II) adsorbed zeolites were analysed by FT-IR. As a result according to the FT-IR spectra, the incorporation of manganese(II) cation into the zeolite structure causes changes in the spectra. These changes are expected particularly in the pseudolattice bands connected with the presence of alumino and silicooxygen tetrahedral rings in the zeolite structure. Furthermore, the catalytic activities of the Mn(II) adsorbed zeolites for the disproportionation of hydrogen peroxide were investigated in the presence of imidazole. The Mn(II) adsorbed zeolites display efficiency in the disproportion reactions of hydrogen peroxide, producing water and dioxygen in catalase-like activity.

Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O 2 activation by non-adiabatic oxidative addition to a single metal center

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

Akturk, Eser S.; Yap, Glenn P. A.; Theopold, Klaus H.

2015-10-16

A chromium(I) dinitrogen complex reacts rapidly with O 2 to form the mononuclear dioxo complex [Tp tBu,MeCr V(O) 2] (Tp tBu,Me=hydrotris(3- tert-butyl-5-methylpyrazolyl)borate), whereas the analogous reaction with sulfur stops at the persulfido complex [Tp tBu,MeCr III(S 2)]. The transformation of the putative peroxo intermediate [Tp tBu,MeCr III(O 2)] (S= 3/ 2) into [Tp tBu,MeCr V(O) 2] (S= 1/ 2) is spin-forbidden. The minimum-energy crossing point for the two potential energy surfaces has been identified. Finally, although the dinuclear complex [(Tp tBu,MeCr) 2(μ-O) 2] exists, mechanistic experiments suggest that O 2 activation occurs on a single metal center, by an oxidativemore » addition on the quartet surface followed by crossover to the doublet surface.« less

A DFT Study of the cis-Dihydroxylation of Nitroaromatic Compounds Catalyzed by Nitrobenzene Dioxygenase

PubMed Central

2014-01-01

The mechanism of cis-dihydroxylation of nitrobenzene and 2-nitrotoluene catalyzed by nitrobenzene 1,2-dioxygenase (NBDO), a member of the naphthalene family of Rieske non-heme iron dioxygenases, was studied by means of the density functional theory method using four models of the enzyme active site. Different possible reaction pathways for the substrate dioxygenation initiated either by the FeIII–OOH or HO–FeV=O attack on the aromatic ring were considered and the computed activation barriers compared with the Gibbs free energy of activation for the oxygen–oxygen cleavage leading to the formation of the iron(V)–oxo species from its ferric hydroperoxo precursor. The mechanism of the substrate cis-dihydroxylation leading to the formation of a cis-dihydrodiol was then investigated, and the most feasible mechanism was found to be starting with the attack of the high-valent iron–oxo species on the substrate ring yielding a radical intermediate, which further evolves toward the final product. PMID:24624972

Effect of ascorbic acid on storage of Greyhound erythrocytes.

PubMed

Fontes, Jorge A; Banerjee, Uddyalok; Iazbik, M Cristina; Marín, Liliana M; Couto, C Guillermo; Palmer, Andre F

2015-09-01

To assess changes in biochemical and biophysical properties of canine RBCs during cold (1° to 6°C) storage in a licensed RBC additive solution (the RBC preservation solution designated AS-1) supplemented with ascorbic acid. Blood samples from 7 neutered male Greyhounds; all dogs had negative results when tested for dog erythrocyte antigen 1.1. Blood was collected into citrate-phosphate-dextrose and stored in AS-1. Stored RBCs were supplemented with 7.1mM ascorbic acid or with saline (0.9% NaCl) solution (control samples). Several biochemical and biophysical properties of RBCs were measured, including percentage hemolysis, oxygen-hemoglobin equilibrium, and the kinetic rate constants for O2 dissociation, carbon monoxide association, and nitric oxide dioxygenation. Greyhound RBCs stored in AS-1 supplemented with ascorbic acid did not have significantly decreased hemolysis, compared with results for the control samples, during the storage period. In this study, ascorbic acid did not reduce hemolysis during storage. Several changes in stored canine RBCs were identified as part of the hypothermic storage lesion.

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.

Structure and reactivity of a mononuclear gold(II) complex

NASA Astrophysics Data System (ADS)

Preiß, Sebastian; Förster, Christoph; Otto, Sven; Bauer, Matthias; Müller, Patrick; Hinderberger, Dariush; Hashemi Haeri, Haleh; Carella, Luca; Heinze, Katja

2017-12-01

Mononuclear gold(II) complexes are very rare labile species. Transient gold(II) species have been suggested in homogeneous catalysis and in medical applications, but their geometric and electronic structures have remained essentially unexplored: even fundamental data, such as the ionic radius of gold(II), are unknown. Now, an unprecedentedly stable neutral gold(II) complex of a porphyrin derivative has been isolated, and its structural and spectroscopic features determined. The gold atom adopts a 2+2 coordination mode in between those of gold(III) (four-coordinate square planar) and gold(I) (two-coordinate linear), owing to a second-order Jahn-Teller distortion enabled by the relativistically lowered 6s orbital of gold. The reactivity of this gold(II) complex towards dioxygen, nitrosobenzene and acids is discussed. This study provides insight on the ionic radius of gold(II), and allows it to be placed within the homologous series of nd9 Cu/Ag/Au divalent ions and the 5d8/9/10 Pt/Au/Hg 'relativistic' triad in the periodic table.

Self-assembly of supramolecular triarylamine nanowires in mesoporous silica and biocompatible electrodes thereof.

PubMed

Licsandru, Erol-Dan; Schneider, Susanne; Tingry, Sophie; Ellis, Thomas; Moulin, Emilie; Maaloum, Mounir; Lehn, Jean-Marie; Barboiu, Mihail; Giuseppone, Nicolas

2016-03-14

Biocompatible silica-based mesoporous materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. The formation of hybrid electroactive silica nanostructures is thus expected to be of great interest for the design of biocompatible conducting materials such as bioelectrodes. Here we show that we can grow supramolecular stacks of triarylamine molecules in the confined space of oriented mesopores of a silica nanolayer covering a gold electrode. This addressable bottom-up construction is triggered from solution simply by light irradiation. The resulting self-assembled nanowires act as highly conducting electronic pathways crossing the silica layer. They allow very efficient charge transfer from the redox species in solution to the gold surface. We demonstrate the potential of these hybrid constitutional materials by implementing them as biocathodes and by measuring laccase activity that reduces dioxygen to produce water.

Molecular simulations enlighten the binding mode of quercetin to lipoxygenase-3.

PubMed

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

2008-11-01

Inhibition of lipoxygenases (LOXs) by flavonoid compounds is now well documented, but the description of the associated mechanism remains controversial due to a lack of information at the molecular level. For instance, X-ray determination of quercetin/LOX-3 system has led to a structure where the enzyme was cocrystallized with a degradation product of the substrate, which rendered the interpretation of the reported interactions between this flavonoid compound and the enzyme difficult. Molecular modeling simulations can in principle allow obtaining precious insights that could fill this lack of structural information. Thus, in this study, we have investigated various binding modes of quercetin to LOX-3 enzyme in order to understand the first step of the inhibition process, that is the association of the two entities. Molecular dynamics simulations and free energy calculations suggest that quercetin binds the metal center via its 3-hydroxychromone function. Moreover, enzyme/substrate interactions within the cavity impose steric hindrances to quercetin that may activate a direct dioxygen addition on the substrate. (c) 2008 Wiley-Liss, Inc.

Reversible Oxygenation of 2,4-Diaminobutanoic Acid-Co(II) Complexes

PubMed Central

Li, Hui; Yue, Fan; Wen, Hongmei

2016-01-01

This paper introduces the structural characterization and studies on reversible oxygenation behavior of a new oxygen carrier Co(II)-2,4-diaminobutanoic acid (DABA) complex in aqueous solution. The composition of the oxygenated complex was determined by gas volumetric method, molar ratio method, and mass spectrometry, and the formula of the oxygenated complex was determined to be [Co(DABA)2O2]. In aqueous solution, the complex can continuously uptake and release dioxygen and exhibit excellent reversibility of oxygenation and deoxygenation ability. This complex can maintain 50% of its original oxygenation capacity after 30 cycles in 24 h and retain 5% of the original oxygenation capacity after more than 260 cycles after 72 h. When a ligand analogue was linked to histidine (His), the new complex exhibited as excellent reversible oxygenation property as His-Co(II) complex. Insight into the relationship between structural detail and oxygenation properties will provide valuable suggestion for a new family of oxygen carriers. PMID:27648004