The burnup dependence of light water reactor spent fuel oxidation

International Nuclear Information System (INIS)

Hanson, B.D.

1998-07-01

Over the temperature range of interest for dry storage or for placement of spent fuel in a permanent repository under the conditions now being considered, UO 2 is thermodynamically unstable with respect to oxidation to higher oxides. The multiple valence states of uranium allow for the accommodation of interstitial oxygen atoms in the fuel matrix. A variety of stoichiometric and nonstoichiometric phases is therefore possible as the fuel oxidizers from UO 2 to higher oxides. The oxidation of UO 2 has been studied extensively for over 40 years. It has been shown that spent fuel and unirradiated UO 2 oxidize via different mechanisms and at different rates. The oxidation of LWR spent fuel from UO 2 to UO 2.4 was studied previously and is reasonably well understood. The study presented here was initiated to determine the mechanism and rate of oxidation from UO 2.4 to higher oxides. During the early stages of this work, a large variability in the oxidation behavior of samples oxidized under nearly identical conditions was found. Based on previous work on the effect of dopants on UO 2 oxidation and this initial variability, it was hypothesized that the substitution of fission product and actinide impurities for uranium atoms in the spent fuel matrix was the cause of the variable oxidation behavior. Since the impurity concentration is roughly proportional to the burnup of a specimen, the oxidation behavior of spent fuel was expected to be a function of both temperature and burnup. This report (1) summarizes the previous oxidation work for both unirradiated UO 2 and spent fuel (Section 2.2) and presents the theoretical basis for the burnup (i.e., impurity concentration) dependence of the rate of oxidation (Sections 2.3, 2.4, and 2.5), (2) describes the experimental approach (Section 3) and results (Section 4) for the current oxidation tests on spent fuel, and (3) establishes a simple model to determine the activation energies associated with spent fuel oxidation (Section 5)

Relationships among oxidation-reduction and acid-base properties of the actinides in high oxidation states

International Nuclear Information System (INIS)

Morss, L.R.

1992-01-01

The first chemical identification of plutonium, its subsequent isolation on the macroscopic scale, and more recent chemical separation schemes were achieved by taking advantage of the differences among the oxidation states of uranium, neptunium, and plutonium. Many acid-base properties modify the relative stabilities of oxidation states of the actinides. In the solid state, strongly basic compounds such as Cs 2 O yield complex oxides with oxidation states of Np(VII), Pu(VI), and Am(VI) whereas more acidic compounds such as CsF yield complex fluorides with lower oxidation states. In aqueous solution, high basicity and strongly covalent complexes favor high oxidation states. In nonaqueous solvent systems, high acidity generally favors low oxidation states. This paper elucidates and attempts to interpret the effects of these acid-base properties in a systematic fashion

REDOX IMAGING OF THE p53-DEPENDENT MITOCHONDRIAL REDOX STATE IN COLON CANCER EX VIVO

Science.gov (United States)

XU, HE N.; FENG, MIN; MOON, LILY; DOLLOFF, NATHAN; EL-DEIRY, WAFIK; LI, LIN Z.

2015-01-01

The mitochondrial redox state and its heterogeneity of colon cancer at tissue level have not been previously reported. Nor has how p53 regulates mitochondrial respiration been measured at (deep) tissue level, presumably due to the unavailability of the technology that has sufficient spatial resolution and tissue penetration depth. Our prior work demonstrated that the mitochondrial redox state and its intratumor heterogeneity is associated with cancer aggressiveness in human melanoma and breast cancer in mouse models, with the more metastatic tumors exhibiting localized regions of more oxidized redox state. Using the Chance redox scanner with an in-plane spatial resolution of 200 μm, we imaged the mitochondrial redox state of the wild-type p53 colon tumors (HCT116 p53 wt) and the p53-deleted colon tumors (HCT116 p53−/−) by collecting the fluorescence signals of nicotinamide adenine dinucleotide (NADH) and oxidized flavoproteins [Fp, including flavin adenine dinucleotide (FAD)] from the mouse xenografts snap-frozen at low temperature. Our results show that: (1) both tumor lines have significant degree of intratumor heterogeneity of the redox state, typically exhibiting a distinct bi-modal distribution that either correlates with the spatial core–rim pattern or the “hot/cold” oxidation-reduction patches; (2) the p53−/− group is significantly more heterogeneous in the mitochondrial redox state and has a more oxidized tumor core compared to the p53 wt group when the tumor sizes of the two groups are matched; (3) the tumor size dependence of the redox indices (such as Fp and Fp redox ratio) is significant in the p53−/− group with the larger ones being more oxidized and more heterogeneous in their redox state, particularly more oxidized in the tumor central regions; (4) the H&E staining images of tumor sections grossly correlate with the redox images. The present work is the first to reveal at the submillimeter scale the intratumor heterogeneity pattern

Plutonium disproportionation. Hydrolysis and local oxidation-state maxima

International Nuclear Information System (INIS)

Silver, G.L.

2014-01-01

Local maxima in the fractions of the trivalent and hexavalent oxidation states are inherent in the algebra of Pu disproportionation reactions. A new method predicts the pH and the oxidation-state fractions at maximum. Tabulated results illustrate the effects of the Pu oxidation number and Pu(IV) hydrolysis on the maxima. This method suggests a new laboratory approach for discovering Pu oxidation-state maxima. (author)

Water Oxidation by Ru-Polyoxometalate Catalysts: Overpotential Dependency on the Number and Charge of the Metal Centers

Directory of Open Access Journals (Sweden)

Simone Piccinin

2015-09-01

Full Text Available Water oxidation is efficiently catalyzed by several Ru-based polyoxometalate (POM molecular catalysts differing in the number, local atomistic environment and oxidation state of the Ru sites. We employ density functional theory calculations to rationalize the dependency of the reaction overpotential on the main structural and electronic molecular properties. In particular, we compare the thermodynamics of the water oxidation cycle for single-site Ru-POM and multiple-site Ru4-POM complexes. For the Ru-POM case, we also investigate the reaction free energy as a function of the Ru oxidation state. We find that the overpotential of these molecular catalysts is primarily determined by the oxidation state of the metal center and is minimum for Ru(IV. In solution, the number of active sites is shown to play a minor role on the reaction energetics. The results are rationalized and discussed in terms of the local structure around the active sites and of the electrostatic screening due to the molecular structure or the solvent.

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

Directory of Open Access Journals (Sweden)

Matthias Augustin

2015-01-01

Full Text Available Manganese oxides are one of the most important groups of materials in energy storage science. In order to fully leverage their application potential, precise control of their properties such as particle size, surface area and Mnx+ oxidation state is required. Here, Mn3O4 and Mn5O8 nanoparticles as well as mesoporous α-Mn2O3 particles were synthesized by calcination of Mn(II glycolate nanoparticles obtained through an economical route based on a polyol synthesis. The preparation of the different manganese oxides via one route facilitates assigning actual structure–property relationships. The oxidation process related to the different MnOx species was observed by in situ X-ray diffraction (XRD measurements showing time- and temperature-dependent phase transformations occurring during oxidation of the Mn(II glycolate precursor to α-Mn2O3 via Mn3O4 and Mn5O8 in O2 atmosphere. Detailed structural and morphological investigations using transmission electron microscopy (TEM and powder XRD revealed the dependence of the lattice constants and particle sizes of the MnOx species on the calcination temperature and the presence of an oxidizing or neutral atmosphere. Furthermore, to demonstrate the application potential of the synthesized MnOx species, we studied their catalytic activity for the oxygen reduction reaction in aprotic media. Linear sweep voltammetry revealed the best performance for the mesoporous α-Mn2O3 species.

99Tc and Re incorporated into metal oxide polyoxometalates: oxidation state stability elucidated by electrochemistry and theory.

Science.gov (United States)

McGregor, Donna; Burton-Pye, Benjamin P; Mbomekalle, Israel M; Aparicio, Pablo A; Romo, Susanna; López, Xavier; Poblet, Josep M; Francesconi, Lynn C

2012-08-20

The radioactive element technetium-99 ((99)Tc, half-life = 2.1 × 10(5) years, β(-) of 253 keV), is a major byproduct of (235)U fission in the nuclear fuel cycle. (99)Tc is also found in radioactive waste tanks and in the environment at National Lab sites and fuel reprocessing centers. Separation and storage of the long-lived (99)Tc in an appropriate and stable waste-form is an important issue that needs to be addressed. Considering metal oxide solid-state materials as potential storage matrixes for Tc, we are examining the redox speciation of Tc on the molecular level using polyoxometalates (POMs) as models. In this study we investigate the electrochemistry of Tc complexes of the monovacant Wells-Dawson isomers, α(1)-P(2)W(17)O(61)(10-) (α1) and α(2)-P(2)W(17)O(61)(10-) (α2) to identify features of metal oxide materials that can stabilize the immobile Tc(IV) oxidation state accessed from the synthesized Tc(V)O species and to interrogate other possible oxidation states available to Tc within these materials. The experimental results are consistent with density functional theory (DFT) calculations. Electrochemistry of K(7-n)H(n)[Tc(V)O(α(1)-P(2)W(17)O(61))] (Tc(V)O-α1), K(7-n)H(n)[Tc(V)O(α(2)-P(2)W(17)O(61))] (Tc(V)O-α2) and their rhenium analogues as a function of pH show that the Tc-containing derivatives are always more readily reduced than their Re analogues. Both Tc and Re are reduced more readily in the lacunary α1 site as compared to the α2 site. The DFT calculations elucidate that the highest oxidation state attainable for Re is VII while, under the same electrochemistry conditions, the highest oxidation state for Tc is VI. The M(V)→ M(IV) reduction processes for Tc(V)O-α1 are not pH dependent or only slightly pH dependent suggesting that protonation does not accompany reduction of this species unlike the M(V)O-α2 (M = (99)Tc, Re) and Re(V)O-α1 where M(V/IV) reduction process must occur hand in hand with protonation of the terminal M═O to

Oxidation of extracellular cysteine/cystine redox state in bleomycin-induced lung fibrosis.

Science.gov (United States)

Iyer, Smita S; Ramirez, Allan M; Ritzenthaler, Jeffrey D; Torres-Gonzalez, Edilson; Roser-Page, Susanne; Mora, Ana L; Brigham, Kenneth L; Jones, Dean P; Roman, Jesse; Rojas, Mauricio

2009-01-01

Several lines of evidence indicate that depletion of glutathione (GSH), a critical thiol antioxidant, is associated with the pathogenesis of idiopathic pulmonary fibrosis (IPF). However, GSH synthesis depends on the amino acid cysteine (Cys), and relatively little is known about the regulation of Cys in fibrosis. Cys and its disulfide, cystine (CySS), constitute the most abundant low-molecular weight thiol/disulfide redox couple in the plasma, and the Cys/CySS redox state (E(h) Cys/CySS) is oxidized in association with age and smoking, known risk factors for IPF. Furthermore, oxidized E(h) Cys/CySS in the culture media of lung fibroblasts stimulates proliferation and expression of transitional matrix components. The present study was undertaken to determine whether bleomycin-induced lung fibrosis is associated with a decrease in Cys and/or an oxidation of the Cys/CySS redox state and to determine whether these changes were associated with changes in E(h) GSH/glutathione disulfide (GSSG). We observed distinct effects on plasma GSH and Cys redox systems during the progression of bleomycin-induced lung injury. Plasma E(h) GSH/GSSG was selectively oxidized during the proinflammatory phase, whereas oxidation of E(h) Cys/CySS occurred at the fibrotic phase. In the epithelial lining fluid, oxidation of E(h) Cys/CySS was due to decreased food intake. Thus the data show that decreased precursor availability and enhanced oxidation of Cys each contribute to the oxidation of extracellular Cys/CySS redox state in bleomycin-induced lung fibrosis.

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Predicting storage-dependent damage to red blood cells using nitrite oxidation kinetics, peroxiredoxin-2 oxidation, and hemoglobin and free heme measurements.

Science.gov (United States)

Oh, Joo-Yeun; Stapley, Ryan; Harper, Victoria; Marques, Marisa B; Patel, Rakesh P

2015-12-01

Storage-dependent damage to red blood cells (RBCs) varies significantly. Identifying RBC units that will undergo higher levels of hemolysis during storage may allow for more efficient inventory management decision-making. Oxidative-stress mediates storage-dependent damage to RBCs and will depend on the oxidant:antioxidant balance. We reasoned that this balance or redox tone will serve as a determinant of how a given RBC unit stores and that its assessment in "young" RBCs will predict storage-dependent hemolysis. RBCs were sampled from bags and segments stored for 7 to 42 days. Redox tone was assessed by nitrite oxidation kinetics and peroxiredoxin-2 (Prx-2) oxidation. In parallel, hemolysis was assessed by measuring cell-free hemoglobin (Hb) and free heme (hemin). Correlation analyses were performed to determine if Day 7 measurements predicted either the level of hemolysis at Day 35 or the increase in hemolysis during storage. Higher Day 7 Prx-2 oxidation was associated with higher Day 35 Prx-2 oxidation, suggesting that early assessment of this variable may identify RBCs that will incur the most oxidative damage during storage. RBCs that oxidized nitrite faster on Day 7 were associated with the greatest levels of storage-dependent hemolysis and increases in Prx-2 oxidation. An inverse relationship between storage-dependent changes in oxyhemoglobin and free heme was observed underscoring an unappreciated reciprocity between these molecular species. Moreover, free heme was higher in the bag compared to paired segments, with opposite trends observed for free Hb. Measurement of Prx-2 oxidation and nitrite oxidation kinetics early during RBC storage may predict storage-dependent damage to RBC including hemolysis-dependent formation of free Hb and heme. © 2015 AABB.

Glymphatic clearance controls state-dependent changes in brain lactate concentration

DEFF Research Database (Denmark)

Lundgaard, Iben; Lu, Minh Lon; Yang, Ezra

2017-01-01

Brain lactate concentration is higher during wakefulness than in sleep. However, it is unknown why arousal is linked to an increase in brain lactate and why lactate declines within minutes of sleep. Here, we show that the glymphatic system is responsible for state-dependent changes in brain lacta......-lymphatic clearance. This analysis provides fundamental new insight into brain energy metabolism by demonstrating that glucose that is not fully oxidized can be exported as lactate via glymphatic-lymphatic fluid transport.......Brain lactate concentration is higher during wakefulness than in sleep. However, it is unknown why arousal is linked to an increase in brain lactate and why lactate declines within minutes of sleep. Here, we show that the glymphatic system is responsible for state-dependent changes in brain lactate...... concentration. Suppression of glymphatic function via acetazolamide treatment, cisterna magna puncture, aquaporin 4 deletion, or changes in body position reduced the decline in brain lactate normally observed when awake mice transition into sleep or anesthesia. Concurrently, the same manipulations diminished...

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

Energy Technology Data Exchange (ETDEWEB)

Jernigan, Glenn Geoffrey [California Univ., Berkeley, CA (United States). Dept. of Chemistry

1994-10-01

Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu₂O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu₂O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu₂O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N₂ and CO₂. At the end of each reaction, the catalyst was found to be Cu₂O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

Activity of Mn-Oxidizing Peroxidases of Ganoderma lucidum Depending on Cultivation Conditions

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Jasmina Ćilerdžić

2015-11-01

Full Text Available Trunks and stumps of various deciduous species act as natural habitats for Ganoderma lucidum. The chemical composition of their cell wall affects the development of fungal ligninolytic enzyme system as well as its ability to degrade lignin from the plant cell wall. Additionally, numerous compounds structurally similar to lignin can be degraded by the G. lucidum enzyme system which could take important roles in various biotechnological processes. The laccases, which are the dominant enzymes synthesized by G. lucidum, have been studied more extensively than the Mn-oxidizing peroxidases. Therefore, this study aimed to create the dynamics profile of Mn-oxidizing peroxidases activities in four G. lucidum strains, classifying and determining their properties depending on the cultivation type and plant residue as a carbon source in the medium, as well as to establish whether intraspecific variety exists. The findings suggest that submerged cultivation appeared to be a more appropriate cultivation type for enzyme activities compared with solid-state cultivation, and oak sawdust was a better carbon source than wheat straw. Under the optimum conditions, on day 14, G. lucidum BEOFB 431 was characterized by the highest levels of both Mn-dependent and Mn-independent peroxidase activities (4795.5 and 5170.5 U/L, respectively. Strain, cultivation type, and carbon source were factors that affected the profiles of Mn-oxidizing peroxidases isoenzymes.

GDH-Dependent Glutamate Oxidation in the Brain Dictates Peripheral Energy Substrate Distribution

DEFF Research Database (Denmark)

Karaca, Melis; Frigerio, Francesca; Migrenne, Stephanie

2015-01-01

in a central energy-deprivation state with increased ADP/ATP ratios and phospho-AMPK in the hypothalamus. This induced changes in the autonomous nervous system balance, with increased sympathetic activity promoting hepatic glucose production and mobilization of substrates reshaping peripheral energy stores...... glutamate dehydrogenase (GDH) activity. Here, we investigated the significance of glutamate as energy substrate for the brain. Upon glutamate exposure, astrocytes generated ATP in a GDH-dependent way. The observed lack of glutamate oxidation in brain-specific GDH null CnsGlud1(-/-) mice resulted...

ATM-dependent pathways of chromatin remodelling and oxidative DNA damage responses.

Science.gov (United States)

Berger, N Daniel; Stanley, Fintan K T; Moore, Shaun; Goodarzi, Aaron A

2017-10-05

Ataxia-telangiectasia mutated (ATM) is a serine/threonine protein kinase with a master regulatory function in the DNA damage response. In this role, ATM commands a complex biochemical network that signals the presence of oxidative DNA damage, including the dangerous DNA double-strand break, and facilitates subsequent repair. Here, we review the current state of knowledge regarding ATM-dependent chromatin remodelling and epigenomic alterations that are required to maintain genomic integrity in the presence of DNA double-strand breaks and/or oxidative stress. We will focus particularly on the roles of ATM in adjusting nucleosome spacing at sites of unresolved DNA double-strand breaks within complex chromatin environments, and the impact of ATM on preserving the health of cells within the mammalian central nervous system.This article is part of the themed issue 'Chromatin modifiers and remodellers in DNA repair and signalling'. © 2017 The Author(s).

Susceptibility of β1 Na+-K+ pump subunit to glutathionylation and oxidative inhibition depends on conformational state of pump.

Science.gov (United States)

Liu, Chia-Chi; Garcia, Alvaro; Mahmmoud, Yasser A; Hamilton, Elisha J; Galougahi, Keyvan Karimi; Fry, Natasha A S; Figtree, Gemma A; Cornelius, Flemming; Clarke, Ronald J; Rasmussen, Helge H

2012-04-06

Glutathionylation of cysteine 46 of the β1 subunit of the Na(+)-K(+) pump causes pump inhibition. However, the crystal structure, known in a state analogous to an E2·2K(+)·P(i) configuration, indicates that the side chain of cysteine 46 is exposed to the lipid bulk phase of the membrane and not expected to be accessible to the cytosolic glutathione. We have examined whether glutathionylation depends on the conformational changes in the Na(+)-K(+) pump cycle as described by the Albers-Post scheme. We measured β1 subunit glutathionylation and function of Na(+)-K(+)-ATPase in membrane fragments and in ventricular myocytes. Signals for glutathionylation in Na(+)-K(+)-ATPase-enriched membrane fragments suspended in solutions that preferentially induce E1ATP and E1Na(3) conformations were much larger than signals in solutions that induce the E2 conformation. Ouabain further reduced glutathionylation in E2 and eliminated an increase seen with exposure to the oxidant peroxynitrite (ONOO(-)). Inhibition of Na(+)-K(+)-ATPase activity after exposure to ONOO(-) was greater when the enzyme had been in the E1Na(3) than the E2 conformation. We exposed myocytes to different extracellular K(+) concentrations to vary the membrane potential and hence voltage-dependent conformational poise. K(+) concentrations expected to shift the poise toward E2 species reduced glutathionylation, and ouabain eliminated a ONOO(-)-induced increase. Angiotensin II-induced NADPH oxidase-dependent Na(+)-K(+) pump inhibition was eliminated by conditions expected to shift the poise toward the E2 species. We conclude that susceptibility of the β1 subunit to glutathionylation depends on the conformational poise of the Na(+)-K(+) pump.

Susceptibility of β1 Na+-K+ Pump Subunit to Glutathionylation and Oxidative Inhibition Depends on Conformational State of Pump*

Science.gov (United States)

Liu, Chia-Chi; Garcia, Alvaro; Mahmmoud, Yasser A.; Hamilton, Elisha J.; Galougahi, Keyvan Karimi; Fry, Natasha A. S.; Figtree, Gemma A.; Cornelius, Flemming; Clarke, Ronald J.; Rasmussen, Helge H.

2012-01-01

Glutathionylation of cysteine 46 of the β1 subunit of the Na+-K+ pump causes pump inhibition. However, the crystal structure, known in a state analogous to an E2·2K+·Pi configuration, indicates that the side chain of cysteine 46 is exposed to the lipid bulk phase of the membrane and not expected to be accessible to the cytosolic glutathione. We have examined whether glutathionylation depends on the conformational changes in the Na+-K+ pump cycle as described by the Albers-Post scheme. We measured β1 subunit glutathionylation and function of Na+-K+-ATPase in membrane fragments and in ventricular myocytes. Signals for glutathionylation in Na+-K+-ATPase-enriched membrane fragments suspended in solutions that preferentially induce E1ATP and E1Na3 conformations were much larger than signals in solutions that induce the E2 conformation. Ouabain further reduced glutathionylation in E2 and eliminated an increase seen with exposure to the oxidant peroxynitrite (ONOO−). Inhibition of Na+-K+-ATPase activity after exposure to ONOO− was greater when the enzyme had been in the E1Na3 than the E2 conformation. We exposed myocytes to different extracellular K+ concentrations to vary the membrane potential and hence voltage-dependent conformational poise. K+ concentrations expected to shift the poise toward E2 species reduced glutathionylation, and ouabain eliminated a ONOO−-induced increase. Angiotensin II-induced NADPH oxidase-dependent Na+-K+ pump inhibition was eliminated by conditions expected to shift the poise toward the E2 species. We conclude that susceptibility of the β1 subunit to glutathionylation depends on the conformational poise of the Na+-K+ pump. PMID:22354969

Conformational Toggling of Yeast Iso-1-Cytochrome c in the Oxidized and Reduced States

Science.gov (United States)

Yang, Zhongzheng; Zhu, Jing; Ying, Tianlei; Jiang, Xianwang; Zhang, Xu; Wu, Houming; Liu, Maili; Tan, Xiangshi; Cao, Chunyang; Huang, Zhong-Xian

2011-01-01

To convert cyt c into a peroxidase-like metalloenzyme, the P71H mutant was designed to introduce a distal histidine. Unexpectedly, its peroxidase activity was found even lower than that of the native, and that the axial ligation of heme iron was changed to His71/His18 in the oxidized state, while to Met80/His18 in the reduced state, characterized by UV-visible, circular dichroism, and resonance Raman spectroscopy. To further probe the functional importance of Pro71 in oxidation state dependent conformational changes occurred in cyt c, the solution structures of P71H mutant in both oxidation states were determined. The structures indicate that the half molecule of cyt c (aa 50–102) presents a kind of “zigzag riveting ruler” structure, residues at certain positions of this region such as Pro71, Lys73 can move a big distance by altering the tertiary structure while maintaining the secondary structures. This finding provides a molecular insight into conformational toggling in different oxidation states of cyt c that is principle significance to its biological functions in electron transfer and apoptosis. Structural analysis also reveals that Pro71 functions as a key hydrophobic patch in the folding of the polypeptide of the region (aa 50–102), to prevent heme pocket from the solvent. PMID:22087268

Speciation of the oxidation states of plutonium in aqueous solutions by UV/Vis spectroscopy, CE-ICP-MS and CE-RIMS

International Nuclear Information System (INIS)

Buerger, S.; Banik, N.L.; Buda, R.A.; Kratz, J.V.; Kuczewski, B.; Trautmann, N.

2007-01-01

For the speciation of the plutonium oxidation states in aqueous solutions, the online coupling of capillary electrophoresis (CE) with inductively coupled plasma mass spectrometry (ICP-MS) has been developed. Depending on the radius/electrical charge ratio, the oxidation states III, IV, V, and VI of plutonium are separated by CE, based on the different migration times through the capillary and are detected by ICP-MS. The detection limit is 20 ppb, i.e. 10 9 -10 10 atoms (10 -12 -10 -13 g) for one oxidation state with an uncertainty of the reproducibility of the migration times of ≤ 1% and ≤ 5% for the peak area. The redox kinetics of the different plutonium oxidation states in the presence of humic substances (humic and fulvic acid) have been studied. A relatively rapid reduction of Pu(VI) (10 to 1000 h) in contact with Gorleben fulvic or Aldrich humic acid could be observed, depending on the pH of the solution. Furthermore, at pH=1, a reduction to Pu(III) and Pu(IV) in a mixture of all four oxidation states in contact with Gorleben fulvic acid after one month has been observed. In order to improve the sensitivity of the CE method, the offline coupling of CE to resonance ionization mass spectrometry (RIMS) has been explored. First applications of this new speciation method are presented. (orig.)

Influence of microorganisms on the oxidation state distribution of multivalent actinides under anoxic conditions

International Nuclear Information System (INIS)

Reed, Donald Timothy; Borkowski, Marian; Lucchini, Jean-Francois; Ams, David; Richmann, M.K.; Khaing, H.; Swanson, J.S.

2010-01-01

The fate and potential mobility of multivalent actinides in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium, uranium and neptunium are the near-surface multivalent contaminants of concern and are also key contaminants for the deep geologic disposal of nuclear waste. Their mobility is highly dependent on their redox distribution at their contamination source as well as along their potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. Under anoxic conditions, indirect and direct bioreduction mechanisms exist that promote the prevalence of lower-valent species for multivalent actinides. Oxidation-state-specific biosorption is also an important consideration for long-term migration and can influence oxidation state distribution. Results of ongoing studies to explore and establish the oxidation-state specific interactions of soil bacteria (metal reducers and sulfate reducers) as well as halo-tolerant bacteria and Archaea for uranium, neptunium and plutonium will be presented. Enzymatic reduction is a key process in the bioreduction of plutonium and uranium, but co-enzymatic processes predominate in neptunium systems. Strong sorptive interactions can occur for most actinide oxidation states but are likely a factor in the stabilization of lower-valent species when more than one oxidation state can persist under anaerobic microbiologically-active conditions. These results for microbiologically active systems are interpreted in the context of their overall importance in defining the potential migration of multivalent actinides in the subsurface.

Size-dependent cytotoxicity of yttrium oxide nanoparticles on primary osteoblasts in vitro

Energy Technology Data Exchange (ETDEWEB)

Zhou, Guoqiang, E-mail: zhougq1982@163.com; Li, Yunfei; Ma, Yanyan; Liu, Zhu; Cao, Lili; Wang, Da; Liu, Sudan; Xu, Wenshi; Wang, Wenying [Hebei University, Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of Ministry of Education, Key Laboratory of Chemical Biology of Hebei Province, College of Chemistry and Environmental Science (China)

2016-05-15

Yttrium oxide nanoparticles are an excellent host material for the rare earth metals and have high luminescence efficiency providing a potential application in photodynamic therapy and biological imaging. In this study, the effects of yttrium oxide nanoparticles with four different sizes were investigated using primary osteoblasts in vitro. The results demonstrated that the cytotoxicity generated by yttrium oxide nanoparticles depended on the particle size, and smaller particles possessed higher toxicological effects. For the purpose to elucidate the relationship between reactive oxygen species generation and cell damage, cytomembrane integrity, intracellular reactive oxygen species level, mitochondrial membrane potential, cell apoptosis rate, and activity of caspase-3 in cells were then measured. Increased reactive oxygen species level was also observed in a size-dependent way. Thus, our data demonstrated that exposure to yttrium oxide nanoparticles resulted in a size-dependent cytotoxicity in cultured primary osteoblasts, and reactive oxygen species generation should be one possible damage pathway for the toxicological effects produced by yttrium oxide particles. The results may provide useful information for more rational applications of yttrium oxide nanoparticles in the future.

Analog memory and spike-timing-dependent plasticity characteristics of a nanoscale titanium oxide bilayer resistive switching device

International Nuclear Information System (INIS)

Seo, Kyungah; Park, Sangsu; Lee, Kwanghee; Lee, Byounghun; Hwang, Hyunsang; Kim, Insung; Jung, Seungjae; Jo, Minseok; Park, Jubong; Shin, Jungho; Biju, Kuyyadi P; Kong, Jaemin

2011-01-01

We demonstrated analog memory, synaptic plasticity, and a spike-timing-dependent plasticity (STDP) function with a nanoscale titanium oxide bilayer resistive switching device with a simple fabrication process and good yield uniformity. We confirmed the multilevel conductance and analog memory characteristics as well as the uniformity and separated states for the accuracy of conductance change. Finally, STDP and a biological triple model were analyzed to demonstrate the potential of titanium oxide bilayer resistive switching device as synapses in neuromorphic devices. By developing a simple resistive switching device that can emulate a synaptic function, the unique characteristics of synapses in the brain, e.g. combined memory and computing in one synapse and adaptation to the outside environment, were successfully demonstrated in a solid state device.

Radioiodine therapy induces dose-dependent in-vivo oxidation injury

International Nuclear Information System (INIS)

Sinzinger, H.; Resch, U.; Tatzber, F.; Weiss, K.

2002-01-01

Until now, radiation hazards as a consequence of radioiodine therapy are not examined in detail. Oxidation of lipoproteins may favour vasculopathy. We studied the influence of a single radioiodine therapy with 5 (n=8; 46-71a), 10 (n=6; 54-75a), 20 (n=11; 45-73a), 80 (n=6; 37-75a) or 200 (n=6; 43-67a) mCi on in-vivo oxidation injury in blood (plasma [P], serum [Se]), urine (U) and saliva (Sa) in patients suffering from hyperthyroidism opr thyroid cancer, respectively. The isoprostane 8-epi-prostaglandin (PG) F 2α as a marker of in-vivo oxidation injury (Sa, Se, P, U), oxidation of lipoproteins (LDL, HDL), thromboxane B2 (Sa, Se, P, U), PGE 2 , PGF 2α and circulating endothelial cells (CEC) were examined before therapy, daily for 7 days and weekly thereafter for 6 weeks. Blood was also analyzed for thiobarbituric acid reactive substances (TBARS), relative electrophoretic mobility (REM), baseline dienes (BD), endogenous peroxides (POX) and formation of conjugated dienes in copper-mediated oxidation (CD) expressed in lag-time and rate of propagation. There is a dose-dependent increase in 8-epi-PGF 2α being most pronounced in saliva (p 2 and HDL 3 subfractions 24 h after application, but 48 h and 72 h after application there was a significant increase in TBARS, REM, BD, POX and rate of propagation and a decrease in lag-time in HDL-subfractions independently from applied dose. Also HDL 2 showed more TBARS, REM, BD, POX and shorter lag-time than HDL 3 48 h after application, but this effect was reversed 72 h after application. HDL is the lipoprotein most prone to oxidation by radioiodine treatment. Apparently, when LDL becomes oxidized, it shifts metabolically its oxidation products to HDL. These findings show a significant temporary and dose-dependent endothelial desquamation, oxidation of lipoproteins and long-lasting in-vivo oxidation injury (saliva > urine > blood) as side effect of radioiodine therapy, altogether being potentially proatherogenic

First-principles calculations of orientation dependence of Si thermal oxidation based on Si emission model

Science.gov (United States)

Nagura, Takuya; Kawachi, Shingo; Chokawa, Kenta; Shirakawa, Hiroki; Araidai, Masaaki; Kageshima, Hiroyuki; Endoh, Tetsuo; Shiraishi, Kenji

2018-04-01

It is expected that the off-state leakage current of MOSFETs can be reduced by employing vertical body channel MOSFETs (V-MOSFETs). However, in fabricating these devices, the structure of the Si pillars sometimes cannot be maintained during oxidation, since Si atoms sometimes disappear from the Si/oxide interface (Si missing). Thus, in this study, we used first-principles calculations based on the density functional theory, and investigated the Si emission behavior at the various interfaces on the basis of the Si emission model including its atomistic structure and dependence on Si crystal orientation. The results show that the order in which Si atoms are more likely to be emitted during thermal oxidation is (111) > (110) > (310) > (100). Moreover, the emission of Si atoms is enhanced as the compressive strain increases. Therefore, the emission of Si atoms occurs more easily in V-MOSFETs than in planar MOSFETs. To reduce Si missing in V-MOSFETs, oxidation processes that induce less strain, such as wet or pyrogenic oxidation, are necessary.

Coherent states for certain time-dependent systems

International Nuclear Information System (INIS)

Pedrosa, I.A.

1989-01-01

Hartley and Ray have constructed and studied coherent states for the time-dependent oscillator. Here we show how to construct states for more general time-dependent systems. We also show that these states are equivalent to the well-known squeezed states. (author) [pt

Genome-enabled studies of anaerobic, nitrate-dependent iron oxidation in the chemolithoautotrophic bacterium Thiobacillus denitrificans

Directory of Open Access Journals (Sweden)

Harry R Beller

2013-08-01

Full Text Available Thiobacillus denitrificans is a chemolithoautotrophic bacterium capable of anaerobic, nitrate-dependent U(IV and Fe(II oxidation, both of which can strongly influence the long-term efficacy of in situ reductive immobilization of uranium in contaminated aquifers. We previously identified two c-type cytochromes involved in nitrate-dependent U(IV oxidation in T. denitrificans and hypothesized that c-type cytochromes would also catalyze Fe(II oxidation, as they have been found to play this role in anaerobic phototrophic Fe(II-oxidizing bacteria. Here we report on efforts to identify genes associated with nitrate-dependent Fe(II oxidation, namely (a whole-genome transcriptional studies [using FeCO3, Fe2+, and U(IV oxides as electron donors under denitrifying conditions], (b Fe(II oxidation assays performed with knockout mutants targeting primarily highly expressed or upregulated c-type cytochromes, and (c random transposon-mutagenesis studies with screening for Fe(II oxidation. Assays of mutants for 26 target genes, most of which were c-type cytochromes, indicated that none of the mutants tested were significantly defective in nitrate-dependent Fe(II oxidation. The non-defective mutants included the c1-cytochrome subunit of the cytochrome bc1 complex (complex III, which has relevance to a previously proposed role for this complex in nitrate-dependent Fe(II oxidation and to current concepts of reverse electron transfer. A transposon mutant with a disrupted gene associated with NADH:ubiquinone oxidoreductase (complex I was ~35% defective relative to the wild-type strain; this strain was similarly defective in nitrate reduction with thiosulfate as the electron donor. Overall, our results indicate that nitrate-dependent Fe(II oxidation in T. denitrificans is not catalyzed by the same c-type cytochromes involved in U(IV oxidation, nor have other c-type cytochromes yet been implicated in the process.

Cytosolic NADP(+)-dependent isocitrate dehydrogenase status modulates oxidative damage to cells.

Science.gov (United States)

Lee, Su Min; Koh, Ho-Jin; Park, Dong-Chan; Song, Byoung J; Huh, Tae-Lin; Park, Jeen-Woo

2002-06-01

NADPH is an important cofactor in many biosynthesis pathways and the regeneration of reduced glutathione, critically important in cellular defense against oxidative damage. It is mainly produced by glucose 6-phosphate dehydrogenase (G6PD), malic enzyme, and the cytosolic form of NADP(+)-dependent isocitrate dehydrogenase (IDPc). Little information is available about the role of IDPc in antioxidant defense. In this study we investigated the role of IDPc against cytotoxicity induced by oxidative stress by comparing the relative degree of cellular responses in three different NIH3T3 cells with stable transfection with the cDNA for mouse IDPc in sense and antisense orientations, where IDPc activities were 3-4-fold higher and 35% lower, respectively, than that in the parental cells carrying the vector alone. Although the activities of other antioxidant enzymes, such as superoxide dismutase, catalase, glutathione reductase, glutathione peroxidase, and G6PD, were comparable in all transformed cells, the ratio of GSSG to total glutathione was significantly higher in the cells expressing the lower level of IDPc. This finding indicates that IDPc is essential for the efficient glutathione recycling. Upon transient exposure to increasing concentrations of H(2)O(2) or menadione, an intracellular source of free radicals and reactive oxygen species, the cells with low levels of IDPc became more sensitive to oxidative damage by H(2)O(2) or menadione. Lipid peroxidation, oxidative DNA damage, and intracellular peroxide generation were higher in the cell-line expressing the lower level of IDPc. However, the cells with the highly over-expressed IDPc exhibited enhanced resistance against oxidative stress, compared to the control cells. This study provides direct evidence correlating the activities of IDPc and the maintenance of the cellular redox state, suggesting that IDPc plays an important role in cellular defense against oxidative stress.

Concentration-dependent toxicity of iron oxide nanoparticles mediated by increased oxidative stress

Directory of Open Access Journals (Sweden)

Saba Naqvi

2010-11-01

Full Text Available Saba Naqvi1, Mohammad Samim2, MZ Abdin3, Farhan Jalees Ahmed4, AN Maitra5, CK Prashant6, Amit K Dinda61Faculty of Engineering and Interdisciplinary Sciences, 2Department of Chemistry, 3Department of Biotechnology, Faculty of Science, 4Department of Pharmaceutics, Faculty of Pharmacy, Jamia Hamdard, Hamdard University, 5Department of Chemistry, University of Delhi, 6Department of Pathology, All India Institute of Medical Sciences, New Delhi, IndiaAbstract: Iron oxide nanoparticles with unique magnetic properties have a high potential for use in several biomedical, bioengineering and in vivo applications, including tissue repair, magnetic resonance imaging, immunoassay, drug delivery, detoxification of biologic fluids, cell sorting, and hyperthermia. Although various surface modifications are being done for making these nonbiodegradable nanoparticles more biocompatible, their toxic potential is still a major concern. The current in vitro study of the interaction of superparamagnetic iron oxide nanoparticles of mean diameter 30 nm coated with Tween 80 and murine macrophage (J774 cells was undertaken to evaluate the dose- and time-dependent toxic potential, as well as investigate the role of oxidative stress in the toxicity. A 15–30 nm size range of spherical nanoparticles were characterized by transmission electron microscopy and zeta sizer. MTT assay showed >95% viability of cells in lower concentrations (25–200 µg/mL and up to three hours of exposure, whereas at higher concentrations (300–500 µg/mL and prolonged (six hours exposure viability reduced to 55%–65%. Necrosis-apoptosis assay by propidium iodide and Hoechst-33342 staining revealed loss of the majority of the cells by apoptosis. H2DCFDDA assay to quantify generation of intracellular reactive oxygen species (ROS indicated that exposure to a higher concentration of nanoparticles resulted in enhanced ROS generation, leading to cell injury and death. The cell membrane injury

Context-Dependent Role of Oxidized Lipids and Lipoproteins in Inflammation.

Science.gov (United States)

Miller, Yury I; Shyy, John Y-J

2017-02-01

Oxidized low-density lipoprotein (OxLDL), which contains hundreds of different oxidized lipid molecules, is a hallmark of hyperlipidemia and atherosclerosis. The same oxidized lipids found in OxLDL are also formed in apoptotic cells, and are present in tissues as well as in the circulation under pathological conditions. In many disease contexts, oxidized lipids constitute damage signals, or patterns, that activate pattern-recognition receptors (PRRs) and significantly contribute to inflammation. Here, we review recent discoveries and emerging trends in the field of oxidized lipids and the regulation of inflammation, focusing on oxidation products of polyunsaturated fatty acids esterified into cholesteryl esters (CEs) and phospholipids (PLs). We also highlight context-dependent activation and biased agonism of Toll-like receptor-4 (TLR4) and the NLRP3 inflammasome, among other signaling pathways activated by oxidized lipids. Copyright © 2016 Elsevier Ltd. All rights reserved.

Calcium Co-regulates Oxidative Metabolism and ATP Synthase-dependent Respiration in Pancreatic Beta Cells

Science.gov (United States)

De Marchi, Umberto; Thevenet, Jonathan; Hermant, Aurelie; Dioum, Elhadji; Wiederkehr, Andreas

2014-01-01

Mitochondrial energy metabolism is essential for glucose-induced calcium signaling and, therefore, insulin granule exocytosis in pancreatic beta cells. Calcium signals are sensed by mitochondria acting in concert with mitochondrial substrates for the full activation of the organelle. Here we have studied glucose-induced calcium signaling and energy metabolism in INS-1E insulinoma cells and human islet beta cells. In insulin secreting cells a surprisingly large fraction of total respiration under resting conditions is ATP synthase-independent. We observe that ATP synthase-dependent respiration is markedly increased after glucose stimulation. Glucose also causes a very rapid elevation of oxidative metabolism as was followed by NAD(P)H autofluorescence. However, neither the rate of the glucose-induced increase nor the new steady-state NAD(P)H levels are significantly affected by calcium. Our findings challenge the current view, which has focused mainly on calcium-sensitive dehydrogenases as the target for the activation of mitochondrial energy metabolism. We propose a model of tight calcium-dependent regulation of oxidative metabolism and ATP synthase-dependent respiration in beta cell mitochondria. Coordinated activation of matrix dehydrogenases and respiratory chain activity by calcium allows the respiratory rate to change severalfold with only small or no alterations of the NAD(P)H/NAD(P)+ ratio. PMID:24554722

Higher Americium Oxidation State Research Roadmap

Energy Technology Data Exchange (ETDEWEB)

Mincher, Bruce J. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Law, Jack D. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Goff, George S. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Moyer, Bruce A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Burns, Jon D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lumetta, Gregg J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Sinkov, Sergey I. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Shehee, Thomas C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hobbs, David T. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2015-12-18

The partitioning of hexavalent Am from dissolved nuclear fuel requires the ability to efficiently oxidize Am(III) to Am(VI) and to maintain that oxidation state for a length of time sufficient to perform the separation. Several oxidants have been, or are being developed. Chemical oxidants include Ag-catalyzed ozone, Ag-catalyzed peroxydisulfate, Cu(III) periodate, and sodium bismuthate. Hexavalent americium has also now successfully been prepared by electrolysis, using functionalized electrodes. So-called auto-reduction rates of Am(VI) are sufficiently slow to allow for separations. However, for separations based on solvent extraction or ion exchange using organic resins, the high valence state must be maintained under the reducing conditions of the organic phase contact, and a holding oxidant is probably necessary. Until now, only Cu(III) periodate and sodium bismuthate oxidation have been successfully combined with solvent extraction separations. Bismuthate oxidation provided the higher DAm, since it acts as its own holding oxidant, and a successful hot test using centrifugal contactors was performed. For the other oxidants, Ag-catalyzed peroxydisulfate will not oxidize americium in nitric acid concentrations above 0.3 M, and it is not being further investigated. Peroxydisulfate in the absence of Ag catalysis is being used to prepare Am(V) in ion exchange work, discussed below. Preliminary work with Ag-catalyzed ozone has been unsuccessful for extractions of Am(VI) from 6.5 M HNO3, and only one attempt at extraction, also from 6.5 M HNO3, using the electrolytic oxidation has been attempted. However, this high acid concentration was based on the highest Am extraction efficiency using the bismuthate oxidant; which is only sparingly soluble, and thus the oxidation yield is based on bismuthate solubility. Lower acid concentrations may be sufficient with alternative oxidants and work with Ag-ozone, Cu(III) and electrolysis is on-going. Two non

Depth-resolved detection and process dependence of traps at ultrathin plasma-oxidized and deposited SiO2/Si interfaces

International Nuclear Information System (INIS)

Brillson, L. J.; Young, A. P.; White, B. D.; Schaefer, J.; Niimi, H.; Lee, Y. M.; Lucovsky, G.

2000-01-01

Low-energy electron-excited nanoluminescence spectroscopy reveals depth-resolved optical emission associated with traps near the interface between ultrathin SiO 2 deposited by plasma-enhanced chemical vapor deposition on plasma-oxidized crystalline Si. These near-interface states exhibit a strong dependence on local chemical bonding changes introduced by thermal/gas processing, layer-specific nitridation, or depth-dependent radiation exposure. The depth-dependent results provide a means to test chemical and structural bond models used to develop advanced dielectric-semiconductor junctions. (c) 2000 American Vacuum Society

Grain and burnup dependence of spent fuel oxidation: geological repository impact

International Nuclear Information System (INIS)

Hanson, B. D.; Kansa, E. J.; Stoot, R.B.

1998-01-01

Further refinements to the oxidation model of Stout et al. have been made. The present model incorporates the burnup dependence of the oxidation rate in addition to an allowance for a distribution of grain sizes. The model was tested by comparing the model results with the oxidation histories of spent fuel samples oxidized in Thermogravimetric Analysis (TGA) or Oven Dry-Bath (ODB) experiments. The comparison between the experimental and model results are remarkably close and confirm the assumption that grain-size distributions and activation energies are the important parameters to predicting oxidation behavior. The burnup dependence of the activation energy was shown to have a greater effect than decreasing the effective grain size in suppressing the rate of the reaction U 4 O 9 (rightwards arrow)U 3 O 4 . Model results predict that U 3 O 8 formation of spent fuels exposed to oxygen will be suppressed even for high burnup fuels that have undergone restructuring in the rim region, provided the repository temperature is kept sufficient

The oxidation state of sulfur in apatite: A new oxybarometer?

Science.gov (United States)

Fiege, A.; Konecke, B.; Kim, Y.; Simon, A. C.; Becker, U.; Parat, F.

2016-12-01

Oxygen fugacity (fO2) of magmatic and hydrothermal systems influences, for instance, crystallization and degassing processes as well as metal solubilities in melts and fluids. Apatite is a ubiquitous mineral in magmatic and hydrothermal environments that can record and preserve volatile zonation. It can contain several thousand μg/g of the redox sensitive element sulfur (S), making S-in-apatite a potential fO2 sensor. Despite the polyvalent properties of S (e.g., S2-, S4+, S6+), the oxidation state and incorporation mechanisms of S in the apatite structure are poorly understood. In this study, the oxidation state of S-in-apatite as a function of fO2 is investigated using X-ray absorption near-edge structures (XANES) spectroscopy at the S K-edge. Apatites crystallized from lamproitic melts at 1000°C, 300 MPa and over a broad range of fO2 and sulfur fugacities (fS2) were measured. Peaks corresponding to S6+ ( 2482 eV), S4+ ( 2478 eV) and S2- ( 2470 eV) were identified in apatite. The integrated S6+/STotal (STotal = S6+ + S4+ + S2-) peak area ratios show a distinct positive correlation with fO2, increasing from 0.17 at FMQ+0 to 0.96 at FMQ+3. Ab-initio calculations were performed to further understand the energetics and geometry of incorporation of S6+, S4+ and S2- into the apatite (F-, Cl-, OH-) end-members. The results confirm that apatite can contain three different oxidations states of S (S6+, S4+, S2-) as a function of fO2. This makes apatite probably the first geologically relevant mineral to incorporate reduced (S2-), intermediate (S4+), and oxidized (S6+) S in variable proportions. We emphasize that the strong dependence of the S oxidation state in apatite as a function of fO2 is also coupled with changing S content of apatite and co-existing melt (i.e., with changing fS2), resulting in a complex correlation between [1] apatite-melt (or fluid) partitioning, [2] redox conditions and [3] the melt and/or fluid composition, making the application of previously

Strategies for state-dependent quantum deleting

International Nuclear Information System (INIS)

Song Wei; Yang Ming; Cao Zhuoliang

2004-01-01

A quantum state-dependent quantum deleting machine is constructed. We obtain a upper bound of the global fidelity on N-to-M quantum deleting from a set of K non-orthogonal states. Quantum networks are constructed for the above state-dependent quantum deleting machine when K=2. Our deleting protocol only involves a unitary interaction among the initial copies, with no ancilla. We also present some analogies between quantum cloning and deleting

Layer Dependence of Graphene for Oxidation Resistance of Cu Surface

Institute of Scientific and Technical Information of China (English)

Yu-qing Song; Xiao-ping Wang

2017-01-01

We studied the oxidation resistance of graphene-coated Cu surface and its layer dependence by directly growing monolayer graphene with different multilayer structures coexisted,diminishing the influence induced by residue and transfer technology.It is found that the Cu surface coated with the monolayer graphene demonstrate tremendous difference in oxidation pattern and oxidation rate,compared to that coated with the bilayer graphene,which is considered to be originated from the strain-induced linear oxidation channel in monolayer graphene and the intersection of easily-oxidized directions in each layer of bilayer graphene,respectively.We reveal that the defects on the graphene basal plane but not the boundaries are the main oxidation channel for Cu surface under graphene protection.Our finding indicates that compared to putting forth efforts to improve the quality of monolayer graphene by reducing defects,depositing multilayer graphene directly on metal is a simple and effective way to enhance the oxidation resistance of graphene-coated metals.

Grain size and burnup dependence of spent fuel oxidation: Geological repository impact

International Nuclear Information System (INIS)

Kansa, E.J.; Hanson, B.D.; Stout, R.B.

1999-01-01

Further refinements to the oxidation model of Stout et al. have been made. The present model incorporates the burnup dependence of the oxidation rate and an allowance for a distribution of grain sizes. The model was tested by comparing the model results with the oxidation histories of spent-fuel samples oxidized in thermogravimetric analysis (TGA) or oven dry-bath (ODB) experiments. The experimental and model results are remarkably close and confirm the assumption that grain-size distributions and activation energies are the important parameters to predicting oxidation behavior. The burnup dependence of the activation energy was shown to have a greater effect than decreasing the effective grain size in suppressing the rate of the reaction U 4 O 9 r↓U 3 O 8 . Model results predict that U 3 O 8 formation of spent fuels exposed to oxygen will be suppressed even for high burnup fuels that have undergone restructuring in the rim region, provided the repository temperature is kept sufficiently low

Effect of microorganisms on the plutonium oxidation states

International Nuclear Information System (INIS)

Lukšienė, Benedikta; Druteikienė, Rūta; Pečiulytė, Dalia; Baltrūnas, Dalis; Remeikis, Vidmantas; Paškevičius, Algimantas

2012-01-01

Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to 239 Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state. - Highlights: ► Particular microbes from low-level radioactive waste repository were exposed to Pu (IV). ► Some tested bacteria induced slight Pu (IV) reduction at low pH under aerobic conditions. ► Tested fungi did not show peculiarities to alter Pu oxidation state. ► The modified radiochemical method was applied to differentiate Pu oxidation states.

Nitrate-Dependent Iron Oxidation: A Potential Mars Metabolism

Science.gov (United States)

Price, Alex; Pearson, Victoria K.; Schwenzer, Susanne P.; Miot, Jennyfer; Olsson-Francis, Karen

2018-01-01

This work considers the hypothetical viability of microbial nitrate-dependent Fe2+ oxidation (NDFO) for supporting simple life in the context of the early Mars environment. This draws on knowledge built up over several decades of remote and in situ observation, as well as recent discoveries that have shaped current understanding of early Mars. Our current understanding is that certain early martian environments fulfill several of the key requirements for microbes with NDFO metabolism. First, abundant Fe2+ has been identified on Mars and provides evidence of an accessible electron donor; evidence of anoxia suggests that abiotic Fe2+ oxidation by molecular oxygen would not have interfered and competed with microbial iron metabolism in these environments. Second, nitrate, which can be used by some iron oxidizing microorganisms as an electron acceptor, has also been confirmed in modern aeolian and ancient sediment deposits on Mars. In addition to redox substrates, reservoirs of both organic and inorganic carbon are available for biosynthesis, and geochemical evidence suggests that lacustrine systems during the hydrologically active Noachian period (4.1–3.7 Ga) match the circumneutral pH requirements of nitrate-dependent iron-oxidizing microorganisms. As well as potentially acting as a primary producer in early martian lakes and fluvial systems, the light-independent nature of NDFO suggests that such microbes could have persisted in sub-surface aquifers long after the desiccation of the surface, provided that adequate carbon and nitrates sources were prevalent. Traces of NDFO microorganisms may be preserved in the rock record by biomineralization and cellular encrustation in zones of high Fe2+ concentrations. These processes could produce morphological biosignatures, preserve distinctive Fe-isotope variation patterns, and enhance preservation of biological organic compounds. Such biosignatures could be detectable by future missions to Mars with appropriate

Nitrate-Dependent Iron Oxidation: A Potential Mars Metabolism

Directory of Open Access Journals (Sweden)

Alex Price

2018-03-01

Full Text Available This work considers the hypothetical viability of microbial nitrate-dependent Fe2+ oxidation (NDFO for supporting simple life in the context of the early Mars environment. This draws on knowledge built up over several decades of remote and in situ observation, as well as recent discoveries that have shaped current understanding of early Mars. Our current understanding is that certain early martian environments fulfill several of the key requirements for microbes with NDFO metabolism. First, abundant Fe2+ has been identified on Mars and provides evidence of an accessible electron donor; evidence of anoxia suggests that abiotic Fe2+ oxidation by molecular oxygen would not have interfered and competed with microbial iron metabolism in these environments. Second, nitrate, which can be used by some iron oxidizing microorganisms as an electron acceptor, has also been confirmed in modern aeolian and ancient sediment deposits on Mars. In addition to redox substrates, reservoirs of both organic and inorganic carbon are available for biosynthesis, and geochemical evidence suggests that lacustrine systems during the hydrologically active Noachian period (4.1–3.7 Ga match the circumneutral pH requirements of nitrate-dependent iron-oxidizing microorganisms. As well as potentially acting as a primary producer in early martian lakes and fluvial systems, the light-independent nature of NDFO suggests that such microbes could have persisted in sub-surface aquifers long after the desiccation of the surface, provided that adequate carbon and nitrates sources were prevalent. Traces of NDFO microorganisms may be preserved in the rock record by biomineralization and cellular encrustation in zones of high Fe2+ concentrations. These processes could produce morphological biosignatures, preserve distinctive Fe-isotope variation patterns, and enhance preservation of biological organic compounds. Such biosignatures could be detectable by future missions to Mars with

Nitrate-Dependent Iron Oxidation: A Potential Mars Metabolism.

Science.gov (United States)

Price, Alex; Pearson, Victoria K; Schwenzer, Susanne P; Miot, Jennyfer; Olsson-Francis, Karen

2018-01-01

This work considers the hypothetical viability of microbial nitrate-dependent Fe 2+ oxidation (NDFO) for supporting simple life in the context of the early Mars environment. This draws on knowledge built up over several decades of remote and in situ observation, as well as recent discoveries that have shaped current understanding of early Mars. Our current understanding is that certain early martian environments fulfill several of the key requirements for microbes with NDFO metabolism. First, abundant Fe 2+ has been identified on Mars and provides evidence of an accessible electron donor; evidence of anoxia suggests that abiotic Fe 2+ oxidation by molecular oxygen would not have interfered and competed with microbial iron metabolism in these environments. Second, nitrate, which can be used by some iron oxidizing microorganisms as an electron acceptor, has also been confirmed in modern aeolian and ancient sediment deposits on Mars. In addition to redox substrates, reservoirs of both organic and inorganic carbon are available for biosynthesis, and geochemical evidence suggests that lacustrine systems during the hydrologically active Noachian period (4.1-3.7 Ga) match the circumneutral pH requirements of nitrate-dependent iron-oxidizing microorganisms. As well as potentially acting as a primary producer in early martian lakes and fluvial systems, the light-independent nature of NDFO suggests that such microbes could have persisted in sub-surface aquifers long after the desiccation of the surface, provided that adequate carbon and nitrates sources were prevalent. Traces of NDFO microorganisms may be preserved in the rock record by biomineralization and cellular encrustation in zones of high Fe 2+ concentrations. These processes could produce morphological biosignatures, preserve distinctive Fe-isotope variation patterns, and enhance preservation of biological organic compounds. Such biosignatures could be detectable by future missions to Mars with appropriate

Effect of microorganisms on the plutonium oxidation states

Energy Technology Data Exchange (ETDEWEB)

Luksiene, Benedikta, E-mail: bena@ar.fi.lt [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Druteikiene, Ruta [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Peciulyte, Dalia [Nature Research Centre, Akademijos street 2, LT-08412 Vilnius (Lithuania); Baltrunas, Dalis; Remeikis, Vidmantas [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Paskevicius, Algimantas [Nature Research Centre, Akademijos street 2, LT-08412 Vilnius (Lithuania)

2012-03-15

Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to {sup 239}Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state. - Highlights: Black-Right-Pointing-Pointer Particular microbes from low-level radioactive waste repository were exposed to Pu (IV). Black-Right-Pointing-Pointer Some tested bacteria induced slight Pu (IV) reduction at low pH under aerobic conditions. Black-Right-Pointing-Pointer Tested fungi did not show peculiarities to alter Pu oxidation state. Black-Right-Pointing-Pointer The modified radiochemical method was applied to differentiate Pu oxidation states.

Oxidation-state maxima in plutonium chemistry

International Nuclear Information System (INIS)

Silver, G.L.

2013-01-01

Maxima in the fractions of the trivalent and hexavalent oxidation states of plutonium are inherent in the algebra of its disproportionation reactions. The maxima do not support overall disproportionation equations as satisfactory representations of aqueous plutonium. (author)

Temperature-dependent electrical property transition of graphene oxide paper

International Nuclear Information System (INIS)

Huang Xingyi; Jiang Pingkai; Zhi Chunyi; Golberg, Dmitri; Bando, Yoshio; Tanaka, Toshikatsu

2012-01-01

Reduction of graphene oxide is primarily important because different reduction methods may result in graphene with totally different properties. For systematically exploring the reduction of graphene oxide, studies of the temperature-dependent electrical properties of graphene oxide (GO) are urgently required. In this work, for the first time, broadband dielectric spectroscopy was used to carry out an in situ investigation on the transition of the electrical properties of GO paper from −40 to 150 °C. The results clearly reveal a very interesting four-stage transition of electrical properties of GO paper with increasing temperature: insulator below 10 °C (stage 1), semiconductor at between 10 and 90 °C (stage 2), insulator at between 90 and 100 °C (stage 3), and semiconductor again at above 100 °C (stage 4). Subsequently, the transition mechanism was discussed in combination with detailed dielectric properties, microstructure and thermogravimetric analyses. It is suggested that the temperature-dependent transition of electronic properties of GO is closely associated with the ion mobility, water molecules removal and the reduction of GO in the GO paper. Most importantly, the present work clearly demonstrates the reduction of GO paper starts at above 100 °C. (paper)

Temperature dependence of hole mobility in Mott insulators: Normal-state resistivity of high-T/sub c/ superconductors

International Nuclear Information System (INIS)

Kumar, N.

1989-01-01

We consider the diffusion of a hole injected in a Mott insulator described by a one-band Hubbard Hamiltonian at half-filling and in the atomic limit. The diffusion coefficient turns out to be temperature independent exactly giving 1/T dependence for the drift mobility via the Einstein relation. This is in marked disagreement with the (1/T)/sup 1/2/ dependence obtaining in the self-retracing path approximation at low temperatures. We note the possible relevance of our result to the linear T dependence of the normal-state resistivity observed in the high-T/sub c/ oxide superconductors

Cellular inactivation of nitric oxide induces p53-dependent ...

African Journals Online (AJOL)

Tropical Journal of Pharmaceutical Research August 2016; 15 (8): 1595-1603 ... Cellular inactivation of nitric oxide induces p53-dependent apoptosis in ... apoptosis induced by a selective iNOS inhibitor, N-[(3-aminomethyl) benzyl] acetamidine (1400W), .... and nitrate. ... Nitrite production was measured in culture media.

Impact of aerobic exercise on cognitive impairment and oxidative stress markers in methamphetamine-dependent patients.

Science.gov (United States)

Zhang, Kai; Zhang, Qiaoyang; Jiang, Haifeng; Du, Jiang; Zhou, Chenglin; Yu, Shunying; Hashimoto, Kenji; Zhao, Min

2018-03-17

This study aimed to investigate whether 12-week moderate-intensity aerobic exercise has beneficial effects on oxidative stress markers in blood and on cognitive functions in patients who have methamphetamine dependence. Serum levels of oxidative stress markers, including total anti-oxidation capability, super oxide dismutase (SOD), catalase (CAT), and methane dicarboxylic aldehyde (MDA), were measured at baseline (all participants) and the 12-week follow-up (methamphetamine-dependent patients). Serum levels of CAT and MDA in methamphetamine-dependent patients (n = 68) were higher than those in healthy controls (n = 35) at baseline. Furthermore, the international shopping list (ISL) task scores of methamphetamine-dependent patients were significantly lower than those of the controls, indicating verbal memory deficits in methamphetamine-dependent patients. Although there were no significant interactions for all cognitive function scores, aerobic exercise improved the processing speed in methamphetamine-dependent patients. Of interest, aerobic exercise significantly attenuated a spontaneous increase in serum MDA levels in methamphetamine-dependent patients after 12-weeks of abstinence. In conclusion, this study showed that methamphetamine-dependent patients with verbal learning and memory deficits have higher serum levels of MDA, and that a 12-week aerobic exercise program may have beneficial effects on the processing speed as well as blood lipid peroxidation in methamphetamine-dependent patients. Copyright © 2018. Published by Elsevier B.V.

State Dependence in Unemployment

DEFF Research Database (Denmark)

Ahmad, Nisar

2014-01-01

This study examines the extent state dependence among unemployed immigrants in a dynamic discrete choice framework. Three alternative methodologies are employed to control for the problem of the initial condition. The empirical findings show that there is a considerable correlation between the un...

State-dependent classical potentials

International Nuclear Information System (INIS)

D'Amico, M.

2001-01-01

As alternative treatment to the potential operators of standard quantum mechanics is presented. The method is derived from Bohm's mechanics. The operator scalar (V) and vector (A) potential functions are replaced by a quantum potential. It is argued that the classical potential is a special limiting case of a more general quantum potential. The theory is illustrated by deriving an equivalent single-particle equation for the i-th particle of an n-body Bohmian system. The resulting effective state-dependent potential holds the interaction between the single-particle self-wave ψ s and the environment wave ψ e of the n - 1 remaining particles. The effective state-dependent potential is offered as a resolution to the Aharonov-Bohm effect where the phase difference is shown to result from the presence of ψ e . Finally, the interaction between ψ s and ψ e is illustrated graphically

Age-dependent oxidation of extracellular cysteine/cystine redox state (Eh(Cys/CySS)) in mouse lung fibroblasts is mediated by a decline in Slc7a11 expression.

Science.gov (United States)

Zheng, Yuxuan; Ritzenthaler, Jeffrey D; Burke, Tom J; Otero, Javier; Roman, Jesse; Watson, Walter H

2018-04-01

Aging is associated with progressive oxidation of the extracellular environment. The redox state of human plasma, defined by the concentrations of cysteine (Cys) and cystine (CySS), becomes more oxidized as we age. Recently, we showed that fibroblasts isolated from the lungs of young and old mice retain this differential phenotype; old cells produce and maintain a more oxidizing extracellular redox potential (E h (Cys/CySS)) than young cells. Microarray analysis identified down-regulation of Slc7a11, the light subunit of the CySS/glutamate transporter, as a potential mediator of age-related oxidation in these cells. The purpose of the present study was to investigate the mechanistic link between Slc7a11 expression and extracellular E h (Cys/CySS). Sulforaphane treatment or overexpression of Slc7a11 was used to increase Slc7a11 in lung fibroblasts from old mice, and sulfasalazine treatment or siRNA-mediated knock down was used to decrease Slc7a11 in young fibroblasts. Slc7a11 mRNA levels were measured by real-time PCR, Slc7a11 activity was determined by measuring the rate of glutamate release, Cys, CySS, glutathione (GSH) and its disulfide (GSSG) were measured by HPLC, and E h (Cys/CySS) was calculated from the Nernst equation. The results showed that both E h (Cys/CySS) and E h (GSH/GSSG) were more oxidized in the conditioned media of old cells than in young cells. Up-regulation of Slc7a11 via overexpression or sulforaphane treatment restored extracellular E h (Cys/CySS) in cultures of old cells, whereas down-regulation reproduced the oxidizing E h (Cys/CySS) in young cells. Only sulforaphane treatment was able to increase total GSH and restore E h (GSH/GSSG), whereas overexpression, knock down and sulfasalazine had no effect on these parameters. In addition, inhibition of GSH synthesis with buthionine sulfoximine had no effect on the ability of cells to restore their extracellular redox potential in response to an oxidative challenge. In conclusion, our study

Community Composition and Ultrastructure of a Nitrate-Dependent Anaerobic Methane-Oxidizing Enrichment Culture.

Science.gov (United States)

Gambelli, Lavinia; Guerrero-Cruz, Simon; Mesman, Rob J; Cremers, Geert; Jetten, Mike S M; Op den Camp, Huub J M; Kartal, Boran; Lueke, Claudia; van Niftrik, Laura

2018-02-01

Methane is a very potent greenhouse gas and can be oxidized aerobically or anaerobically through microbe-mediated processes, thus decreasing methane emissions in the atmosphere. Using a complementary array of methods, including phylogenetic analysis, physiological experiments, and light and electron microscopy techniques (including electron tomography), we investigated the community composition and ultrastructure of a continuous bioreactor enrichment culture, in which anaerobic oxidation of methane (AOM) was coupled to nitrate reduction. A membrane bioreactor was seeded with AOM biomass and continuously fed with excess methane. After 150 days, the bioreactor reached a daily consumption of 10 mmol nitrate · liter -1 · day -1 The biomass consisted of aggregates that were dominated by nitrate-dependent anaerobic methane-oxidizing " Candidatus Methanoperedens"-like archaea (40%) and nitrite-dependent anaerobic methane-oxidizing " Candidatus Methylomirabilis"-like bacteria (50%). The " Ca Methanoperedens" spp. were identified by fluorescence in situ hybridization and immunogold localization of the methyl-coenzyme M reductase (Mcr) enzyme, which was located in the cytoplasm. The " Ca Methanoperedens" sp. aggregates consisted of slightly irregular coccoid cells (∼1.5-μm diameter) which produced extruding tubular structures and putative cell-to-cell contacts among each other. " Ca Methylomirabilis" sp. bacteria exhibited the polygonal cell shape typical of this genus. In AOM archaea and bacteria, cytochrome c proteins were localized in the cytoplasm and periplasm, respectively, by cytochrome staining. Our results indicate that AOM bacteria and archaea might work closely together in the process of anaerobic methane oxidation, as the bacteria depend on the archaea for nitrite. Future studies will be aimed at elucidating the function of the cell-to-cell interactions in nitrate-dependent AOM. IMPORTANCE Microorganisms performing nitrate- and nitrite-dependent anaerobic

Solid-phase extraction of plutonium in various oxidation states from simulated groundwater using N-benzoylphenylhydroxylamine

International Nuclear Information System (INIS)

Perevalov, S.A.; Malofeeva, G.I.; Kuzovkina, E.V.; Spivakov, B.Ya.

2013-01-01

Solid-phase extraction of plutonium in different individual and mixed oxidation states from simulated groundwater (pH 8.5) was studied. The extraction of plutonium species was carried out in a dynamic mode using DIAPAK C16 cartridges modified by N-benzoylphenylhydroxylamine (BPHA). It was shown that the extent of recovery depends on the oxidation state of plutonium. The extraction of Pu(IV) was at the level of 98-99% regardless of the volume and flow-rate of the sample solution. Pu(V) was extracted by 90-95% and 75-80% from 10- and 100-mL aliquots of the samples, respectively, whereas the extraction of Pu(VI) did not exceed 45-50%. An equimolar mixture of Pu(IV), Pu(V), and Pu(VI) was extracted by 74%. The distribution coefficients (K d ) and kinetic exchange capacities (S) of plutonium in various oxidation states were measured. It was found that during the sorption process, Pu(V) was reduced to Pu(IV) by 80-90% after an hour-long contact with the solid phase. Pu(VI) is reduced to Pu(V) by 34% and to Pu(IV) by 55%. In the case of mixed-valent solution of plutonium, only Pu(V) and Pu(IV) were found in the effluents. (author)

The shared role of oxidative stress and inflammation in major depressive disorder and nicotine dependence.

Science.gov (United States)

Nunes, Sandra Odebrecht Vargas; Vargas, Heber Odebrecht; Prado, Eduardo; Barbosa, Decio Sabbatini; de Melo, Luiz Picoli; Moylan, Steven; Dodd, Seetal; Berk, Michael

2013-09-01

Nicotine dependence is common in people with mood disorders; however the operative pathways are not well understood. This paper reviews the contribution of inflammation and oxidative stress pathways to the co-association of depressive disorder and nicotine dependence, including increased levels of pro-inflammatory cytokines, increased acute phase proteins, decreased levels of antioxidants and increased oxidative stress. These could be some of the potential pathophysiological mechanisms involved in neuroprogression. The shared inflammatory and oxidative stress pathways by which smoking may increase the risk for development of depressive disorders are in part mediated by increased levels of pro-inflammatory cytokines, diverse neurotransmitter systems, activation the hypothalamic-pituitary-adrenal (HPA) axis, microglial activation, increased production of oxidative stress and decreased levels of antioxidants. Depressive disorder and nicotine dependence are additionally linked imbalance between neuroprotective and neurodegenerative metabolites in the kynurenine pathway that contribute to neuroprogression. These pathways provide a mechanistic framework for understanding the interaction between nicotine dependence and depressive disorder. Copyright © 2013. Published by Elsevier Ltd.

pH-sensor properties of electrochemically grown iridium oxide

NARCIS (Netherlands)

Olthuis, Wouter; Robben, M.A.M.; Bergveld, Piet; Bos, M.; van der Linden, W.E.

1990-01-01

The open-circuit potential of an electrochemically grown iridium oxide film is measured and shows a pH sensitivity between −60 and −80 mV/pH. This sensitivity is found to depend on the state of oxidation of the iridium oxide film; for a higher state of oxidation (or more of the oxide in the high

Data of oxygen- and pH-dependent oxidation of resveratrol

Directory of Open Access Journals (Sweden)

Annabell Plauth

2016-12-01

Full Text Available We show here if under physiologically relevant conditions resveratrol (RSV remains stable or not. We further show under which circumstances various oxidation products of RSV such as ROS can be produced. For example, in addition to the widely known effect of bicarbonate ions, high pH values promote the decay of RSV. Moreover, we analyse the impact of reduction of the oxygen partial pressure on the pH-dependent oxidation of RSV. For further interpretation and discussion of these focused data in a broader context we refer to the article “Hormetic shifting of redox environment by pro-oxidative resveratrol protects cells against stress” (Plauth et al., in press [1].

Air oxidation of Zr65Cu17.5Ni10Al7.5 in its amorphous and supercooled liquid states, studied by thermogravimetric analysis

International Nuclear Information System (INIS)

Dhawan, A.; Sharma, S.K.; Raetzke, K.; Faupel, F.

2003-01-01

The oxidation behaviour of the bulk amorphous alloy Zr 65 Cu 17.5 Ni 10 Al 7.5 was studied in air at various temperatures in the temperature range 591-732 K using a thermogravimetric analyser (TGA). The oxidation kinetics of the alloy obeys the parabolic rate law showing two different linear regions (in the plots of mass gain versus square root of oxidation time) which are attributed to the amorphous and the supercooled liquid states of the alloy. The value of the activation energy Q for the amorphous state as calculated from the temperature dependence of the rate constants is found to be 1.80±0.1 eV and the corresponding value obtained for the supercooled liquid state is 1.20±0.1 eV. It is suggested that the rate controlling process during oxidation of the amorphous state is the back-diffusion of Ni, and possibly Cu also, while the oxidation in the supercooled liquid state is dominated by the inward diffusion of oxygen. (copyright 2003 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites.

Science.gov (United States)

Gandhiraman, Ram P; Nordlund, Dennis; Javier, Cristina; Koehne, Jessica E; Chen, Bin; Meyyappan, M

2014-08-14

The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties as the graphene oxide transformation to reduced-graphene oxide is a key step in the synthesis of the electrode materials. Polarized behavior of the synchrotron X-rays and the angular dependency of the near-edge X-ray absorption fine structures (NEXAFS) have been utilized to study the orientation of the σ and π bonds of the graphene oxide and graphene oxide-metal oxide nanocomposites. The core-level transitions of individual metal oxides and that of the graphene oxide nanocomposite showed that the interaction of graphene oxide with the metal oxide nanostructures has not altered the electronic structure of either of them. As the restoration of the π network is important for good electrical conductivity, the C K edge NEXAFS spectra of reduced graphene oxide nanocomposites confirms the same through increased intensity of the sp 2 -derived unoccupied states π* band. A pronounced angular dependency of the reduced sample and the formation of excitonic peaks confirmed the formation of extended conjugated network.

Radiation oxidation of polypropylene: A solid-state 13C NMR study using selective isotopic labeling

International Nuclear Information System (INIS)

Mowery, Daniel M.; Assink, Roger A.; Derzon, Dora K.; Klamo, Sara B.; Bernstein, Robert; Clough, Roger L.

2007-01-01

Polypropylene samples, in which the three different carbon atoms along the chain were selectively labeled with carbon-13, were subjected to radiation under inert and air atmospheres, and to post-irradiation exposure in air at various temperatures. By using solid-state 13 C NMR measurements at room temperature, we have been able to identify and quantify the oxidation products. The isotopic labeling provides insight into chemical reaction mechanisms, since oxidation products can be traced back to their positions of origin on the macromolecule. The major products include peroxides and alcohols, both formed at tertiary carbon sites along the chain. Other products include methyl ketones, acids, esters, peresters, and hemiketals formed from reaction at the tertiary carbon, together with in-chain ketones and esters from reaction at the secondary chain carbon. No evidence is found of products arising from reactions at the methyl side chain. Significant temperature-dependent differences are apparent; for example much higher yields of chain-end methyl ketones, which are the indicator product of chain scission, are generated for both elevated temperature irradiation and for post-irradiation treatment at elevated temperatures. Time-dependent plots of yields of the various oxidation products have been obtained under a wide range of conditions, including the post-irradiation oxidation of a sample at room temperature in air that has been monitored for 2 years. Radiation-oxidation products of polypropylene are contrasted to products measured for 13 C-labeled polyethylene in an earlier investigation: the peroxides formed in irradiated polypropylene are remarkably longer lived, the non-peroxidic products are significantly different, and the overall ratios of oxidation products in polypropylene change relatively little as a function of the extent of oxidation

Lung injury-dependent oxidative status and chymotrypsin-like activity of skeletal muscles in hamsters with experimental emphysema

Directory of Open Access Journals (Sweden)

Tonon Jair

2013-01-01

Full Text Available Abstract Background Peripheral skeletal muscle is altered in patients suffering from emphysema and chronic obstructive pulmonary disease (COPD. Oxidative stress have been demonstrated to participate on skeletal muscle loss of several states, including disuse atrophy, mechanical ventilation, and chronic diseases. No evidences have demonstrated the occurance in a severity manner. Methods We evaluated body weight, muscle loss, oxidative stress, and chymotrypsin-like proteolytic activity in the gastrocnemius muscle of emphysemic hamsters. The experimental animals had 2 different severities of lung damage from experimental emphysema induced by 20 mg/mL (E20 and 40 mg/mL (E40 papain. Results The severity of emphysema increased significantly in E20 (60.52 ± 2.8, p Conclusions Taken together, the results of the present study suggest that muscle atrophy observed in this model of emphysema is mediated by increased muscle chymotrypsin-like activity, with possible involvement of oxidative stress in a severity-dependent manner.

Study of uranium oxidation states in geological material.

Science.gov (United States)

Pidchenko, I; Salminen-Paatero, S; Rothe, J; Suksi, J

2013-10-01

A wet chemical method to determine uranium (U) oxidation states in geological material has been developed and tested. The problem faced in oxidation state determinations with wet chemical methods is that U redox state may change when extracted from the sample material, thereby leading to erroneous results. In order to quantify and monitor U redox behavior during the acidic extraction in the procedure, an analysis of added isotopic redox tracers, (236)U(VI) and (232)U(IV), and of variations in natural uranium isotope ratio ((234)U/(238)U) of indigenous U(IV) and U(VI) fractions was performed. Two sample materials with varying redox activity, U bearing rock and U-rich clayey lignite sediment, were used for the tests. The Fe(II)/Fe(III) redox-pair of the mineral phases was postulated as a potentially disturbing redox agent. The impact of Fe(III) on U was studied by reducing Fe(III) with ascorbic acid, which was added to the extraction solution. We observed that ascorbic acid protected most of the U from oxidation. The measured (234)U/(238)U ratio in U(IV) and U(VI) fractions in the sediment samples provided a unique tool to quantify U oxidation caused by Fe(III). Annealing (sample heating) to temperatures above 500 °C was supposed to heal ionizing radiation induced defects in the material that can disturb U redox state during extraction. Good agreement between two independent methods was obtained for DL-1a material: an average 38% of U(IV) determined by redox tracer corrected wet chemistry and 45% for XANES. Copyright © 2013 Elsevier Ltd. All rights reserved.

Pu oxidation state distributions in suspensions of the Mont Terri Opalinus Clay isolate Sporomusa sp. MT-2.99

Energy Technology Data Exchange (ETDEWEB)

Moll, Henry [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biogeochemistry; Cherkouk, Andrea [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). HZDR Young Investigator Group; Bok, Frank [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes

2017-06-01

The time-dependent {sup 242}Pu oxidation state distribution in the presence of Sporomusa sp. cells as a function of pH with or without Na-pyruvate was analyzed. In all cases, the presence of bacterial cells enhanced removal of Pu from solution and accelerated Pu interaction reactions, e.g. biosorption and bioreduction.

A magnetic route to measure the average oxidation state of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS).

Science.gov (United States)

Shen, Xiong-Fei; Ding, Yun-Shuang; Liu, Jia; Han, Zhao-Hui; Budnick, Joseph I; Hines, William A; Suib, Steven L

2005-05-04

A magnetic route has been applied for measurement of the average oxidation state (AOS) of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS). The method gives AOS measurement results in good agreement with titration methods. A maximum analysis deviation error of +/-7% is obtained from 10 sample measurements. The magnetic method is able to (1) confirm the presence of mixed-valent manganese and (2) evaluate AOS and the spin states of d electrons of both single oxidation state and mixed-valent state Mn in manganese oxides. In addition, the magnetic method may be extended to (1) determine AOS of Mn in manganese oxide OMS with dopant "diamagnetic" ions, such as reducible V5+ (3d0) ions, which is inappropriate for the titration method due to interference of redox reactions between these dopant ions and titration reagents, such as KMnO4, (2) evaluate the dopant "paramagnetic" ions that are present as clusters or in the OMS framework, and (3) determine AOS of other mixed-valent/single oxidation state ion systems, such as Mo3+(3d3)-Mo4+(3d2) systems and Fe3+ in FeCl3.

Age-dependent oxidative stress-induced DNA damage in Down's lymphocytes

International Nuclear Information System (INIS)

Zana, Marianna; Szecsenyi, Anita; Czibula, Agnes; Bjelik, Annamaria; Juhasz, Anna; Rimanoczy, Agnes; Szabo, Krisztina; Vetro, Agnes; Szucs, Peter; Varkonyi, Agnes; Pakaski, Magdolna; Boda, Krisztina; Rasko, Istvan; Janka, Zoltan; Kalman, Janos

2006-01-01

The aim of the present study was to investigate the oxidative status of lymphocytes from children (n = 7) and adults (n = 18) with Down's syndrome (DS). The basal oxidative condition, the vulnerability to in vitro hydrogen peroxide exposure, and the repair capacity were measured by means of the damage-specific alkaline comet assay. Significantly and age-independently elevated numbers of single strand breaks and oxidized bases (pyrimidines and purines) were found in the nuclear DNA of the lymphocytes in the DS group in the basal condition. These results may support the role of an increased level of endogenous oxidative stress in DS and are similar to those previously demonstrated in Alzheimer's disease. In the in vitro oxidative stress-induced state, a markedly higher extent of DNA damage was observed in DS children as compared with age- and gender-matched healthy controls, suggesting that young trisomic lymphocytes are more sensitive to oxidative stress than normal ones. However, the repair ability itself was not found to be deteriorated in either DS children or DS adults

Shape-dependent bactericidal activity of copper oxide nanoparticle mediated by DNA and membrane damage

International Nuclear Information System (INIS)

Laha, Dipranjan; Pramanik, Arindam; Laskar, Aparna; Jana, Madhurya; Pramanik, Panchanan; Karmakar, Parimal

2014-01-01

Highlights: • Spherical and sheet shaped copper oxide nanoparticles were synthesized. • Physical characterizations of these nanoparticles were done by TEM, DLS, XRD, FTIR. • They showed shape dependent antibacterial activity on different bacterial strain. • They induced both membrane damage and ROS mediated DNA damage in bacteria. - Abstract: In this work, we synthesized spherical and sheet shaped copper oxide nanoparticles and their physical characterizations were done by the X-ray diffraction, fourier transform infrared spectroscopy, transmission electron microscopy and dynamic light scattering. The antibacterial activity of these nanoparticles was determined on both gram positive and gram negative bacterial. Spherical shaped copper oxide nanoparticles showed more antibacterial property on gram positive bacteria where as sheet shaped copper oxide nanoparticles are more active on gram negative bacteria. We also demonstrated that copper oxide nanoparticles produced reactive oxygen species in both gram negative and gram positive bacteria. Furthermore, they induced membrane damage as determined by atomic force microscopy and scanning electron microscopy. Thus production of and membrane damage are major mechanisms of the bactericidal activity of these copper oxide nanoparticles. Finally it was concluded that antibacterial activity of nanoparticles depend on physicochemical properties of copper oxide nanoparticles and bacterial strain

Shape-dependent bactericidal activity of copper oxide nanoparticle mediated by DNA and membrane damage

Energy Technology Data Exchange (ETDEWEB)

Laha, Dipranjan; Pramanik, Arindam [Department of Life Science and Biotechnology, Jadavpur University, 188, Raja S C Mallick Road, Kolkata 700032 (India); Laskar, Aparna [CSIR-Indian Institute of Chemical Biology, Kolkata 700032 (India); Jana, Madhurya [Department of Life Science and Biotechnology, Jadavpur University, 188, Raja S C Mallick Road, Kolkata 700032 (India); Pramanik, Panchanan [Department of Chemistry, Indian Institute of Technology, Kharagpur 721302 (India); Karmakar, Parimal, E-mail: pkarmakar_28@yahoo.co.in [Department of Life Science and Biotechnology, Jadavpur University, 188, Raja S C Mallick Road, Kolkata 700032 (India)

2014-11-15

Highlights: • Spherical and sheet shaped copper oxide nanoparticles were synthesized. • Physical characterizations of these nanoparticles were done by TEM, DLS, XRD, FTIR. • They showed shape dependent antibacterial activity on different bacterial strain. • They induced both membrane damage and ROS mediated DNA damage in bacteria. - Abstract: In this work, we synthesized spherical and sheet shaped copper oxide nanoparticles and their physical characterizations were done by the X-ray diffraction, fourier transform infrared spectroscopy, transmission electron microscopy and dynamic light scattering. The antibacterial activity of these nanoparticles was determined on both gram positive and gram negative bacterial. Spherical shaped copper oxide nanoparticles showed more antibacterial property on gram positive bacteria where as sheet shaped copper oxide nanoparticles are more active on gram negative bacteria. We also demonstrated that copper oxide nanoparticles produced reactive oxygen species in both gram negative and gram positive bacteria. Furthermore, they induced membrane damage as determined by atomic force microscopy and scanning electron microscopy. Thus production of and membrane damage are major mechanisms of the bactericidal activity of these copper oxide nanoparticles. Finally it was concluded that antibacterial activity of nanoparticles depend on physicochemical properties of copper oxide nanoparticles and bacterial strain.

Time-dependence hole and electron trapping effects in SIMOX buried oxides

International Nuclear Information System (INIS)

Boesch, H.E. Jr.; Taylor, T.L.; Hite, L.R.; Bailey, W.E.

1990-01-01

Back-channel threshold shift associated with the buried oxide layers of separation by implanted oxygen (SIMOX) and zone-melted recrystallization (ZMR) field-effect transistors (FETs) was measured following pulsed irradiation as a function of temperature and back-gate bias using a fast time-resolved I-V measurement technique. The SIMOX FETs showed large initial negative voltage shifts at 0.2 ms after irradiation followed by temperature- and bias-dependent additional negative shifts to 800s. Analysis and modeling of the results indicate efficient deep trapping of radiation-generated holes in the bulk of the oxide, substantial initial trapping of radiation-generated electrons in the oxide, and rapid removal of the trapped electrons by a thermal detrapping process. The ZMR FETs showed evidence of substantial trapping of holes alone in the oxide bulk

Origin of interface states and oxide charges generated by ionizing radiation

International Nuclear Information System (INIS)

Sah, C.T.

1976-01-01

The randomly located trivalent silicon atoms are shown to account for the thermally generated interface states at the SiO 2 -Si interface. The interface state density is greatly reduced in water containing ambients at low temperatures (450 0 C) by forming trivalent silicon hydroxide bonds. Interface states are regenerated when the /triple bond/Si-OH bonds are broken by ionizing radiation and the OH ions are drifted away. In the bulk of the oxide film, the trivalent silicon and the interstitial oxygen donor centers are shown to be responsible for the heat and radiation generated positive space charge build-up (oxide charge) in thermally grown silicon oxide

Pu oxidation state distributions in suspensions of the Mont Terri Opalinus Clay isolate Sporomusa sp. MT-2.99

International Nuclear Information System (INIS)

Moll, Henry; Cherkouk, Andrea; Bok, Frank

2017-01-01

The time-dependent "2"4"2Pu oxidation state distribution in the presence of Sporomusa sp. cells as a function of pH with or without Na-pyruvate was analyzed. In all cases, the presence of bacterial cells enhanced removal of Pu from solution and accelerated Pu interaction reactions, e.g. biosorption and bioreduction.

Oxidative Stress and Heart Failure in Altered Thyroid States

Directory of Open Access Journals (Sweden)

Pallavi Mishra

2012-01-01

Full Text Available Increased or reduced action of thyroid hormone on certain molecular pathways in the heart and vasculature causes relevant cardiovascular derangements. It is well established that hyperthyroidism induces a hyperdynamic cardiovascular state, which is associated with a faster heart rate, enhanced left ventricular systolic and diastolic function whereas hypothyroidism is characterized by the opposite changes. Hyperthyroidism and hypothyroidism represent opposite clinical conditions, albeit not mirror images. Recent experimental and clinical studies have suggested the involvement of ROS tissue damage under altered thyroid status. Altered-thyroid state-linked changes in heart modify their susceptibility to oxidants and the extent of the oxidative damage they suffer following oxidative challenge. Chronic increase in the cellular levels of ROS can lead to a catastrophic cycle of DNA damage, mitochondrial dysfunction, further ROS generation and cellular injury. Thus, these cellular events might play an important role in the development and progression of myocardial remodeling and heart failure in altered thyroid states (hypo- and hyper-thyroidism. The present review aims at elucidating the various signaling pathways mediated via ROS and their modulation under altered thyroid state and the possibility of antioxidant therapy.

State-dependent impulses boundary value problems on compact interval

CERN Document Server

Rachůnková, Irena

2015-01-01

This book offers the reader a new approach to the solvability of boundary value problems with state-dependent impulses and provides recently obtained existence results for state dependent impulsive problems with general linear boundary conditions. It covers fixed-time impulsive boundary value problems both regular and singular and deals with higher order differential equations or with systems that are subject to general linear boundary conditions. We treat state-dependent impulsive boundary value problems, including a new approach giving effective conditions for the solvability of the Dirichlet problem with one state-dependent impulse condition and we show that the depicted approach can be extended to problems with a finite number of state-dependent impulses. We investigate the Sturm–Liouville boundary value problem for a more general right-hand side of a differential equation. Finally, we offer generalizations to higher order differential equations or differential systems subject to general linear boundary...

State-dependent choice and ecological rationality.

Science.gov (United States)

Nevai, Andrew L; Waite, Thomas A; Passino, Kevin M

2007-08-07

Decision makers who minimize costly errors should flexibly adjust the way they trade off competing demands, depending on their current state. We explore how state (amount of hoarded food) affects willingness to take extra predation risk to obtain larger food rewards, particularly in animals that may overemphasize safety. Assuming a sigmoid fitness function, we explore how a supplement in state influences this willingness trade danger for food energy. Above a threshold, the model predicts the supplement will weaken this willingness. Incremental increases in state in the deceleratory phase yield smaller fitness gains, so it pays to increase emphasis on safety after receiving a supplement. Below this threshold, the model makes the opposite prediction because incremental increases in state yield bigger fitness gains and so it pays to decrease emphasis on safety. We use the model to explain why hoarding gray jays (Perisoreus canadensis) were induced by an experimental subsidy to accept greater danger. This formerly puzzling finding makes sense if the jays' effective hoard was relatively small, due to theft and decomposition. We discuss adaptive state-dependent choice as a general explanation for apparently irrational behavior.

Trace methane oxidation and the methane dependency of sulfate reduction in anaerobic granular sludge

KAUST Repository

Meulepas, Roel J.W.

2010-05-01

This study investigates the oxidation of labeled methane (CH4) and the CH4 dependence of sulfate reduction in three types of anaerobic granular sludge. In all samples, 13C-labeled CH4 was anaerobically oxidized to 13C-labeled CO2, while net endogenous CH4 production was observed. Labeled-CH4 oxidation rates followed CH4 production rates, and the presence of sulfate hampered both labeled-CH4 oxidation and methanogenesis. Labeled-CH4 oxidation was therefore linked to methanogenesis. This process is referred to as trace CH4 oxidation and has been demonstrated in methanogenic pure cultures. This study shows that the ratio between labeled-CH4 oxidation and methanogenesis is positively affected by the CH4 partial pressure and that this ratio is in methanogenic granular sludge more than 40 times higher than that in pure cultures of methanogens. The CH4 partial pressure also positively affected sulfate reduction and negatively affected methanogenesis: a repression of methanogenesis at elevated CH4 partial pressures confers an advantage to sulfate reducers that compete with methanogens for common substrates, formed from endogenous material. The oxidation of labeled CH 4 and the CH4 dependence of sulfate reduction are thus not necessarily evidence of anaerobic oxidation of CH4 coupled to sulfate reduction. © 2010 Federation of European Microbiological Societies.

Prenatal iron deficiency causes sex-dependent mitochondrial dysfunction and oxidative stress in fetal rat kidneys and liver.

Science.gov (United States)

Woodman, Andrew G; Mah, Richard; Keddie, Danae; Noble, Ronan M N; Panahi, Sareh; Gragasin, Ferrante S; Lemieux, Hélène; Bourque, Stephane L

2018-06-01

Prenatal iron deficiency alters fetal developmental trajectories, which results in persistent changes in organ function. Here, we studied the effects of prenatal iron deficiency on fetal kidney and liver mitochondrial function. Pregnant Sprague-Dawley rats were fed partially or fully iron-restricted diets to induce a state of moderate or severe iron deficiency alongside iron-replete control rats. We assessed mitochondrial function via high-resolution respirometry and reactive oxygen species generation via fluorescence microscopy on gestational d 21. Hemoglobin levels were reduced in dams in the moderate (-31%) and severe groups (-54%) compared with controls, which was accompanied by 55% reductions in fetal hemoglobin levels in both moderate and severe groups versus controls. Male iron-deficient kidneys exhibited globally reduced mitochondrial content and respiration, as well as increased cytosolic superoxide and decreased NO. Female iron-deficient kidneys exhibited complex II down-regulation and increased mitochondrial oxidative stress. Male iron-deficient livers exhibited reduced complex IV respiration and increased cytosolic superoxide, whereas female liver tissues exhibited no alteration in oxidant levels or mitochondrial function. These findings indicate that prenatal iron deficiency causes changes in mitochondrial content and function as well as oxidant status in a sex- and organ-dependent manner, which may be an important mechanism that underlies the programming of cardiovascular disease.-Woodman, A. G., Mah, R., Keddie, D., Noble, R. M. N., Panahi, S., Gragasin, F. S., Lemieux, H., Bourque, S. L. Prenatal iron deficiency causes sex-dependent mitochondrial dysfunction and oxidative stress in fetal rat kidneys and liver.

Photochemical oxidants: state of the science.

Science.gov (United States)

Kley, D; Kleinmann, M; Sanderman, H; Krupa, S

1999-01-01

Atmospheric photochemical processes resulting in the production of tropospheric ozone (O(3)) and other oxidants are described. The spatial and temporal variabilities in the occurrence of surface level oxidants and their relationships to air pollution meteorology are discussed. Models of photooxidant formation are reviewed in the context of control strategies and comparisons are provided of the air concentrations of O(3) at select geographic locations around the world. This overall oxidant (O(3)) climatology is coupled to human health and ecological effects. The discussion of the effects includes both acute and chronic responses, mechanisms of action, human epidemiological and plant population studies and briefly, efforts to establish cause-effect relationships through numerical modeling. A short synopsis is provided of the interactive effects of O(3) with other abiotic and biotic factors. The overall emphasis of the paper is on identifying the current uncertainties and gaps in our understanding of the state of the science and some suggestions as to how they may be addressed.

Intertime jump statistics of state-dependent Poisson processes.

Science.gov (United States)

Daly, Edoardo; Porporato, Amilcare

2007-01-01

A method to obtain the probability distribution of the interarrival times of jump occurrences in systems driven by state-dependent Poisson noise is proposed. Such a method uses the survivor function obtained by a modified version of the master equation associated to the stochastic process under analysis. A model for the timing of human activities shows the capability of state-dependent Poisson noise to generate power-law distributions. The application of the method to a model for neuron dynamics and to a hydrological model accounting for land-atmosphere interaction elucidates the origin of characteristic recurrence intervals and possible persistence in state-dependent Poisson models.

Thermodynamic Ground States of Complex Oxide Heterointerfaces

DEFF Research Database (Denmark)

Gunkel, F.; Hoffmann-Eifert, S.; Heinen, R. A.

2017-01-01

The formation mechanism of 2-dimensional electron gases (2DEGs) at heterointerfaces between nominally insulating oxides is addressed with a thermodynamical approach. We provide a comprehensive analysis of the thermodynamic ground states of various 2DEG systems directly probed in high temperature...

Trace methane oxidation and the methane dependency of sulfate reduction in anaerobic granular sludge

KAUST Repository

Meulepas, Roel J.W.; Jagersma, Christian G.; Zhang, Yu; Petrillo, Michele; Cai, Hengzhe; Buisman, Cees J.N.; Stams, Alfons J.M.; Lens, Piet N.L.

2010-01-01

This study investigates the oxidation of labeled methane (CH4) and the CH4 dependence of sulfate reduction in three types of anaerobic granular sludge. In all samples, 13C-labeled CH4 was anaerobically oxidized to 13C-labeled CO2, while net

Novel approaches to improving endothelium-dependent nitric oxide-mediated vasodilatation

DEFF Research Database (Denmark)

Simonsen, Ulf; Rodriguez-Rodriguez, Rosalia; Dalsgaard, Thomas

2009-01-01

Endothelial dysfunction, which is defined by decreased endothelium-dependent vasodilatation, is associated with an increased number of cardiovascular events. Nitric oxide (NO) bioavailability is reduced by altered endothelial signal transduction or increased formation of radical oxygen species...... reacting with NO. Endothelial dysfunction is therapeutically reversible and physical exercise, calcium channel blockers, angiotensin converting enzyme inhibitors, and angiotensin receptor antagonists improve flow-evoked endothelium-dependent vasodilation in patients with hypertension and diabetes. We have...... the endothelial signal transduction pathways involved in vasorelaxation and NO release induced by an olive oil component, oleanolic acid, and (3) investigated the role of calcium-activated K channels in the release of NO induced by receptor activation. Tempol increases endothelium-dependent vasodilatation...

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

International Nuclear Information System (INIS)

Minasi, L.E.

1989-01-01

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

A microbial-mineralization-inspired approach for synthesis of manganese oxide nanostructures with controlled oxidation states and morphologies

Energy Technology Data Exchange (ETDEWEB)

Oba, Manabu; Oaki, Yuya; Imai, Hiroaki [Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan)

2010-12-21

Manganese oxide nanostructures are synthesized by a route inspired by microbial mineralization in nature. The combination of organic molecules, which include antioxidizing and chelating agents, facilitates the parallel control of oxidation states and morphologies in an aqueous solution at room temperature. Divalent manganese hydroxide (Mn(OH){sub 2}) is selectively obtained as a stable dried powder by using a combination of ascorbic acid as an antioxidizing agent and other organic molecules with the ability to chelate to manganese ions. The topotactic oxidation of the resultant Mn(OH){sub 2} leads to the selective formation of trivalent manganese oxyhydroxide ({beta}-MnOOH) and trivalent/tetravalent sodium manganese oxide (birnessite, Na{sub 0.55}Mn{sub 2}O{sub 4}.1.5H{sub 2}O). For microbial mineralization in nature, similar synthetic routes via intermediates have been proposed in earlier works. Therefore, these synthetic routes, which include in the present study the parallel control over oxidation states and morphologies of manganese oxides, can be regarded as new biomimetic routes for synthesis of transition metal oxide nanostructures. As a potential application, it is demonstrated that the resultant {beta}-MnOOH nanostructures perform as a cathode material for lithium ion batteries. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Synergistic Effect of Rapamycin and Metformin Against Age-Dependent Oxidative Stress in Rat Erythrocytes.

Science.gov (United States)

Singh, Abhishek Kumar; Garg, Geetika; Singh, Sandeep; Rizvi, Syed Ibrahim

2017-10-01

Erythrocytes are particularly vulnerable toward age-dependent oxidative stress-mediated damage. Caloric restriction mimetics (CRMs) may provide a novel strategy for the maintenance of redox balance as well as effective treatment of age-associated diseases. Herein, we have investigated the beneficial effect of cotreatment with CRM-candidate drugs, rapamycin (an immunosuppressant drug and inhibitor of mammalian target of rapamycin) and metformin (an antidiabetic biguanide and activator of adenosine monophosphate kinase), against aging-induced oxidative stress in erythrocytes and plasma of aging rats. Male Wistar rats of age 4 (young) and 24 months (old) were coexposed to rapamycin (0.5 mg/kg body weight [b.w.]) and metformin (300 mg/kg b.w.), and data were compared with the response of rats receiving an independent exposure to these chemicals at similar doses. The exposure of individual candidate drugs significantly reversed the age-dependent alterations in the endpoints associated with oxidative stress such as reactive oxygen species, ferric reducing ability of plasma, malondialdehyde, reduced glutathione, plasma membrane redox system, plasma protein carbonyl, and acetyl cholinesterase in erythrocytes and plasma of aging rats. However, the cotreatment with rapamycin and metformin showed a significant augmented effect compared with individual drug interventions on reversal of these age-dependent biomarkers of oxidative stress, suggesting a synergistic response. Thus, the findings open up further possibilities for the design of new combinatorial therapies to prevent oxidative stress- and age-associated health problems.

Oxidatively generated DNA/RNA damage in psychological stress states

DEFF Research Database (Denmark)

Jørgensen, Anders

2013-01-01

age-related somatic disorders. The overall aim of the PhD project was to investigate the relation between psychopathology, psychological stress, stress hormone secretion and oxidatively generated DNA and RNA damage, as measured by the urinary excretion of markers of whole-body DNA/RNA oxidation (8...... between the 24 h urinary cortisol excretion and the excretion of 8-oxodG/8-oxoGuo, determined in the same samples. Collectively, the studies could not confirm an association between psychological stress and oxidative stress on nucleic acids. Systemic oxidatively generated DNA/RNA damage was increased......Both non-pathological psychological stress states and mental disorders are associated with molecular, cellular and epidemiological signs of accelerated aging. Oxidative stress on nucleic acids is a critical component of cellular and organismal aging, and a suggested pathogenic mechanism in several...

An unusual temperature dependence in the oxidation of oxycarbide layers on uranium

Science.gov (United States)

Ellis, Walton P.

1981-09-01

An anomalous temperature dependence has been observed for the oxidation kinetics of outermost oxycarbide layers on polycrystalline uranium metal. Normally, oxidation or corrosion reactions are expected to proceed more rapidly as the temperature is elevated. Thus, it came as a surprise when we observed that the removal of the outermost atomic layers of carbon from uranium oxycarbide by O 2 reproducibly proceeds at a much faster rate at 25°C than at 280°C.

The problem of oxidation state stabilisation and some regularities of a Periodic system of the elements

International Nuclear Information System (INIS)

Kiselev, Yurii M; Tretyakov, Yuri D

1999-01-01

The general principles of the concept of oxidation state stabilisation are formulated. Problems associated with the preparation and provision of the highest valent forms of transition elements are considered. The empirical data concerning the synthesis of new compounds of rare-earth elements and d elements in unusually high oxidation states are analysed. The possibility of occurrence of the oxidation states + 9 and + 10 for some elements (for example, for iridium and platinum in tetraoxo ions) are discussed. Approaches to the realisation of these states are outlined and it is demonstrated that solid phases or matrices containing alkali metal cations are the most promising systems for the stabilisation of these high oxidation states. Selected thermodynamic features typical of metal halides and oxides and the regularities of the changes in the extreme oxidation states of d elements are considered. The bibliography includes 266 references.

Nano rare-earth oxides induced size-dependent vacuolization: an independent pathway from autophagy.

Science.gov (United States)

Zhang, Ying; Yu, Chenguang; Huang, Guanyi; Wang, Changli; Wen, Longping

2010-09-07

Four rare earth oxides have been shown to induce autophagy. Interestingly, we often noticed plentiful vacuolization, which was not always involved in this autophagic process. In this study, we investigated three other rare-earth elements, including Yttrium (Y), Ytterbium (Yb), and Lanthanum (La). Autophagic effect could be induced by all of them but only Y(2)O(3) and Yb(2)O(3) could cause massive vacuolization. Y(2)O(3) and Yb(2)O(3) treated by sonication or centrifugation to reduce particle size were used to test vacuolization level in HeLa cell lines. The results showed that rare earth oxides-induced vacuolization is size-dependent and differs from autophagic pathway. To further clarify the characteristics of this autophagic process, we used MEF Atg-5 (autophagy associated gene 5) knockout cell line, and the result showed that the autophagic process induced by rare earth oxides is Atg-5-dependent and the observed vacuolization was independent from autophagy. Similar results could also be observed in our tests on 3-methyladenine(3-MA), a well-known autophagy inhibitor. In conclusion, for the first time, we clarified the relationship between massive vacuolization and autophagic process induced by rare earth oxides and pointed out the size effect of rare earth oxides on the formation of vacuoles, which give clues to further investigation on the mechanisms underlying their biological effects.

Heterogeneous Oxidation of Atmospheric Organic Aerosol: Kinetics of Changes to the Amount and Oxidation State of Particle-Phase Organic Carbon.

Science.gov (United States)

Kroll, Jesse H; Lim, Christopher Y; Kessler, Sean H; Wilson, Kevin R

2015-11-05

Atmospheric oxidation reactions are known to affect the chemical composition of organic aerosol (OA) particles over timescales of several days, but the details of such oxidative aging reactions are poorly understood. In this study we examine the rates and products of a key class of aging reaction, the heterogeneous oxidation of particle-phase organic species by the gas-phase hydroxyl radical (OH). We compile and reanalyze a number of previous studies from our laboratories involving the oxidation of single-component organic particles. All kinetic and product data are described on a common basis, enabling a straightforward comparison among different chemical systems and experimental conditions. Oxidation chemistry is described in terms of changes to key ensemble properties of the OA, rather than to its detailed molecular composition, focusing on two quantities in particular, the amount and the oxidation state of the particle-phase carbon. Heterogeneous oxidation increases the oxidation state of particulate carbon, with the rate of increase determined by the detailed chemical mechanism. At the same time, the amount of particle-phase carbon decreases with oxidation, due to fragmentation (C-C scission) reactions that form small, volatile products that escape to the gas phase. In contrast to the oxidation state increase, the rate of carbon loss is nearly uniform among most systems studied. Extrapolation of these results to atmospheric conditions indicates that heterogeneous oxidation can have a substantial effect on the amount and composition of atmospheric OA over timescales of several days, a prediction that is broadly in line with available measurements of OA evolution over such long timescales. In particular, 3-13% of particle-phase carbon is lost to the gas phase after one week of heterogeneous oxidation. Our results indicate that oxidative aging represents an important sink for particulate organic carbon, and more generally that fragmentation reactions play a major

Light-Dependent Aerobic Methane Oxidation Reduces Methane Emissions from Seasonally Stratified Lakes

Science.gov (United States)

Oswald, Kirsten; Milucka, Jana; Brand, Andreas; Littmann, Sten; Wehrli, Bernhard; Kuypers, Marcel M. M.; Schubert, Carsten J.

2015-01-01

Lakes are a natural source of methane to the atmosphere and contribute significantly to total emissions compared to the oceans. Controls on methane emissions from lake surfaces, particularly biotic processes within anoxic hypolimnia, are only partially understood. Here we investigated biological methane oxidation in the water column of the seasonally stratified Lake Rotsee. A zone of methane oxidation extending from the oxic/anoxic interface into anoxic waters was identified by chemical profiling of oxygen, methane and δ13C of methane. Incubation experiments with 13C-methane yielded highest oxidation rates within the oxycline, and comparable rates were measured in anoxic waters. Despite predominantly anoxic conditions within the zone of methane oxidation, known groups of anaerobic methanotrophic archaea were conspicuously absent. Instead, aerobic gammaproteobacterial methanotrophs were identified as the active methane oxidizers. In addition, continuous oxidation and maximum rates always occurred under light conditions. These findings, along with the detection of chlorophyll a, suggest that aerobic methane oxidation is tightly coupled to light-dependent photosynthetic oxygen production both at the oxycline and in the anoxic bottom layer. It is likely that this interaction between oxygenic phototrophs and aerobic methanotrophs represents a widespread mechanism by which methane is oxidized in lake water, thus diminishing its release into the atmosphere. PMID:26193458

Subjective Probabilities for State-Dependent Continuous Utility

NARCIS (Netherlands)

P.P. Wakker (Peter)

1987-01-01

textabstractFor the expected utility model with state dependent utilities, Karni, Schmeidler and Vind (1983) have shown how to recover uniquely the involved subjective probabilities if the preferences, contingent on a hypothetical probability distribution over the state space, are known. This they

Characterization of Interface State in Silicon Carbide Metal Oxide Semiconductor Capacitors

Science.gov (United States)

Kao, Wei-Chieh

Silicon carbide (SiC) has always been considered as an excellent material for high temperature and high power devices. Since SiC is the only compound semiconductor whose native oxide is silicon dioxide (SiO2), it puts SiC in a unique position. Although SiC metal oxide semiconductor (MOS) technology has made significant progress in recent years, there are still a number of issues to be overcome before more commercial SiC devices can enter the market. The prevailing issues surrounding SiC MOSFET devices are the low channel mobility, the low quality of the oxide layer and the high interface state density at the SiC/SiO2 interface. Consequently, there is a need for research to be performed in order to have a better understanding of the factors causing the poor SiC/SiO2 interface properties. In this work, we investigated the generation lifetime in SiC materials by using the pulsed metal oxide semiconductor (MOS) capacitor method and measured the interface state density distribution at the SiC/SiO2 interface by using the conductance measurement and the high-low frequency capacitance technique. These measurement techniques have been performed on n-type and p-type SiC MOS capacitors. In the course of our investigation, we observed fast interface states at semiconductor-dielectric interfaces in SiC MOS capacitors that underwent three different interface passivation processes, such states were detected in the nitrided samples but not observed in PSG-passivated samples. This result indicate that the lack of fast states at PSG-passivated interface is one of the main reasons for higher channel mobility in PSG MOSFETs. In addition, the effect of mobile ions in the oxide on the response time of interface states has been investigated. In the last chapter we propose additional methods of investigation that can help elucidate the origin of the particular interface states, enabling a more complete understanding of the SiC/SiO2 material system.

Structural and functional characteristics of cGMP-dependent methionine oxidation in Arabidopsis thaliana proteins

KAUST Repository

Marondedze, Claudius

2013-01-05

Background: Increasing structural and biochemical evidence suggests that post-translational methionine oxidation of proteins is not just a result of cellular damage but may provide the cell with information on the cellular oxidative status. In addition, oxidation of methionine residues in key regulatory proteins, such as calmodulin, does influence cellular homeostasis. Previous findings also indicate that oxidation of methionine residues in signaling molecules may have a role in stress responses since these specific structural modifications can in turn change biological activities of proteins. Findings. Here we use tandem mass spectrometry-based proteomics to show that treatment of Arabidopsis thaliana cells with a non-oxidative signaling molecule, the cell-permeant second messenger analogue, 8-bromo-3,5-cyclic guanosine monophosphate (8-Br-cGMP), results in a time-dependent increase in the content of oxidised methionine residues. Interestingly, the group of proteins affected by cGMP-dependent methionine oxidation is functionally enriched for stress response proteins. Furthermore, we also noted distinct signatures in the frequency of amino acids flanking oxidised and un-oxidised methionine residues on both the C- and N-terminus. Conclusions: Given both a structural and functional bias in methionine oxidation events in response to a signaling molecule, we propose that these are indicative of a specific role of such post-translational modifications in the direct or indirect regulation of cellular responses. The mechanisms that determine the specificity of the modifications remain to be elucidated. 2013 Marondedze et al.; licensee BioMed Central Ltd.

Determination of Model Kinetics for Forced Unsteady State Operation of Catalytic CH4 Oxidation

Directory of Open Access Journals (Sweden)

Effendy Mohammad

2016-01-01

Full Text Available The catalytic oxidation of methane for abating the emission vented from coal mine or natural gas transportation has been known as most reliable method. A reverse flow reactor operation has been widely used to oxidize this methane emission due to its capability for autothermal operation and heat production. The design of the reverse flow reactor requires a proper kinetic rate expression, which should be developed based on the operating condition. The kinetic rate obtained in the steady state condition cannot be applied for designing the reactor operated under unsteady state condition. Therefore, new approach to develop the dynamic kinetic rate expression becomes indispensable, particularly for periodic operation such as reverse flow reactor. This paper presents a novel method to develop the kinetic rate expression applied for unsteady state operation. The model reaction of the catalytic methane oxidation over Pt/-Al2O3 catalyst was used with kinetic parameter determined from laboratory experiments. The reactor used was a fixed bed, once-through operation, with a composition modulation in the feed gas. The switching time was set at 3 min by varying the feed concentration, feed flow rate, and reaction temperature. The concentrations of methane in the feed and product were measured and analysed using gas chromatography. The steady state condition for obtaining the kinetic rate expression was taken as a base case and as a way to judge its appropriateness to be applied for dynamic system. A Langmuir-Hinshelwood reaction rate model was developed. The time period during one cycle was divided into some segments, depending on the ratio of CH4/O2. The experimental result shows that there were kinetic regimes occur during one cycle: kinetic regime controlled by intrinsic surface reaction and kinetic regime controlled by external diffusion. The kinetic rate obtained in the steady state operation was not appropriate when applied for unsteady state operation

Glymphatic clearance controls state-dependent changes in brain lactate concentration.

Science.gov (United States)

Lundgaard, Iben; Lu, Minh Lon; Yang, Ezra; Peng, Weiguo; Mestre, Humberto; Hitomi, Emi; Deane, Rashid; Nedergaard, Maiken

2017-06-01

Brain lactate concentration is higher during wakefulness than in sleep. However, it is unknown why arousal is linked to an increase in brain lactate and why lactate declines within minutes of sleep. Here, we show that the glymphatic system is responsible for state-dependent changes in brain lactate concentration. Suppression of glymphatic function via acetazolamide treatment, cisterna magna puncture, aquaporin 4 deletion, or changes in body position reduced the decline in brain lactate normally observed when awake mice transition into sleep or anesthesia. Concurrently, the same manipulations diminished accumulation of lactate in cervical, but not in inguinal lymph nodes when mice were anesthetized. Thus, our study suggests that brain lactate is an excellent biomarker of the sleep-wake cycle and increases further during sleep deprivation, because brain lactate is inversely correlated with glymphatic-lymphatic clearance. This analysis provides fundamental new insight into brain energy metabolism by demonstrating that glucose that is not fully oxidized can be exported as lactate via glymphatic-lymphatic fluid transport.

Reversal magnetization dependence with the Cr and Fe oxidation states in YFe1−xCrxO3 (0≤x≤1) perovskites

International Nuclear Information System (INIS)

Fabian, F.A.; Pedra, P.P.; Moura, K.O.; Duque, J.G.S.; Meneses, C.T.

2016-01-01

In this work, we have carried out a detailed study of the magnetic and structural properties of YFe 1−x Cr x O 3 (0≤x≤1) samples with orthorhombic structure obtained by co-precipitation method. Analysis of X-ray diffraction data using Rietveld refinement show that all samples present an orthorhombic crystal system with space group Pnma. Besides, we have observed a reduction of unit cell volume with increasing of the Cr concentration. SEM images show the formation of grains of micrometer order. X-ray Absorption near edge spectroscopy (XANES) measurements show a shift of absorption edge which can be indicate there is (i) different oxidation states to Fe and Cr ions and/or (ii) a changing in the point symmetry of Fe and Cr ions to the compounds. The magnetization measurements indicate a continuous decreasing of the magnetic transition temperature as function of chromium doping. The reversal magnetization effect was observed to concentrations around x=0.5. Besides, the deviation of the Curie–Weiss law and a weak ferromagnetic behavior observed at room temperature in the M vs H curves can be attributed to the strong magnetic interactions between the transition metals with different oxidation states. - Highlights: • YFe 1−x Cr x O 3 (0≤x≤1) samples were synthesized by co-precipitation method. • XRD dates showed a reduction of unit cell volume with addition of Cr. • XANES dates showed difference in the oxidation states to Cr and Fe. • MZFC-MFC indicate a decreasing of the T N as function of chromium doping. • MFC curve for x=0.5 concentration was observed the reverse magnetization effect.

Temperature-Dependent Evolution of the Oxidation States of Cobalt and Platinum in Co _1–x Pt _x Clusters under H ₂ and CO + H ₂ Atmospheres

Energy Technology Data Exchange (ETDEWEB)

Yang, Bing; Khadra, Ghassan; Tuaillon-Combes, Juliette; Tyo, Eric C.; Pellin, Michael J.; Reinhart, Benjamin; Seifert, Sönke; Chen, Xinqi; Dupuis, Veronique; Vajda, Stefan

2016-09-29

Co1-xPtx clusters of 2.9-nm size with a range of atomically precise Pt/Co atomic ratios (x = 0, 0.25, 0.5, 0.75, 1) were synthesized using the mass-selected low-energy cluster beam deposition (LECBD) technique and soft-landed onto an amorphous alumina thin film prepared by atomic layer deposition (ALD). Utilizing ex situ X-ray photoemission spectroscopy (XPS), the oxidation state of the as-made clusters supported on Al2O3 was determined after both a 1-h-long exposure to air and aging for several weeks while exposed to air. Next, the aged duster samples were characterized by grazing-incidence X-ray absorption spectroscopy (GIXAS) and then pretreated with diluted hydrogen and further exposed to the mixture of diluted CO and H-2 up to 225 degrees C at atmospheric pressure, and the temperature-dependent evolutions of the particle size/shape and the oxidation states of the individual metal components within the dusters were monitored using in situ grazing-incidence small-angle X-ray scattering and X-ray absorption spectroscopy (GISAXS/GIXAS). The changes in the oxidation states of Co and Pt exhibited a nonlinear dependence on the Pt/Co atomic ratio of the dusters. For example, a low Pt/Co ratio (x <= 0.5) facilitates the formation of Co(OH)(2), whereas a high Pt/Co ratio (x = 0.75) stabilizes the Co3O4 composition instead through the formation of a Co-Pt core-shell structure where the platinum shell inhibits the reduction of cobalt in the core of the Co1-xPtx alloy dusters. The obtained results indicate methods for optimizing the composition and structure of binary alloy clusters for catalysis.

Magnetic susceptibility as a direct measure of oxidation state in LiFePO4 batteries and cyclic water gas shift reactors.

Science.gov (United States)

Kadyk, Thomas; Eikerling, Michael

2015-08-14

The possibility of correlating the magnetic susceptibility to the oxidation state of the porous active mass in a chemical or electrochemical reactor was analyzed. The magnetic permeability was calculated using a hierarchical model of the reactor. This model was applied to two practical examples: LiFePO4 batteries, in which the oxidation state corresponds with the state-of-charge, and cyclic water gas shift reactors, in which the oxidation state corresponds to the depletion of the catalyst. In LiFePO4 batteries phase separation of the lithiated and delithiated phases in the LiFePO4 particles in the positive electrode gives rise to a hysteresis effect, i.e. the magnetic permeability depends on the history of the electrode. During fast charge or discharge, non-uniform lithium distributionin the electrode decreases the hysteresis effect. However, the overall sensitivity of the magnetic response to the state-of-charge lies in the range of 0.03%, which makes practical measurement challenging. In cyclic water gas shift reactors, the sensitivity is 4 orders of magnitude higher and without phase separation, no hysteresis occurs. This shows that the method is suitable for such reactors, in which large changes of the magnetic permeability of the active material occurs.

Extracellular redox state: refining the definition of oxidative stress in aging.

Science.gov (United States)

Jones, Dean P

2006-01-01

Oxidative stress in aging can result from an imbalance of prooxidants and antioxidants with excessive, destructive free radical chemistry. Thiol systems are important in the control of these processes, both by protecting against damage and serving in redox signaling mechanisms to sense danger and repair the damage. Studies by a number of research groups in collaboration with the Emory Clinical Biomarkers Laboratory show that the redox state of the central tissue antioxidant, glutathione (GSH), can be measured in human plasma and provides a quantitative systemic indicator of oxidative stress. Plasma GSH/GSSG redox in humans becomes oxidized with age, in response to chemotherapy, as a consequence of cigarette smoking, and in association with common age-related diseases (e.g., type 2 diabetes, cardiovascular disease). However, the GSH/GSSG redox is not equilibrated with the larger plasma cysteine/cystine (Cys/CySS) pool, and the Cys/CySS redox varies with age in a pattern that is distinct from that of GSH/GSSG redox. Furthermore, in vitro studies show that variation in Cys/CySS redox over the range found in vivo affects signaling pathways, which control cell proliferation and oxidant-induced apoptosis. The results point to the conclusion that free radical scavenging antioxidants are of increased importance when thiol/disulfide redox states are oxidized. Because thiol/disulfide redox states, per se, function in redox signaling and control as well as antioxidant protection, GSH/GSSG and Cys/CySS redox states may provide central parameters to link environmental influences and progression of changes associated with aging.

How different oxidation states of crystalline myoglobin are influenced by X-rays.

Science.gov (United States)

Hersleth, Hans-Petter; Andersson, K Kristoffer

2011-06-01

X-ray induced radiation damage of protein crystals is well known to occur even at cryogenic temperatures. Redox active sites like metal sites seem especially vulnerable for these radiation-induced reductions. It is essential to know correctly the oxidation state of metal sites in protein crystal structures to be able to interpret the structure-function relation. Through previous structural studies, we have tried to characterise and understand the reactions between myoglobin and peroxides. These reaction intermediates are relevant because myoglobin is proposed to take part as scavenger of reactive oxygen species during oxidative stress, and because these intermediates are similar among the haem peroxidases and oxygenases. We have in our previous studies shown that these different myoglobin states are influenced by the X-rays used. In this study, we have in detail investigated the impact that X-rays have on these different oxidation states of myoglobin. An underlying goal has been to find a way to be able to determine mostly unreduced states. We have by using single-crystal light absorption spectroscopy found that the different oxidation states of myoglobin are to a different extent influenced by the X-rays (e.g. ferric Fe(III) myoglobin is faster reduced than ferryl Fe(IV)═O myoglobin). We observe that the higher oxidation states are not reduced to normal ferrous Fe(II) or ferric Fe(III) states, but end up in some intermediate and possibly artificial states. For ferric myoglobin, it seems that annealing of the radiation-induced/reduced state can reversibly more or less give the starting point (ferric myoglobin). Both scavengers and different dose-rates might influence to which extent the different states are affected by the X-rays. Our study shows that it is essential to do a time/dose monitoring of the influence X-rays have on each specific redox-state with spectroscopic techniques like single-crystal light absorption spectroscopy. This will determine to which

Interstitial pressure dependence of the thermal conductivity of some rare earth oxide powders

International Nuclear Information System (INIS)

Pradeep, P.

1997-01-01

Thermal transport properties of powdered materials depend upon interstitial gas pressure. The present study reports the experimental results for the effective thermal conductivity of three rare earth oxide powders viz. yttrium oxide, samarium oxide, and gadolinium oxide, at various interstitial pressures by using transient plane source (TPS) method. A theoretical model is also proposed for the interpretation of the variation of the effective thermal conductivity with interstitial gas pressure. Its validity is found to be good in low pressure range of 45 mm Hg to normal pressure when compared with the experimental results. Also an attempt has been made to calculate the variation of thermal conductivity with interstitial pressure in the high pressure range up to 2 kbar using the proposed model. (author)

Investigation of electrochemical behaviour and structure of oxide films on Ni60Nb40 alloy in amorphous and crystalline states

International Nuclear Information System (INIS)

Tomashov, N.D.; Skvortsova, I.B.; Gorodetskij, A.E.; Bogomolov, D.B.

1987-01-01

Electrochemical properties of Ni 60 Nb 40 alloy in amorphous and crystalline states as well as structure of oxide films forming during anode polarization in electrolytes on the surface of this alloy in both its states are investigated. It is stated that increased passive ability of Ni 60 Nb 40 alloys in amorphous state and high efficiency of chlorine evolution (2 n NaCl+HCl up to pH=0) anode process in comparison with crystalline state are defined by increased homogeneity and uniformity of passive films forming on amorphous alloy and their increased electron conductivity, that is in direct dependence on different structure of passive films forming on alloys in amorphous and crystalline states

Cellular defense against singlet oxygen-induced oxidative damage by cytosolic NADP+-dependent isocitrate dehydrogenase.

Science.gov (United States)

Kim, Sun Yee; Park, Jeen-Woo

2003-03-01

Singlet oxygen (1O2) is a highly reactive form of molecular oxygen that may harm living systems by oxidizing critical cellular macromolecules. Recently, we have shown that NADP+-dependent isocitrate dehydrogenase is involved in the supply of NADPH needed for GSH production against cellular oxidative damage. In this study, we investigated the role of cytosolic form of NADP+-dependent isocitrate dehydrogenase (IDPc) against singlet oxygen-induced cytotoxicity by comparing the relative degree of cellular responses in three different NIH3T3 cells with stable transfection with the cDNA for mouse IDPc in sense and antisense orientations, where IDPc activities were 2.3-fold higher and 39% lower, respectively, than that in the parental cells carrying the vector alone. Upon exposure to singlet oxygen generated from photoactivated dye, the cells with low levels of IDPc became more sensitive to cell killing. Lipid peroxidation, protein oxidation, oxidative DNA damage and intracellular peroxide generation were higher in the cell-line expressing the lower level of IDPc. However, the cells with the highly over-expressed IDPc exhibited enhanced resistance against singlet oxygen, compared to the control cells. The data indicate that IDPc plays an important role in cellular defense against singlet oxygen-induced oxidative injury.

Optoelectronic properties of valence-state-controlled amorphous niobium oxide

Science.gov (United States)

Onozato, Takaki; Katase, Takayoshi; Yamamoto, Akira; Katayama, Shota; Matsushima, Koichi; Itagaki, Naho; Yoshida, Hisao; Ohta, Hiromichi

2016-06-01

In order to understand the optoelectronic properties of amorphous niobium oxide (a-NbO x ), we have investigated the valence states, local structures, electrical resistivity, and optical absorption of a-NbO x thin films with various oxygen contents. It was found that the valence states of Nb ion in a-NbO x films can be controlled from 5+  to 4+  by reducing oxygen pressure during film deposition at room temperature, together with changing the oxide-ion arrangement around Nb ion from Nb2O5-like to NbO2-like local structure. As a result, a four orders of magnitude reduction in the electrical resistivity of a-NbO x films was observed with decreasing oxygen content, due to the carrier generation caused by the appearance and increase of an oxygen-vacancy-related subgap state working as an electron donor. The tunable optoelectronic properties of a-NbO x films by valence-state-control with oxygen-vacancy formation will be useful for potential flexible optoelectronic device applications.

Time-dependent problems in quantum-mechanical state reconstruction

International Nuclear Information System (INIS)

Leonhardt, U.; Bardroff, P. J.

1997-01-01

We study the state reconstruction of wave packets that travel in time-dependent potentials. We solve the problem for explicitly time-dependent potentials. We solve the problem for explicitly time-dependent harmonic oscillators and sketch a general adaptive technique for finding the wave function that matches and observed evolution. (authors)

Nitric oxide, cholesterol oxides and endothelium-dependent vasodilation in plasma of patients with essential hypertension

Directory of Open Access Journals (Sweden)

P. Moriel

2002-11-01

Full Text Available The objective of the present study was to identify disturbances of nitric oxide radical (·NO metabolism and the formation of cholesterol oxidation products in human essential hypertension. The concentrations of·NO derivatives (nitrite, nitrate, S-nitrosothiols and nitrotyrosine, water and lipid-soluble antioxidants and cholesterol oxides were measured in plasma of 11 patients with mild essential hypertension (H: 57.8 ± 9.7 years; blood pressure, 148.3 ± 24.8/90.8 ± 10.2 mmHg and in 11 healthy subjects (N: 48.4 ± 7.0 years; blood pressure, 119.4 ± 9.4/75.0 ± 8.0 mmHg.Nitrite, nitrate and S-nitrosothiols were measured by chemiluminescence and nitrotyrosine was determined by ELISA. Antioxidants were determined by reverse-phase HPLC and cholesterol oxides by gas chromatography. Hypertensive patients had reduced endothelium-dependent vasodilation in response to reactive hyperemia (H: 9.3 and N: 15.1% increase of diameter 90 s after hyperemia, and lower levels of ascorbate (H: 29.2 ± 26.0, N: 54.2 ± 24.9 µM, urate (H: 108.5 ± 18.9, N: 156.4 ± 26.3 µM, ß-carotene (H: 1.1 ± 0.8, N: 2.5 ± 1.2 nmol/mg cholesterol, and lycopene (H: 0.4 ± 0.2, N: 0.7 ± 0.2 nmol/mg cholesterol, in plasma, compared to normotensive subjects. The content of 7-ketocholesterol, 5alpha-cholestane-3ß,5,6ß-triol and 5,6alpha-epoxy-5alpha-cholestan-3alpha-ol in LDL, and the concentration of endothelin-1 (H: 0.9 ± 0.2, N: 0.7 ± 0.1 ng/ml in plasma were increased in hypertensive patients. No differences were found for ·NO derivatives between groups. These data suggest that an increase in cholesterol oxidation is associated with endothelium dysfunction in essential hypertension and oxidative stress, although ·NO metabolite levels in plasma are not modified in the presence of elevated cholesterol oxides.

Time-Dependent-Asymmetric-Linear-Parsimonious Ancestral State Reconstruction.

Science.gov (United States)

Didier, Gilles

2017-10-01

The time-dependent-asymmetric-linear parsimony is an ancestral state reconstruction method which extends the standard linear parsimony (a.k.a. Wagner parsimony) approach by taking into account both branch lengths and asymmetric evolutionary costs for reconstructing quantitative characters (asymmetric costs amount to assuming an evolutionary trend toward the direction with the lowest cost). A formal study of the influence of the asymmetry parameter shows that the time-dependent-asymmetric-linear parsimony infers states which are all taken among the known states, except for some degenerate cases corresponding to special values of the asymmetry parameter. This remarkable property holds in particular for the Wagner parsimony. This study leads to a polynomial algorithm which determines, and provides a compact representation of, the parametric reconstruction of a phylogenetic tree, that is for all the unknown nodes, the set of all the possible reconstructed states associated with the asymmetry parameters leading to them. The time-dependent-asymmetric-linear parsimony is finally illustrated with the parametric reconstruction of the body size of cetaceans.

Oxidation state analyses of uranium with emphasis on chemical speciation in geological media

International Nuclear Information System (INIS)

Ervanne, H.

2004-01-01

This thesis focuses on chemical methods suitable for the determination of uranium redox species in geological materials. Nd-coprecipitation method was studied for the determination of uranium oxidation states in ground waters. This method is ideally suited for the separation of uranium oxidation states in the field, which means that problems associated with the instability of U(IV) during transport are avoided. An alternative method, such as ion exchange, is recommended for the analysis of high saline and calcium- and iron-rich ground waters. U(IV)/Utot was 2.8-7.2% in ground waters in oxidizing conditions and 60-93% in anoxic conditions. From thermodynamic model calculations applied to results from anoxic ground waters it was concluded that uranium can act as redox buffer in granitic ground waters. An ion exchange method was developed for the analysis of uranium oxidation states in different solid materials of geological origin. These included uranium minerals, uraniumbearing minerals, fracture coatings and bulk rock. U(IV)/Utot was 50-70% in uraninites, 5.8-8.7% in secondary uranium minerals, 15-49% in different fracture coatings and 64- 77% in samples from deep bedrock. In the uranium-bearing minerals, U(IV)/Utot was 33-43% (allanites), 5.9% (fergusonite) and 93% (monazite). Although the ion exchange method gave reliable results, there is a risk for the conversion of uranium oxidation states during analysis of heterogeneous samples due to the redox reactions that take place in the presence of some iron compounds. This risk was investigated in a study of several common iron-bearing minerals. The risk for conversion of uranium oxidation states can be screened by sample selection and minimized with use of a redox buffer compound such as polyacrylic acid (PAA). In studies of several carboxylic acids, PAA was found to be the most suitable for extending the application of the method. The stability of uranium oxidation states during analysis and the selectivity

Corrosion-product transport, oxidation state and remedial measures

International Nuclear Information System (INIS)

Sawicki, J.A.; Brett, M.E.; Tapping, R.L.

1998-10-01

The issues associated with monitoring and controlling corrosion-product transport (CPT) in the balance-of-plant (BOP) and steam generators (SG) of CANDU stations are briefly reviewed. Efforts are focused on minimizing corrosion of carbon steel, which is used extensively in the CANDU primary and secondary systems. Emphasis is placed on the corrosion-product oxidation state as a monitor of water chemistry effectiveness and as a monitor of system corrosion effects. The discussion is based mostly on the results of observations from Ontario Hydro plants, and their comparisons with pressurized-water reactors. The effects of low oxygen and elevated hydrazine chemistry are reviewed, as well as the effects of layup and various startup conditions. Progress in monitoring electrochemical potential (ECP) at Ontario Hydro plants and its relationship to the oxidation state of corrosion products is reviewed. Observations on CPT on the primary side of SGs are also discussed. (author)

Tantalum high-temperature oxidation kinetics

International Nuclear Information System (INIS)

Grigor'ev, Yu.M.; Sarkisyan, A.A.; Merzhanov, A.G.

1981-01-01

Kinetics of heat release and scale growth during tantalum oxidation within 650-1300 deg C temperature range in oxygen-containing media is investigated. Kinetic equations and temperature and pressure dependences of constants are ound Applicability of the kinetic Lorie mechanism for the description of the tantalum oxidation kinetics applicably to rapid-passing processes is shown. It is stated that the process rate (reaction ability) is determined by adsorption desorption factors on the external surface of the ''protective'' oxide for the ''linear'' oxidation stage [ru

Reversal magnetization dependence with the Cr and Fe oxidation states in YFe1-xCrxO3 (0≤x≤1) perovskites

Science.gov (United States)

Fabian, F. A.; Pedra, P. P.; Moura, K. O.; Duque, J. G. S.; Meneses, C. T.

2016-06-01

In this work, we have carried out a detailed study of the magnetic and structural properties of YFe1-xCrxO3 (0≤x≤1) samples with orthorhombic structure obtained by co-precipitation method. Analysis of X-ray diffraction data using Rietveld refinement show that all samples present an orthorhombic crystal system with space group Pnma. Besides, we have observed a reduction of unit cell volume with increasing of the Cr concentration. SEM images show the formation of grains of micrometer order. X-ray Absorption near edge spectroscopy (XANES) measurements show a shift of absorption edge which can be indicate there is (i) different oxidation states to Fe and Cr ions and/or (ii) a changing in the point symmetry of Fe and Cr ions to the compounds. The magnetization measurements indicate a continuous decreasing of the magnetic transition temperature as function of chromium doping. The reversal magnetization effect was observed to concentrations around x=0.5. Besides, the deviation of the Curie-Weiss law and a weak ferromagnetic behavior observed at room temperature in the M vs H curves can be attributed to the strong magnetic interactions between the transition metals with different oxidation states.

Generalized molybdenum oxide surface chemical state XPS determination via informed amorphous sample model

Energy Technology Data Exchange (ETDEWEB)

Baltrusaitis, Jonas, E-mail: job314@lehigh.edu [Department of Chemical Engineering, Lehigh University, B336 Iacocca Hall, 111 Research Drive, Bethlehem, PA 18015 (United States); PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Mendoza-Sanchez, Beatriz [CRANN, Chemistry School, Trinity College Dublin, Dublin (Ireland); Fernandez, Vincent [Institut des Matériaux Jean Rouxel, 2 rue de la Houssinière, BP 32229, F-44322 Nantes Cedex 3 (France); Veenstra, Rick [PhotoCatalytic Synthesis group, MESA+ Institute for Nanotechnology, Faculty of Science and Technology, University of Twente, Meander 229, P.O. Box 217, 7500 AE Enschede (Netherlands); Dukstiene, Nijole [Department of Physical and Inorganic Chemistry, Kaunas University of Technology, Radvilenu pl. 19, LT-50254 Kaunas (Lithuania); Roberts, Adam [Kratos Analytical Ltd, Trafford Wharf Road, Wharfside, Manchester, M17 1GP (United Kingdom); Fairley, Neal [Casa Software Ltd, Bay House, 5 Grosvenor Terrace, Teignmouth, Devon TQ14 8NE (United Kingdom)

2015-01-30

Highlights: • We analyzed and modeled spectral envelopes of complex molybdenum oxides. • Molybdenum oxide films of varying valence and crystallinity were synthesized. • MoO{sub 3} and MoO{sub 2} line shapes from experimental data were created. • Informed amorphous sample model (IASM) developed. • Amorphous molybdenum oxide XPS envelopes were interpreted. - Abstract: Accurate elemental oxidation state determination for the outer surface of a complex material is of crucial importance in many science and engineering disciplines, including chemistry, fundamental and applied surface science, catalysis, semiconductors and many others. X-ray photoelectron spectroscopy (XPS) is the primary tool used for this purpose. The spectral data obtained, however, is often very complex and can be subject to incorrect interpretation. Unlike traditional XPS spectra fitting procedures using purely synthetic spectral components, here we develop and present an XPS data processing method based on vector analysis that allows creating XPS spectral components by incorporating key information, obtained experimentally. XPS spectral data, obtained from series of molybdenum oxide samples with varying oxidation states and degree of crystallinity, were processed using this method and the corresponding oxidation states present, as well as their relative distribution was elucidated. It was shown that monitoring the evolution of the chemistry and crystal structure of a molybdenum oxide sample due to an invasive X-ray probe could be used to infer solutions to complex spectral envelopes.

The oxidation states of elements in pure and Ca-doped BiCuSeO thermoelectric oxides

International Nuclear Information System (INIS)

Hsiao, Chun-Lung; Qi, Xiaoding

2016-01-01

Bi 1−x Ca x CuSeO (x = 0–0.3) was synthesized at 650 °C in an air-tight system flowing with pure argon. The Ca doping resulted in an increase in the thermoelectric figure of merit (ZT) as the consequence of increased carrier concentration. X-ray photoelectron spectroscopy (XPS) was carried out to check the oxidation states in Bi 1−x Ca x CuSeO. The results indicated that in addition to the expected Bi 3+ and Cu 1+ , there existed Bi 2+ and Cu 2+ in the undoped BiCuSeO, whereas in the Ca-doped BiCuSeO, Bi 4+ , Cu 3+ and Cu 2+ were observed. The Ca dopant was confirmed to be in the 2+ oxidation state. Two broad peaks centered at 54.22 and 58.59 eV were recorded in the vicinity around the binding energy of Se 3d. The former is often observed in the Se-containing intermetallics while the latter is often found in the Se-containing oxides, indicating that along with the expected Se–Cu bonding, a bonding between Se and O may also exist. Based on the XPS results, the charge compensation mechanisms were proposed for Bi 1−x Ca x CuSeO, which may shed some light on the origins of charge carriers. BiCuSeO based oxides have recently be discovered to have a large ZT comparable to the best alloys currently in use, because of the large Seebeck coefficient and small thermal conductivity. However, their electrical conductivity is lower compared to the best thermoelectrics. This work may provide some hints for the further improvement of ZT in BiCuSeO based oxides. - Graphical abstract: The oxidation states, charge compensation mechanisms, and origins of charge carriers in Bi 1−x Ca x CuSeO thermoelectrics. Display Omitted

Disability and multi-state labour force choices with state dependence

OpenAIRE

Oguzoglu, Umut

2010-01-01

I use a dynamic mixed multinomial logit model with unobserved heterogeneity to study the impact of work limiting disabilities on disaggregated labour choices. The first seven waves of the Household Income and Labour Dynamics in Australia survey are used to investigate this relationship. Findings point out to strong state dependence in employment choices. Further, the impact of disability on employment outcomes is highly significant. Model simulations suggest that high cross and own state depe...

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

Directory of Open Access Journals (Sweden)

Victoria J. Orphan

2011-11-01

Full Text Available On Earth, marine anaerobic methane oxidation (AOM can be driven by the microbial reduction of sulfate, iron, and manganese. Here, we have further characterized marine sediment incubations to determine if the mineral dependent methane oxidation involves similar microorganisms to those found for sulfate-dependent methane oxidation. Through FISH and FISH-SIMS analyses using 13C and 15N labeled substrates, we find that the most active cells during manganese dependent AOM are primarily mixed and mixed-cluster aggregates of archaea and bacteria. Overall, our control experiment using sulfate showed two active bacterial clusters, two active shell aggregates, one active mixed aggregate, and an active archaeal sarcina, the last of which appeared to take up methane in the absence of a closely-associated bacterial partner. A single example of a shell aggregate appeared to be active in the manganese incubation, along with three mixed aggregates and an archaeal sarcina. These results suggest that the microorganisms (e.g., ANME-2 found active in the manganese-dependent incubations are likely capable of sulfate-dependent AOM. Similar metabolic flexibility for Martian methanotrophs would mean that the same microbial groups could inhabit a diverse set of Martian mineralogical crustal environments. The recently discovered seasonal Martian plumes of methane outgassing could be coupled to the reduction of abundant surface sulfates and extensive metal oxides, providing a feasible metabolism for present and past Mars. In an optimistic scenario Martian methanotrophy consumes much of the periodic methane released supporting on the order of 10,000 microbial cells per cm2 of Martian surface. Alternatively, most of the methane released each year could be oxidized through an abiotic process requiring biological methane oxidation to be more limited. If under this scenario, 1% of this methane flux were oxidized by biology in surface soils or in subsurface aquifers (prior to

Mn K-edge XANES spectroscopy of photosynthetic water oxidation enzyme in the S0-, S1-, S2- and S3-states induced by flash excitation

International Nuclear Information System (INIS)

Ono, Taka-aki; Noguchi, Takumi; Inoue, Yorinao; Kusunoki, Masami; Matsushita, Tadashi; Oyanagi, Hiroyuki.

1993-01-01

Electronic and structural rearrangement of the Mn-cluster during the four step oxidation of water in photosynthetic oxygen evolution was studied by XANES spectroscopy. The Mn K-edge energy of the spectrum was changed with flash number to show a clear quadruple oscillation, indicating a periodic change in oxidation and electronic state of the Mn-cluster depending on Joliot and Kok's oxygen clock. (author)

Corrosion-product transport, oxidation state and remedial measures

International Nuclear Information System (INIS)

Sawicki, J.A.; Brett, M.E.; Tapping, R.L.

1998-01-01

The issues associated with monitoring and controlling corrosion-product transport (CPT) in the balance-of-plant (BOP) and steam generators (SG) of CANDU stations are briefly reviewed. The efforts are focused on minimizing corrosion of carbon steel, which is used extensively in the CANDU primary and secondary systems. Emphasis is placed on the corrosion-product oxidation state as a monitor of water chemistry effectiveness, and as a monitor of system corrosion effects. The discussion is based mostly on the results and observations from Ontario Hydro plants, and their comparisons with PWRs. The effects of low oxygen and elevated hydrazine chemistry are reviewed, as well as the effects of lay-up and various start-up conditions. Progress in monitoring electrochemical potential (ECP) at Ontario Hydro plants and its relationship to the oxidation state of corrosion products is reviewed. Observations on corrosion-product transport on the primary side of steam generators are also discussed. (author)

State dependent pseudo-resonances and excess noise

OpenAIRE

Papoff, F.; D'Alessandro, G.; Oppo, G.Luca

2008-01-01

We show that strong response to nonresonant modulations and excess noise are state dependent in generic nonlinear systems; i.e., they affect some output states but are absent from others. This is demonstrated in complex Swift-Hohenberg models relevant to optics, where it is caused by the non-normality of the linearized stability operators around selected output states, even though the cavity modes are orthogonal. In particular, we find the effective parameters that control excess noise and th...

Hard X-ray photoemission spectroscopy of transition-metal oxide thin films and interfaces

International Nuclear Information System (INIS)

Wadati, H.; Fujimori, A.

2013-01-01

Highlights: •Photoemission spectroscopy is a powerful technique to study the electronic structures of transition-metal oxides. •Hard X-ray photoemission spectroscopy (HXPES) is a new type of photoemission spectroscopy which can probe bulk states. •HXPES is very suitable for studying oxide thin films such as the composition dependence and the film thickness dependence. -- Abstract: Photoemission spectroscopy is a powerful experimental technique to study the electronic structures of solids, especially of transition-metal oxides. Recently, hard X-ray photoemission spectroscopy (HXPES) has emerged as a more relevant experimental technique to obtain clear information about bulk states. Here, we describe how HXPES can be conveniently applied to study the interesting subjects on oxide thin films such as the composition dependence and the film thickness dependence of the electronic structures and the interfacial electronic structure of multilayers

Energy dependence of critical state of single-component systems

International Nuclear Information System (INIS)

Volchenkova, R.A.

1985-01-01

Equations of critical states of the single-component systems: Psub(cr)(/Psub(o)=(Tsub(cr)/Tsub(o))x0.73, Tsub(cr)=K(Tsub(boil))sup(1.116) and Hsub(cr)(/Hsub(B)=Tsub(sr)/Tsub(B))sup(1.48) where Tsub(B)=1K, Hsub(B)-2 kcal/g-at, K-dimension factor are presented. It is shown that the revealed dependence Hsub(cr)=H(Tsub(cr)) is an energy boundary of a liquid-vapour phase state of the single-component systems beyond limits of which difference between liquid and vapour phases vanishes in increasing the system energy content. The given equations of state are true for all the single-component systems and permit to consider physicomechanical properties of substances in dynamic state depending on external conditions. Critical temperatures and dependences for elements from the most fusible He to infusible W and Re have been calculated

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

International Nuclear Information System (INIS)

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

1987-01-01

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

State-Dependent Implication and Equivalence in Quantum Logic

Directory of Open Access Journals (Sweden)

Fedor Herbut

2012-01-01

Full Text Available Ideal occurrence of an event (projector leads to the known change of a state (density operator into (the Lüders state. It is shown that two events and give the same Lüders state if and only if the equivalence relation is valid. This relation determines equivalence classes. The set of them and each class, are studied in detail. It is proved that the range projector of the Lüders state can be evaluated as , where denotes the greatest lower bound, and is the null projector of . State-dependent implication extends absolute implication (which, in turn, determines the entire structure of quantum logic. and are investigated in a closely related way to mutual benefit. Inherent in the preorder is the state-dependent equivalence , defining equivalence classes in a given Boolean subalgebra. The quotient set, in which the classes are the elements, has itself a partially ordered structure, and so has each class. In a complete Boolean subalgebra, both structures are complete lattices. Physical meanings are discussed.

Studies of Tc oxidation states in humic acid solutions

International Nuclear Information System (INIS)

Wang Bo; Liu Dejun; Yao Jun

2011-01-01

The oxidation state of Tc is an important aspect of the speciation in groundwater which contained organic substances due to it control the precipitation, complexation, sorption and colloid formation behavior of the Tc under HWL geological disposal conditions. In present work, the oxidation states of Tc were investigated using the LaCl 3 coagulation method and solution extraction method in aqueous solutions in which the humic acid concentration range is from 0 to 20 mg/L and the Tc (VII) concentration is about 10 -8 mol/L. The radiocounting of 99 Tc was determined using liquid scintillation spectrometry. The humic acid will influence the radiocounting ratio of 99 Tc apparently, however, the quenching effect can be restrained once keep the volume of the cocktail to about twenty times of the sample volume. The LaCl 3 coagulation method was carried out for the investigation of Tc oxidation states in humic acid aqueous systems at about pH 8. The tetraphenylarsonium chloride (TPA)-chloroform extraction method was used also simultaneously to investigation the concentrations of Tc (IV) and Tc (VII) for the availability of the LaCl 3 precipitation method, and the experimental results demonstrate that tetravalent technetium and pertechnetate concentration are well agreement with the LaCl 3 precipitation method. These two experimental results demonstrated that Tc (VII) is very stable in the Tc (VII)-humic acid system during a 350 days experimental period, and the Tc (IV) concentrations are very lower, that is indicate that there didn't oxidizing reactions between the Fluka humic acid and Tc (VII) in aqueous solutions under anaerobic conditions. That means the presence of humic acids even in anaerobic groundwater is disadvantage for the retardance of radionuclides. (authors)

Titanium oxidation-reduction at low oxygen pressure under electron bombardment

International Nuclear Information System (INIS)

Brasca, R.; Passeggi, M.C.G.; Ferron, J.

2006-01-01

The effect of the electron bombardment on the first stages of the titanium oxidation process has been studied by means of Auger Electron Spectroscopy. Using Factor Analysis and the valence electron dependence behaviour of the titanium LMV Auger transition, we found that the process is strongly dependent on the oxygen pressure and electron current density. Depending on the irradiation conditions, films of different thickness and Ti oxidized states are obtained

Predicting spent fuel oxidation states in a tuff repository

International Nuclear Information System (INIS)

Einziger, R.E.; Woodley, R.E.

1987-01-01

Nevada Nuclear Waste Storage Investigations Project (NNWSI) is studying the suitability of the tuffaceous rocks at Yucca Mountain as a waste repository for spent fuel disposal. The oxidation state of the LWR spent fuel in the moist air environment of a tuff repository could be a significant factor in determining its leaching and dissolution characteristics. Predictions as to which oxidation states would be present are important in analyzing such a repository and thus the present study was undertaken. A set of TGA (thermogravimetric analysis) tests were conducted on well-controlled samples of irradiated PWR fuel with time and temperature as the only variables. The tests were conducted between 140 and 225 0 C for a duration up to 2200 hours. The weight gain curves were analyzed in terms of diffusion through a layer of U 3 O 7 , diffusion into the grains to form a solid solution, a simplified empirical representation of a combination of grain boundary diffusion and bulk grain oxidation. Reaction rate constants were determined in each case, but analysis of these data could not establish a definitive mechanism. 21 refs., 10 figs., 3 tabs

Annealing-temperature-dependent voltage-sign reversal in all-oxide spin Seebeck devices using RuO2

Science.gov (United States)

Kirihara, Akihiro; Ishida, Masahiko; Yuge, Ryota; Ihara, Kazuki; Iwasaki, Yuma; Sawada, Ryohto; Someya, Hiroko; Iguchi, Ryo; Uchida, Ken-ichi; Saitoh, Eiji; Yorozu, Shinichi

2018-04-01

Thermoelectric converters based on the spin Seebeck effect (SSE) have attracted great attention due to their potential to offer novel applications such as energy harvesting and heat-flow sensing. For converting a SSE-induced spin current into an electric current, a transition metal film such as Pt, which exhibits large inverse spin-Hall effect (ISHE), has been typically used. In this work, we show an all-oxide SSE device using ruthenium oxide (RuO2) as a conductive film. We found that both the sign and magnitude of the SSE-induced ISHE voltage V appearing in the RuO2 film changes depending on the post annealing temperature, and that the magnitude can become larger than that of a standard SSE device using Pt. The similar sign change was also observed in Hall-resistance measurements of the RuO2 films. X-ray absorption fine structure (XAFS) spectra of as-deposited and annealed RuO2 revealed that the annealing process substantially improved the long-range crystalline order in RuO2. This suggests that change in the crystalline order may modify the dominant ISHE mechanism or electronic states in RuO2, leading to the sign reversal of V as well as the Hall coefficient. Our result demonstrates that RuO2 is an interesting material not only as a practical ISHE film but also as a testbed to study physics of spin-to-charge converters that depend on their crystalline order.

Mitochondrial isocitrate dehydrogenase is inactivated upon oxidation and reactivated by thioredoxin-dependent reduction in Arabidopsis

Directory of Open Access Journals (Sweden)

Keisuke eYoshida

2014-09-01

Full Text Available Regulation of mitochondrial metabolism is essential for ensuring cellular growth and maintenance in plants. Based on redox-proteomics analysis, several proteins involved in diverse mitochondrial reactions have been identified as potential redox-regulated proteins. NAD+-dependent isocitrate dehydrogenase (IDH, a key enzyme in the tricarboxylic acid cycle, is one such candidate. In this study, we investigated the redox regulation mechanisms of IDH by biochemical procedures. In contrast to mammalian and yeast counterparts reported to date, recombinant IDH in Arabidopsis mitochondria did not show adenylate-dependent changes in enzymatic activity. Instead, IDH was inactivated by oxidation treatment and partially reactivated by subsequent reduction. Functional IDH forms a heterodimer comprising regulatory (IDH-r and catalytic (IDH-c subunits. IDH-r was determined to be the target of oxidative modifications forming an oligomer via intermolecular disulfide bonds. Mass spectrometric analysis combined with tryptic digestion of IDH-r indicated that Cys128 and Cys216 are involved in intermolecular disulfide bond formation. Furthermore, we showed that mitochondria-localized o-type thioredoxin (Trx-o promotes the reduction of oxidized IDH-r. These results suggest that IDH-r is susceptible to oxidative stress, and Trx-o serves to convert oxidized IDH-r to the reduced form that is necessary for active IDH complex.

Violations of the Born rule in cool state-dependent horizons

Science.gov (United States)

Marolf, Donald; Polchinski, Joseph

2016-01-01

The black hole information problem has motivated many proposals for new physics. One idea, known as state-dependence, is that quantum mechanics must be generalized to describe the physics of black holes, and that fixed linear operators do not provide the fundamental description of experiences for infalling observers. Instead, such experiences are to be described by operators with an extra dependence on the global quantum state. By generalizing a previous argument for firewalls in generic black holes, we show that any implementation of this idea strong enough to remove firewalls from generic states requires massive violations of the Born rule. We also demonstrate a sense in which such violations are visible to infalling observers involved in preparing the initial state of the black hole. We emphasize the generality of our results; no details of any specific proposal for state-dependence are required.

Violations of the Born rule in cool state-dependent horizons

Energy Technology Data Exchange (ETDEWEB)

Marolf, Donald [Department of Physics, University of California,Santa Barbara, CA 93106-9530 (United States); Polchinski, Joseph [Kavli Institute for Theoretical Physics, University of California,Santa Barbara, CA 93106-4030 (United States)

2016-01-04

The black hole information problem has motivated many proposals for new physics. One idea, known as state-dependence, is that quantum mechanics must be generalized to describe the physics of black holes, and that fixed linear operators do not provide the fundamental description of experiences for infalling observers. Instead, such experiences are to be described by operators with an extra dependence on the global quantum state. By generalizing a previous argument for firewalls in generic black holes, we show that any implementation of this idea strong enough to remove firewalls from generic states requires massive violations of the Born rule. We also demonstrate a sense in which such violations are visible to infalling observers involved in preparing the initial state of the black hole. We emphasize the generality of our results; no details of any specific proposal for state-dependence are required.

Nitric oxide signaling depends on biotin in Jurkat human lymphoma cells.

Science.gov (United States)

Rodriguez-Melendez, Rocio; Zempleni, Janos

2009-03-01

Biotin affects gene expression through a diverse array of cell signaling pathways. Previous studies provided evidence that cGMP-dependent signaling also depends on biotin, but the mechanistic sequence of cGMP regulation by biotin is unknown. Here we tested the hypothesis that the effects of biotin in cGMP-dependent cell signaling are mediated by nitric oxide (NO). Human lymphoid (Jurkat) cells were cultured in media containing deficient (0.025 nmol/L), physiological (0.25 nmol/L), and pharmacological (10 nmol/L) concentrations of biotin for 5 wk. Both levels of intracellular biotin and NO exhibited a dose-dependent relationship in regard to biotin concentrations in culture media. Effects of biotin on NO levels were disrupted by the NO synthase (NOS) inhibitor N-monomethyl-arginine. Biotin-dependent production of NO was linked with biotin-dependent expression of endothelial and neuronal NOS, but not inducible NOS. Previous studies revealed that NO is an activator of guanylate cyclase. Consistent with these previous observations, biotin-dependent generation of NO increased the abundance of cGMP in Jurkat cells. Finally, the biotin-dependent generation of cGMP increased protein kinase G activity. Collectively, the results of this study are consistent with the hypothesis that biotin-dependent cGMP signaling in human lymphoid cells is mediated by NO.

The Dependence of Chimera States on Initial Conditions

International Nuclear Information System (INIS)

Feng Yue-E; Li Hai-Hong

2015-01-01

A chimera state consisting of both coherent and incoherent groups is a fascinating spatial pattern in non-locally coupled identical oscillators. It is thought that random initial conditions hardly evolve to chimera states. In this work, we study the dependence of chimera states on initial conditions. We show that random initial conditions may lead to chimera states and the chance of realizing chimera states becomes increasing when the model parameters are moving away from the boundary of their stable regime. (paper)

Directional dependence of the threshold displacement energies in metal oxides

Science.gov (United States)

Cowen, Benjamin J.; El-Genk, Mohamed S.

2017-12-01

Molecular dynamics (MD) simulations are performed to investigate the directional dependence and the values of the threshold energies (TDEs) for the displacements of the oxygen and metal atoms and for producing stable Frenkel pairs in five metal oxides of Cr2O3, Al2O3, TiO2, SiO2, and MgO. The TDEs for the Frenkel pairs and atoms displacement are calculated in 66 crystallographic directions, on both the anion and cation sublattices. The performed simulations are for metal and oxygen PKA energies up to 350 and 400 eV, respectively. The calculated probability distributions for the atoms displacement and average number of Frenkel pairs produced in the different oxides are compared. The results revealed unique symmetrical patterns of the TDEs for the displacement of the atoms and the formation of stable Frenkel pairs, confirming the strong dependence on the direction and the crystalline structure of the oxides. Results also showed that the formation of stable Frenkel pairs is associated with the displacements of the PKAs and/or of the SKAs. The probabilities of the TDEs for the displacement of the oxygen and metal PKAs are consistently lower than those of the atoms in the crystal. In SiO2, TDEs for the displacement of oxygen and metal atoms and those for the formation of stable Frenkel pairs are the lowest, while those in TiO2 are among the highest. The results for Cr2O3 and Al2O3, which have the same crystal structure, are similar. The calculated TDEs for MgO, Al2O3 and TiO2 are generally in good agreement with the experimental values and the probability distributions of the TDEs for the PKAs in TiO2 are in good agreement with reported MD simulation results.

Investigation of the oxidation states of Pu isotopes in a hydrochloric acid solution

Energy Technology Data Exchange (ETDEWEB)

Lee, M.H. [Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, P. O. Box 105, Yuseong, Daejeon 305-353 (Korea, Republic of)], E-mail: mhlee@kaeri.re.kr; Kim, J.Y.; Kim, W.H.; Jung, E.C.; Jee, K.Y. [Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, P. O. Box 105, Yuseong, Daejeon 305-353 (Korea, Republic of)

2008-12-15

The characteristics of the oxidation states of Pu in a hydrochloric acid solution were investigated and the results were applied to a separating of Pu isotopes from IAEA reference soils. The oxidation states of Pu(III) and Pu(IV) were prepared by adding hydroxylamine hydrochloride and sodium nitrite to a Pu stock solution, respectively. Also, the oxidation state of Pu(VI) was adjusted with concentrated HNO{sub 3} and HClO{sub 4}. The stability of the various oxidation states of plutonium in a HCl solution with elapsed time after preparation were found to be in the following order: Pu(III){approx}Pu(VI)>Pu(IV)>Pu(V). The chemical recoveries of Pu(IV) in a 9 M HCl solution with an anion exchange resin were similar to those of Pu(VI). This method for the determination of Pu isotopes with an anion exchange resin in a 9 M HCl medium was applied to IAEA reference soils where the activity concentrations of {sup 239,240}Pu and {sup 238}Pu in IAEA-375 and IAEA-326 were consistent with the reference values reported by the IAEA.

State-dependent neutral delay equations from population dynamics.

Science.gov (United States)

Barbarossa, M V; Hadeler, K P; Kuttler, C

2014-10-01

A novel class of state-dependent delay equations is derived from the balance laws of age-structured population dynamics, assuming that birth rates and death rates, as functions of age, are piece-wise constant and that the length of the juvenile phase depends on the total adult population size. The resulting class of equations includes also neutral delay equations. All these equations are very different from the standard delay equations with state-dependent delay since the balance laws require non-linear correction factors. These equations can be written as systems for two variables consisting of an ordinary differential equation (ODE) and a generalized shift, a form suitable for numerical calculations. It is shown that the neutral equation (and the corresponding ODE--shift system) is a limiting case of a system of two standard delay equations.

Decay of hollow states in time-dependent density functional theory

Energy Technology Data Exchange (ETDEWEB)

Kapoor, Varun; Bauer, Dieter [Institut fuer Physik, Wismarsche Str. 43-45, Universitaet Rostock, Rostock-18051 (Germany)

2012-07-01

Hollow or multiply excited states are inaccessible in time dependent density functional theory (TDDFT) using adiabatic Kohn-Sham potentials. We determine the exact Kohn Sham (KS) potential for doubly excited states in an exactly solvable model Helium atom. The exact single-particle density corresponds to the energetically lowest quasi-stationary state in the exact KS potential. We describe how this exact potential controls the decay by a barrier whose origin is traced back to phase of the exact KS orbital. The potential controls the barrier height and width in order for the density to tunnel out and decay with the same rate as the doubly excited state in the ab initio time-dependent Schroedinger calculation. Instead, adiabatic KS potentials only show direct photoionization but no autoionization. A frequency-dependent linear response kernel would be necessary in order to capture the decay of autoionizing states.

Dependence of the specific surface area of the nuclear fuel with the matrix oxidation

International Nuclear Information System (INIS)

Gomez, F.; Quinones, J.; Iglesias, E.; Rodriguez, N.

2008-01-01

This paper is focused on the study of the changes in the specific surface area measured using BET techniques. The objective is to obtain a relation between this parameter and the change in the matrix stoichiometry (i.e., oxidation increase). None of the actual models used for extrapolating the behaviour of the spent fuel matrix under repository conditions have included this dependence yet. In this work the specific surface area of different uranium oxide were measured using N 2 (g) and Kr(g). The starting material was UO 2+x (s) with a size powder distribution lower than 20 μm. The results included in this paper shown a strong dependence on specific surface area with the matrix stoichiometry, i.e., and increase of more than one order of magnitude (SUO 2 = 6 m 2 *g -1 and SU 3 O 8 = 16.07 m 2 *g -1 ). Furthermore, the particle size distribution measured as a function of the thermal treatment done shows changes on the powder size related to the changes observed in the uranium oxide stoichiometry. (authors)

In situ oxidation state profiling of nickel hexacyanoferrate derivatized electrodes using line-imaging Raman spectroscopy and multivariate calibration

International Nuclear Information System (INIS)

Haight, S.M.; Schwartz, D.T.

1999-01-01

Metal hexacyanoferrate compounds show promise as electrochemically switchable ion exchange materials for use in the cleanup of radioactive wastes such as those found in storage basins and underground tanks at the Department of Energy's Hanford Nuclear Reservation. Reported is the use of line-imaging Raman spectroscopy for the in situ determination of oxidation state profiles in nickel hexacyanoferrate derivatized electrodes under potential control in an electrochemical cell. Line-imaging Raman spectroscopy is used to collect 256 contiguous Raman spectra every ∼5 microm from thin films (ca. 80 nm) formed by electrochemical derivatization of nickel electrodes. The cyanide stretching region of the Raman spectrum of the film is shown to be sensitive to iron oxidation state and is modeled by both univariate and multivariate correlations. Although both correlations fit the calibration set well, the multivariate (principle component regression or PCR) model's predictions of oxidation state are less sensitive to noise in the spectrum, yielding a much smoother oxidation state profile than the univariate model. Oxidation state profiles with spatial resolution of approximately 5 microm are shown for a nickel hexacyanoferrate derivatized electrode in reduced, intermediate, and oxidized states. In situ oxidation state profiles indicate that the 647.1 nm laser illumination photo-oxidizes the derivatized electrodes. This observation is confirmed using photoelectrochemical methods

Studies on frequency dependent electrical and dielectric properties of sintered zinc oxide pellets: effects of Al-doping

Science.gov (United States)

Tewari, S.; Ghosh, A.; Bhattacharjee, A.

2016-11-01

Sintered pellets of zinc oxide (ZnO), both undoped and Al-doped are prepared through a chemical process. Dopant concentration of Aluminium in ZnO [Al/Zn in weight percentage (wt%)] is varied from 0 to 3 wt%. After synthesis structural characterisation of the samples are performed with XRD and SEM-EDAX which confirm that all the samples are of ZnO having polycrystalline nature with particle size from 108.6 to 116 nm. Frequency dependent properties like a.c. conductivity, capacitance, impedance and phase angle are measured in the frequency range 10 Hz to 100 kHz as a function of temperature (in the range 25-150 °C). Nature of a.c. conductivity in these samples indicates hopping type of conduction arising from localised defect states. The frequency and temperature dependent properties under study are found to be as per correlated barrier hoping model. Dielectric and impedance properties studied in the samples indicate distributed relaxation, showing decrease of relaxation time with temperature.

Solid oxide fuel cells fueled with reducible oxides

Science.gov (United States)

Chuang, Steven S.; Fan, Liang Shih

2018-01-09

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

Hyperglycaemia-induced impairment of endothelium-dependent vasorelaxation in rat mesenteric arteries is mediated by intracellular methylglyoxal levels in a pathway dependent on oxidative stress

DEFF Research Database (Denmark)

Brouwers, O; Niessen, P M; Haenen, G

2010-01-01

-hydro-5-methylimidazolone (MG-H1) was detected with an antibody against MG-H1 and quantified with ultra-performance liquid chromatography (tandem) mass spectrometry. Reactive oxygen species formation was measured with a 5-(and-6)-chloromethyl-2'7'-dichlorodihydrofluorescein diacetate acetyl ester probe...... for AGE ligand S100b did (p cells and adventitia by fivefold accompanied by an eightfold increase in the oxidative stress marker nitrotyrosine. Antioxidant pre-incubation prevented methylglyoxal......-induced impairment of vasoreactivity. CONCLUSIONS/INTERPRETATION: These data show that hyperglycaemia-induced impairment of endothelium-dependent vasorelaxation is mediated by increased intracellular methylglyoxal levels in a pathway dependent on oxidative stress....

Probabilistic quantum cloning of a subset of linearly dependent states

Science.gov (United States)

Rui, Pinshu; Zhang, Wen; Liao, Yanlin; Zhang, Ziyun

2018-02-01

It is well known that a quantum state, secretly chosen from a certain set, can be probabilistically cloned with positive cloning efficiencies if and only if all the states in the set are linearly independent. In this paper, we focus on probabilistic quantum cloning of a subset of linearly dependent states. We show that a linearly-independent subset of linearly-dependent quantum states {| Ψ 1⟩,| Ψ 2⟩,…,| Ψ n ⟩} can be probabilistically cloned if and only if any state in the subset cannot be expressed as a linear superposition of the other states in the set {| Ψ 1⟩,| Ψ 2⟩,…,| Ψ n ⟩}. The optimal cloning efficiencies are also investigated.

State-dependent fluorescence of neutral atoms in optical potentials

Science.gov (United States)

Martinez-Dorantes, M.; Alt, W.; Gallego, J.; Ghosh, S.; Ratschbacher, L.; Meschede, D.

2018-02-01

Recently we have demonstrated scalable, nondestructive, and high-fidelity detection of the internal state of 87Rb neutral atoms in optical dipole traps using state-dependent fluorescence imaging [M. Martinez-Dorantes, W. Alt, J. Gallego, S. Ghosh, L. Ratschbacher, Y. Völzke, and D. Meschede, Phys. Rev. Lett. 119, 180503 (2017), 10.1103/PhysRevLett.119.180503]. In this paper we provide experimental procedures and interpretations to overcome the detrimental effects of heating-induced trap losses and state leakage. We present models for the dynamics of optically trapped atoms during state-dependent fluorescence imaging and verify our results by comparing Monte Carlo simulations with experimental data. Our systematic study of dipole force fluctuations heating in optical traps during near-resonant illumination shows that off-resonant light is preferable for state detection in tightly confining optical potentials.

The ecological rationality of state-dependent valuation.

Science.gov (United States)

McNamara, J M; Trimmer, P C; Houston, A I

2012-01-01

Laboratory studies on a range of animals have identified a bias that seems to violate basic principles of rational behavior: a preference is shown for feeding options that previously provided food when reserves were low, even though another option had been found to give the same reward with less delay. The bias presents a challenge to normative models of decision making (which only take account of expected rewards and the state of the animal at the decision time). To understand the behavior, we take a broad ecological perspective and consider how valuation mechanisms evolve when the best action depends upon the environment being faced. We show that in a changing and uncertain environment, state-dependent valuation can be favored by natural selection: Individuals should allow their hunger to affect learning for future decisions. The valuation mechanism that typically evolves produces the kind of behavior seen in standard laboratory tests. By providing an insight into why learning should be affected by the state of an individual, we provide a basis for understanding psychological principles in terms of an animal's ecology.

Anomalous temperature dependence of the current in a metal-oxide-polymer resistive switching diode

NARCIS (Netherlands)

Gomes, H.L.; Rocha, P.R.F.; Kiazadeh, A.; Leeuw, de D.M.; Meskers, S.C.J.

2011-01-01

Metal-oxide polymer diodes exhibit non-volatile resistive switching. The current–voltage characteristics have been studied as a function of temperature. The low-conductance state follows a thermally activated behaviour. The high-conductance state shows a multistep-like behaviour and below 300 K an

Influence of Battery Parametric Uncertainties on the State-of-Charge Estimation of Lithium Titanate Oxide-Based Batteries

DEFF Research Database (Denmark)

Stroe, Ana-Irina; Meng, Jinhao; Stroe, Daniel-Ioan

2018-01-01

to describe the battery dynamics. The SOC estimation method proposed in this paper is based on an Extended Kalman Filter (EKF) and nonlinear battery model which was parameterized using extended laboratory tests performed on several 13 Ah lithium titanate oxide (LTO)-based lithium-ion batteries. The developed......State of charge (SOC) is one of the most important parameters in battery management systems, as it indicates the available battery capacity at every moment. There are numerous battery model-based methods used for SOC estimation, the accuracy of which depends on the accuracy of the model considered...... a sensitivity analysis it was showed that the SOC and voltage estimation error are only slightly dependent on the variation of the battery model parameters with the SOC....

Parameter dependence and outcome dependence in dynamical models for state vector reduction

International Nuclear Information System (INIS)

Ghirardi, G.C.; Grassi, R.; Butterfield, J.; Fleming, G.N.

1993-01-01

The authors apply the distinction between parameter independence and outcome independence to the linear and nonlinear models of a recent nonrelativistic theory of continuous state vector reduction. It is shown that in the nonlinear model there is a set of realizations of the stochastic process that drives the state vector reduction for which parameter independence is violated for parallel spin components in the EPR-Bohm setup. Such a set has an appreciable probability of occurrence (∼ 1/2). On the other hand, the linear model exhibits only extremely small parameter dependence effects. Some specific features of the models are investigated and it is recalled that, as has been pointed out recently, to be able to speak of definite outcomes (or equivalently of possessed objective elements of reality) at finite times, the criteria for their attribution to physical systems must be slightly changed. The concluding section is devoted to a detailed discussion of the difficulties met when attempting to take, as a starting point for the formulation of a relativistic theory, a nonrelativistic scheme which exhibits parameter dependence. Here the authors derive a theorem which identifies the precise sense in which the occurrence of parameter dependence forbids a genuinely relativistic generalization. Finally, the authors show how the appreciable parameter dependence of the nonlinear model gives rise to problems with relativity, while the extremely weak parameter dependence of the linear model does not give rise to any difficulty, provided the appropriate criteria for the attribution of definite outcomes are taken into account. 19 refs

Maitra-Burke example of initial-state dependence in time-dependent density-functional theory

International Nuclear Information System (INIS)

Holas, A.; Balawender, R.

2002-01-01

In a recent paper, Maitra and Burke [Phys. Rev. A 63, 042501 (2001); 64, 039901(E) (2001)] have given an interesting and instructive example that illustrates a specific feature of the time-dependent density-functional theory--the dependence of the reconstructed time-dependent potential not only on the electron density, but also on the initial state of the system. However, a concise form of its presentation by these authors is insufficient to reveal all its peculiarities. Our paper represents a very detailed study of this valuable example, intended to facilitate a better understanding and appreciation

The oxidative burst reaction in mammalian cells depends on gravity.

Science.gov (United States)

Adrian, Astrid; Schoppmann, Kathrin; Sromicki, Juri; Brungs, Sonja; von der Wiesche, Melanie; Hock, Bertold; Kolanus, Waldemar; Hemmersbach, Ruth; Ullrich, Oliver

2013-12-20

Gravity has been a constant force throughout the Earth's evolutionary history. Thus, one of the fundamental biological questions is if and how complex cellular and molecular functions of life on Earth require gravity. In this study, we investigated the influence of gravity on the oxidative burst reaction in macrophages, one of the key elements in innate immune response and cellular signaling. An important step is the production of superoxide by the NADPH oxidase, which is rapidly converted to H2O2 by spontaneous and enzymatic dismutation. The phagozytosis-mediated oxidative burst under altered gravity conditions was studied in NR8383 rat alveolar macrophages by means of a luminol assay. Ground-based experiments in "functional weightlessness" were performed using a 2 D clinostat combined with a photomultiplier (PMT clinostat). The same technical set-up was used during the 13th DLR and 51st ESA parabolic flight campaign. Furthermore, hypergravity conditions were provided by using the Multi-Sample Incubation Centrifuge (MuSIC) and the Short Arm Human Centrifuge (SAHC). The results demonstrate that release of reactive oxygen species (ROS) during the oxidative burst reaction depends greatly on gravity conditions. ROS release is 1.) reduced in microgravity, 2.) enhanced in hypergravity and 3.) responds rapidly and reversible to altered gravity within seconds. We substantiated the effect of altered gravity on oxidative burst reaction in two independent experimental systems, parabolic flights and 2D clinostat / centrifuge experiments. Furthermore, the results obtained in simulated microgravity (2D clinorotation experiments) were proven by experiments in real microgravity as in both cases a pronounced reduction in ROS was observed. Our experiments indicate that gravity-sensitive steps are located both in the initial activation pathways and in the final oxidative burst reaction itself, which could be explained by the role of cytoskeletal dynamics in the assembly and function

BCL-2 inhibition targets oxidative phosphorylation and selectively eradicates quiescent human leukemia stem cells

Science.gov (United States)

Lagadinou, Eleni D.; Sach, Alexander; Callahan, Kevin; Rossi, Randall M.; Neering, Sarah J.; Minhajuddin, Mohammad; Ashton, John M.; Pei, Shanshan; Grose, Valerie; O’Dwyer, Kristen M.; Liesveld, Jane L.; Brookes, Paul S.; Becker, Michael W.; Jordan, Craig T.

2013-01-01

Summary Most forms of chemotherapy employ mechanisms involving induction of oxidative stress, a strategy that can be effective due to the elevated oxidative state commonly observed in cancer cells. However, recent studies have shown that relative redox levels in primary tumors can be heterogeneous, suggesting that regimens dependent on differential oxidative state may not be uniformly effective. To investigate this issue in hematological malignancies, we evaluated mechanisms controlling oxidative state in primary specimens derived from acute myelogenous leukemia (AML) patients. Our studies demonstrate three striking findings. First, the majority of functionally-defined leukemia stem cells (LSCs) are characterized by relatively low levels of reactive oxygen species (termed “ROS-low”). Second, ROS-low LSCs aberrantly over-express BCL-2. Third, BCL-2 inhibition reduced oxidative phosphorylation and selectively eradicated quiescent LSCs. Based on these findings, we propose a model wherein the unique physiology of ROS-low LSCs provides an opportunity for selective targeting via disruption of BCL-2-dependent oxidative phosphorylation. PMID:23333149

Structural oxidation state studies of the manganese cluster in the oxygen evolving complex of photosystem II

Energy Technology Data Exchange (ETDEWEB)

Liang, Wenchuan [Univ. of California, Berkeley, CA (United States)

1994-11-01

X-ray absorption spectroscopy (XAS) was performed on Photosystem II (PSII)-enriched membranes prepared from spinach to explore: (1) the correlation between structure and magnetic spin state of the Mn cluster in the oxygen evolving complex (OEC) in the S₂ state; and (2) the oxidation state changes of the Mn cluster in the flash-induced S-states. The structure of the Mn cluster in the S₂ state with the g~4 electron paramagnetic resonance (EPR) signal (S₂-g4 state) was compared with that in the S₂ state with multiline signal (S₂-MLS state) and the S₁ state. The S₂-g4 state has a higher XAS inflection point energy than that of the S₁ state, indicating the oxidation of Mn in the advance from the S₁ to the S₂-g4 state. Differences in the edge shape and in the extended X-ray absorption fine structure (EXAFS) show that the structure of the Mn cluster in the S₂-g4 state is different from that in the S₂-MLS or the S₁ state. In the S₂-g4 state, the second shell of backscatterers from the Mn absorber contains two Mn-Mn distances of 2.73 Å and 2.85 Å. Very little distance disorder exists in the second shell of the S₁ or S₂-MLS states. The third shell of the S₂-g4 state at about 3.3 Å also contains increased heterogeneity relative to that of the S₂-MLS or the S₁ state. Various S-states were prepared at room-temperature by saturating, single-turnover flashes. The flash-dependent oscillation in the amplitude of the MLS was used to characterize the S-state composition and to construct "pure" S-state Mn K-edge spectra. The edge position shifts to higher energy by 1.8 eV upon the S₁ → S₂ transition.

Investigating nitrate-dependent humic substance oxidation and in-service K-12 teachers' understanding of microbiology

Science.gov (United States)

Jones, Nastassia N.

2011-12-01

Humic substances (HS) are the humified portions of totally decomposed soil organic matter that are ubiquitous in nature. Although these substances have been studied for more than 200 years, neither their metabolic capabilities nor a specific chemical structure has yet to be determined. HS have been studied as a carbon source in many environments where they are degraded; however, previous studies have shown that some microorganisms are capable of utilizing humic substances as electron acceptors and electron donors in anaerobic respiration. Even though there have been humic-reducing and humic-oxidizing microorganisms isolated and studied in recent years, the mechanism of humics metabolism and its interaction in the natural environment are not well understood. However, it is known that the continuous change in the redox state of HS is important to the cycling of iron, stability of nitrogen and carbon, and the mobility and bioavailability of inorganic and organic environmental pollutants. In this study, microbial communities were examined to evaluate the community dynamics of nitrate-dependent HS-oxidizing populations and to provide a snapshot of the phylogenetic diversity of these microorganisms. Column studies were performed using nitrate as the sole electron acceptor and the following as the electron donors in different columns: reduced humic acids, oxidized humic acids, and acetate as the control. Liquid buffered media was added to a separate column to serve as an additional control. Polymerase chain reactions of the 16S rRNA genes using DNA from the column studies were performed and analyzed by constructing 16S rDNA clone libraries and by performing denaturing gradient gel electrophoresis (DGGE). Clones from the library have been sequenced and analyzed to paint a phylogenetic picture of the microbial community under the various conditions. Results indicate that the majority of the clones were assigned to four well-characterized divisions, the Acidobacteria, the

Dependency in State Transitions of Wind Turbines

DEFF Research Database (Denmark)

Herp, Jürgen; Ramezani, Mohammad Hossein; S. Nadimi, Esmaeil

2017-01-01

© 2017 IEEE. Turbine states and predicting the transition into failure states ahead of time is important in operation and maintenance of wind turbines. This study presents a method to monitor state transitions of a wind turbine based on the online inference on residuals. In a Bayesian framework...... be abstracted from generated data. Two models are presented: 1) assuming independence and 2) assuming dependence between states. In order to select the right models, machine learning is utilized to update hyperparameters on the conditional probabilities. Comparing fixed to learned hyperparameters points out...... the impact machine learning concepts have on the predictive performance of the presented models. In conclusion, a study on model residuals is performed to highlight the contribution to wind turbine monitoring. The presented algorithm can consistently detect the state transition under various configurations...

Surface structure-dependent pyrite oxidation in relatively dry and moist air: Implications for the reaction mechanism and sulfur evolution

Science.gov (United States)

Zhu, Jianxi; Xian, Haiyang; Lin, Xiaoju; Tang, Hongmei; Du, Runxiang; Yang, Yiping; Zhu, Runliang; Liang, Xiaoliang; Wei, Jingming; Teng, H. Henry; He, Hongping

2018-05-01

Pyrite oxidation not only is environmentally significant in the formation of acid mine (or acid rock) drainage and oxidative acidification of lacustrine sediment but also is a critical stage in geochemical sulfur evolution. The oxidation process is always controlled by the reactivity of pyrite, which in turn is controlled by its surface structure. In this study, the oxidation behavior of naturally existing {1 0 0}, {1 1 1}, and {2 1 0} facets of pyrite was investigated using a comprehensive approach combining X-ray photoelectron spectroscopy, diffuse reflectance Fourier transform infrared spectroscopy, and time-of-flight secondary-ion mass spectrometry with periodic density functional theoretical (DFT) calculations. The experimental results show that (i) the initial oxidation rates of both pyrite {1 1 1} and {2 1 0} are much greater than that of pyrite {1 0 0}; (ii) the initial oxidation rate of pyrite {2 1 0} is greater than that of pyrite {1 1 1} in low relative humidity, which is reversed in high relative humidity; and (iii) inner sphere oxygen-bearing sulfur species are originally generated from surface reactions and then converted to outer sphere species. The facet dependent rate law can be expressed as: r{hkl} =k{hkl}haP0.5(t + 1) - 0.5 , where r{hkl} is the orientation dependent reaction rate, k{hkl} is the orientation dependent rate constant, h is the relative humidity, P is the oxygen partial pressure, and t is the oxidation time in seconds. {1 1 1} is the most sensitive facet for pyrite oxidation. Combined with DFT theoretical investigations, water catalyzed electron transfer is speculated as the rate-limiting step. These findings disclose the structure-reactivity dependence of pyrite, which not only presents new insight into the mechanism of pyrite oxidation but also provides fundamental data to evaluate sulfur speciation evolution, suggesting that the surface structure sensitivity should be considered to estimate the reactivity at the mineral

Oxide Structure Dependence of SiO2/SiOx/3C-SiC/n-Type Si Nonvolatile Resistive Memory on Memory Operation Characteristics

Science.gov (United States)

Yamaguchi, Yuichiro; Shouji, Masatsugu; Suda, Yoshiyuki

2012-11-01

We have investigated the dependence of the oxide layer structure of our previously proposed metal/SiO2/SiOx/3C-SiC/n-Si/metal metal-insulator-semiconductor (MIS) resistive memory device on the memory operation characteristics. The current-voltage (I-V) measurement and X-ray photoemission spectroscopy results suggest that SiOx defect states mainly caused by the oxidation of 3C-SiC at temperatures below 1000 °C are related to the hysteresis memory behavior in the I-V curve. By restricting the SiOx interface region, the number of switching cycles and the on/off current ratio are more enhanced. Compared with a memory device formed by one-step or two-step oxidation of 3C-SiC, a memory device formed by one-step oxidation of Si/3C-SiC exhibits a more restrictive SiOx interface with a more definitive SiO2 layer and higher memory performances for both the endurance switching cycle and on/off current ratio.

A detailed study on the transition from the blocked to the superparamagnetic state of reduction-precipitated iron oxide nanoparticles

International Nuclear Information System (INIS)

Witte, K.; Bodnar, W.; Mix, T.; Schell, N.; Fulda, G.; Woodcock, T.G.; Burkel, E.

2016-01-01

Magnetic iron oxide nanoparticles were prepared by salt-assisted solid-state chemical precipitation method with alternating fractions of the ferric iron content. The physical properties of the precipitated nanoparticles mainly consisting of magnetite were investigated by means of transmission electron microscopy, high energy X-ray diffraction, vibrating sample magnetometry and Mössbauer spectroscopy. With particle sizes ranging from 16.3 nm to 2.1 nm, a gradual transition from the blocked state to the superparamagnetic state was observed. The transition was described as a dependence of the ferric iron content used during the precipitation. Composition, mean particle size, coercivity, saturation polarisation, as well as hyperfine interaction parameters and their evolution were studied systematically over the whole series of iron oxide nanoparticles. - Highlights: • Study of superparamagnetic transition of magnetite varying ferric iron content. • Coercivity is mainly influenced by the particle size. • Saturation polarisation influenced by the goethite content and the particle size. • Number of vacancies tend to increase with increasing ferric iron content. • Fe 3 O 4 B-sites are stronger effected by the reduction of particle size than A-sites.

Coherent states of general time-dependent harmonic oscillator

Indian Academy of Sciences (India)

Abstract. By introducing an invariant operator, we obtain exact wave functions for a general time-dependent quadratic harmonic oscillator. The coherent states, both in x- and p-spaces, are calculated. We confirm that the uncertainty product in coherent state is always larger than Η/2 and is equal to the minimum of the ...

Towards a Mechanistic Understanding of Anaerobic Nitrate Dependent Iron Oxidation: Balancing Electron Uptake and Detoxification

Directory of Open Access Journals (Sweden)

Hans Karl Carlson

2012-02-01

Full Text Available The anaerobic oxidation of Fe(II by subsurface microorganisms is an important part of biogeochemical cycling in the environment, but the biochemical mechanisms used to couple iron oxidation to nitrate respiration are not well understood. Based on our own work and the evidence available in the literature, we propose a mechanistic model for anaerobic nitrate dependent iron oxidation. We suggest that anaerobic iron oxidizing microorganisms likely exist along a continuum including: 1 bacteria that inadvertently oxidize Fe(II by abiotic or biotic reactions with enzymes or chemical intermediates in their metabolic pathways (e.g. denitrification and suffer from toxicity or energetic penalty, 2 Fe(II tolerant bacteria that gain little or no growth benefit from iron oxidation but can manage the toxic reactions, and 3 bacteria that efficiently accept electrons from Fe(II to gain a growth advantage while preventing or mitigating the toxic reactions. Predictions of the proposed model are highlighted and experimental approaches are discussed.

Nitric oxide-dependent activation of CaMKII increases diastolic sarcoplasmic reticulum calcium release in cardiac myocytes in response to adrenergic stimulation.

Science.gov (United States)

Curran, Jerry; Tang, Lifei; Roof, Steve R; Velmurugan, Sathya; Millard, Ashley; Shonts, Stephen; Wang, Honglan; Santiago, Demetrio; Ahmad, Usama; Perryman, Matthew; Bers, Donald M; Mohler, Peter J; Ziolo, Mark T; Shannon, Thomas R

2014-01-01

Spontaneous calcium waves in cardiac myocytes are caused by diastolic sarcoplasmic reticulum release (SR Ca(2+) leak) through ryanodine receptors. Beta-adrenergic (β-AR) tone is known to increase this leak through the activation of Ca-calmodulin-dependent protein kinase (CaMKII) and the subsequent phosphorylation of the ryanodine receptor. When β-AR drive is chronic, as observed in heart failure, this CaMKII-dependent effect is exaggerated and becomes potentially arrhythmogenic. Recent evidence has indicated that CaMKII activation can be regulated by cellular oxidizing agents, such as reactive oxygen species. Here, we investigate how the cellular second messenger, nitric oxide, mediates CaMKII activity downstream of the adrenergic signaling cascade and promotes the generation of arrhythmogenic spontaneous Ca(2+) waves in intact cardiomyocytes. Both SCaWs and SR Ca(2+) leak were measured in intact rabbit and mouse ventricular myocytes loaded with the Ca-dependent fluorescent dye, fluo-4. CaMKII activity in vitro and immunoblotting for phosphorylated residues on CaMKII, nitric oxide synthase, and Akt were measured to confirm activity of these enzymes as part of the adrenergic cascade. We demonstrate that stimulation of the β-AR pathway by isoproterenol increased the CaMKII-dependent SR Ca(2+) leak. This increased leak was prevented by inhibition of nitric oxide synthase 1 but not nitric oxide synthase 3. In ventricular myocytes isolated from wild-type mice, isoproterenol stimulation also increased the CaMKII-dependent leak. Critically, in myocytes isolated from nitric oxide synthase 1 knock-out mice this effect is ablated. We show that isoproterenol stimulation leads to an increase in nitric oxide production, and nitric oxide alone is sufficient to activate CaMKII and increase SR Ca(2+) leak. Mechanistically, our data links Akt to nitric oxide synthase 1 activation downstream of β-AR stimulation. Collectively, this evidence supports the hypothesis that CaMKII is

Plutonium uptake by Scenedesmus obliquus as a function of isotope and oxidation state

International Nuclear Information System (INIS)

Tkacik, M.F.; Giesy, J.P.; Wilhite, E.L.; Corey, J.C.

1979-01-01

Uptake of 238 Pu 4+ , 238 Pu 6+ , 239 Pu 4+ and 239 Pu 6+ by the green alga Scenedesmus obliquus (Turp) Kutz was studied to determine whether isotope or oxidation state differences affect Pu uptake from aqueous medium by algal cells. At equivalent 238 Pu and 239 PU concentrations, even when initial oxidation states differed, accumulations of these isotopes by S.obliquus were not significantly (p>0.05) different. Plutonium accumulation by S.obliquus was log-linear. (author)

Oxidation states of Fe in LaNi1-xFexO3

International Nuclear Information System (INIS)

Goeta, A.E.; Falcon, H.; Carbonio, R.

1994-01-01

The distribution of oxidation states in perovskites of the type LaA 1-x B x O 3 (A and B transition metal ions) can be ''tailored'' by x variation. In particular, in LaNiO 3 it has been shown that Fe substitution for Ni foces some Ni 3+ into Ni 2+ , while some Fe 3+ changes into the unusual Fe 4+ state. In addition, the existence of mixed oxidation states of Fe and/or Ni in LaNi 1-x Fe x O 3 has been related to its catalytic activity in hydrogen peroxide decomposition. The Fe 4+ population, obtained using Moessbauer spectroscopy, was found to be constant for all the analyzed annealing temperatures for x = 0.25 concentration, where the isomer shift difference for both states is the highest and the catalytic activity is maximum. (orig.)

State Dependence in Unemployment among Danish Immigrants

DEFF Research Database (Denmark)

Ahmad, Nisar

This study examines the extent state dependence among unemployed Danish immigrants in a dynamic discrete choice framework. Three alternative methodologies are employed to control for the problem of the initial condition. The empirical findings show that there is a considerable correlation between...

Solid-state voltammetry-based electrochemical immunosensor for Escherichia coli using graphene oxide-Ag nanoparticle composites as labels.

Science.gov (United States)

Jiang, Xiaochun; Chen, Kun; Wang, Jing; Shao, Kang; Fu, Tao; Shao, Feng; Lu, Donglian; Liang, Jiangong; Foda, M Frahat; Han, Heyou

2013-06-21

A new electrochemical immunosensor based on solid-state voltammetry was fabricated for the detection of Escherichia coli (E. coli) by using graphene oxide-Ag nanoparticle composites (P-GO-Ag) as labels. To construct the platform, Au nanoparticles (AuNPs) were first self-assembled on an Au electrode surface through cysteamine and served as an effective matrix for antibody (Ab) attachment. Under a sandwich-type immunoassay format, the analyte and the probe (P-GO-Ag-Ab) were successively captured onto the immunosensor. Finally, the bonded AgNPs were detected through a solid-state redox process in 0.2 M of KCl solution. Combining the advantages of the high-loading capability of graphene oxide with promoted electron-transfer rate of AuNPs, this immunosensor produced a 26.92-fold signal enhancement compared with the unamplified protocol. Under the optimal conditions, the immunosensor exhibited a wide linear dependence on the logarithm of the concentration of E. coli ranging from 50 to 1.0 × 10(6) cfu mL(-1) with a detection limit of 10 cfu mL(-1). Moreover, as a practical application, the proposed immunosensor was used to monitor E. coli in lake water with satisfactory results.

Studies of the Tc oxidation states in humic acid solutions

International Nuclear Information System (INIS)

Wang Bo; Liu Dejun; Yao Jun

2010-01-01

The oxidation state is an important aspect of the speciation of Tc in groundwater that contained organic substances due to it control the precipitation, complexation, sorption and colloid formation behavior of the Tc under HWL geological disposal conditions. In present work, the oxidation states of Tc were investigated using the LaCl 3 coagulation method and solution extraction method in aqueous solutions in which the humic acid concentration range is from 0 to 20 mg L -1 and the Tc (Ⅶ) concentration range is about 10 -8 mol l -1 . The radiocounting of 99 Tc was determined using liquid scintillation spectrometry. The humic acid will influence the radiocounting ratio of 99 Tc apparently, however, the quenching effect can be restrained once keep the volume of the cocktail to about twenty times of the sample volume. The LaCl 3 coagulation methods were carried out for the investigation of Tc oxidation states in humic acid aqueous systems at about pH 8. The tetraphenylarsonium chloride (IPA)-chloroform extraction method was used also simultaneously to investigation the concentrations of Tc (Ⅳ) and Tc (Ⅶ) for the availability of the LaCl 3 precipitation method, and the experimental results demonstrate that tetravalent technetium and pertechnetate concentrations are well agreement with the LaCl 3 precipitation method. These two experimental results demonstrated that Tc (Ⅶ) is very stable in the Tc (Ⅶ)-humic acid system during a 350 days experimental period, and the Tc (Ⅳ) concentrations are very lower, that is indicate that there didn't oxidizing reactions between the Fluka humic acid and Tc (Ⅶ) in aqueous solutions under anaerobic conditions. That is means the presence of humic acids even in anaerobic groundwater is disadvantage for the retardance of radionuclides. (authors)

State-Dependence of the Climate Sensitivity in Earth System Models of Intermediate Complexity

Science.gov (United States)

Pfister, Patrik L.; Stocker, Thomas F.

2017-10-01

Growing evidence from general circulation models (GCMs) indicates that the equilibrium climate sensitivity (ECS) depends on the magnitude of forcing, which is commonly referred to as state-dependence. We present a comprehensive assessment of ECS state-dependence in Earth system models of intermediate complexity (EMICs) by analyzing millennial simulations with sustained 2×CO2 and 4×CO2 forcings. We compare different extrapolation methods and show that ECS is smaller in the higher-forcing scenario in 12 out of 15 EMICs, in contrast to the opposite behavior reported from GCMs. In one such EMIC, the Bern3D-LPX model, this state-dependence is mainly due to the weakening sea ice-albedo feedback in the Southern Ocean, which depends on model configuration. Due to ocean-mixing adjustments, state-dependence is only detected hundreds of years after the abrupt forcing, highlighting the need for long model integrations. Adjustments to feedback parametrizations of EMICs may be necessary if GCM intercomparisons confirm an opposite state-dependence.

Selective maintenance of multi-state systems with structural dependence

International Nuclear Information System (INIS)

Dao, Cuong D.; Zuo, Ming J.

2017-01-01

This paper studies the selective maintenance problem for multi-state systems with structural dependence. Each component can be in one of multiple working levels and several maintenance actions are possible to a component in a maintenance break. The components structurally form multiple hierarchical levels and dependence groups. A directed graph is used to represent the precedence relations of components in the system. A selective maintenance optimization model is developed to maximize the system reliability in the next mission under time and cost constraints. A backward search algorithm is used to determine the assembly sequence for a selective maintenance scenario. The maintenance model helps maintenance managers in determining the best combination of maintenance activities to maximize the probability of successfully completing the next mission. Examples showing the use of the proposed method are presented. - Highlights: • A selective maintenance model for multi-state systems is proposed considering both economic and structural dependence. • Structural dependence is modeled as precedence relationship when disassembling components for maintenance. • Resources for disassembly and maintenance are evaluated using a backward search algorithm. • Maintenance strategies with and without structural dependence are analyzed. • Ignoring structural dependence may lead to over-estimation of system reliability.

State-Dependent Impulsive Control Strategies for a Tumor-Immune Model

Directory of Open Access Journals (Sweden)

Kwang Su Kim

2016-01-01

Full Text Available Controlling the number of tumor cells leads us to expect more efficient strategies for treatment of tumor. Towards this goal, a tumor-immune model with state-dependent impulsive treatments is established. This model may give an efficient treatment schedule to control tumor’s abnormal growth. By using the Poincaré map and analogue of Poincaré criterion, some conditions for the existence and stability of a positive order-1 periodic solution of this model are obtained. Moreover, we carry out numerical simulations to illustrate the feasibility of our main results and compare fixed-time impulsive treatment effects with state-dependent impulsive treatment effects. The results of our simulations say that, in determining optimal treatment timing, the model with state-dependent impulsive control is more efficient than that with fixed-time impulsive control.

Oxidant-Dependent Thermoelectric Properties of Undoped ZnO Films by Atomic Layer Deposition

KAUST Repository

Kim, Hyunho

2017-02-27

Extraordinary oxidant-dependent changes in the thermoelectric properties of undoped ZnO thin films deposited by atomic layer deposition (ALD) have been observed. Specifically, deionized water and ozone oxidants are used in the growth of ZnO by ALD using diethylzinc as a zinc precursor. No substitutional atoms have been added to the ZnO films. By using ozone as an oxidant instead of water, a thermoelectric power factor (σS) of 5.76 × 10 W m K is obtained at 705 K for undoped ZnO films. In contrast, the maximum power factor for the water-based ZnO film is only 2.89 × 10 W m K at 746 K. Materials analysis results indicate that the oxygen vacancy levels in the water- and ozone-grown ZnO films are essentially the same, but the difference comes from Zn-related defects present in the ZnO films. The data suggest that the strong oxidant effect on thermoelectric performance can be explained by a mechanism involving point defect-induced differences in carrier concentration between these two oxides and a self-compensation effect in water-based ZnO due to the competitive formations of both oxygen and zinc vacancies. This strong oxidant effect on the thermoelectric properties of undoped ZnO films provides a pathway to improve the thermoelectric performance of this important material.

High pressure Moessbauer spectroscopy of perovskite iron oxide

International Nuclear Information System (INIS)

Nasu, Saburo; Suenaga, Tomoya; Morimoto, Shotaro; Kawakami, Takateru; Kuzushita, Kaori; Takano, Mikio

2003-01-01

High-pressure 57 Fe Moessbauer spectroscopy using a diamond anvil cell has been performed for perovskite iron oxides SrFeO 3 , CaFeO 3 and La 1/3 Sr 2/3 O 3 . The charge states and the magnetic dependency to pressure were determined. Pressure magnetic phase diagrams of these perovskite iron oxides are determined up to about 70 GPa. To be clear the magnetic ordered state, they are measured up to 7.8 T external magnetic fields at 4.5K. The phase transition of these perovskite oxides to ferromagnetisms with high magnetic ordered temperature is observed. In higher pressure, high spin-low spin transition of oxides besides CaFeO 3 is generated. The feature of Moessbauer spectroscopy, perovskite iron oxide and Moessbauer spectroscopy under high pressure are explained. (S.Y.)

Cyclic AMP Regulates Bacterial Persistence through Repression of the Oxidative Stress Response and SOS-Dependent DNA Repair in Uropathogenic Escherichia coli.

Science.gov (United States)

Molina-Quiroz, Roberto C; Silva-Valenzuela, Cecilia; Brewster, Jennifer; Castro-Nallar, Eduardo; Levy, Stuart B; Camilli, Andrew

2018-01-09

Bacterial persistence is a transient, nonheritable physiological state that provides tolerance to bactericidal antibiotics. The stringent response, toxin-antitoxin modules, and stochastic processes, among other mechanisms, play roles in this phenomenon. How persistence is regulated is relatively ill defined. Here we show that cyclic AMP, a global regulator of carbon catabolism and other core processes, is a negative regulator of bacterial persistence in uropathogenic Escherichia coli , as measured by survival after exposure to a β-lactam antibiotic. This phenotype is regulated by a set of genes leading to an oxidative stress response and SOS-dependent DNA repair. Thus, persister cells tolerant to cell wall-acting antibiotics must cope with oxidative stress and DNA damage and these processes are regulated by cyclic AMP in uropathogenic E. coli IMPORTANCE Bacterial persister cells are important in relapsing infections in patients treated with antibiotics and also in the emergence of antibiotic resistance. Our results show that in uropathogenic E. coli , the second messenger cyclic AMP negatively regulates persister cell formation, since in its absence much more persister cells form that are tolerant to β-lactams antibiotics. We reveal the mechanism to be decreased levels of reactive oxygen species, specifically hydroxyl radicals, and SOS-dependent DNA repair. Our findings suggest that the oxidative stress response and DNA repair are relevant pathways to target in the design of persister-specific antibiotic compounds. Copyright © 2018 Molina-Quiroz et al.

Comprehensive mechanism and structure-sensitivity of ethanol oxidation on platinum: new transition-state searching method for resolving the complex reaction network.

Science.gov (United States)

Wang, Hui-Fang; Liu, Zhi-Pan

2008-08-20

Ethanol oxidation on Pt is a typical multistep and multiselectivity heterogeneous catalytic process. A comprehensive understanding of this fundamental reaction would greatly benefit design of catalysts for use in direct ethanol fuel cells and the degradation of biomass-derived oxygenates. In this work, the reaction network of ethanol oxidation on different Pt surfaces, including close-packed Pt{111}, stepped Pt{211}, and open Pt{100}, is explored thoroughly with an efficient reaction path searching method, which integrates our new transition-state searching technique with periodic density functional theory calculations. Our new technique enables the location of the transition state and saddle points for most surface reactions simply and efficiently by optimization of local minima. We show that the selectivity of ethanol oxidation on Pt depends markedly on the surface structure, which can be attributed to the structure-sensitivity of two key reaction steps: (i) the initial dehydrogenation of ethanol and (ii) the oxidation of acetyl (CH3CO). On open surface sites, ethanol prefers C-C bond cleavage via strongly adsorbed intermediates (CH2CO or CHCO), which leads to complete oxidation to CO2. However, only partial oxidizations to CH3CHO and CH3COOH occur on Pt{111}. Our mechanism points out that the open surface Pt{100} is the best facet to fully oxidize ethanol at low coverages, which sheds light on the origin of the remarkable catalytic performance of Pt tetrahexahedra nanocrystals found recently. The physical origin of the structure-selectivity is rationalized in terms of both thermodynamics and kinetics. Two fundamental quantities that dictate the selectivity of ethanol oxidation are identified: (i) the ability of surface metal atoms to bond with unsaturated C-containing fragments and (ii) the relative stability of hydroxyl at surface atop sites with respect to other sites.

Electrochemistry and time dependent DFT study of a (vinylenedithio)-TTF derivative in different oxidation states

NARCIS (Netherlands)

Halpin, Yvonne; Schulz, Martin; Brooks, Andrew C.; Browne, Wesley R.; Wallis, John D.; Gonzalez, Leticia; Day, Peter; Vos, Johannes G.

2013-01-01

The electrochemical and spectroelectrochemical properties of a bis-pyrid-4-yl functionalised vinylenedithio-TFF derivative, 1, in solution are reported. The compound was immobilised on a Pt electrode and the resulting layers formed were investigated using electrochemical techniques. Two oxidation

Synthesis and characterization of ruthenium fluorides and oxide fluorides with high oxidation states

International Nuclear Information System (INIS)

Meublat, L.

1989-10-01

The synthesis of ruthenium fluorides and oxide fluorides with high oxidation states was attempted from dioxide RuO 2 and tetroxide RuO 4 . Three fluorinating agents were used: fluorine, chlorine trifluoride and krypton difluoride. The reactions were achieved in anhydrous hydrogen fluoride at room temperature. Thus, the reaction of RuO 4 with CIF 3 enabled us to prepare chloryl hexafluororuthenate (V), CIO 2 + RuF 6 - , a new compound well identified by vibrational spectroscopy (infra-red and Raman), the structure of which was determined. The reaction of KrF 2 with RuO 4 gave the oxide tetrafluoride RuOF 4 , the previously published syntheses and properties of which were not in agreement with each other. This compound was definitely characterized here by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. The product of thermal decomposition (70 0 C) of RuOF 4 is presumably RuF 4 since only oxygen is liberated during this decomposition. At last, the reaction of KrF 2 with RuO 2 probably leads to the formation of the new oxide fluoride RuO 2 F 4 . Indeed, no oxygen is given off during this reaction, the chemical analysis of the red-orange coloured solid residue is almost in agreement with the one proposed and its infra-red absorption spectrum indicates the presence of ruthenium-oxygen and ruthenium-terminal and bridging fluorine bonds [fr

Synthesis and characterization of ruthenium fluorides and oxide fluorides with high oxidation states

International Nuclear Information System (INIS)

Meublat, L.

1989-01-01

The synthesis of ruthenium fluorides and oxide fluorides with high oxidation states was attempted from dioxide RuO 2 and tetroxide RuO 4 . Three fluorinating agents were used: fluorine, chlorine trifluoride and krypton difluoride. The reactions were achieved in anhydrous hydrogen fluoride at room temperature. Thus, the reaction of RuO 4 with CIF 3 enabled us to prepare chloryl hexafluororuthenate (V), ClO 2 + RuF 6 - , a new compound well idendified by vibrational spectroscopy (infra-red and Raman), the structure of which was determined. The reaction of KrF 2 with RuO 4 gave the oxide tetrafluoride RuOF 4 , the previously published syntheses and properties of which were not in agreement with each other. This compound was definitely characterized here by chemical analysis, infra-red spectroscopy and X-ray powder diffraction. The product of thermal decomposition (70 0 C) of RuOF 4 is presumably RuF 4 since only oxygen is liberated during this decomposition. At last, the reaction of KrF 2 with RuO 2 probably leads to the formation of the new oxide fluoride RuO 2 F 4 . Indeed, no oxygen is given off during this reaction, the chemical analysis of the red-orange coloured solid residue is almost in agreement with the one proposed and its infra-red absorption spectrum indicates the presence of ruthenium-oxygen and ruthenium-terminal and bridging fluorine bonds [fr

Effect of state-dependent delay on a weakly damped nonlinear oscillator.

Science.gov (United States)

Mitchell, Jonathan L; Carr, Thomas W

2011-04-01

We consider a weakly damped nonlinear oscillator with state-dependent delay, which has applications in models for lasers, epidemics, and microparasites. More generally, the delay-differential equations considered are a predator-prey system where the delayed term is linear and represents the proliferation of the predator. We determine the critical value of the delay that causes the steady state to become unstable to periodic oscillations via a Hopf bifurcation. Using asymptotic averaging, we determine how the system's behavior is influenced by the functional form of the state-dependent delay. Specifically, we determine whether the branch of periodic solutions will be either sub- or supercritical as well as an accurate estimation of the amplitude. Finally, we choose a few examples of state-dependent delay to test our analytical results by comparing them to numerical continuation.

Chloride secretion induced by rotavirus is oxidative stress-dependent and inhibited by Saccharomyces boulardii in human enterocytes.

Science.gov (United States)

Buccigrossi, Vittoria; Laudiero, Gabriella; Russo, Carla; Miele, Erasmo; Sofia, Morena; Monini, Marina; Ruggeri, Franco Maria; Guarino, Alfredo

2014-01-01

Rotavirus (RV) infection causes watery diarrhea via multiple mechanisms, primarily chloride secretion in intestinal epithelial cell. The chloride secretion largely depends on non-structural protein 4 (NSP4) enterotoxic activity in human enterocytes through mechanisms that have not been defined. Redox imbalance is a common event in cells infected by viruses, but the role of oxidative stress in RV infection is unknown. RV SA11 induced chloride secretion in association with an increase in reactive oxygen species (ROS) in Caco-2 cells. The ratio between reduced (GSH) and oxidized (GSSG) glutathione was decreased by RV. The same effects were observed when purified NSP4 was added to Caco-2 cells. N-acetylcysteine (NAC), a potent antioxidant, strongly inhibited the increase in ROS and GSH imbalance. These results suggest a link between oxidative stress and RV-induced diarrhea. Because Saccharomyces boulardii (Sb) has been effectively used to treat RV diarrhea, we tested its effects on RV-infected cells. Sb supernatant prevented RV-induced oxidative stress and strongly inhibited chloride secretion in Caco-2 cells. These results were confirmed in an organ culture model using human intestinal biopsies, demonstrating that chloride secretion induced by RV-NSP4 is oxidative stress-dependent and is inhibited by Sb, which produces soluble metabolites that prevent oxidative stress. The results of this study provide novel insights into RV-induced diarrhea and the efficacy of probiotics.

Cocaine induces state-dependent learning of sexual conditioning in male Japanese quail.

Science.gov (United States)

Gill, Karin E; Rice, Beth Ann; Akins, Chana K

2015-01-01

State dependent learning effects have been widely studied in a variety of drugs of abuse. However, they have yet to be studied in relation to sexual motivation. The current study investigated state-dependent learning effects of cocaine in male Japanese quail (Coturnix japonica) using a sexual conditioning paradigm. Cocaine-induced state-dependent learning effects were investigated using a 2×2 factorial design with training state as one factor and test state as the other factor. During a 14-day training phase, male quail were injected once daily with 10mg/kg cocaine or saline and then placed in a test chamber after 15min. In the test chamber, sexual conditioning trials consisted of presentation of a light conditioned stimulus (CS) followed by sexual reinforcement. During the state dependent test, half of the birds received a shift in drug state from training to testing (Coc→Sal or Sal→Coc) while the other half remained in the same drug state (Coc→Coc or Sal→Sal). Results showed that male quail that were trained and tested in the same state (Coc→Coc or Sal→Sal) showed greater sexual conditioning than male quail that were trained and tested in different states (Sal→Coc) except when cocaine was administered chronically prior to the test (Coc→Sal). For the latter condition, sexual conditioning persisted from cocaine training to the saline test. The findings suggest that state dependent effects may alter sexual motivation and that repeated exposure to cocaine during sexual activity may increase sexual motivation which, in turn, may lead to high risk sexual activities. An alternative explanation for the findings is also discussed. Copyright © 2014 Elsevier Inc. All rights reserved.

Technical test description of activities to determine the potential for spent fuel oxidation in a tuff repository

International Nuclear Information System (INIS)

Einziger, R.E.

1985-06-01

The potential change in the oxidation state of spent fuel during its residence in a repository must be known to evaluate its radionuclide retention capabilities. Once the container breaches, the spent fuel in a repository sited above the water table will be exposed to a moist air atmosphere at low temperatures. Thermodynamically, there is no reason why the fuel should not oxidize to a higher oxidation state under these conditions, given enough time. Depending on the rate of oxidation, higher oxides with potentially higher leach rates may eventually form or the cladding may even split open. If either of these oxidation effects occurs, the ability of spent fuel to retard radionuclide migration will be reduced. A technical test description is presented to study spent fuel oxidation at low temperatures characteristic of the post-container breach period and at high temperatures in a moist inert atmosphere characteristic of a sealed container with waterlogged fuel, early in the repository life. The approach taken will be to perform tests and evaluations to gain understanding of the operative oxidation mechanisms, to obtain oxidation rate data, and to make projections of potential long-term fuel oxidation states. Time and temperature dependence of existing models will be evaluated, and the dependence of the model projections on fuel variables will be determined. 27 refs., 7 figs., 4 tabs

Volume dependence of N-body bound states

Science.gov (United States)

König, Sebastian; Lee, Dean

2018-04-01

We derive the finite-volume correction to the binding energy of an N-particle quantum bound state in a cubic periodic volume. Our results are applicable to bound states with arbitrary composition and total angular momentum, and in any number of spatial dimensions. The only assumptions are that the interactions have finite range. The finite-volume correction is a sum of contributions from all possible breakup channels. In the case where the separation is into two bound clusters, our result gives the leading volume dependence up to exponentially small corrections. If the separation is into three or more clusters, there is a power-law factor that is beyond the scope of this work, however our result again determines the leading exponential dependence. We also present two independent methods that use finite-volume data to determine asymptotic normalization coefficients. The coefficients are useful to determine low-energy capture reactions into weakly bound states relevant for nuclear astrophysics. Using the techniques introduced here, one can even extract the infinite-volume energy limit using data from a single-volume calculation. The derived relations are tested using several exactly solvable systems and numerical examples. We anticipate immediate applications to lattice calculations of hadronic, nuclear, and cold atomic systems.

Evolution of the Oxidation State of the Earth's Mantle

Science.gov (United States)

Danielson, L. R.; Righter, K.; Keller, L.; Christoffersen, E.; Rahman, Z.

2015-01-01

The oxidation state of the Earth's mantle during formation remains an unresolved question, whether it was constant throughout planetary accretion, transitioned from reduced to oxidized, or from oxidized to reduced. We investigate the stability of Fe3(+) at depth, in order to constrain processes (water, late accretion, dissociation of FeO) which may reduce or oxidize the Earth's mantle. In our previous experiments on shergottite compositions, variable fO2, T, and P less than 4 GPa, Fe3(+)/sigma Fe decreased slightly with increasing P, similar to terrestrial basalt. For oxidizing experiments less than 7GPa, Fe3(+)/sigma Fe decreased as well, but it's unclear from previous modelling whether the deeper mantle could retain significant Fe3(+). Our current experiments expand our pressure range deeper into the Earth's mantle and focus on compositions and conditions relevant to the early Earth. Preliminary multi-anvil experiments with Knippa basalt as the starting composition were conducted at 5-7 GPa and 1800 C, using a molybdenum capsule to set the fO2 near IW, by buffering with Mo-MoO3. TEM and EELS analyses revealed the run products quenched to polycrystalline phases, with the major phase pyroxene containing approximately equal to Fe3(+)/2(+). Experiments are underway to produce glassy samples that can be measured by EELS and XANES, and are conducted at higher pressures.

Hydrophobic matrix-free graphene-oxide composites with isotropic and nematic states

Science.gov (United States)

Wåhlander, Martin; Nilsson, Fritjof; Carlmark, Anna; Gedde, Ulf W.; Edmondson, Steve; Malmström, Eva

2016-08-01

We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been immobilised on anionic GO and subsequently grafted with hydrophobic polymer grafts. Dense grafts of PBA, PBMA and PMMA with a wide range of average graft lengths (MW: 1-440 kDa) were polymerised by surface-initiated controlled radical precipitation polymerisation from the statistical MI. The surface modification is designed similarly to bimodal graft systems, where the cationic MI generates nanoparticle repulsion, similar to dense short grafts, while the long grafts offer miscibility in non-polar environments and cohesion. The state-of-the-art dispersions of grafted GO were in the isotropic state. Transparent and translucent matrix-free GO-composites could be melt-processed directly using only grafted GO. After processing, birefringence due to nematic alignment of grafted GO was observed as a single giant Maltese cross, 3.4 cm across. Permeability models for composites containing aligned 2D-fillers were developed, which were compared with the experimental oxygen permeability data and found to be consistent with isotropic or nematic states. The storage modulus of the matrix-free GO-composites increased with GO content (50% increase at 0.67 wt%), while the significant increases in the thermal stability (up to 130 °C) and the glass transition temperature (up to 17 °C) were dependent on graft length. The tuneable matrix-free GO-composites with rapid thermo-responsive shape-memory effects are promising candidates for a vast range of applications, especially selective membranes and sensors.We demonstrate a novel route to synthesise hydrophobic matrix-free composites of polymer-grafted graphene oxide (GO) showing isotropic or nematic alignment and shape-memory effects. For the first time, a cationic macroinitiator (MI) has been

Solid state solubility of copper oxides in hydroxyapatite

Science.gov (United States)

Zykin, Mikhail A.; Vasiliev, Alexander V.; Trusov, Lev A.; Dinnebier, Robert E.; Jansen, Martin; Kazin, Pavel E.

2018-06-01

Samples containing copper oxide doped hydroxyapatite with the composition Ca10(PO4)6(CuxOH1-x-δ)2, x = 0.054 - 0.582, in the mixture with CuO/Cu2O were prepared by a solid-state high-temperature treatment at varying annealing temperatures and at different partial water vapor and oxygen pressures. The crystal structures of the apatite compounds were refined using powder X-ray diffraction patterns and the content of copper ions x in the apatite was determined. Copper ions enter exclusively into the apatite trigonal channels formally substituting protons of OH-groups and the hexagonal cell parameters grow approximately linearly with x, the channel volume mostly expanding while the remaining volume of the crystal lattice changing only slightly. The equilibrium copper content in the apatite increases drastically, by almost a factor of 10 with the annealing temperature rising from 800° to 1200°C. The reduction of the water partial pressure leads to a further increase of x, while the dependence of x on the oxygen partial pressure exhibits a maximum. The observed relations are consistent with the proposed chemical reactions implying the copper introduction is followed by the release of a considerable quantity of gaseous products - water and oxygen. The analysis of interatomic distances suggests that the maximum content of copper ions in the channel cannot exceed 2/3.

Arsenic (+3 oxidation state) methyltransferase and the inorganic arsenic methylation phenotype

International Nuclear Information System (INIS)

Li Jiaxin; Waters, Stephen B.; Drobna, Zuzana; Devesa, Vicenta; Styblo, Miroslav; Thomas, David J.

2005-01-01

Inorganic arsenic is enzymatically methylated; hence, its ingestion results in exposure to the parent compound and various methylated arsenicals. Both experimental and epidemiological evidences suggest that some of the adverse health effects associated with chronic exposure to inorganic arsenic may be mediated by these methylated metabolites. If i As methylation is an activation process, then the phenotype for inorganic arsenic methylation may determine risk associated with exposure to this metalloid. We examined inorganic arsenic methylation phenotypes and arsenic (+3 oxidation state) methyltransferase genotypes in four species: three that methylate inorganic arsenic (human (Homo sapiens), rat (Rattus norwegicus), and mouse (Mus musculus)) and one that does not methylate inorganic arsenic (chimpanzee, Pan troglodytes). The predicted protein products from arsenic (+3 oxidation state) methyltransferase are similar in size for rat (369 amino acid residues), mouse (376 residues), and human (375 residues). By comparison, a 275-nucleotide deletion beginning at nucleotide 612 in the chimpanzee gene sequence causes a frameshift that leads to a nonsense mutation for a premature stop codon after amino acid 205. The null phenotype for inorganic arsenic methylation in the chimpanzee is likely due to the deletion in the gene for arsenic (+3 oxidation state) methyltransferase that yields an inactive truncated protein. This lineage-specific loss of function caused by the deletion event must have occurred in the Pan lineage after Homo-Pan divergence about 5 million years ago

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

Science.gov (United States)

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

2015-01-01

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

On matrix stabilisation of d- and f-transition metal ions in unstable oxidation states

Energy Technology Data Exchange (ETDEWEB)

Kiselev, Yurii M [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation)

2009-01-31

The state-of-the-art in matrix stabilisation of d- and f-transition metal ions in unstable oxidation states is analysed. Main aspects of this problem concerning the genealogy of appropriate matrix systems are classified. Relevant examples are given and the data that contradict the scheme proposed are discussed. The thermodynamics of the matrix stabilisation effect is considered using the concept of isomorphic miscibility. The influence of defects and non-equilibrium on the matrix stabilisation effect is discussed. The problem of identification of the oxidation states in matrix systems is examined and various types of matrix systems are considered.

On matrix stabilisation of d- and f-transition metal ions in unstable oxidation states

International Nuclear Information System (INIS)

Kiselev, Yurii M

2009-01-01

The state-of-the-art in matrix stabilisation of d- and f-transition metal ions in unstable oxidation states is analysed. Main aspects of this problem concerning the genealogy of appropriate matrix systems are classified. Relevant examples are given and the data that contradict the scheme proposed are discussed. The thermodynamics of the matrix stabilisation effect is considered using the concept of isomorphic miscibility. The influence of defects and non-equilibrium on the matrix stabilisation effect is discussed. The problem of identification of the oxidation states in matrix systems is examined and various types of matrix systems are considered.

Temperature Dependence of the Seebeck Coefficient in Zinc Oxide Thin Films

Science.gov (United States)

Noori, Amirreza; Masoumi, Saeed; Hashemi, Najmeh

2017-12-01

Thermoelectric devices are reliable tools for converting waste heat into electricity as they last long, produce no noise or vibration, have no moving elements, and their light weight makes them suitable for the outer space usage. Materials with high thermoelectric figure of merit (zT) have the most important role in the fabrication of efficient thermoelectric devices. Metal oxide semiconductors, specially zinc oxide has recently received attention as a material suitable for sensor, optoelectronic and thermoelectric device applications because of their wide direct bandgap, chemical stability, high-energy radiation endurance, transparency and acceptable zT. Understanding the thermoelectric properties of the undoped ZnO thin films can help design better ZnO-based devices. Here, we report the results of our experimental work on the thermoelectric properties of the undoped polycrystalline ZnO thin films. These films are deposited on alumina substrates by thermal evaporation of zinc in vacuum followed by a controlled oxidation process in air carried out at the 350-500 °C temperature range. The experimental setup including gradient heaters, thermometry system and Seebeck voltage measurement equipment for high resistance samples is described. Seebeck voltage and electrical resistivity of the samples are measured at different conditions. The observed temperature dependence of the Seebeck coefficient is discussed.

Humidity-dependent phase state of SOA particles from biogenic and anthropogenic precursors

Directory of Open Access Journals (Sweden)

E. Saukko

2012-08-01

Full Text Available The physical phase state (solid, semi-solid, or liquid of secondary organic aerosol (SOA particles has important implications for a number of atmospheric processes. We report the phase state of SOA particles spanning a wide range of oxygen to carbon ratios (O / C, used here as a surrogate for SOA oxidation level, produced in a flow tube reactor by photo-oxidation of various atmospherically relevant surrogate anthropogenic and biogenic volatile organic compounds (VOCs. The phase state of laboratory-generated SOA was determined by the particle bounce behavior after inertial impaction on a polished steel substrate. The measured bounce fraction was evaluated as a function of relative humidity and SOA oxidation level (O / C measured by an Aerodyne high resolution time of flight aerosol mass spectrometer (HR-ToF AMS.

The main findings of the study are: (1 biogenic and anthropogenic SOA particles are found to be amorphous solid or semi-solid based on the measured bounced fraction (BF, which was typically higher than 0.6 on a 0 to 1 scale. A decrease in the BF is observed for most systems after the SOA is exposed to relative humidity of at least 80% RH, corresponding to a RH at impaction of 55%. (2 Long-chain alkanes have a low BF (indicating a "liquid-like", less viscous phase particles at low oxidation levels (BF < 0.2 ± 0.05 for O / C = 0.1. However, BF increases substantially upon increasing oxidation. (3 Increasing the concentration of sulphuric acid (H₂SO₄ in solid SOA particles (here tested for longifolene SOA causes a decrease in BF levels. (4 In the majority of cases the bounce behavior of the various SOA systems did not show correlation with the particle O / C. Rather, the molar mass of the gas-phase VOC precursor showed a positive correlation with the resistance to the RH-induced phase change of the formed SOA particles.

l-dependent potential barriers and superdeformed states

International Nuclear Information System (INIS)

Gherghescu, R.A.; Royer, G.

1999-01-01

The macroscopic-microscopic energy of rotating nuclei moving in the fusion-like deformation valley has been determined within a generalized liquid drop model including the nuclear proximity energy, the two-center shell model and the Strutinsky method. The l-dependent potential barriers of the 84 Zr, 132 Ce, 152 Dy and 192 Hg nuclei have been determined. A first minimum having a pure microscopic origin and lodging the normally deformed states, progressively disappears with increasing angular momenta. The microscopic and macroscopic energies contribute to generate a second minimum where superdeformed states may survive. It becomes progressively the lowest one at intermediate spins. At still higher angular momenta, the minimum moves towards the foot of the external fission barrier leading to macroscopic hyper-deformed quasi-molecular states. (authors)

Puerarin activates endothelial nitric oxide synthase through estrogen receptor-dependent PI3-kinase and calcium-dependent AMP-activated protein kinase

International Nuclear Information System (INIS)

Hwang, Yong Pil; Kim, Hyung Gyun; Hien, Tran Thi; Jeong, Myung Ho; Jeong, Tae Cheon; Jeong, Hye Gwang

2011-01-01

The cardioprotective properties of puerarin, a natural product, have been attributed to the endothelial nitric oxide synthase (eNOS)-mediated production of nitric oxide (NO) in EA.hy926 endothelial cells. However, the mechanism by which puerarin activates eNOS remains unclear. In this study, we sought to identify the intracellular pathways underlying eNOS activation by puerarin. Puerarin induced the activating phosphorylation of eNOS on Ser1177 and the production of NO in EA.hy926 cells. Puerarin-induced eNOS phosphorylation required estrogen receptor (ER)-mediated phosphatidylinositol 3-kinase (PI3K)/Akt signaling and was reversed by AMP-activated protein kinase (AMPK) and calcium/calmodulin-dependent kinase II (CaMKII) inhibition. Importantly, puerarin inhibited the adhesion of tumor necrosis factor (TNF)-α-stimulated monocytes to endothelial cells and suppressed the TNF-α induced expression of intercellular cell adhesion molecule-1. Puerarin also inhibited the TNF-α-induced nuclear factor-κB activation, which was attenuated by pretreatment with N G -nitro-L-arginine methyl ester, a NOS inhibitor. These results indicate that puerarin stimulates eNOS phosphorylation and NO production via activation of an estrogen receptor-mediated PI3K/Akt- and CaMKII/AMPK-dependent pathway. Puerarin may be useful for the treatment or prevention of endothelial dysfunction associated with diabetes and cardiovascular disease. -- Highlights: ► Puerarin induced the phosphorylation of eNOS and the production of NO. ► Puerarin activated eNOS through ER-dependent PI3-kinase and Ca 2+ -dependent AMPK. ► Puerarin-induced NO was involved in the inhibition of NF-kB activation. ► Puerarin may help for prevention of vascular dysfunction and diabetes.

Facile solid-state synthesis of oxidation-resistant metal nanoparticles at ambient conditions

Science.gov (United States)

Lee, Kyu Hyung; Jung, Hyuk Joon; Lee, Ju Hee; Kim, Kyungtae; Lee, Byeongno; Nam, Dohyun; Kim, Chung Man; Jung, Myung-Hwa; Hur, Nam Hwi

2018-05-01

A simple and scalable method for the synthesis of metal nanoparticles in the solid-state was developed, which can produce nanoparticles in the absence of solvents. Nanoparticles of coinage metals were synthesized by grinding solid hydrazine and the metal precursors in their acetates and oxides at 25 °C. The silver and gold acetates converted completely within 6 min into Ag and Au nanoparticles, respectively, while complete conversion of the copper acetate to the Cu sub-micrometer particles took about 2 h. Metal oxide precursors were also converted into metal nanoparticles by grinding alone. The resulting particles exhibit distinctive crystalline lattice fringes, indicating the formation of highly crystalline phases. The Cu sub-micrometer particles are better resistant to oxidation and exhibit higher conductivity compared to conventional Cu nanoparticles. This solid-state method was also applied for the synthesis of platinum group metals and intermetallic Cu3Au, which can be further extended to synthesize other metal nanoparticles.

Generalized trends in the formation energies of perovskite oxides.

Science.gov (United States)

Zeng, ZhenHua; Calle-Vallejo, Federico; Mogensen, Mogens B; Rossmeisl, Jan

2013-05-28

Generalized trends in the formation energies of several families of perovskite oxides (ABO3) and plausible explanations to their existence are provided in this study through a combination of DFT calculations, solid-state physics analyses and simple physical/chemical descriptors. The studied elements at the A site of perovskites comprise rare-earth, alkaline-earth and alkaline metals, whereas 3d and 5d metals were studied at the B site. We also include ReO3-type compounds, which have the same crystal structure of cubic ABO3 perovskites except without A-site elements. From the observations we extract the following four conclusions for the perovskites studied in the present paper: for a given cation at the B site, (I) perovskites with cations of identical oxidation state at the A site possess close formation energies; and (II) perovskites with cations of different oxidation states at the A site usually have quite different but ordered formation energies. On the other hand, for a given A-site cation, (III) the formation energies of perovskites vary linearly with respect to the atomic number of the elements at the B site within the same period of the periodic table, and the slopes depend systematically on the oxidation state of the A-site cation; and (IV) the trends in formation energies of perovskites with elements from different periods at the B site depend on the oxidation state of A-site cations. Since the energetics of perovskites is shown to be the superposition of the individual contributions of their constituent oxides, the trends can be rationalized in terms of A-O and B-O interactions in the ionic crystal. These findings reveal the existence of general systematic trends in the formation energies of perovskites and provide further insight into the role of ion-ion interactions in the properties of ternary compounds.

Endothelium derived nitric oxide synthase negatively regulates the PDGF-survivin pathway during flow-dependent vascular remodeling.

Directory of Open Access Journals (Sweden)

Jun Yu

Full Text Available Chronic alterations in blood flow initiate structural changes in vessel lumen caliber to normalize shear stress. The loss of endothelial derived nitric oxide synthase (eNOS in mice promotes abnormal flow dependent vascular remodeling, thus uncoupling mechanotransduction from adaptive vascular remodeling. However, the mechanisms of how the loss of eNOS promotes abnormal remodeling are not known. Here we show that abnormal flow-dependent remodeling in eNOS knockout mice (eNOS (-/- is associated with activation of the platelet derived growth factor (PDGF signaling pathway leading to the induction of the inhibitor of apoptosis, survivin. Interfering with PDGF signaling or survivin function corrects the abnormal remodeling seen in eNOS (-/- mice. Moreover, nitric oxide (NO negatively regulates PDGF driven survivin expression and cellular proliferation in cultured vascular smooth muscle cells. Collectively, our data suggests that eNOS negatively regulates the PDGF-survivin axis to maintain proportional flow-dependent luminal remodeling and vascular quiescence.

The impact of new evidence on state-of-knowledge dependence

International Nuclear Information System (INIS)

Haim, M.; Apostolakis, G.

1987-01-01

When modeling a SOK (state-of-knowledge) dependence it is sometimes essential to apply a multivariate SOK distribution, e.g. when a new evidence is used to update a current assessment. As shown a SOK dependence may arise due to updating a prior distribution by dependent test-results. In two specific extreme cases SOK dependence (independence) cannot be influenced by updating the prior by new evidence: the case of identical units (a complete dependence), the case of independence (i.e., no SOK dependence) and evidence consists of conditionally independent test-results. (orig./HP)

The Sr2.75Ce0.25Co2O7-δ oxide, n=2 member of the Ruddlesden-Popper series: Structural and magnetic evolution depending on oxygen stoichiometry

International Nuclear Information System (INIS)

Demont, A.; Hebert, S.; Pelloquin, D.; Maignan, A.

2008-01-01

The second member of the Ruddlesden-Popper series, n=2 in Sr n+1 Co n O 3n+1 , has been stabilized by substituting cerium for strontium leading to the pure compound Sr 2.75 Ce 0.25 Co 2 O 7-δ . The oxygen vacancies of this phase can be partially filled by a post-annealing oxidizing treatment with δ decreasing from 1.1 to 0.3 for the as-prepared and oxidized phases, respectively. As the samples are oxidized from δ∼1.1 to 0.3, the a and b unit cell parameters decrease from 3.836 to 3.815 A and from 20.453 to 20.047 A, respectively. Despite the average value of the cobalt valence state, V Co ∼+3.5, obtained in the oxidized Sr 2.75 Ce +4 0.25 Co 2 O 6.7 phase, a clear ferromagnetic state wit T C =175 K and M S =0.8 μB/Co is reached. - Graphical abstract: Temperature dependence of the magnetic susceptibility of as-prepared and PO 2 annealing Sr 2.75 Ce 0.25 Co 2 O 7-δ RP2-type structures

Nitrate-dependent iron oxidation limits iron transport in anoxic ocean regions

Science.gov (United States)

Scholz, Florian; Löscher, Carolin R.; Fiskal, Annika; Sommer, Stefan; Hensen, Christian; Lomnitz, Ulrike; Wuttig, Kathrin; Göttlicher, Jörg; Kossel, Elke; Steininger, Ralph; Canfield, Donald E.

2016-11-01

Iron is an essential element for life on Earth and limits primary production in large parts of the ocean. Oxygen-free continental margin sediments represent an important source of bioavailable iron to the ocean, yet little of the iron released from the seabed reaches the productive sea surface. Even in the anoxic water of oxygen minimum zones, where iron solubility should be enhanced, most of the iron is rapidly re-precipitated. To constrain the mechanism(s) of iron removal in anoxic ocean regions we explored the sediment and water in the oxygen minimum zone off Peru. During our sampling campaign the water column featured two distinct redox boundaries separating oxic from nitrate-reducing (i.e., nitrogenous) water and nitrogenous from weakly sulfidic water. The sulfidic water mass in contact with the shelf sediment contained elevated iron concentrations >300 nM. At the boundary between sulfidic and nitrogenous conditions, iron concentrations dropped sharply to <20 nM coincident with a maximum in particulate iron concentration. Within the iron gradient, we found an increased expression of the key functional marker gene for nitrate reduction (narG). Part of this upregulation was related to the activity of known iron-oxidizing bacteria. Collectively, our data suggest that iron oxidation and removal is induced by nitrate-reducing microbes, either enzymatically through anaerobic iron oxidation or by providing nitrite for an abiotic reaction. Given the important role that iron plays in nitrogen fixation, photosynthesis and respiration, nitrate-dependent iron oxidation likely represents a key-link between the marine biogeochemical cycles of nitrogen, oxygen and carbon.

Electronic structure of the amorphous oxide semiconductor a-InGaZnO4-x: Tauc-Lorentz optical model and origins of subgap states

International Nuclear Information System (INIS)

Kamiya, Toshio; Nomura, Kenji; Hosono, Hideo

2009-01-01

This paper discusses an optical model and subgap electronic states for a representative amorphous oxide semiconductor, InGaZnO 4 (a-IGZO). Parameterized optical models were developed based on the Tauc-Lorentz model combined with a Lorentz-type oscillator. The measured optical absorption spectra exhibit nearly linear dependences on photon energy (E) between 3 eV 0,TL ) being around 4 eV. The optimized parameters for the fixed E 0,TL of 3.7 eV are provided for four different a-IGZO films with root-mean-square errors less than 1%. Formation energies of crystalline IGZO, stoichiometric a-IGZO, oxygen deficient a-IGZO and their constituent oxides were calculated by the density functional theory using the local density approximation (LDA) and generalized gradient approximation with PBE96 functionals (PBE). PBE gives larger unit cell volumes at the ground states and better agreement in the formation energies than LDA does. The formation energies of an oxygen deficiency in a-IGZO were calculated to be 3.2-3.5 eV. The calculated electronic structures of stoichiometric a-IGZO models exhibit somewhat large dispersions for conduction bands (CB), which are not largely affected by the disordered structure in a-IGZO, while the dispersions of the valence bands (VBs) are very small, unlike the crystalline IGZO, showing that a-IGZO have strongly localized states at the VB maximums (VBMs). Oxygen-deficient a-IGZO models showed that oxygen deficiencies form both a deep localized state at 0.4-1 eV above VBM and a shallow donor state depending on local atomic configurations. An oxygen deficiency that forms a deep state breaks the dispersion of the CB, which could be an origin of the subgap states observed near CB. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Chloride secretion induced by rotavirus is oxidative stress-dependent and inhibited by Saccharomyces boulardii in human enterocytes.

Directory of Open Access Journals (Sweden)

Vittoria Buccigrossi

Full Text Available Rotavirus (RV infection causes watery diarrhea via multiple mechanisms, primarily chloride secretion in intestinal epithelial cell. The chloride secretion largely depends on non-structural protein 4 (NSP4 enterotoxic activity in human enterocytes through mechanisms that have not been defined. Redox imbalance is a common event in cells infected by viruses, but the role of oxidative stress in RV infection is unknown. RV SA11 induced chloride secretion in association with an increase in reactive oxygen species (ROS in Caco-2 cells. The ratio between reduced (GSH and oxidized (GSSG glutathione was decreased by RV. The same effects were observed when purified NSP4 was added to Caco-2 cells. N-acetylcysteine (NAC, a potent antioxidant, strongly inhibited the increase in ROS and GSH imbalance. These results suggest a link between oxidative stress and RV-induced diarrhea. Because Saccharomyces boulardii (Sb has been effectively used to treat RV diarrhea, we tested its effects on RV-infected cells. Sb supernatant prevented RV-induced oxidative stress and strongly inhibited chloride secretion in Caco-2 cells. These results were confirmed in an organ culture model using human intestinal biopsies, demonstrating that chloride secretion induced by RV-NSP4 is oxidative stress-dependent and is inhibited by Sb, which produces soluble metabolites that prevent oxidative stress. The results of this study provide novel insights into RV-induced diarrhea and the efficacy of probiotics.

State-dependent intrinsic predictability of cortical network dynamics.

Directory of Open Access Journals (Sweden)

Leila Fakhraei

Full Text Available The information encoded in cortical circuit dynamics is fleeting, changing from moment to moment as new input arrives and ongoing intracortical interactions progress. A combination of deterministic and stochastic biophysical mechanisms governs how cortical dynamics at one moment evolve from cortical dynamics in recently preceding moments. Such temporal continuity of cortical dynamics is fundamental to many aspects of cortex function but is not well understood. Here we study temporal continuity by attempting to predict cortical population dynamics (multisite local field potential based on its own recent history in somatosensory cortex of anesthetized rats and in a computational network-level model. We found that the intrinsic predictability of cortical dynamics was dependent on multiple factors including cortical state, synaptic inhibition, and how far into the future the prediction extends. By pharmacologically tuning synaptic inhibition, we obtained a continuum of cortical states with asynchronous population activity at one extreme and stronger, spatially extended synchrony at the other extreme. Intermediate between these extremes we observed evidence for a special regime of population dynamics called criticality. Predictability of the near future (10-100 ms increased as the cortical state was tuned from asynchronous to synchronous. Predictability of the more distant future (>1 s was generally poor, but, surprisingly, was higher for asynchronous states compared to synchronous states. These experimental results were confirmed in a computational network model of spiking excitatory and inhibitory neurons. Our findings demonstrate that determinism and predictability of network dynamics depend on cortical state and the time-scale of the dynamics.

Study of oxidation states of the transition metals in a series of Prussian blue analogs using x-ray absorption near edge structure (XANES) spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Adak, S. [Department of Physics, New Mexico State University, Las Cruces, NM, 88003 (United States); Hartl, M., E-mail: monika.hartl@esss.se [European Spallation Source ESS AB, 22100, Lund (Sweden); Manuel Lujan Jr. Neutron Scattering Center (LANSCE-LC), Los Alamos National Laboratory, Los Alamos, NM, 87545 (United States); Daemen, L. [Spallation Neutron Source, Oak Ridge National Laboratory, Oak Ridge, TN, 37830 (United States); Manuel Lujan Jr. Neutron Scattering Center (LANSCE-LC), Los Alamos National Laboratory, Los Alamos, NM, 87545 (United States); Fohtung, E.; Nakotte, H. [Department of Physics, New Mexico State University, Las Cruces, NM, 88003 (United States)

2017-01-15

Highlights: • Systematic XANES measurements on Prussian blue analogs shows oxidation state of transition metals. • Cobal-iron bimetallic hexacyanometallates show unexpected oxidation states. • Iron(II) ions in hexacyanometallates(III) show varying spin state depending on their bond to the “N” end or “C” end of the cyanide ligand. • Thermal expansion coefficients have been linked to the XANES results. - Abstract: There have been renewed interests in metal-organic framework classes of materials such as Prussian blue analogues (PBAs) due to their potential usage in energy storage applications. In particular, due to their high surface areas, controllable structures and excellent electrochemical properties, PBAs such as hexacyanometalates M{sup II}{sub 3}[A{sup III}(CN){sub 6}]{sub 2*}nH{sub 2}O (M = Mn, Fe, Co, Ni, Cu, Zn; A = Co, Fe, Cr; n = no. of water molecules present), M{sup II}{sub 2}[Fe{sup II}(CN){sub 6}]{sub 2*}nH{sub 2}O (M = Mn, Co, Ni, Cu, Zn) and mixed hexacyanometalates(III) (Fe{sub 1-x}Co{sub x}){sub 3}[B{sup III}(CN){sub 6}]{sub 2}·nH{sub 2}O (x = 0.25, 0.5, 0.75; B = Co, Fe) could have possible usage as a new class of cathode and even anode materials for rechargeable batteries. Detailed knowledge of the oxidation states of the transition metals in PBAs is required to improve efficiency and durability of such devices. Furthermore, a link between the thermal expansion observed in these materials and the oxidation state of the transition metal is of interest to synthesize materials with a desired thermal expansion behavior, Here we demonstrate the use of Synchrotron based X-ray absorption near-edge structure (XANES) spectra to identify transition metal oxidation states. Our analysis reveals the presence of divalent, trivalent and/or mixed valence transition metals in the materials as well as high-spin and low-spin complexes.

Arsenic K-edge X-ray absorption near-edge spectroscopy to determine oxidation states of arsenic of a coastal aquifer–aquitard system

International Nuclear Information System (INIS)

Wang, Ya; Jiao, Jiu Jimmy; Zhu, Sanyuan; Li, Yiliang

2013-01-01

Determination of oxidation states of solid-phase arsenic in bulk sediments is a valuable step in the evaluation of its bioavailability and environmental fate in deposits, but is difficult when the sediments have low arsenic contents and heterogeneous distribution of arsenic species. As K-edge X-ray absorption near-edge spectroscopy (XANES) was used to determine quantitatively the oxidation states of arsenic in sediments collected from different depths of boreholes in the Pearl River Delta, China, where the highest aquatic arsenic concentration is 161.4 μg/L, but the highest solid arsenic content only 39.6 mg/kg. The results demonstrated that XANES is efficient in determining arsenic oxidation states of the sediments with low arsenic contents and multiple arsenic species. The study on the high-resolution vertical variations of arsenic oxidation states also indicated that these states are influenced strongly by groundwater activities. With the help of geochemical data, solid arsenic speciation, toxicity and availability were further discussed. -- Highlights: •XANES is efficient in determining arsenic oxidation states of the bulk sediments. •Distribution of arsenic oxidation states is consistent with geochemical conditions. •Arsenic oxidation states are influenced strongly by groundwater activities. -- As K-edge X-ray absorption near-edge spectroscopy is efficient in determining arsenic oxidation states of the bulk sediments with low arsenic contents and heterogeneous distribution of arsenic species

Delay-distribution-dependent H∞ state estimation for delayed neural networks with (x,v)-dependent noises and fading channels.

Science.gov (United States)

Sheng, Li; Wang, Zidong; Tian, Engang; Alsaadi, Fuad E

2016-12-01

This paper deals with the H ∞ state estimation problem for a class of discrete-time neural networks with stochastic delays subject to state- and disturbance-dependent noises (also called (x,v)-dependent noises) and fading channels. The time-varying stochastic delay takes values on certain intervals with known probability distributions. The system measurement is transmitted through fading channels described by the Rice fading model. The aim of the addressed problem is to design a state estimator such that the estimation performance is guaranteed in the mean-square sense against admissible stochastic time-delays, stochastic noises as well as stochastic fading signals. By employing the stochastic analysis approach combined with the Kronecker product, several delay-distribution-dependent conditions are derived to ensure that the error dynamics of the neuron states is stochastically stable with prescribed H ∞ performance. Finally, a numerical example is provided to illustrate the effectiveness of the obtained results. Copyright © 2016 Elsevier Ltd. All rights reserved.

IEP as a parameter characterizing the pH-dependent surface charging of materials other than metal oxides.

Science.gov (United States)

Kosmulski, Marek

2012-01-01

The numerical values of points of zero charge (PZC, obtained by potentiometric titration) and of isoelectric points (IEP) of various materials reported in the literature have been analyzed. In sets of results reported for the same chemical compound (corresponding to certain chemical formula and crystallographic structure), the IEP are relatively consistent. In contrast, in materials other than metal oxides, the sets of PZC are inconsistent. In view of the inconsistence in the sets of PZC and of the discrepancies between PZC and IEP reported for the same material, it seems that IEP is more suitable than PZC as the unique number characterizing the pH-dependent surface charging of materials other than metal oxides. The present approach is opposite to the usual approach, in which the PZC and IEP are considered as two equally important parameters characterizing the pH-dependent surface charging of materials other than metal oxides. Copyright © 2012 Elsevier B.V. All rights reserved.

Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

Energy Technology Data Exchange (ETDEWEB)

Massachusetts Institute of Technology; Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.; Kessler, Sean H.; Canagaratna, Manjula R.; Wilson, Kevin R.; Altieri, Katye E.; Mazzoleni, Lynn R.; Wozniak, Andrew S.; Bluhm, Hendrik; Mysak, Erin R.; Smith, Jared D.; Kolb, Charles E.; Worsnop, Douglas R.

2010-11-05

A detailed understanding of the sources, transformations, and fates of organic species in the environment is crucial because of the central roles that organics play in human health, biogeochemical cycles, and Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state (OSC), a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of OSC , using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number (nC).

State-age-dependent maintenance policies for deteriorating systems with Erlang sojourn time distributions

International Nuclear Information System (INIS)

Yeh, R.H.

1997-01-01

This paper investigates state-age-dependent maintenance policies for multistate deteriorating systems with Erlang sojourn time distributions. Since Erlang distributions are serial combinations of exponential phases, the deteriorating process can be modeled by a multi-phase Markovian model and hence easily analyzed. Based on the Markovian model, the optimal phase-dependent inspection and replacement policy can be obtained by using a policy improvement algorithm. However, since phases are fictitious and can not be identified by inspections, two procedures are developed to construct state-age-dependent policies based on the optimal phase-dependent policy. The properties of the constructed state-age-dependent policies are further investigated and the performance of the policy is evaluated through a numerical example

Self-Employment Dynamics, State Dependence and Cross-Mobility Patterns

OpenAIRE

Caliendo, Marco; Uhlendorff, Arne

2008-01-01

This paper analyzes the mobility between self-employment, wage employment and non-employment. Using data for men in West Germany, we find strong true state dependence in all three states. Moreover, compared to wage employment, non-employment increases the probability of self-employment significantly, and self-employment goes along with a higher risk of future non-employment.

High pressure Moessbauer spectroscopy of perovskite iron oxide

CERN Document Server

Nasu, S; Morimoto, S; Kawakami, T; Kuzushita, K; Takano, M

2003-01-01

High-pressure sup 5 sup 7 Fe Moessbauer spectroscopy using a diamond anvil cell has been performed for perovskite iron oxides SrFeO sub 3 , CaFeO sub 3 and La sub 1 sub / sub 3 Sr sub 2 sub / sub 3 O sub 3. The charge states and the magnetic dependency to pressure were determined. Pressure magnetic phase diagrams of these perovskite iron oxides are determined up to about 70 GPa. To be clear the magnetic ordered state, they are measured up to 7.8 T external magnetic fields at 4.5K. The phase transition of these perovskite oxides to ferromagnetisms with high magnetic ordered temperature is observed. In higher pressure, high spin-low spin transition of oxides besides CaFeO sub 3 is generated. The feature of Moessbauer spectroscopy, perovskite iron oxide and Moessbauer spectroscopy under high pressure are explained. (S.Y.)

Near interface traps in SiO{sub 2}/4H-SiC metal-oxide-semiconductor field effect transistors monitored by temperature dependent gate current transient measurements

Energy Technology Data Exchange (ETDEWEB)

Fiorenza, Patrick; La Magna, Antonino; Vivona, Marilena; Roccaforte, Fabrizio [Consiglio Nazionale delle Ricerche-Istituto per la Microelettronica e Microsistemi (CNR-IMM), Strada VIII 5, Zona Industriale 95121 Catania (Italy)

2016-07-04

This letter reports on the impact of gate oxide trapping states on the conduction mechanisms in SiO{sub 2}/4H-SiC metal-oxide-semiconductor field effect transistors (MOSFETs). The phenomena were studied by gate current transient measurements, performed on n-channel MOSFETs operated in “gate-controlled-diode” configuration. The measurements revealed an anomalous non-steady conduction under negative bias (V{sub G} > |20 V|) through the SiO{sub 2}/4H-SiC interface. The phenomenon was explained by the coexistence of a electron variable range hopping and a hole Fowler-Nordheim (FN) tunnelling. A semi-empirical modified FN model with a time-depended electric field is used to estimate the near interface traps in the gate oxide (N{sub trap} ∼ 2 × 10{sup 11} cm{sup −2}).

Puerarin activates endothelial nitric oxide synthase through estrogen receptor-dependent PI3-kinase and calcium-dependent AMP-activated protein kinase

Energy Technology Data Exchange (ETDEWEB)

Hwang, Yong Pil; Kim, Hyung Gyun [Department of Toxicology, College of Pharmacy, Chungnam National University, Daejeon (Korea, Republic of); Hien, Tran Thi [College of Pharmacy, Chosun University, Gwangju (Korea, Republic of); Jeong, Myung Ho [Heart Research Center, Chonnam National University Hospital, Gwangju (Korea, Republic of); Jeong, Tae Cheon, E-mail: taecheon@ynu.ac.kr [College of Pharmacy, Yeungnam University, Gyungsan (Korea, Republic of); Jeong, Hye Gwang, E-mail: hgjeong@cnu.ac.kr [Department of Toxicology, College of Pharmacy, Chungnam National University, Daejeon (Korea, Republic of)

2011-11-15

The cardioprotective properties of puerarin, a natural product, have been attributed to the endothelial nitric oxide synthase (eNOS)-mediated production of nitric oxide (NO) in EA.hy926 endothelial cells. However, the mechanism by which puerarin activates eNOS remains unclear. In this study, we sought to identify the intracellular pathways underlying eNOS activation by puerarin. Puerarin induced the activating phosphorylation of eNOS on Ser1177 and the production of NO in EA.hy926 cells. Puerarin-induced eNOS phosphorylation required estrogen receptor (ER)-mediated phosphatidylinositol 3-kinase (PI3K)/Akt signaling and was reversed by AMP-activated protein kinase (AMPK) and calcium/calmodulin-dependent kinase II (CaMKII) inhibition. Importantly, puerarin inhibited the adhesion of tumor necrosis factor (TNF)-{alpha}-stimulated monocytes to endothelial cells and suppressed the TNF-{alpha} induced expression of intercellular cell adhesion molecule-1. Puerarin also inhibited the TNF-{alpha}-induced nuclear factor-{kappa}B activation, which was attenuated by pretreatment with N{sup G}-nitro-L-arginine methyl ester, a NOS inhibitor. These results indicate that puerarin stimulates eNOS phosphorylation and NO production via activation of an estrogen receptor-mediated PI3K/Akt- and CaMKII/AMPK-dependent pathway. Puerarin may be useful for the treatment or prevention of endothelial dysfunction associated with diabetes and cardiovascular disease. -- Highlights: Black-Right-Pointing-Pointer Puerarin induced the phosphorylation of eNOS and the production of NO. Black-Right-Pointing-Pointer Puerarin activated eNOS through ER-dependent PI3-kinase and Ca{sup 2+}-dependent AMPK. Black-Right-Pointing-Pointer Puerarin-induced NO was involved in the inhibition of NF-kB activation. Black-Right-Pointing-Pointer Puerarin may help for prevention of vascular dysfunction and diabetes.

Reduced coupling of oxidative phosphorylation in vivo precedes electron transport chain defects due to mild oxidative stress in mice.

Directory of Open Access Journals (Sweden)

Michael P Siegel

Full Text Available Oxidative stress and mitochondrial function are at the core of many degenerative conditions. However, the interaction between oxidative stress and in vivo mitochondrial function is unclear. We used both pharmacological (2 week paraquat (PQ treatment of wild type mice and transgenic (mice lacking Cu, Zn-superoxide dismutase (SOD1(-/- models to test the effect of oxidative stress on in vivo mitochondrial function in skeletal muscle. Magnetic resonance and optical spectroscopy were used to measure mitochondrial ATP and oxygen fluxes and cell energetic state. In both models of oxidative stress, coupling of oxidative phosphorylation was significantly lower (lower P/O at rest in vivo in skeletal muscle and was dose-dependent in the PQ model. Despite this reduction in efficiency, in vivo mitochondrial phosphorylation capacity (ATPmax was maintained in both models, and ex vivo mitochondrial respiration in permeabilized muscle fibers was unchanged following PQ treatment. In association with the reduced P/O, PQ treatment led to a dose-dependent reduction in PCr/ATP ratio and increased phosphorylation of AMPK. These results indicate that oxidative stress uncouples oxidative phosphorylation in vivo and results in energetic stress in the absence of defects in the mitochondrial electron transport chain.

Cytosolic NADP(+)-dependent isocitrate dehydrogenase protects macrophages from LPS-induced nitric oxide and reactive oxygen species.

Science.gov (United States)

Maeng, Oky; Kim, Yong Chan; Shin, Han-Jae; Lee, Jie-Oh; Huh, Tae-Lin; Kang, Kwang-il; Kim, Young Sang; Paik, Sang-Gi; Lee, Hayyoung

2004-04-30

Macrophages activated by microbial lipopolysaccharides (LPS) produce bursts of nitric oxide and reactive oxygen species (ROS). Redox protection systems are essential for the survival of the macrophages since the nitric oxide and ROS can be toxic to them as well as to pathogens. Using suppression subtractive hybridization (SSH) we found that cytosolic NADP(+)-dependent isocitrate dehydrogenase (IDPc) is strongly upregulated by nitric oxide in macrophages. The levels of IDPc mRNA and of the corresponding enzymatic activity were markedly increased by treatment of RAW264.7 cells or peritoneal macrophages with LPS or SNAP (a nitric oxide donor). Over-expression of IDPc reduced intracellular peroxide levels and enhanced the survival of H2O2- and SNAP-treated RAW264.7 macrophages. IDPc is known to generate NADPH, a cellular reducing agent, via oxidative decarboxylation of isocitrate. The expression of enzymes implicated in redox protection, superoxide dismutase (SOD) and catalase, was relatively unaffected by LPS and SNAP. We propose that the induction of IDPc is one of the main self-protection mechanisms of macrophages against LPS-induced oxidative stress.

Model for thickness dependence of radiation charging in MOS structures

Science.gov (United States)

Viswanathan, C. R.; Maserjian, J.

1976-01-01

The model considers charge buildup in MOS structures due to hole trapping in the oxide and the creation of sheet charge at the silicon interface. The contribution of hole trapping causes the flatband voltage to increase with thickness in a manner in which square and cube dependences are limiting cases. Experimental measurements on samples covering a 200 - 1000 A range of oxide thickness are consistent with the model, using independently obtained values of hole-trapping parameters. An important finding of our experimental results is that a negative interface charge contribution due to surface states created during irradiation compensates most of the positive charge in the oxide at flatband. The tendency of the surface states to 'track' the positive charge buildup in the oxide, for all thicknesses, applies both in creation during irradiation and in annihilation during annealing. An explanation is proposed based on the common defect origin of hole traps and potential surface states.

Adsorption of trace elements of radionuclides on hydrous iron oxides

International Nuclear Information System (INIS)

Music, S.; Ristic, M.

1988-01-01

Factors that influence the adsorption of trace elements or radionuclides on hydrous iron oxides were investigated. The adsorption of monovalent cations (Cs + , Rb + ) on hydrous iron oxides is not strongly pH-dependent and it can be regarded as nonspecific. On the other hand, the adsorption of Ag + , divalent cations (Zn 2+ , Cd 2+ , Mn 2+ , Sr 2+ ) or trivalent cations (Cr 3+ , La 3+ , Ce 3+ , Eu 3+ , Gd 3+ , Er 3+ , Yb 3+ ) is strongly pH-dependent. The regularities of the adsorption of these cations on hydrous iron oxides are discussed. The differences in the adsorption behaviour of some divalent and trivalent cations are also explained. Freshly precipitated iron(III) hydroxide can be used for the decontamination of radionuclides from low-level waste solutions. However, the efficacy of decontamination depends on the oxidation state and the chemical properties of radionuclides. (author) 40 refs.; 9 figs

Evaluation of the energy dependence of a zinc oxide nanofilm X-ray detector

International Nuclear Information System (INIS)

Valenca, C.P.V.; Silveira, M.A.L.; Macedo, M.A.; Santos, L.A.P

2015-01-01

International organizations of human health and radiation protection have recommended certain care for using of the X-ray as a diagnosis tool to avoid any type of radiological accident or overdose to the patient. This can be done assessing the parameters of the X-ray equipment and there are various types of detectors available for that: ionizing chamber, electronic semiconductor devices, etc. These detectors must be calibrated so that they can be used for any energy range and such a procedure is correlated with what is called the energy dependence of the detector. In accordance with the stated requirements of IEC 61267, the standard radiation quality beams and irradiation conditions (RQRs) are the tools and techniques for calibrating diagnostic X-Ray instruments and detectors. The purpose of this work is to evaluate the behavior of the energy dependence of a detector fabricated from a zinc oxide (ZnO) nanofilm. A Pantak industrial X-ray equipment was used to generate the RQR radiation quality beams and test three ZnO detector samples. A 6430 sub-femto-ammeter, Keithley, was used to bias the ZnO detector and simultaneously perform the output readings. The results showed that the ZnO device has some increase in its sensitivity to the ionizing radiation as the X-ray effective energy decreases unlike other types of semiconductor electronic devices typically used as an X-ray detector. We can conclude that the ZnO device can be used as a diagnostic X-ray detector with an appropriate calibration. (author)

Electronic Structure and Excited-State Dynamics of an Arduengo-Type Carbene and its Imidazolone Oxidation Product.

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Schmitt, Hans-Christian; Flock, Marco; Welz, Eileen; Engels, Bernd; Schneider, Heidi; Radius, Udo; Fischer, Ingo

2017-03-02

We describe an investigation of the excited-state dynamics of isolated 1,3-di-tert-butyl-imidazoline-2-ylidene (tBu 2 Im, C 11 H 20 N 2 , m/z=180), an Arduengo-type carbene, by time- and frequency-resolved photoionization using a picosecond laser system. The energies of several singlet and triplet excited states were calculated by time-dependent density functional theory (TD-DFT). The S 1 state of the carbene deactivates on a 100 ps time scale possibly by intersystem crossing. In the experiments we observed an additional signal at m/z=196, that was assigned to the oxidation product 1,3-di-tert-butyl-imidazolone, tBu 2 ImO. It shows a well-resolved resonance-enhanced multiphoton ionization (REMPI) spectrum with an origin located at 36951 cm -1 . Several low-lying vibrational bands could be assigned, with a lifetime that depends strongly on the excitation energy. At the origin the lifetime is longer than 3 ns, but drops to 49 ps at higher excess energies. To confirm formation of the imidazolone we also performed experiments on benzimidazolone (BzImO) for comparison. Apart from a redshift for BzImO the spectra of the two compounds are very similar. The TD-DFT values display a very good agreement with the experimental data. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparative studies of MOS-gate/oxide-passivated AlGaAs/InGaAs pHEMTs by using ozone water oxidation technique

International Nuclear Information System (INIS)

Lee, Ching-Sung; Hung, Chun-Tse; Chou, Bo-Yi; Hsu, Wei-Chou; Liu, Han-Yin; Ho, Chiu-Sheng; Lai, Ying-Nan

2012-01-01

Al 0.22 Ga 0.78 As/In 0.24 Ga 0.76 As pseudomorphic high-electron-mobility transistors (pHEMTs) with metal-oxide-semiconductor (MOS)-gate structure or oxide passivation by using ozone water oxidation treatment have been comprehensively investigated. Annihilated surface states, enhanced gate insulating property and improved device gain have been achieved by the devised MOS-gate structure and oxide passivation. The present MOS-gated or oxide-passivated pHEMTs have demonstrated superior device performances, including superior breakdown, device gain, noise figure, high-frequency characteristics and power performance. Temperature-dependent device characteristics of the present designs at 300–450 K are also studied. (paper)

Infertility and recurrent miscarriage with complex II deficiency-dependent mitochondrial oxidative stress in animal models.

Science.gov (United States)

Ishii, Takamasa; Yasuda, Kayo; Miyazawa, Masaki; Mitsushita, Junji; Johnson, Thomas E; Hartman, Phil S; Ishii, Naoaki

2016-04-01

Oxidative stress is associated with some forms of both male and female infertility. However, there is insufficient knowledge of the influence of oxidative stress on the maintenance of a viable pregnancy, including pregnancy complications and fetal development. There are a number of animal models for understanding age-dependent decrease of reproductive ability and diabetic embryopathy, especially abnormal spermatogenesis, oogenesis and embryogenesis with mitochondrial dysfunctions. Several important processes occur in mitochondria, including ATP synthesis, calcium ion storage, induction of apoptosis and production of reactive oxygen species (ROS). These events have different effects on the several aspects of reproductive function. Tet-mev-1 conditional transgenic mice, developed after studies with the mev-1 mutant of the nematode C. elegans, offer the ability to carefully regulate expression of doxycycline-induced mutated SDHC(V69E) levels and hence modulate endogenous oxidative stress. The mev-1 models have served to illuminate the effects of complex II deficiency-dependent mitochondrial ROS production, although interestingly they maintain normal mitochondrial and intracellular ATP levels. In this review, the reproductive dysfunctions are presented focusing on fertility potentials in each gamete, early embryogenesis, maternal conditions with placental function and neonatal development. Copyright © 2016. Published by Elsevier Ireland Ltd.

Reversal magnetization dependence with the Cr and Fe oxidation states in YFe{sub 1−x}Cr{sub x}O{sub 3} (0≤x≤1) perovskites

Energy Technology Data Exchange (ETDEWEB)

Fabian, F.A., E-mail: fernandafabianro@gmail.com [Universidade Federal de Sergipe, Campus Prof. Aloísio Campos, Departamento de Física, 49100−000 São Cristóvão, SE (Brazil); Pedra, P.P. [Universidade Federal de Sergipe, Campus Prof. Aloísio Campos, Departamento de Física, 49100−000 São Cristóvão, SE (Brazil); Moura, K.O. [Universidade Estadual de Campinas, Instituto de Física “Gleb Wataghin”, 13083−859 Campinas, SP (Brazil); Duque, J.G.S.; Meneses, C.T. [Universidade Federal de Sergipe, Campus Prof. Alberto Carvalho, Departamento de Física, 49500−000 Itabaiana, SE (Brazil)

2016-06-15

In this work, we have carried out a detailed study of the magnetic and structural properties of YFe{sub 1−x}Cr{sub x}O{sub 3} (0≤x≤1) samples with orthorhombic structure obtained by co-precipitation method. Analysis of X-ray diffraction data using Rietveld refinement show that all samples present an orthorhombic crystal system with space group Pnma. Besides, we have observed a reduction of unit cell volume with increasing of the Cr concentration. SEM images show the formation of grains of micrometer order. X-ray Absorption near edge spectroscopy (XANES) measurements show a shift of absorption edge which can be indicate there is (i) different oxidation states to Fe and Cr ions and/or (ii) a changing in the point symmetry of Fe and Cr ions to the compounds. The magnetization measurements indicate a continuous decreasing of the magnetic transition temperature as function of chromium doping. The reversal magnetization effect was observed to concentrations around x=0.5. Besides, the deviation of the Curie–Weiss law and a weak ferromagnetic behavior observed at room temperature in the M vs H curves can be attributed to the strong magnetic interactions between the transition metals with different oxidation states. - Highlights: • YFe{sub 1−x}Cr{sub x}O{sub 3} (0≤x≤1) samples were synthesized by co-precipitation method. • XRD dates showed a reduction of unit cell volume with addition of Cr. • XANES dates showed difference in the oxidation states to Cr and Fe. • MZFC-MFC indicate a decreasing of the T{sub N} as function of chromium doping. • MFC curve for x=0.5 concentration was observed the reverse magnetization effect.

Charge states of fast heavy ions in solids; target atomic number dependence

International Nuclear Information System (INIS)

Shima, Kunihiro

1985-01-01

Discussions were carried out on the origin of Z 2 (atomic number) dependent charge states with respect to projectile electron loss and capture process, and on relationship between the Z 2 dependence and that of mean charge states for heavy ions of 1 MeV/u energy region. Present and previously reported results were examined on the equilibrium charge distributions, 9-bar, of 120 MeV 63 Cu, 25 and 40 MeV 35 Cl, 109 MeV Si and 59 MeV F ions. It was clarified that 9-bar became generally higher for lower Z 2 depending on increasing energy, and osillatory behavior with energy-depending amplitude was seen in 9-bar vs Z 2 . Discussions were carrid out on these phenomena and related matters. Z 2 oscillations of 9-bar of fast heavy ions might be due to those of electron capture cross section into projectile K and L vacancies for high and intermediate charge states, respectively. A quantitative interpretation of the Z 2 -dependent 9-bar values is in progress based on collision process and observation of projectile x-ray. The 9-bar value dependency on Z 2 in ion passing foils and decrease of Z 2 oscillation amplitude with increasing collision energy were quite similar to the Z 2 dependence in stopping powers or in effective charge states estimated from stopping powers. But there was some discrepancies in the Z 2 oscillation of 9-bar and that of stopping powers. (Takagi, S.)

The dependence of the discharge of nitrous oxide by ordinary chernozem steppe of the Central-Chernozem Region of Russia from the content of humus, nitrogen and enzymatic activity

Science.gov (United States)

Avksentev, Alexey; Negrobova, Elena; Kramareva, Tatiana; Moiseeva, Evgenya

2016-04-01

The dependence of the discharge of nitrous oxide by ordinary chernozem steppe of the Central-Chernozem Region of Russia from the content of humus, nitrogen and enzymatic activity Alexey Avksentev, Elena Negrobova, Tatiana Kramareva, Evgenya Moiseeva 394000 Voronezh, Universitetskaya square, 1 Voronezh State University Nitrous oxide is emitted by soil as a result of microbiological processes, ranks third in the list of aggressive greenhouse gas after carbon dioxide and methane. Nitrous oxide is formed during nitrification and denitrification of ammonia that enters the soil during microbial decomposition of complex organic compounds. Denitrification can be direct and indirect. In the microbiological process of recovery of nitrates involved of the organic substance. In aerobic conditions microorganisms denitrificator behave like normal saprotrophs and oxidize organic matter in the act of breathing oxygen. Thus, they operate at different times two enzyme systems: the electron transport chain with an oxygen acceptor in aerobic and restoration of nitrates under anaerobic conditions. Investigation of the emission of nitrous oxide by ordinary Chernozem steppe of the Central-Chernozem Region showed that it depends on the type of cenosis and the content of available forms of nitrogen. Natural ecosystems emit nitrous oxide more than the soil of arable land. The dependence of the emission of nitrous oxide from the humus content shows positive trend, but the aggregation of data, significant differences are not detected. Research shows that nitrous oxide emissions are seasonal. So the autumn season is characterized by nitrous oxide emissions than spring. Enzymatic processes are an important link in the biological cycle of elements and, consequently, participate in the process of decomposition of organic matter, nitrification and other processes. Analysis of the data on enzyme activity of ordinary Chernozem and the intensity of emission of N20 shows a clear relationship between

Opposing effects of oxidative challenge and carotenoids on antioxidant status and condition-dependent sexual signalling.

Science.gov (United States)

Tomášek, Oldřich; Gabrielová, Barbora; Kačer, Petr; Maršík, Petr; Svobodová, Jana; Syslová, Kamila; Vinkler, Michal; Albrecht, Tomáš

2016-03-22

Several recent hypotheses consider oxidative stress to be a primary constraint ensuring honesty of condition-dependent carotenoid-based signalling. The key testable difference between these hypotheses is the assumed importance of carotenoids for redox homeostasis, with carotenoids being either antioxidant, pro-oxidant or unimportant. We tested the role of carotenoids in redox balance and sexual signalling by exposing adult male zebra finches (Taeniopygia guttata) to oxidative challenge (diquat dibromide) and manipulating carotenoid intake. As the current controversy over the importance of carotenoids as antioxidants could stem from the hydrophilic basis of commonly-used antioxidant assays, we used the novel measure of in vivo lipophilic antioxidant capacity. Oxidative challenge reduced beak pigmentation but elicited an increase in antioxidant capacity suggesting resource reallocation from signalling to redox homeostasis. Carotenoids counteracted the effect of oxidative challenge on lipophilic (but not hydrophilic) antioxidant capacity, thereby supporting carotenoid antioxidant function in vivo. This is inconsistent with hypotheses proposing that signalling honesty is maintained through either ROS-induced carotenoid degradation or the pro-oxidant effect of high levels of carotenoid-cleavage products acting as a physiological handicap. Our data further suggest that assessment of lipophilic antioxidant capacity is necessary to fully understand the role of redox processes in ecology and evolution.

Study on the solid state chemistry of ternary uranium oxides

International Nuclear Information System (INIS)

Yamashita, Toshiyuki

1988-03-01

With the increase of burnup of uranium oxide fuels, various kinds of fission products are formed, and the oxygen atoms combined with the consumed heavy atoms are freed. The solid state chemical and/or thermodynamic properties of these elements at high temperatures are complex, and have not been well clarified. In the present report, an approach was taken that the chemical interactions between UO 2 and these fission products can be regarded as causing overlapped effects of composing ternary uranium oxides, and formation reactions and phase behavior were studied for several ternary uranium oxides with typical fission product elements such as alkaline earth metals and rare earth elements. Precise determination methods for the composition of ternary uranium oxides were developed. The estimated accuracies for x and y values in M y U 1-y O 2+x were ± 0.006 and ± 0.004, respectively. The thermodynamic properties and the lattice parameters of the phases in the Ca-U-O and Pr-U-O systems were discussed in relation to the composition determined by the methods. Crystal structure analyses of cadmium monouranates were made with X-ray diffraction method. (author) 197 refs

DJ-1-dependent regulation of oxidative stress in the retinal pigment epithelium (RPE.

Directory of Open Access Journals (Sweden)

Karen G Shadrach

Full Text Available DJ-1 is found in many tissues, including the brain, where it has been extensively studied due to its association with Parkinson's disease. DJ-1 functions as a redox-sensitive molecular chaperone and transcription regulator that robustly protects cells from oxidative stress.Retinal pigment epithelial (RPE cultures were treated with H2O2 for various times followed by biochemical and immunohistological analysis. Cells were transfected with adenoviruses carrying the full-length human DJ-1 cDNA and a mutant construct, which has the cysteine residues at amino acid 46, 53 and 106 mutated to serine (C to S prior to stress experiments. DJ-1 localization, levels of expression and reactive oxygen species (ROS generation were also analyzed in cells expressing exogenous DJ-1 under baseline and oxidative stress conditions. The presence of DJ-1 and oxidized DJ-1 was evaluated in human RPE total lysates. The distribution of DJ-1 was assessed in AMD and non-AMD cryosectionss and in isolated human Bruch's membrane (BM/choroid from AMD eyes.DJ-1 in RPE cells under baseline conditions, displays a diffuse cytoplasmic and nuclear staining. After oxidative challenge, more DJ-1 was associated with mitochondria. Increasing concentrations of H2O2 resulted in a dose-dependent increase in DJ-1. Overexpression of DJ-1 but not the C to S mutant prior to exposure to oxidative stress led to significant decrease in the generation of ROS. DJ-1 and oxDJ-1 intensity of immunoreactivity was significantly higher in the RPE lysates from AMD eyes. More DJ-1 was localized to RPE cells from AMD donors with geographic atrophy and DJ-1 was also present in isolated human BM/choroid from AMD eyes.DJ-1 regulates RPE responses to oxidative stress. Most importantly, increased DJ-1 expression prior to oxidative stress leads to decreased generation of ROS, which will be relevant for future studies of AMD since oxidative stress is a known factor affecting this disease.

Influence of extra-cellular and intra-cellular acting thiol oxidants on the 45calcium uptake by the islets of Langerhans of the rat

International Nuclear Information System (INIS)

Haegele, R.G.

1981-01-01

The glucose-stimulated calcium uptake by the islets of Langerhans is dependent on the intra-cellular GSH/GSSG ratios. The inhibition of calcium uptake is not the consequence of a direct oxidation of membrane-fixed thiol groups. In contrast, direct oxidation of extra cellular thiols leads to an increase in calcium uptake when intra-cellular oxidation is simultaneously prevented. Since this effect only occurs at high intra-cellular GSH/GSSG ratios it can be assumed that the redox state of extra-cellular thiols is dependent on the redox state of the intra-cellular GSH/GSSG ratios. These findings support the theory that the oxidation of extra-cellular thiols by thiol oxidants leads to an increase in calcium uptake and that the extent of uptake is higher, the more the redox state of the extra-cellular thiols tends towards the reduced state prior to oxidation. (orig./MG) [de

Crystal habit dependent quantum confined photoluminescence of zinc oxide nanostructures

International Nuclear Information System (INIS)

Arellano, Ian Harvey J.; Payawan, Leon Jr. M.; Sarmago, Roland V.

2008-01-01

Diverse zinc oxide crystal habits namely wire, rods, tubes, whiskers and tetrapods were synthesized via hydrothermal and carbothermal reduction routes. A vapor current induced regionalization in the carbothermal synthesis lead to the isolation of these crystal habits for characterization. The surface morphology of the nanostructures was analyzed via field emission scanning electron microscopy (FESEM). The morphology and crystallinity of the as-synthesized nanostructure architectural motifs were related to their photoluminescence (PL). The photoluminescence at 157 nm was taken using F2 excimer laser and a crystal habit dependent response was observed. X-ray diffraction (XRD) analyses were conducted to deduce the degree of crystallinity showing results consistent with the excitonic emission at the band edge and visible emission at the electron-hole recombination sites. The presence of minimal crystal defects which gave the green emission was supported by energy dispersive spectroscopy (EDS) data. Transmission spectroscopy for the tetrapods exhibited an interesting PL reduction associated with high-energy deep traps in the nanostructures. Furthermore, some intensity dependent characteristics were deduced indicating quantum confined properties of these nano structures. (author)

Anaerobic Oxidization of Methane in a Minerotrophic Peatland: Enrichment of Nitrite-Dependent Methane-Oxidizing Bacteria

Science.gov (United States)

Zhu, Baoli; van Dijk, Gijs; Fritz, Christian; Smolders, Alfons J. P.; Pol, Arjan; Jetten, Mike S. M.

2012-01-01

The importance of anaerobic oxidation of methane (AOM) as a methane sink in freshwater systems is largely unexplored, particularly in peat ecosystems. Nitrite-dependent anaerobic methane oxidation (n-damo) was recently discovered and reported to be catalyzed by the bacterium “Candidatus Methylomirabilis oxyfera,” which is affiliated with the NC10 phylum. So far, several “Ca. Methylomirabilis oxyfera” enrichment cultures have been obtained using a limited number of freshwater sediments or wastewater treatment sludge as the inoculum. In this study, using stable isotope measurements and porewater profiles, we investigated the potential of n-damo in a minerotrophic peatland in the south of the Netherlands that is infiltrated by nitrate-rich ground water. Methane and nitrate profiles suggested that all methane produced was oxidized before reaching the oxic layer, and NC10 bacteria could be active in the transition zone where countergradients of methane and nitrate occur. Quantitative PCR showed high NC10 bacterial cell numbers at this methane-nitrate transition zone. This soil section was used to enrich the prevalent NC10 bacteria in a continuous culture supplied with methane and nitrite at an in situ pH of 6.2. An enrichment of nitrite-reducing methanotrophic NC10 bacteria was successfully obtained. Phylogenetic analysis of retrieved 16S rRNA and pmoA genes showed that the enriched bacteria were very similar to the ones found in situ and constituted a new branch of NC10 bacteria with an identity of less than 96 and 90% to the 16S rRNA and pmoA genes of “Ca. Methylomirabilis oxyfera,” respectively. The results of this study expand our knowledge of the diversity and distribution of NC10 bacteria in the environment and highlight their potential contribution to nitrogen and methane cycles. PMID:23042166

The contribution of ketone bodies to basal and activity-dependent neuronal oxidation in vivo.

Science.gov (United States)

Chowdhury, Golam M I; Jiang, Lihong; Rothman, Douglas L; Behar, Kevin L

2014-07-01

The capacity of ketone bodies to replace glucose in support of neuronal function is unresolved. Here, we determined the contributions of glucose and ketone bodies to neocortical oxidative metabolism over a large range of brain activity in rats fasted 36 hours and infused intravenously with [2,4-(13)C₂]-D-β-hydroxybutyrate (BHB). Three animal groups and conditions were studied: awake ex vivo, pentobarbital-induced isoelectricity ex vivo, and halothane-anesthetized in vivo, the latter data reanalyzed from a recent study. Rates of neuronal acetyl-CoA oxidation from ketone bodies (V(acCoA-kbN)) and pyruvate (V(pdhN)), and the glutamate-glutamine cycle (V(cyc)) were determined by metabolic modeling of (13)C label trapped in major brain amino acid pools. V(acCoA-kbN) increased gradually with increasing activity, as compared with the steeper change in tricarboxylic acid (TCA) cycle rate (V(tcaN)), supporting a decreasing percentage of neuronal ketone oxidation: ∼100% (isoelectricity), 56% (halothane anesthesia), 36% (awake) with the BHB plasma levels achieved in our experiments (6 to 13 mM). In awake animals ketone oxidation reached saturation for blood levels >17 mM, accounting for 62% of neuronal substrate oxidation, the remainder (38%) provided by glucose. We conclude that ketone bodies present at sufficient concentration to saturate metabolism provides full support of basal (housekeeping) energy needs and up to approximately half of the activity-dependent oxidative needs of neurons.

The effect of oxide shell thickness on the structural, electronic, and optical properties of Si-SiO{sub 2} core-shell nano-crystals: A (time dependent)density functional theory study

Energy Technology Data Exchange (ETDEWEB)

Nazemi, Sanaz, E-mail: s.nazemi@ut.ac.ir, E-mail: pourfath@ut.ac.ir; Soleimani, Ebrahim Asl [School of Electrical and Computer Engineering, University of Tehran, Tehran 14395-515 (Iran, Islamic Republic of); Pourfath, Mahdi, E-mail: s.nazemi@ut.ac.ir, E-mail: pourfath@ut.ac.ir [School of Electrical and Computer Engineering, University of Tehran, Tehran 14395-515 (Iran, Islamic Republic of); Institute for Microelectronics, Technische Universität Wien, Wien A-1040 (Austria); Kosina, Hans [Institute for Microelectronics, Technische Universität Wien, Wien A-1040 (Austria)

2016-04-14

Due to their tunable properties, silicon nano-crystals (NC) are currently being investigated. Quantum confinement can generally be employed for size-dependent band-gap tuning at dimensions smaller than the Bohr radius (∼5 nm for silicon). At the nano-meter scale, however, increased surface-to-volume ratio makes the surface effects dominant. Specifically, in Si-SiO{sub 2} core-shell semiconductor NCs the interfacial transition layer causes peculiar electronic and optical properties, because of the co-existence of intermediate oxidation states of silicon (Si{sup n+}, n = 0–4). Due to the presence of the many factors involved, a comprehensive understanding of the optical properties of these NCs has not yet been achieved. In this work, Si-SiO{sub 2} NCs with a diameter of 1.1 nm and covered by amorphous oxide shells with thicknesses between 2.5 and 4.75 Å are comprehensively studied, employing density functional theory calculations. It is shown that with increased oxide shell thickness, the low-energy part of the optical transition spectrum of the NC is red shifted and attenuated. Moreover, the absorption coefficient is increased in the high-energy part of the spectrum which corresponds to SiO{sub 2} transitions. Structural examinations indicate a larger compressive stress on the central silicon cluster with a thicker oxide shell. Examination of the local density of states reveals the migration of frontier molecular orbitals from the oxide shell into the silicon core with the increase of silica shell thickness. The optical and electrical properties are explained through the analysis of the density of states and the spatial distribution of silicon sub-oxide species.

Orthorhombic Ti2O3: A Polymorph-Dependent Narrow-Bandgap Ferromagnetic Oxide

KAUST Repository

Li, Yangyang

2017-12-16

Magnetic semiconductors are highly sought in spintronics, which allow not only the control of charge carriers like in traditional electronics, but also the control of spin states. However, almost all known magnetic semiconductors are featured with bandgaps larger than 1 eV, which limits their applications in long-wavelength regimes. In this work, the discovery of orthorhombic-structured Ti2O3 films is reported as a unique narrow-bandgap (≈0.1 eV) ferromagnetic oxide semiconductor. In contrast, the well-known corundum-structured Ti2O3 polymorph has an antiferromagnetic ground state. This comprehensive study on epitaxial Ti2O3 thin films reveals strong correlations between structure, electrical, and magnetic properties. The new orthorhombic Ti2O3 polymorph is found to be n-type with a very high electron concentration, while the bulk-type trigonal-structured Ti2O3 is p-type. More interestingly, in contrast to the antiferromagnetic ground state of trigonal bulk Ti2O3, unexpected ferromagnetism with a transition temperature well above room temperature is observed in the orthorhombic Ti2O3, which is confirmed by X-ray magnetic circular dichroism measurements. Using first-principles calculations, the ferromagnetism is attributed to a particular type of oxygen vacancies in the orthorhombic Ti2O3. The room-temperature ferromagnetism observed in orthorhombic-structured Ti2O3, demonstrates a new route toward controlling magnetism in epitaxial oxide films through selective stabilization of polymorph phases.

Orthorhombic Ti2O3: A Polymorph-Dependent Narrow-Bandgap Ferromagnetic Oxide

KAUST Repository

Li, Yangyang; Weng, Yakui; Yin, Xinmao; Yu, Xiaojiang; Sarath Kumar, S. R.; Wehbe, Nimer; Wu, Haijun; Alshareef, Husam N.; Pennycook, Stephen J.; Breese, Mark B. H.; Chen, Jingsheng; Dong, Shuai; Wu, Tao

2017-01-01

Magnetic semiconductors are highly sought in spintronics, which allow not only the control of charge carriers like in traditional electronics, but also the control of spin states. However, almost all known magnetic semiconductors are featured with bandgaps larger than 1 eV, which limits their applications in long-wavelength regimes. In this work, the discovery of orthorhombic-structured Ti2O3 films is reported as a unique narrow-bandgap (≈0.1 eV) ferromagnetic oxide semiconductor. In contrast, the well-known corundum-structured Ti2O3 polymorph has an antiferromagnetic ground state. This comprehensive study on epitaxial Ti2O3 thin films reveals strong correlations between structure, electrical, and magnetic properties. The new orthorhombic Ti2O3 polymorph is found to be n-type with a very high electron concentration, while the bulk-type trigonal-structured Ti2O3 is p-type. More interestingly, in contrast to the antiferromagnetic ground state of trigonal bulk Ti2O3, unexpected ferromagnetism with a transition temperature well above room temperature is observed in the orthorhombic Ti2O3, which is confirmed by X-ray magnetic circular dichroism measurements. Using first-principles calculations, the ferromagnetism is attributed to a particular type of oxygen vacancies in the orthorhombic Ti2O3. The room-temperature ferromagnetism observed in orthorhombic-structured Ti2O3, demonstrates a new route toward controlling magnetism in epitaxial oxide films through selective stabilization of polymorph phases.

Graphene Oxide flakes: methods and techniques for properties at interfaces

OpenAIRE

Paola, Zuppella; Sara, Zuccon; Marco, Nardello; Jody, Corso Alain; Simone, Silvestrini; Michele, Maggini; Guglielmina, Pelizzo Maria

2014-01-01

Graphene Oxide and reduced Graphene Oxide are intriguing materials for photonics and electronic devices both for intrinsic characteristics and as precursors for the synthesis of graphene. Whatever the application and the engineering purpose, a fine control of the chemical and physical properties is required since the performances of graphene based systems depend on the reduction state of Graphene Oxide and can be strongly affected by interfaces interactions and neighboring effects. Then, a me...

Brain state-dependence of electrically evoked potentials monitored with head-mounted electronics.

Science.gov (United States)

Richardson, Andrew G; Fetz, Eberhard E

2012-11-01

Inferring changes in brain connectivity is critical to studies of learning-related plasticity and stimulus-induced conditioning of neural circuits. In addition, monitoring spontaneous fluctuations in connectivity can provide insight into information processing during different brain states. Here, we quantified state-dependent connectivity changes throughout the 24-h sleep-wake cycle in freely behaving monkeys. A novel, head-mounted electronic device was used to electrically stimulate at one site and record evoked potentials at other sites. Electrically evoked potentials (EEPs) revealed the connectivity pattern between several cortical sites and the basal forebrain. We quantified state-dependent changes in the EEPs. Cortico-cortical EEP amplitude increased during slow-wave sleep, compared to wakefulness, while basal-cortical EEP amplitude decreased. The results demonstrate the utility of using portable electronics to document state-dependent connectivity changes in freely behaving primates.

Tetrahydrobiopterin Has a Glucose-Lowering Effect by Suppressing Hepatic Gluconeogenesis in an Endothelial Nitric Oxide Synthase–Dependent Manner in Diabetic Mice

Science.gov (United States)

Abudukadier, Abulizi; Fujita, Yoshihito; Obara, Akio; Ohashi, Akiko; Fukushima, Toru; Sato, Yuichi; Ogura, Masahito; Nakamura, Yasuhiko; Fujimoto, Shimpei; Hosokawa, Masaya; Hasegawa, Hiroyuki; Inagaki, Nobuya

2013-01-01

Endothelial nitric oxide synthase (eNOS) dysfunction induces insulin resistance and glucose intolerance. Tetrahydrobiopterin (BH4) is an essential cofactor of eNOS that regulates eNOS activity. In the diabetic state, BH4 is oxidized to 7,8-dihydrobiopterin, which leads to eNOS dysfunction owing to eNOS uncoupling. The current study investigates the effects of BH4 on glucose metabolism and insulin sensitivity in diabetic mice. Single administration of BH4 lowered fasting blood glucose levels in wild-type mice with streptozotocin (STZ)-induced diabetes and alleviated eNOS dysfunction by increasing eNOS dimerization in the liver of these mice. Liver has a critical role in glucose-lowering effects of BH4 through suppression of hepatic gluconeogenesis. BH4 activated AMP kinase (AMPK), and the suppressing effect of BH4 on gluconeogenesis was AMPK-dependent. In addition, the glucose-lowering effect and activation of AMPK by BH4 did not appear in mice with STZ-induced diabetes lacking eNOS. Consecutive administration of BH4 in ob/ob mice ameliorated glucose intolerance and insulin resistance. Taken together, BH4 suppresses hepatic gluconeogenesis in an eNOS-dependent manner, and BH4 has a glucose-lowering effect as well as an insulin-sensitizing effect in diabetic mice. BH4 has potential in the treatment of type 2 diabetes. PMID:23649519

True versus spurious state dependence in firm performance

DEFF Research Database (Denmark)

Kaiser, Ulrich; Kongsted, Hans Christian

2008-01-01

This paper analyzes the persistence of firms' exporting behavior in a panel of German manufacturing firms using dynamic binary choice models. We distinguish between true and spurious state dependence in exports and apply fixed effects methods that allow us to verify the robustness of our results ...... determinants. Our results, which are consistent with the findings of previous studies on firms in developing countries and in the United States, show the presence of important sunk costs in export market entry and a depreciation of knowledge and experience in export markets....

True Versus Spurious State Dependence in Firm Performance

DEFF Research Database (Denmark)

Kaiser, Ulrich; Kongsted, Hans Christian

This paper analyzes the persistence of firms' exporting behavior in a panel of German manufacturing firms using dynamic binary choice models. We distinguish between true and spurious state dependence in exports and apply fixed effects methods that allow us to verify the robustness of our results ...... determinants. Our results, which are consistent with the findings of previous studies on firms in developing countries and in the United States, show the presence of important sunk costs in export market entry and a depreciation of knowledge and experience in export markets...

Selective maintenance for multi-state series–parallel systems under economic dependence

International Nuclear Information System (INIS)

Dao, Cuong D.; Zuo, Ming J.; Pandey, Mayank

2014-01-01

This paper presents a study on selective maintenance for multi-state series–parallel systems with economically dependent components. In the selective maintenance problem, the maintenance manager has to decide which components should receive maintenance activities within a finite break between missions. All the system reliabilities in the next operating mission, the available budget and the maintenance time for each component from its current state to a higher state are taken into account in the optimization models. In addition, the components in series–parallel systems are considered to be economically dependent. Time and cost savings will be achieved when several components are simultaneously repaired in a selective maintenance strategy. As the number of repaired components increases, the saved time and cost will also increase due to the share of setting up between components and another additional reduction amount resulting from the repair of multiple identical components. Different optimization models are derived to find the best maintenance strategy for multi-state series–parallel systems. A genetic algorithm is used to solve the optimization models. The decision makers may select different components to be repaired to different working states based on the maintenance objective, resource availabilities and how dependent the repair time and cost of each component are

Crystalline-like temperature dependence of the electrical characteristics in amorphous Indium-Gallium-Zinc-Oxide thin film transistors

Science.gov (United States)

Estrada, M.; Hernandez-Barrios, Y.; Cerdeira, A.; Ávila-Herrera, F.; Tinoco, J.; Moldovan, O.; Lime, F.; Iñiguez, B.

2017-09-01

A crystalline-like temperature dependence of the electrical characteristics of amorphous Indium-Gallium-Zinc-Oxide (a-IGZO) thin film transistors (TFTs) is reported, in which the drain current reduces as the temperature is increased. This behavior appears for values of drain and gate voltages above which a change in the predominant conduction mechanism occurs. After studying the possible conduction mechanisms, it was determined that, for gate and drain voltages below these values, hopping is the predominant mechanism with the current increasing with temperature, while for values above, the predominant conduction mechanism becomes percolation in the conduction band or band conduction and IDS reduces as the temperature increases. It was determined that this behavior appears, when the effect of trapping is reduced, either by varying the density of states, their characteristic energy or both. Simulations were used to further confirm the causes of the observed behavior.

Short review of high-pressure crystal growth and magnetic and electrical properties of solid-state osmium oxides

Energy Technology Data Exchange (ETDEWEB)

Yamaura, Kazunari, E-mail: YAMAURA.Kazunari@nims.go.jp [Superconducting Properties Unit, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); Graduate School of Chemical Sciences and Engineering, Hokkaido University, North 10 West 8, Kita-ku, Sapporo, Hokkaido 060-0810 (Japan)

2016-04-15

High-pressure crystal growth and synthesis of selected solid-state osmium oxides, many of which are perovskite-related types, are briefly reviewed, and their magnetic and electrical properties are introduced. Crystals of the osmium oxides, including NaOsO{sub 3}, LiOsO{sub 3}, and Na{sub 2}OsO{sub 4}, were successfully grown under high-pressure and high-temperature conditions at 6 GPa in the presence of an appropriate amount of flux in a belt-type apparatus. The unexpected discovery of a magnetic metal–insulator transition in NaOsO{sub 3}, a ferroelectric-like transition in LiOsO{sub 3}, and high-temperature ferrimagnetism driven by a local structural distortion in Ca{sub 2}FeOsO{sub 6} may represent unique features of the osmium oxides. The high-pressure and high-temperature synthesis and crystal growth has played a central role in the development of solid-state osmium oxides and the elucidation of their magnetic and electronic properties toward possible use in multifunctional devices. - Graphical Abstract: Flux-grown crystals of NaOsO{sub 3} under high-pressure and high-temperature conditions in a belt-type apparatus. The crystal shows a magnetically driven metal–insulator transition at a temperature of 410 K. - Highlights: • Short review of high-pressure crystal growth of solid-state osmium oxides. • Wide variety of magnetic properties of solid-state osmium oxides. • Perovskite and related dense structures stabilized at 3–17 GPa.

The role of oxidation states in F A1 Tl n+ (n = 1, 3) lasers and CO interactions at the (1 0 0) surface of NaCl: An ab initio study

International Nuclear Information System (INIS)

Shalabi, A.S.; Abdel Aal, S.; Kamel, M.A.; Taha, H.O.; Ammar, H.Y.; Abdel Halim, W.S.

2006-01-01

The oxidation states of Thallium in F A1 Tl +n (n = 1, 3) color centers at the (1 0 0) surface of NaCl play important role in laser light generation and adsorbate-substrate interactions. Double-well potentials at these surfaces are investigated by using quantum mechanical ab initio methods. Quantum clusters of variable sizes were embedded in the simulated Coulomb fields that closely approximate the Madelung fields of the host surfaces, and ions that were the nearest neighbors to the F A1 Tl +n (n 1, 3) defect site were allowed to relax to equilibrium.The calculated Stokes shifts suggest that laser light generation is sensitive to the oxidation states of Thallium. The relaxed excited states of the defect-containing surface were deep below the lower edge of the conduction bands of the ground state defect-free surface, suggesting that the F A1 Tl +n (n = 1, 3) centers are suitable laser defects. The dependence of the orientational destruction and recording sensitivity on the oxidation state of Thallium is clarified. The Glasner-Tompkins empirical rule is generalized to include the oxidation state of the impurity cation. The adsorption energies of CO and OC over NaCl(1 0 0) was found to be sensitive to the oxidation state of the impurity cation. F A1 Tl +n (n = 1, 3) centers changed the physical adsorption of CO to chemical adsorption. While the artificial flow of charge was significant in the case of Tl +1 impurity, it was negligible in the case of Tl +3 impurity, and the results were explained in terms of the electrostatic potential curves

Heterogeneous catalysis in liquid-phase oxidation of olefin--2. Dependence of the structure of vanadium-chromium binary oxide catalyst for oxidation of cyclohexene on the method of preparation

Energy Technology Data Exchange (ETDEWEB)

Takehira, K; Hayakawa, T; Ishikawa, T

1978-01-01

Dependence of the structure of vanadium-chromium binary oxide catalyst for oxidation of cyclohexene on the method of preparation was studied in an extension of previous work by using three series of binary oxide catalysts, D, E, and F, which were prepared by coprecipitation from acidic, neutral, and alkaline media, respectively. The specific activity at 60/sup 0/C, 1 atm oxygen, and benzene solvent decreased in the order D > E > F, but all three series showed maximum activity at 90% chromium. The selectivity for epoxide also followed the order D > E > F, but the maximum selectivity occurred at 50% chromium for D, 75% for E, and 90% for F. Comparison of these results with X-ray diffraction and ESR spectral structural analysis of the various chromium(III) vanadate phases supported the previously proposed mechanism, with cyclohexene autoxidation initiated by free radical decomposition of cyclohexene hydroperoxide occurring on a different type of active site.

Knockdown of cytosolic NADP(+) -dependent isocitrate dehydrogenase enhances MPP(+) -induced oxidative injury in PC12 cells.

Science.gov (United States)

Yang, Eun Sun; Park, Jeen-Woo

2011-05-01

1-Methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP) and its toxic metabolite 1-methyl-4-phenylpyridium ion (MPP(+)) have been shown to induce Parkinson's disease-like symptoms as well as neurotoxicity in humans and animal species. Recently, we reported that maintenance of redox balance and cellular defense against oxidative damage are primary functions of the novel antioxidant enzyme cytosolic NADP(+) -dependent isocitrate dehydrogenase (IDPc). In this study, we examined the role of IDPc in cellular defense against MPP(+) -induced oxidative injury using PC12 cells transfected with IDPc small interfering RNA (siRNA). Our results demonstrate that MPP(+) -mediated disruption of cellular redox status, oxidative damage to cells, and apoptotic cell death were significantly enhanced by knockdown of IDPc.

The role of extra-atomic relaxation in determining Si2p binding energy shifts at silicon/silicon oxide interfaces

International Nuclear Information System (INIS)

Zhang, K.Z.; Greeley, J.N.; Banaszak Holl, M.M.; McFeely, F.R.

1997-01-01

The observed binding energy shift for silicon oxide films grown on crystalline silicon varies as a function of film thickness. The physical basis of this shift has previously been ascribed to a variety of initial state effects (Si endash O ring size, strain, stoichiometry, and crystallinity), final state effects (a variety of screening mechanisms), and extrinsic effects (charging). By constructing a structurally homogeneous silicon oxide film on silicon, initial state effects have been minimized and the magnitude of final state stabilization as a function of film thickness has been directly measured. In addition, questions regarding the charging of thin silicon oxide films on silicon have been addressed. From these studies, it is concluded that initial state effects play a negligible role in the thickness-dependent binding energy shift. For the first ∼30 Angstrom of oxide film, the thickness-dependent binding energy shift can be attributed to final state effects in the form of image charge induced stabilization. Beyond about 30 Angstrom, charging of the film occurs. copyright 1997 American Institute of Physics

Melatonin membrane receptor (MT1R) expression and nitro-oxidative stress in testis of golden hamster, Mesocricetus auratus: An age-dependent study.

Science.gov (United States)

Mukherjee, Arun; Haldar, Chandana

2015-09-01

Age-dependent decline in melatonin level induces nitro-oxidative stress that compromises physiological homeostasis including reproduction. However, less information exist regarding the age-dependent variation in local melatonin (lMel) concentration and MT1R expression in testis and its interaction with testicular steroidogenesis and nitro-oxidative stress in golden hamster, Mesocricetus auratus. Therefore, we evaluated lMel level along with MT1R expression and its possible interaction with steroidogenesis and nitro-oxidative stress in testes of young (6weeks), adult (15weeks) and old (2years) aged hamsters. Further, we injected the old hamsters with melatonin to address whether age-related decline in lMel and MT1R is responsible for the reduction in testicular steroidogenesis and antioxidant status. Increased expression of steroidogenic markers suggests increased testicular steroidogenesis in adult hamsters that declined in old hamsters. An age-dependent elevation in the level of NOX, TBARS, corticosterone and the expression of iNOS and GR with a concomitant decrease in enzyme activities for SOD, CAT, GSH-PX indicate increased nitro-oxidative stress in testes. Data suggest that reproductive senescence in male hamsters might be a consequence of declined lMel concentration with MT1R expression inducing nitro-oxidative stress resulting in diminished testicular steroidogenesis. However, administration of Mel in old-aged hamsters significantly increased steroidogenesis and antioxidant status without a significant variation in lMel concentration and MT1R expression in testes. Therefore, decreased lMel and MT1R might not be the causative factor underlying the age-associated decrease in antioxidant defence and steroidogenesis in testes. In conclusion, Mel induced amelioration of testicular oxidative insult and elevation of steroidogenic activity suggests a potential role of increased nitro-oxidative stress underlying the age-dependent decrease in steroidogenesis. Copyright

Morphology-dependent activity of Pt nanocatalysts for ethanol oxidation in acidic media: Nanowires versus nanoparticles

International Nuclear Information System (INIS)

Zhou Weiping; Li Meng; Koenigsmann, Christopher; Ma Chao; Wong, Stanislaus S.; Adzic, Radoslav R.

2011-01-01

Highlights: → We demonstrate the morphology effect of Pt catalysts in electrooxidation of ethanol and CO in an acidic solution. → Pt nanowires and nanoparticles were used as catalysts. → Pt nanowires display a higher catalytic activity by a factor of at least two relative to those nanoparticles for ethanol oxidation. → The rate for CO monolayer oxidation exhibits similar morphology-dependent behavior with a markedly enhanced rate on the Pt nanowires. - Abstract: The morphology of nanostructured Pt catalysts is known to affect significantly the kinetics of various reactions. Herein, we report on a pronounced morphology effect in the electrooxidation of ethanol and carbon monoxide (CO) on Pt nanowires and nanoparticles in an acidic solution. The high resolution transmission electron microscopy analysis showed the inherent morphology difference between these two nanostructured catalysts. Voltammetric and chronoamperometric studies of the ethanol electrooxidation revealed that these nanowires had a higher catalytic activity by a factor of two relative to these nanoparticles. The rate for CO monolayer oxidation exhibits similar morphology-dependent behavior with a markedly enhanced rate on the Pt nanowires. In situ infrared reflection-absorption spectroscopy measurements revealed a different trend for chemisorbed CO formation and CO 2 -to-acetic acid reaction product ratios on these two nanostructures. The morphology-induced change in catalytic activity and selectivity in ethanol electrocatalysis is discussed in detail.

Morphology-dependent activity of Pt nanocatalysts for ethanol oxidation in acidic media: Nanowires versus nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Zhou Weiping, E-mail: wpzhou@bnl.gov [Chemistry Department, Brookhaven National Laboratory, Upton, NY 11973 (United States); Li Meng [Chemistry Department, Brookhaven National Laboratory, Upton, NY 11973 (United States); Koenigsmann, Christopher [Department of Chemistry, State University of New York at Stony Brook, Stony Brook, NY 11794 (United States); Ma Chao [Condensed Matter Physics and Materials Sciences Department, Brookhaven National Laboratory, Building 480, Upton, NY 11973 (United States); Wong, Stanislaus S. [Department of Chemistry, State University of New York at Stony Brook, Stony Brook, NY 11794 (United States); Condensed Matter Physics and Materials Sciences Department, Brookhaven National Laboratory, Building 480, Upton, NY 11973 (United States); Adzic, Radoslav R. [Chemistry Department, Brookhaven National Laboratory, Upton, NY 11973 (United States)

2011-11-30

Highlights: > We demonstrate the morphology effect of Pt catalysts in electrooxidation of ethanol and CO in an acidic solution. > Pt nanowires and nanoparticles were used as catalysts. > Pt nanowires display a higher catalytic activity by a factor of at least two relative to those nanoparticles for ethanol oxidation. > The rate for CO monolayer oxidation exhibits similar morphology-dependent behavior with a markedly enhanced rate on the Pt nanowires. - Abstract: The morphology of nanostructured Pt catalysts is known to affect significantly the kinetics of various reactions. Herein, we report on a pronounced morphology effect in the electrooxidation of ethanol and carbon monoxide (CO) on Pt nanowires and nanoparticles in an acidic solution. The high resolution transmission electron microscopy analysis showed the inherent morphology difference between these two nanostructured catalysts. Voltammetric and chronoamperometric studies of the ethanol electrooxidation revealed that these nanowires had a higher catalytic activity by a factor of two relative to these nanoparticles. The rate for CO monolayer oxidation exhibits similar morphology-dependent behavior with a markedly enhanced rate on the Pt nanowires. In situ infrared reflection-absorption spectroscopy measurements revealed a different trend for chemisorbed CO formation and CO{sub 2}-to-acetic acid reaction product ratios on these two nanostructures. The morphology-induced change in catalytic activity and selectivity in ethanol electrocatalysis is discussed in detail.

Shape-Dependent Activity of Ceria for Hydrogen Electro-Oxidation in Reduced-Temperature Solid Oxide Fuel Cells.

Science.gov (United States)

Tong, Xiaofeng; Luo, Ting; Meng, Xie; Wu, Hao; Li, Junliang; Liu, Xuejiao; Ji, Xiaona; Wang, Jianqiang; Chen, Chusheng; Zhan, Zhongliang

2015-11-04

Single crystalline ceria nanooctahedra, nanocubes, and nanorods are hydrothermally synthesized, colloidally impregnated into the porous La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) scaffolds, and electrochemically evaluated as the anode catalysts for reduced temperature solid oxide fuel cells (SOFCs). Well-defined surface terminations are confirmed by the high-resolution transmission electron microscopy--(111) for nanooctahedra, (100) for nanocubes, and both (110) and (100) for nanorods. Temperature-programmed reduction in H2 shows the highest reducibility for nanorods, followed sequentially by nanocubes and nanooctahedra. Measurements of the anode polarization resistances and the fuel cell power densities reveal different orders of activity of ceria nanocrystals at high and low temperatures for hydrogen electro-oxidation, i.e., nanorods > nanocubes > nanooctahedra at T ≤ 450 °C and nanooctahedra > nanorods > nanocubes at T ≥ 500 °C. Such shape-dependent activities of these ceria nanocrystals have been correlated to their difference in the local structure distortions and thus in the reducibility. These findings will open up a new strategy for design of advanced catalysts for reduced-temperature SOFCs by elaborately engineering the shape of nanocrystals and thus selectively exposing the crystal facets. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the behavior of Bronsted-Evans-Polanyi Relations for Transition Metal Oxides

Energy Technology Data Exchange (ETDEWEB)

Vojvodic, Aleksandra

2011-08-22

Versatile Broensted-Evans-Polanyi (BEP) relations are found from density functional theory for a wide range of transition metal oxides including rutiles and perovskites. For oxides, the relation depends on the type of oxide, the active site and the dissociating molecule. The slope of the BEP relation is strongly coupled to the adsorbate geometry in the transition state. If it is final state-like the dissociative chemisorption energy can be considered as a descriptor for the dissociation. If it is initial state-like, on the other hand, the dissociative chemisorption energy is not suitable as descriptor for the dissociation. Dissociation of molecules with strong intramolecular bonds belong to the former and molecules with weak intramolecular bonds to the latter group. We show, for the prototype system La-perovskites, that there is a 'cyclic' behavior in the transition state characteristics upon change of the active transition metal of the oxide.

The oxidative costs of reproduction are group-size dependent in a wild cooperative breeder.

Science.gov (United States)

Cram, Dominic L; Blount, Jonathan D; Young, Andrew J

2015-11-22

Life-history theory assumes that reproduction entails a cost, and research on cooperatively breeding societies suggests that the cooperative sharing of workloads can reduce this cost. However, the physiological mechanisms that underpin both the costs of reproduction and the benefits of cooperation remain poorly understood. It has been hypothesized that reproductive costs may arise in part from oxidative stress, as reproductive investment may elevate exposure to reactive oxygen species, compromising survival and future reproduction and accelerating senescence. However, experimental evidence of oxidative costs of reproduction in the wild remains scarce. Here, we use a clutch-removal experiment to investigate the oxidative costs of reproduction in a wild cooperatively breeding bird, the white-browed sparrow weaver, Plocepasser mahali. Our results reveal costs of reproduction that are dependent on group size: relative to individuals in groups whose eggs were experimentally removed, individuals in groups that raised offspring experienced an associated cost (elevated oxidative damage and reduced body mass), but only if they were in small groups containing fewer or no helpers. Furthermore, during nestling provisioning, individuals that provisioned at higher rates showed greater within-individual declines in body mass and antioxidant protection. Our results provide rare experimental evidence that reproduction can negatively impact both oxidative status and body mass in the wild, and suggest that these costs can be mitigated in cooperative societies by the presence of additional helpers. These findings have implications for our understanding of the energetic and oxidative costs of reproduction, and the benefits of cooperation in animal societies. © 2015 The Authors.

Non steady-state model for dry oxidation of nuclear wastes metallic containers in long term interim storage conditions

International Nuclear Information System (INIS)

Bertrand, Nathalie; Desgranges, Clara; Poquillon, Dominique; Monceau, Daniel

2006-01-01

For high-level nuclear waste containers in long-term interim storage, dry oxidation will be the first and the main degradation mode. The reason is that, for this kind of waste, the temperature on the surface of the containers will be high enough to avoid any condensation phenomena for several years. Even if the scale growth kinetics is expected to be very slow since the temperature will be moderate at the beginning of the storage (around 300 deg. C) and will keep on decreasing, the metal thickness lost by dry oxidation over such a long period must be evaluated with a good reliability. To achieve this goal, modelling of the oxide scale growth is necessary and this is the aim of the dry oxidation studies, performed in the frame of the COCON programme. All existing oxidation models are based on the two main oxidation theories developed by Wagner between the 1930's and 1970's on the one hand, and by Cabrera and Mott in the 1960 and next by Fromhold on the other hand. These used to be associated with high temperature behaviour for Wagner's theory and with low temperature for the second one. Indeed it is certainly more relevant to consider their range of application in terms of the oxide scale thickness rather than in terms of temperature. The question is posed about which theory should an appropriate model rely on. It can be expected that the oxide scale could have a thickness ranging from a few tens of nanometers up to several tens of micrometers depending on temperature and class of alloys chosen. At the present time, low-alloyed steels or carbon steels are considered candidate materials for high-level nuclear waste containers in long term interim storage. For this type of alloys, the scale formed during the dry oxidation stage will be 'rapidly' thick enough to neglect the Mott field. Hence, in a first step, some basic models based on a parabolic rate assumption, that is to say Wagner's model, have been derived from experimental data on iron and on low-alloy steel

Dose dependent oxidation kinetics of lipids in fish during irradiation processing

International Nuclear Information System (INIS)

Tukenmez, I.; Ersen, M.S.; Bakioglu, A.T.; Bicer, A.; Pamuk, V.

1997-01-01

Kinetic aspects of the development of lipid oxidation in complex foods as fish in the course of irradiation were analyzed with respect to the associated formation of malonaldehyde (MA) through the reactions modified so as to be consistent with those in complex foods as fish. Air-packed anchovy (Engraulis encrasicholus) samples in polyethylene pouches were irradiated at the doses of 1, 2, 5, 10, 15,20 and 25 kGy at 20 o C in a Cs-137 gamma irradiator of 1.806 kGy/h dose rate. Immediately after each irradiation, MA contents of irradiated and unirradiated samples were determined by thiobarbituric acid test. Based on the MA formation, a kinetic model to simulate the apparent oxidation of lipid in fish as a function of irradiation dose was derived from the rate equations consistent with modified reactions. Kinetic parameters and simulation were related to conditions of lipid oxidation, and associated rancidity state of fish with respect to the doses applied in different irradiation-preservation processes. Numerical values of kinetic parameters based on the MA formation were found as a threshold dose of 0.375 kGy, an apparent yield of 1.871 μmol/kg kGy, and a maximum attainable concentration of 15.853 μmol/kg which may be used for process control and dosimetry. (author)

State Dependence in Unemployment among Danish Immigrants

DEFF Research Database (Denmark)

Ahmad, Nisar

2009-01-01

This study examines the extent state dependence among unemployed Danish immigrants in a dynamic discrete choice framework. Three alternative methodologies are employed to control for the problem of the initial condition. The empirical findings show that there is a considerable correlation between...... compared to an individual who was employed at period “t-1”. This average partial effect is the same for western compared to non-western immigrants and women compared to men....

The United States facing their petroleum dependence

International Nuclear Information System (INIS)

Noel, P.

2002-06-01

In the framework of ''the energy crisis of 2000-2001'', the Cheney report and the petroleum dependence, this study presents a critical examination of the United States petroleum situation, its perception in the american political milieu and the public policies implementing during the last ten years. The first section is devoted to the petroleum supply. In the second section, the american petroleum policy and the energy safety are studied. (A.L.B.)

Influence of steam generator surface state on corrosion and oxide formation

International Nuclear Information System (INIS)

Mazenc, Arnaud; Leclercq, Stephanie; Seyeux, Antoine; Galtayries, Anouk; Marcus, Philippe

2012-09-01

The corrosion and release of nickel-based alloy Steam Generator tubes are partly due to their surface state. Among the most important parameters influencing the corrosion, the effect of grain size and the effect of grain crystallographic orientation have been chosen to be studied. The aim of this study is to determine how these parameters have an impact on the corrosion of Steam Generator tubes. Thermal treatments (700 deg. C and 1050 deg. C) have been performed on several samples in Alloy 690 to obtain homogeneous grain sizes, varying from 25 μm to 110 μm. Two samples have been oxidised for four days in a recirculating autoclave, reproducing primary conditions. The changes of oxide composition and thickness were examined by ToF-SIMS on samples exposed to primary water conditions. The intensity profiles versus thicknesses of characteristic oxide anions, such as CrO - , NiO - or FeO - enable us to evaluate the effect of grain size and crystallographic orientation on the formation of an enriched inner chromium layer. As regards to the grain size, there was no effect on the growth, but smaller grains led to a chromium-rich oxide layer. The effect of crystallographic orientation was observed on the oxidation kinetics and the composition of oxide scales. (authors)

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

Science.gov (United States)

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

2014-07-01

The discovery of hydroxymethyl-, formyl- and carboxylcytosine, generated through oxidation of methylcytosine by TET dioxygenases, raised the question how these modifications contribute to epigenetic regulation. As they are subjected to complex regulation in vivo, we dissected links to gene expression with in vitro modified reporter constructs. We used an Oct4 promoter-driven reporter gene and demonstrated that in vitro methylation causes gene silencing while subsequent oxidation with purified catalytic domain of TET1 leads to gene reactivation. To identify proteins involved in this pathway we screened for TET interacting factors and identified TDG, PARP1, XRCC1 and LIG3 that are involved in base-excision repair. Knockout and rescue experiments demonstrated that gene reactivation depended on the glycosylase TDG, but not MBD4, while NEIL1, 2 and 3 could partially rescue the loss of TDG. These results clearly show that oxidation of methylcytosine by TET dioxygenases and subsequent removal by TDG or NEIL glycosylases and the BER pathway results in reactivation of epigenetically silenced genes. © The Author(s) 2014. Published by Oxford University Press on behalf of Nucleic Acids Research.

Exotic Paired States with Anisotropic Spin-Dependent Fermi Surfaces

International Nuclear Information System (INIS)

Feiguin, Adrian E.; Fisher, Matthew P. A.

2009-01-01

We propose a model for realizing exotic paired states in cold Fermi gases by using a spin-dependent optical lattice to engineer mismatched Fermi surfaces for each hyperfine species. The BCS phase diagram shows a stable paired superfluid state with coexisting pockets of momentum space with gapless unpaired carriers, similar to the Sarma state in polarized mixtures, but in our case the system is unpolarized. We propose the possible existence of an exotic 'Cooper-pair Bose-metal' phase, which has a gap for single fermion excitations but gapless and uncondensed 'Cooper-pair' excitations residing on a 'Bose surface' in momentum space.

“Covalent Hydration” Reactions in Model Monomeric Ru 2,2'-Bipyridine Complexes: Thermodynamic Favorability as a Function of Metal Oxidation and Overall Spin States

Energy Technology Data Exchange (ETDEWEB)

Ozkanlar, Abdullah; Cape, Jonathan L.; Hurst, James K.; Clark, Aurora E.

2011-09-05

Density functional theory (DFT) has been used to investigate the plausibility of water addition to the simple mononuclear ruthenium complexes, [(NH{sub 3}){sub 3}(bpy)Ru=O]{sup 2+}/{sup 3+} and [(NH{sub 3}){sub 3}(bpy)RuOH]{sup 3+}, in which the OH fragment adds to the 2,2{prime}-bipyridine (bpy) ligand. Activation of bpy toward water addition has frequently been postulated within the literature, although there exists little definitive experimental evidence for this type of 'covalent hydration'. In this study, we examine the energetic dependence of the reaction upon metal oxidation state, overall spin state of the complex, as well as selectivity for various positions on the bipyridine ring. The thermodynamic favorability is found to be highly dependent upon all three parameters, with free energies of reaction that span favorable and unfavorable regimes. Aqueous addition to [(NH{sub 3}){sub 3}(bpy)Ru=O]{sup 3+} was found to be highly favorable for the S = 1/2 state, while reduction of the formal oxidation state on the metal center makes the reaction highly unfavorable. Examination of both facial and meridional isomers reveals that when bipyridine occupies the position trans to the ruthenyl oxo atom, reactivity toward OH addition decreases and the site preferences are altered. The electronic structure and spectroscopic signatures (EPR parameters and simulated spectra) have been determined to aid in recognition of 'covalent hydration' in experimental systems. EPR parameters are found to uniquely characterize the position of the OH addition to the bpy as well as the overall spin state of the system.

The Traditional Herbal Medicine, Dangkwisoo-San, Prevents Cerebral Ischemic Injury through Nitric Oxide-Dependent Mechanisms

Directory of Open Access Journals (Sweden)

Ji Hyun Kim

2011-01-01

Full Text Available Dangkwisoo-San (DS is an herbal extract that is widely used in traditional Korean medicine to treat traumatic ecchymosis and pain by promoting blood circulation and relieving blood stasis. However, the effect of DS in cerebrovascular disease has not been examined experimentally. The protective effects of DS on focal ischemic brain were investigated in a mouse model. DS stimulated nitric oxide (NO production in human brain microvascular endothelial cells (HBMECs. DS (10–300 μg/mL produced a concentration-dependent relaxation in mouse aorta, which was significantly attenuated by the nitric oxide synthase (NOS inhibitor L-NAME, suggesting that DS causes vasodilation via a NO-dependent mechanism. DS increased resting cerebral blood flow (CBF, although it caused mild hypotension. To investigate the effect of DS on the acute cerebral injury, C57/BL6J mice received 90 min of middle cerebral artery occlusion followed by 22.5 h of reperfusion. DS administered 3 days before arterial occlusion significantly reduced cerebral infarct size by 53.7% compared with vehicle treatment. However, DS did not reduce brain infarction in mice treated with the relatively specific endothelial NOS (eNOS inhibitor, N5-(1-iminoethyl-L-ornithine, suggesting that the neuroprotective effect of DS is primarily endothelium-dependent. This correlated with increased phosphorylation of eNOS in the brains of DS-treated mice. DS acutely improves CBF in eNOS-dependent vasodilation and reduces infarct size in focal cerebral ischemia. These data provide causal evidence that DS is cerebroprotective via the eNOS-dependent production of NO, which ameliorates blood circulation.

Adsorption of CO, CO2, H2, and H2O on titania surfaces with different oxidation states

International Nuclear Information System (INIS)

Raupp, G.B.; Dumesic, J.A.

1985-01-01

The adsorptive properties of titania surfaces with different oxidation states were proved by temperature-programmed desorption (TPD) of CO, H 2 , CO 2 , and H 2 O. Auger electron spectroscopy and X-ray photoelectron spectroscopy revealed that vacuum annealing an oxidized titanium foil at temperatures from 300 to 800 K was an effective means of systematically varying the average surface oxidation state from Ti 4+ to Ti 2+ . Carbon monoxide weakly adsorbed (desorption energy of 44-49 kJ x mol -1 ) in a carbonyl fashion on coordinatively unsaturated cation sites. Titania surfaces were inert with respect to H 2 adsorption and dissociation. Carbon dioxide adsorbed in a linear molecular fashion. Water adsorbed both molecularly and dissociatively. Results are discussed in terms of the role of titania oxidation state in CO hydrogenation over titania-supported metal catalysts. 74 references, 7 figures

State-dependent sensorimotor processing: gaze and posture stability during simulated flight in birds.

Science.gov (United States)

McArthur, Kimberly L; Dickman, J David

2011-04-01

Vestibular responses play an important role in maintaining gaze and posture stability during rotational motion. Previous studies suggest that these responses are state dependent, their expression varying with the environmental and locomotor conditions of the animal. In this study, we simulated an ethologically relevant state in the laboratory to study state-dependent vestibular responses in birds. We used frontal airflow to simulate gliding flight and measured pigeons' eye, head, and tail responses to rotational motion in darkness, under both head-fixed and head-free conditions. We show that both eye and head response gains are significantly higher during flight, thus enhancing gaze and head-in-space stability. We also characterize state-specific tail responses to pitch and roll rotation that would help to maintain body-in-space orientation during flight. These results demonstrate that vestibular sensorimotor processing is not fixed but depends instead on the animal's behavioral state.

Chelation and stabilization of berkelium in oxidation state +IV

Science.gov (United States)

Deblonde, Gauthier J.-P.; Sturzbecher-Hoehne, Manuel; Rupert, Peter B.; An, Dahlia D.; Illy, Marie-Claire; Ralston, Corie Y.; Brabec, Jiri; de Jong, Wibe A.; Strong, Roland K.; Abergel, Rebecca J.

2017-09-01

Berkelium (Bk) has been predicted to be the only transplutonium element able to exhibit both +III and +IV oxidation states in solution, but evidence of a stable oxidized Bk chelate has so far remained elusive. Here we describe the stabilization of the heaviest 4+ ion of the periodic table, under mild aqueous conditions, using a siderophore derivative. The resulting Bk(IV) complex exhibits luminescence via sensitization through an intramolecular antenna effect. This neutral Bk(IV) coordination compound is not sequestered by the protein siderocalin—a mammalian metal transporter—in contrast to the negatively charged species obtained with neighbouring trivalent actinides americium, curium and californium (Cf). The corresponding Cf(III)-ligand-protein ternary adduct was characterized by X-ray diffraction analysis. Combined with theoretical predictions, these data add significant insight to the field of transplutonium chemistry, and may lead to innovative Bk separation and purification processes.

Composition and oxidation state of sulfur in atmospheric particulate matter

Directory of Open Access Journals (Sweden)

A. F. Longo

2016-10-01

Full Text Available The chemical and physical speciation of atmospheric sulfur was investigated in ambient aerosol samples using a combination of sulfur near-edge x-ray fluorescence spectroscopy (S-NEXFS and X-ray fluorescence (XRF microscopy. These techniques were used to determine the composition and oxidation state of sulfur in common primary emission sources and ambient particulate matter collected from the greater Atlanta area. Ambient particulate matter samples contained two oxidation states: S0 and S+VI. Ninety-five percent of the individual aerosol particles (> 1 µm analyzed contain S0. Linear combination fitting revealed that S+VI in ambient aerosol was dominated by ammonium sulfate as well as metal sulfates. The finding of metal sulfates provides further evidence for acidic reactions that solubilize metals, such as iron, during atmospheric transport. Emission sources, including biomass burning, coal fly ash, gasoline, diesel, volcanic ash, and aerosolized Atlanta soil, and the commercially available bacterium Bacillus subtilis, contained only S+VI. A commercially available Azotobacter vinelandii sample contained approximately equal proportions of S0 and S+VI. S0 in individual aerosol particles most likely originates from primary emission sources, such as aerosolized bacteria or incomplete combustion.

Effects of oxide traps, interface traps, and ''border traps'' on metal-oxide-semiconductor devices

International Nuclear Information System (INIS)

Fleetwood, D.M.; Winokur, P.S.; Reber, R.A. Jr.; Meisenheimer, T.L.; Schwank, J.R.; Shaneyfelt, M.R.; Riewe, L.C.

1993-01-01

We have identified several features of the 1/f noise and radiation response of metal-oxide-semiconductor (MOS) devices that are difficult to explain with standard defect models. To address this issue, and in response to ambiguities in the literature, we have developed a revised nomenclature for defects in MOS devices that clearly distinguishes the language used to describe the physical location of defects from that used to describe their electrical response. In this nomenclature, ''oxide traps'' are simply defects in the SiO 2 layer of the MOS structure, and ''interface traps'' are defects at the Si/SiO 2 interface. Nothing is presumed about how either type of defect communicates with the underlying Si. Electrically, ''fixed states'' are defined as trap levels that do not communicate with the Si on the time scale of the measurements, but ''switching states'' can exchange charge with the Si. Fixed states presumably are oxide traps in most types of measurements, but switching states can either be interface traps or near-interfacial oxide traps that can communicate with the Si, i.e., ''border traps'' [D. M. Fleetwood, IEEE Trans. Nucl. Sci. NS-39, 269 (1992)]. The effective density of border traps depends on the time scale and bias conditions of the measurements. We show the revised nomenclature can provide focus to discussions of the buildup and annealing of radiation-induced charge in non-radiation-hardened MOS transistors, and to changes in the 1/f noise of MOS devices through irradiation and elevated-temperature annealing

Oxidized Nitrogen Balance over 15 Months at Rural and Urban New York State Locations

Science.gov (United States)

Schwab, J. J.; Ninneman, M.; Marto, J.; Edgerton, E. S.; Blanchard, C. L.; Shaw, S. L.

2017-12-01

Continuous measurements of oxidized nitrogen species (NO, NO2, and HNO3), families of species (NOy, alkyl nitrates [or ANs], and peroxyacetyl nitrates [or PANs]), and particle nitrate (pNO3) were carried out for a fifteen-month period from August 2016 through October 2017 at two locations in New York State. The two sites were a rural research station at Pinnacle State Park in Addison, NY and an urban research station at Queens College in New York City. Four different chemiluminescence analyzers with various converters and denuders were employed to make these measurements. Instrumentation used for the study will be described, as well as some of the challenges created by combining data from these independent analyzers to address the oxidized nitrogen budget at the two sites. The Pinnacle State Park site often experiences quite clean air with low ppb levels of total NOy and a greater fraction of oxidized nitrogen products (NOz species). This contrasts with the urban Queens College location, which experiences stronger NOx sources. Seasonal differences in the NOx/NOy and NOz/NOy ratios, and the makeup of the NOz species, are also significant and will be explored in the presentation.

Medical marijuana laws in 50 states: investigating the relationship between state legalization of medical marijuana and marijuana use, abuse and dependence.

Science.gov (United States)

Cerdá, Magdalena; Wall, Melanie; Keyes, Katherine M; Galea, Sandro; Hasin, Deborah

2012-01-01

Marijuana is the most frequently used illicit substance in the United States. Little is known of the role that macro-level factors, including community norms and laws related to substance use, play in determining marijuana use, abuse and dependence. We tested the relationship between state-level legalization of medical marijuana and marijuana use, abuse, and dependence. We used the second wave of the National Epidemiologic Survey on Alcohol and Related Conditions (NESARC), a national survey of adults aged 18+ (n=34,653). Selected analyses were replicated using the National Survey on Drug Use and Health (NSDUH), a yearly survey of ∼68,000 individuals aged 12+. We measured past-year cannabis use and DSM-IV abuse/dependence. In NESARC, residents of states with medical marijuana laws had higher odds of marijuana use (OR: 1.92; 95% CI: 1.49-2.47) and marijuana abuse/dependence (OR: 1.81; 95% CI: 1.22-2.67) than residents of states without such laws. Marijuana abuse/dependence was not more prevalent among marijuana users in these states (OR: 1.03; 95% CI: 0.67-1.60), suggesting that the higher risk for marijuana abuse/dependence in these states was accounted for by higher rates of use. In NSDUH, states that legalized medical marijuana also had higher rates of marijuana use. States that legalized medical marijuana had higher rates of marijuana use. Future research needs to examine whether the association is causal, or is due to an underlying common cause, such as community norms supportive of the legalization of medical marijuana and of marijuana use. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

A thioredoxin-dependent peroxiredoxin Q from Corynebacterium glutamicum plays an important role in defense against oxidative stress.

Directory of Open Access Journals (Sweden)

Tao Su

Full Text Available Peroxiredoxin Q (PrxQ that belonged to the cysteine-based peroxidases has long been identified in numerous bacteria, but the information on the physiological and biochemical functions of PrxQ remain largely lacking in Corynebacterium glutamicum. To better systematically understand PrxQ, we reported that PrxQ from model and important industrial organism C. glutamicum, encoded by the gene ncgl2403 annotated as a putative PrxQ, played important roles in adverse stress resistance. The lack of C. glutamicum prxQ gene resulted in enhanced cell sensitivity, increased ROS accumulation, and elevated protein carbonylation levels under adverse stress conditions. Accordingly, PrxQ-mediated resistance to adverse stresses mainly relied on the degradation of ROS. The physiological roles of PrxQ in resistance to adverse stresses were corroborated by its induced expression under adverse stresses, regulated directly by the stress-responsive ECF-sigma factor SigH. Through catalytical kinetic activity, heterodimer formation, and bacterial two-hybrid analysis, we proved that C. glutamicum PrxQ catalytically eliminated peroxides by exclusively receiving electrons from thioredoxin (Trx/thioredoxin reductase (TrxR system and had a broad range of oxidizing substrates, but a better efficiency for peroxynitrite and cumene hydroperoxide (CHP. Site-directed mutagenesis confirmed that the conserved Cys49 and Cys54 are the peroxide oxidation site and the resolving Cys residue, respectively. It was also discovered that C. glutamicum PrxQ mainly existed in monomer whether under its native state or functional state. Based on these results, a catalytic model of PrxQ is being proposed. Moreover, our result that C. glutamicum PrxQ can prevent the damaging effects of adverse stresses by acting as thioredoxin-dependent monomeric peroxidase could be further applied to improve the survival ability and robustness of the important bacterium during fermentation process.

Quantitative chemical state XPS analysis of first row transition metals, oxides and hydroxides

International Nuclear Information System (INIS)

Biesinger, M C; Payne, B P; McIntryre, N S; Hart, B R; Lau, L Wm; Grosvenor, A P; Smart, R StC

2008-01-01

Practical quantitative chemical state X-ray photoelectron spectroscopy (XPS) analysis of first row transition metals, oxides and hydroxides is challenging due to the complexity of their M 2p spectra. Complex multiplet splitting, shake-up and plasmon loss structure can play a role in the interpretation of the chemical states present. This paper will show practical curve fitting procedures for the quantitative measurement of different chemical states for metal oxides and hydroxides from a survey of transition metals. It will also discuss some of the limitations and pitfalls present as well as give practical examples of their successful use. These curve-fitting procedures are based on 1) standard spectra from quality reference samples, 2) a survey of appropriate literature databases and/or a compilation of literature references, 3) fitting of multiplet split spectra based on spectra of numerous reference materials and theoretical modelling, 4) spectral subtractions routines, again using reference spectra, and 5) specific literature references where fitting procedures are available

Quantitative chemical state XPS analysis of first row transition metals, oxides and hydroxides

Energy Technology Data Exchange (ETDEWEB)

Biesinger, M C; Payne, B P; McIntryre, N S [Department of Chemistry, University of Western Ontario, London, Ontario, N6A 5B7 (Canada); Hart, B R; Lau, L Wm [Surface Science Western, Room G1, Western Science Centre, University of Western Ontario, London, Ontario, N6A 5B7 (Canada); Grosvenor, A P [Department of Chemistry, Gunning/Lemieux Chemistry Centre, University of Alberta, Edmonton, Alberta, T6G 2G2 (Canada); Smart, R StC [ACeSSS, Applied Centre for Structural and Synchrotron Studies, University of South Australia, Mawson Lakes, SA 5095 (Australia)], E-mail: biesingr@uwo.ca

2008-03-15

Practical quantitative chemical state X-ray photoelectron spectroscopy (XPS) analysis of first row transition metals, oxides and hydroxides is challenging due to the complexity of their M 2p spectra. Complex multiplet splitting, shake-up and plasmon loss structure can play a role in the interpretation of the chemical states present. This paper will show practical curve fitting procedures for the quantitative measurement of different chemical states for metal oxides and hydroxides from a survey of transition metals. It will also discuss some of the limitations and pitfalls present as well as give practical examples of their successful use. These curve-fitting procedures are based on 1) standard spectra from quality reference samples, 2) a survey of appropriate literature databases and/or a compilation of literature references, 3) fitting of multiplet split spectra based on spectra of numerous reference materials and theoretical modelling, 4) spectral subtractions routines, again using reference spectra, and 5) specific literature references where fitting procedures are available.

Towards the improvement of the oxidation resistance of Nb-silicides in situ composites: A solid state diffusion approach

International Nuclear Information System (INIS)

Mathieu, S.; Knittel, S.; François, M.; Portebois, L.; Mathieu, S.; Vilasi, M.

2014-01-01

Highlights: •Local equilibrium is attained during oxidation at phase boundaries (steady state conditions). •A solid state diffusion model explains the oxidation mechanism of Nb-silicides composites. •The Nb ss fraction is not the only parameters governing the oxidation rate of Nb-silicides. •Aluminium increases the thermodynamic activity of Si in the Nb-silicides composites. •The results indicate the need to develop a Nb–Ti–Hf–Al–Cr–Si thermodynamic database. -- Abstract: The present study focuses on the oxidation mechanism of Nb-silicide composites and on the effect of the composition on the oxidation rate at 1100 °C. A theoretical approach is proposed based on experimental results and used to optimise the oxidation resistance. The growth model based on multiphase diffusion was experimentally tested and confirmed by manufacturing seven composites with different compositions. It was also found that the effect of the composition has to be evaluated at 1100 °C within a short time duration (50 h), where the oxide scale and the internal oxidation zone both grow according to parabolic kinetics

Effect of surface state on the oxidation behavior of welded 308L in simulated nominal primary water of PWR

Science.gov (United States)

Ming, Hongliang; Zhang, Zhiming; Wang, Jiazhen; Zhu, Ruolin; Ding, Jie; Wang, Jianqiu; Han, En-Hou; Ke, Wei

2015-05-01

The oxidation behavior of 308L weld metal (WM) with different surface state in the simulated nominal primary water of pressurized water reactor (PWR) was studied by scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) analyzer and X-ray photoelectron spectroscopy (XPS). After 480 h immersion, a duplex oxide film composed of a Fe-rich outer layer (Fe3O4, Fe2O3 and a small amount of NiFe2O4, Ni(OH)2, Cr(OH)3 and (Ni, Fe)Cr2O4) and a Cr-rich inner layer (FeCr2O4 and NiCr2O4) can be formed on the 308L WM samples with different surface state. The surface state has no influence on the phase composition of the oxide films but obviously affects the thickness of the oxide films and the morphology of the oxides (number & size). With increasing the density of dislocations and subgrain boundaries in the cold-worked superficial layer, the thickness of the oxide film, the number and size of the oxides decrease.

Pentavalent Uranium Chemistry - Synthetic Pursuit Of A Rare Oxidation State

Energy Technology Data Exchange (ETDEWEB)

Graves, Christopher R [Los Alamos National Laboratory; Kiplinger, Jaqueline L [Los Alamos National Laboratory

2009-01-01

This feature article presents a comprehensive overview of pentavalent uranium systems in non-aqueous solution with a focus on the various synthetic avenues employed to access this unusual and very important oxidation state. Selected characterization data and theoretical aspects are also included. The purpose is to provide a perspective on this rapidly evolving field and identify new possibilities for future developments in pentavalent uranium chemistry.

Verification of Large State/Event Systems using Compositionality and Dependency Analysis

DEFF Research Database (Denmark)

Lind-Nielsen, Jørn; Andersen, Henrik Reif; Hulgaard, Henrik

2001-01-01

A state/event model is a concurrent version of Mealy machines used for describing embedded reactive systems. This paper introduces a technique that uses compositionality and dependency analysis to significantly improve the efficiency of symbolic model checking of state/event models. It makes...

Verification of Large State/Event Systems using Compositionality and Dependency Analysis

DEFF Research Database (Denmark)

Lind-Nielsen, Jørn; Andersen, Henrik Reif; Behrmann, Gerd

1999-01-01

A state/event model is a concurrent version of Mealy machines used for describing embedded reactive systems. This paper introduces a technique that uses \\emph{compositionality} and \\emph{dependency analysis} to significantly improve the efficiency of symbolic model checking of state/event models...

The influence of iridium chemical oxidation state on the performance and durability of oxygen evolution catalysts in PEM electrolysis

Science.gov (United States)

Siracusano, S.; Baglio, V.; Grigoriev, S. A.; Merlo, L.; Fateev, V. N.; Aricò, A. S.

2017-10-01

Nanosized Ir-black (3 nm) and Ir-oxide (5 nm) oxygen evolution electrocatalysts showing high performance in polymer electrolyte membrane (PEM) water electrolysis based on Aquivion® short-side chain ionomer membrane are investigated to understand the role of the Ir oxidation state on the electrocatalytic activity and stability. Despite the smaller mean crystallite size, the Ir-black electrocatalyst shows significantly lower initial performance than the Ir-oxide. During operation at high current density, the Ir-black shows a decrease of cell potential with time whereas the Ir-oxide catalyst shows increasing cell potential resulting in a degradation rate of about 10 μV/h, approaching 1000 h. The unusual behaviour of the Ir-black results from the oxidation of metallic Ir to IrOx. The Ir-oxide catalyst shows instead a hydrated structure on the surface and a negative shift of about 0.5 eV for the Ir 4f binding energy after 1000 h electrolysis operation. This corresponds to the formation of a sub-stoichiometric Ir-oxide on the surface. These results indicate that a hydrated IrO2 with high oxidation state on the surface is favourable in decreasing the oxygen evolution overpotential. Modifications of the Ir chemical oxidation state during operation can affect significantly the catalytic activity and durability of the electrolysis system.

Measurement of soil carbon oxidation state and oxidative ratio by 13C nuclear magnetic resonance

Science.gov (United States)

Hockaday, W.C.; Masiello, C.A.; Randerson, J.T.; Smernik, R.J.; Baldock, J.A.; Chadwick, O.A.; Harden, J.W.

2009-01-01

The oxidative ratio (OR) of the net ecosystem carbon balance is the ratio of net O2 and CO2 fluxes resulting from photosynthesis, respiration, decomposition, and other lateral and vertical carbon flows. The OR of the terrestrial biosphere must be well characterized to accurately estimate the terrestrial CO2 sink using atmospheric measurements of changing O2 and CO2 levels. To estimate the OR of the terrestrial biosphere, measurements are needed of changes in the OR of aboveground and belowground carbon pools associated with decadal timescale disturbances (e.g., land use change and fire). The OR of aboveground pools can be measured using conventional approaches including elemental analysis. However, measuring the OR of soil carbon pools is technically challenging, and few soil OR data are available. In this paper we test three solid-state nuclear magnetic resonance (NMR) techniques for measuring soil OR, all based on measurements of the closely related parameter, organic carbon oxidation state (Cox). Two of the three techniques make use of a molecular mixing model which converts NMR spectra into concentrations of a standard suite of biological molecules of known C ox. The third technique assigns Cox values to each peak in the NMR spectrum. We assess error associated with each technique using pure chemical compounds and plant biomass standards whose Cox and OR values can be directly measured by elemental analyses. The most accurate technique, direct polarization solid-state 13C NMR with the molecular mixing model, agrees with elemental analyses to ??0.036 Cox units (??0.009 OR units). Using this technique, we show a large natural variability in soil Cox and OR values. Soil Cox values have a mean of -0.26 and a range from -0.45 to 0.30, corresponding to OR values of 1.08 ?? 0.06 and a range from 0.96 to 1.22. We also estimate the OR of the carbon flux from a boreal forest fire. Analysis of soils from nearby intact soil profiles imply that soil carbon losses associated

Nitric oxide-mediated maintenance of redox homeostasis contributes to NPR1-dependent plant innate immunity triggered by lipopolysaccharides.

Science.gov (United States)

Sun, Aizhen; Nie, Shengjun; Xing, Da

2012-10-01

The perception of lipopolysaccharides (LPS) by plant cells can lead to nitric oxide (NO) production and defense gene induction. However, the signaling cascades underlying these cellular responses have not yet been resolved. This work investigated the biosynthetic origin of NO and the role of NONEXPRESSOR OF PATHOGENESIS-RELATED GENES1 (NPR1) to gain insight into the mechanism involved in LPS-induced resistance of Arabidopsis (Arabidopsis thaliana). Analysis of inhibitors and mutants showed that LPS-induced NO synthesis was mainly mediated by an arginine-utilizing source of NO generation. Furthermore, LPS-induced NO caused transcript accumulation of alternative oxidase genes and increased antioxidant enzyme activity, which enhanced antioxidant capacity and modulated redox state. We also analyzed the subcellular localization of NPR1 to identify the mechanism for protein-modulated plant innate immunity triggered by LPS. LPS-activated defense responses, including callose deposition and defense-related gene expression, were found to be regulated through an NPR1-dependent pathway. In summary, a significant NO synthesis induced by LPS contributes to the LPS-induced defense responses by up-regulation of defense genes and modulation of cellular redox state. Moreover, NPR1 plays an important role in LPS-triggered plant innate immunity.

Microwave-Based Oxidation State and Soot Loading Determination on Gasoline Particulate Filters with Three-Way Catalyst Coating for Homogenously Operated Gasoline Engines.

Science.gov (United States)

Dietrich, Markus; Jahn, Christoph; Lanzerath, Peter; Moos, Ralf

2015-09-02

Recently, a novel method emerged to determine the oxygen storage degree of three way catalysts (TWC) by a microwave-based method. Up to now, this method has been investigated only in lab-scale reactors or under steady state conditions. This work expands those initial studies. A TWC-coated gasoline particulate filter was investigated in a dynamic engine test bench simulating a typical European driving cycle (NEDC). It could be shown that both the oxygen storage degree and the soot loading can be monitored directly, but not simultaneously due to their competitive effects. Under normal driving conditions, no soot accumulation was observed, related to the low raw emissions and the catalytic coating of the filter. For the first time, the quality factor of the cavity resonator in addition to the resonance frequency was used, with the benefit of less cross sensitivity to inconstant temperature and water. Therefore, a temperature dependent calibration of the microwave signal was created and applied to monitor the oxidation state in transient driving cycles. The microwave measurement mirrors the oxidation state determined by lambda probes and can be highly beneficial in start-stop phases (where lambda-probes do not work) and to determine the oxygen storage capacity (OSC) without unnecessary emissions.

Microwave-Based Oxidation State and Soot Loading Determination on Gasoline Particulate Filters with Three-Way Catalyst Coating for Homogenously Operated Gasoline Engines

Directory of Open Access Journals (Sweden)

Markus Dietrich

2015-09-01

Full Text Available Recently, a novel method emerged to determine the oxygen storage degree of three way catalysts (TWC by a microwave-based method. Up to now, this method has been investigated only in lab-scale reactors or under steady state conditions. This work expands those initial studies. A TWC-coated gasoline particulate filter was investigated in a dynamic engine test bench simulating a typical European driving cycle (NEDC. It could be shown that both the oxygen storage degree and the soot loading can be monitored directly, but not simultaneously due to their competitive effects. Under normal driving conditions, no soot accumulation was observed, related to the low raw emissions and the catalytic coating of the filter. For the first time, the quality factor of the cavity resonator in addition to the resonance frequency was used, with the benefit of less cross sensitivity to inconstant temperature and water. Therefore, a temperature dependent calibration of the microwave signal was created and applied to monitor the oxidation state in transient driving cycles. The microwave measurement mirrors the oxidation state determined by lambda probes and can be highly beneficial in start-stop phases (where lambda-probes do not work and to determine the oxygen storage capacity (OSC without unnecessary emissions.

The Impact of Environmental Factors in Influencing Epigenetics Related to Oxidative States in the Cardiovascular System

Directory of Open Access Journals (Sweden)

Francesco Angelini

2017-01-01

Full Text Available Oxidative states exert a significant influence on a wide range of biological and molecular processes and functions. When their balance is shifted towards enhanced amounts of free radicals, pathological phenomena can occur, as the generation of reactive oxygen species (ROS in tissue microenvironment or in the systemic circulation can be detrimental. Epidemic chronic diseases of western societies, such as cardiovascular disease, obesity, and diabetes correlate with the imbalance of redox homeostasis. Current advances in our understanding of epigenetics have revealed a parallel scenario showing the influence of oxidative stress as a major regulator of epigenetic gene regulation via modification of DNA methylation, histones, and microRNAs. This has provided both the biological link and a potential molecular explanation between oxidative stress and cardiovascular/metabolic phenomena. Accordingly, in this review, we will provide current insights on the physiological and pathological impact of changes in oxidative states on cardiovascular disorders, by specifically focusing on the influence of epigenetic regulation. A special emphasis will highlight the effect on epigenetic regulation of human’s current life habits, external and environmental factors, including food intake, tobacco, air pollution, and antioxidant-based approaches. Additionally, the strategy to quantify oxidative states in humans in order to determine which biological marker could best match a subject’s profile will be discussed.

The dual effects of nitrite on hemoglobin-dependent redox reactions.

Science.gov (United States)

Lu, Naihao; Chen, Chao; He, Yingjie; Tian, Rong; Xiao, Qiang; Peng, Yi-Yuan

2014-08-31

Evidence to support the role of heme proteins-dependent reactions as major inducers of oxidative damage is increasingly present. Nitrite (NO2(-)) is one of the major end products of NO metabolism, and from the daily consumption. Although the biological significance of heme proteins/NO2(-)-mediated protein tyrosine nitration is a subject of great interest, the important roles of NO2(-) on heme proteins-dependent redox reactions have been greatly underestimated. In this study, we investigated the influence of NO2(-) on met-hemoglobin (Hb)-dependent oxidative and nitrative stress. It was found that NO2(-) effectively reduced cytotoxic ferryl intermediate back to ferric Hb in a biphasic kinetic reaction. However, the presence of NO2(-) surprisingly exerted pro-oxidant effect on Hb-H2O2-induced protein (bovine serum albumin, enolase) oxidation at low concentrations and enhanced the loss of HepG2 cell viability. In the reduction of ferryl Hb to ferric state, NO2(-) was decreased and oxidized to a nitrating agent NO2, Tyr12 and Tyr191 in enolase were subsequently nitrated. In contrast to the frequently inhibitive effect of nitrotyrosine, NO2(-)-triggered tyrosine nitration might play an important role in enolase activation. These data provided novel evidence that the dietary intake and potential therapeutic application of NO2(-) would possess anti- and pro-oxidant activities through interfering in hemoglobin-dependent redox reactions. Besides the classic role in protein tyrosine nitration, the dual effects on hemoglobin-triggered oxidative stress may provide new insights into the physiological and toxicological implications of NO2(-) with heme proteins. Copyright © 2014 Elsevier Inc. All rights reserved.

Hydroxylamine-dependent anaerobic ammonium oxidation (anammox) by "Candidatus Brocadia sinica".

Science.gov (United States)

Oshiki, Mamoru; Ali, Muhammad; Shinyako-Hata, Kaori; Satoh, Hisashi; Okabe, Satoshi

2016-09-01

Although metabolic pathways and associated enzymes of anaerobic ammonium oxidation (anammox) of 'Ca. Kuenenia stuttgartiensis' have been studied, those of other anammox bacteria are still poorly understood. NO2- reduction to NO is considered to be the first step in the anammox metabolism of 'Ca. K. stuttgartiensis', however, 'Ca. Brocadia' lacks the genes that encode canonical NO-forming nitrite reductases (NirS or NirK) in its genome, which is different from 'Ca. K. stuttgartiensis'. Here, we studied the anammox metabolism of 'Ca. Brocadia sinica'. (15) N-tracer experiments demonstrated that 'Ca. B. sinica' cells could reduce NO2- to NH2 OH, instead of NO, with as yet unidentified nitrite reductase(s). Furthermore, N2 H4 synthesis, downstream reaction of NO2- reduction, was investigated using a purified 'Ca. B. sinica' hydrazine synthase (Hzs) and intact cells. Both the 'Ca. B. sinica' Hzs and cells utilized NH2 OH and NH4+, but not NO and NH4+, for N2 H4 synthesis and further oxidized N2 H4 to N2 gas. Taken together, the metabolic pathway of 'Ca. B. sinica' is NH2 OH-dependent and different from the one of 'Ca. K. stuttgartiensis', indicating metabolic diversity of anammox bacteria. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

Homoleptic Ce(III) and Ce(IV) Nitroxide Complexes: Significant Stabilization of the 4+ Oxidation State

Energy Technology Data Exchange (ETDEWEB)

Bogart, Justin A.; Lewis, Andrew J.; Medling, Scott A.; Piro, Nicholas A.; Carroll, Patrick J.; Booth, Corwin H.; Schelter, Eric J.

2014-06-25

Electrochemical experiments performed on the complex Ce-IV[2-((BuNO)-Bu-t)py](4), where [2-((BuNO)-Bu-t)py](-) = N-tert-butyl-N-2-pyridylnitroxide, indicate a 2.51 V stabilization of the 4+ oxidation state of Ce compared to [(Bu4N)-Bu-n](2)[Ce(NO3)(6)] in acetonitrile and a 2.95 V stabilization compared to the standard potential for the ion under aqueous conditions. Density functional theory calculations suggest that this preference for the higher oxidation state is a result of the tetrakis(nitroxide) ligand framework at the Ce cation, which allows for effective electron donation into, and partial covalent overlap with, vacant 4f orbitals with delta symmetry. The results speak to the behavior of CeO2 and related solid solutions in oxygen uptake and transport applications, in particular an inherent local character of bonding that stabilizes the 4+ oxidation state. The results indicate a cerium(IV) complex that has been stabilized to an unprecedented degree through tuning of its ligand-field environment.

The tongue and its control by sleep state-dependent modulators.

Science.gov (United States)

Horner, R L

2011-12-01

The neural networks controlling vital functions such as breathing are embedded in the brain, the neural and chemical environment of which changes with state, i.e., wakefulness, non-rapid eye movement (non-REM) sleep and REM sleep, and with commonly administered drugs such as anaesthetics, sedatives and ethanol. One particular output from the state-dependent chemical brain is the focus of attention in this paper; the motor output to the muscles of the tongue, specifically the actions of state-dependent modulators acting at the hypoglossal motor pool. Determining the mechanisms underlying the modulation of the hypoglossal motor output during sleep is relevant to understanding the spectrum of increased upper airway resistance, airflow limitation, hypoventilation and airway obstructions that occur during natural and drug-influenced sleep in humans. Understanding the mechanisms underlying upper airway dysfunction in sleep-disordered breathing is also important given the large and growing prevalence of obstructive sleep apnea syndrome which constitutes a major public health problem with serious clinical, social and economic consequences.

The effect of interfaces on solid-state reactions between oxides

International Nuclear Information System (INIS)

Johnson, M.T.; Carter, C.B.

1998-01-01

A thin-film geometry has been used to study fundamental solid-state reaction processes occurring at interfaces in two spinel-forming oxide systems. In the first system, NiO/Al 2 O 3 , epitactic NiO films were deposited on various orientations of single-crystal α-Al 2 O 3 . In this case, the reaction kinetics were studied and correlated with the interfacial structure (or substrate orientation). In the second, In 2 O 3 /MgO, solid-state reactions were studied under the influence of an electric field. The electric field provides a driving force for mass transport that affects both the reaction process and the morphological stability of an interface

A Class of Stochastic Hybrid Systems with State-Dependent Switching Noise

DEFF Research Database (Denmark)

Leth, John-Josef; Rasmussen, Jakob Gulddahl; Schiøler, Henrik

2012-01-01

In this paper, we develop theoretical results based on a proposed method for modeling switching noise for a class of hybrid systems with piecewise linear partitioned state space, and state-depending switching. We devise a stochastic model of such systems, whose global dynamics is governed...

Event-Based $H_\\infty $ State Estimation for Time-Varying Stochastic Dynamical Networks With State- and Disturbance-Dependent Noises.

Science.gov (United States)

Sheng, Li; Wang, Zidong; Zou, Lei; Alsaadi, Fuad E

2017-10-01

In this paper, the event-based finite-horizon H ∞ state estimation problem is investigated for a class of discrete time-varying stochastic dynamical networks with state- and disturbance-dependent noises [also called (x,v) -dependent noises]. An event-triggered scheme is proposed to decrease the frequency of the data transmission between the sensors and the estimator, where the signal is transmitted only when certain conditions are satisfied. The purpose of the problem addressed is to design a time-varying state estimator in order to estimate the network states through available output measurements. By employing the completing-the-square technique and the stochastic analysis approach, sufficient conditions are established to ensure that the error dynamics of the state estimation satisfies a prescribed H ∞ performance constraint over a finite horizon. The desired estimator parameters can be designed via solving coupled backward recursive Riccati difference equations. Finally, a numerical example is exploited to demonstrate the effectiveness of the developed state estimation scheme.

Oxidation of an aluminium-magnesium alloy in liquid state. Methodology of determination of mechanisms from not necessarily repeatable experiments

International Nuclear Information System (INIS)

Surla, Karine

1998-01-01

This research thesis reports the study of the oxidation of an aluminium-5 pc magnesium alloy in its liquid state in an oxygen environment, using thermogravimetric analysis and that of magnesium in its solid state. In a first part, the author reports a thermodynamic and bibliographical study on magnesium transformation in its solid state (Mg/O 2 and Mg/H 2 O systems, transformation with dry and humid synthetic air, oxidation inhibitors) and on Al-Mg alloy transformation in presence of oxygen (thermodynamic properties of aluminium-rich Al-Mg alloys, Al-Mg/O 2 /N 2 and Al-Mg/O 2 /N 2 /H 2 O systems). The next parts address the selection of reaction systems for the different cases (oxidation of solid magnesium in oxygen, oxidation of the Al-Mg alloy in oxygen), the modelling of the formation of magnesia from solid magnesium and from the Al-Mg alloy, and the modelling of the liquid Al-Mg A5182 alloy oxidation in oxygen [fr

Coupled interactions between volatile activity and Fe oxidation state during arc crustal processes

Science.gov (United States)

Humphreys, Madeleine C.S.; Brooker, R; Fraser, D.C.; Burgisser, A; Mangan, Margaret T.; McCammon, C

2015-01-01

Arc magmas erupted at the Earth’s surface are commonly more oxidized than those produced at mid-ocean ridges. Possible explanations for this high oxidation state are that the transfer of fluids during the subduction process results in direct oxidation of the sub-arc mantle wedge, or that oxidation is caused by the effect of later crustal processes, including protracted fractionation and degassing of volatile-rich magmas. This study sets out to investigate the effect of disequilibrium crustal processes that may involve coupled changes in H2O content and Fe oxidation state, by examining the degassing and hydration of sulphur-free rhyolites. We show that experimentally hydrated melts record strong increases in Fe3+/∑Fe with increasing H2O concentration as a result of changes in water activity. This is relevant for the passage of H2O-undersaturated melts from the deep crust towards shallow crustal storage regions, and raises the possibility that vertical variations in fO2 might develop within arc crust. Conversely, degassing experiments produce an increase in Fe3+/∑Fe with decreasing H2O concentration. In this case the oxidation is explained by loss of H2 as well as H2O into bubbles during decompression, consistent with thermodynamic modelling, and is relevant for magmas undergoing shallow degassing en route to the surface. We discuss these results in the context of the possible controls on fO2 during the generation, storage and ascent of magmas in arc settings, in particular considering the timescales of equilibration relative to observation as this affects the quality of the petrological record of magmatic fO2.

Integrated vehicle dynamics control using State Dependent Riccati Equations

NARCIS (Netherlands)

Bonsen, B.; Mansvelders, R.; Vermeer, E.

2010-01-01

In this paper we discuss a State Dependent Riccati Equations (SDRE) solution for Integrated Vehicle Dynamics Control (IVDC). The SDRE approach is a nonlinear variant of the well known Linear Quadratic Regulator (LQR) and implements a quadratic cost function optimization. A modified version of this

Asymptotic inference for jump diffusions with state-dependent intensity

NARCIS (Netherlands)

Becheri, Gaia; Drost, Feico; Werker, Bas

2016-01-01

We establish the local asymptotic normality property for a class of ergodic parametric jump-diffusion processes with state-dependent intensity and known volatility function sampled at high frequency. We prove that the inference problem about the drift and jump parameters is adaptive with respect to

State-dependent factors and attention in Whiplash Associated Disorder

NARCIS (Netherlands)

Blokhorst, Mariëtte G.B.G.

2005-01-01

The main aim of this thesis is to investigate the relationship between state- dependent factors (headache, neck pain, fatigue, distress) and attention in WAD patients. Furthermore, the focus is on ‘noise-distractibility’ and ‘noise- intolerance’, which are symptoms related to attention and often

The effect of time-dependent coupling on non-equilibrium steady states

DEFF Research Database (Denmark)

Cornean, Horia; Neidhardt, Hagen; Zagrebnov, Valentin

Consider (for simplicity) two one-dimensional semi-infinite leads coupled to a quantum well via time dependent point interactions. In the remote past the system is decoupled, and each of its components is at thermal equilibrium. In the remote future the system is fully coupled. We define...... and compute the non equilibrium steady state (NESS) generated by this evolution. We show that when restricted to the subspace of absolute continuity of the fully coupled system, the state does not depend at all on the switching. Moreover, we show that the stationary charge current has the same invariant...

The effect of time-dependent coupling on non-equilibrium steady states

DEFF Research Database (Denmark)

Cornean, Horia; Neidhardt, Hagen; Zagrebnov, Valentin A.

2009-01-01

Consider (for simplicity) two one-dimensional semi-infinite leads coupled to a quantum well via time dependent point interactions. In the remote past the system is decoupled, and each of its components is at thermal equilibrium. In the remote future the system is fully coupled. We define...... and compute the non equilibrium steady state (NESS) generated by this evolution. We show that when restricted to the subspace of absolute continuity of the fully coupled system, the state does not depend at all on the switching. Moreover, we show that the stationary charge current has the same invariant...

Ion bombardment effects on surface states in selected oxide systems: rutile and alkaline earth titanates

International Nuclear Information System (INIS)

Gruen, D.M.

1978-01-01

In this paper, the nature of the surface states of n-type TiO 2 and SrTiO 3 is discussed and the role of ion bombardment in modifying the properties of these states is elucidated. Insofar as possible, the interrelationships between oxide nonstoichiometry, surface states, ion bombardment effects and photoelectrolysis are explored

Optically induced bistable states in metal/tunnel-oxide/semiconductor /MTOS/ junctions

Science.gov (United States)

Lai, S. K.; Dressendorfer, P. V.; Ma, T. P.; Barker, R. C.

1981-01-01

A new switching phenomenon in metal-oxide semiconductor tunnel junction has been discovered. With a sufficiently large negative bias applied to the electrode, incident visible light of intensity greater than about 1 microW/sq cm causes the reverse-biased junction to switch from a low-current to a high-current state. It is believed that hot-electron-induced impact ionization provides the positive feedback necessary for switching, and causes the junction to remain in its high-current state after the optical excitation is removed. The junction may be switched back to the low-current state electrically. The basic junction characteristics have been measured, and a simple model for the switching phenomenon has been developed.

Effect of high doses of L-ascorbic acid on the antioxidative/oxidative state in the rats

DEFF Research Database (Denmark)

Niemiec, T.; Sawosz, E.; Chwalibog, André

2005-01-01

The objective of this study was to determine the effects of mega-doses of vitamin C (0.3, 0.6 and 0.9% of diet) as a dietary supplement for rats on selected indices of the antioxidative/oxidative state in 40 growing Wistar rats (4x10). It was found that L-ascorbic acid and Total Antioxidative State...... (TAS) in plasma did not increase with increasing vitamin C supply. The results indicate that high doses of L-ascorbic acid (0.3 and 0.9 but not 0.6%) increased the concentration of this antioxidant in plasma. Supplementation of vitamin C above 0.3% to the diets had pro-oxidative effects on lipid...... structures, while application of 0.9% promoted oxidative degradation of rat livers....

Performance of nitrate-dependent anaerobic ferrous oxidizing (NAFO) process: a novel prospective technology for autotrophic denitrification.

Science.gov (United States)

Zhang, Meng; Zheng, Ping; Li, Wei; Wang, Ru; Ding, Shuang; Abbas, Ghulam

2015-03-01

Nitrate-dependent anaerobic ferrous oxidizing (NAFO) is a valuable biological process, which utilizes ferrous iron to convert nitrate into nitrogen gas, removing nitrogen from wastewater. In this work, the performance of NAFO process was investigated as a nitrate removal technology. The results showed that NAFO system was feasible for autotrophic denitrification. The volumetric loading rate (VLR) and volumetric removal rate (VRR) under steady state were 0.159±0.01 kg-N/(m(3) d) and 0.073±0.01 kg-N/(m(3) d), respectively. In NAFO system, the effluent pH was suggested as an indicator which demonstrated a good correlation with nitrogen removal. The nitrate concentration was preferred to be less than 130 mg-N/L. Organic matters had little influence on NAFO performance. Abundant iron compounds were revealed to accumulate in NAFO sludge with peak value of 51.73% (wt), and they could be recycled for phosphorus removal, with capacity of 16.57 mg-P/g VS and removal rate of 94.77±2.97%, respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

Visualizing chemical states and defects induced magnetism of graphene oxide by spatially-resolved-X-ray microscopy and spectroscopy.

Science.gov (United States)

Wang, Y F; Singh, Shashi B; Limaye, Mukta V; Shao, Y C; Hsieh, S H; Chen, L Y; Hsueh, H C; Wang, H T; Chiou, J W; Yeh, Y C; Chen, C W; Chen, C H; Ray, Sekhar C; Wang, J; Pong, W F; Takagi, Y; Ohigashi, T; Yokoyama, T; Kosugi, N

2015-10-20

This investigation studies the various magnetic behaviors of graphene oxide (GO) and reduced graphene oxides (rGOs) and elucidates the relationship between the chemical states that involve defects therein and their magnetic behaviors in GO sheets. Magnetic hysteresis loop reveals that the GO is ferromagnetic whereas photo-thermal moderately reduced graphene oxide (M-rGO) and heavily reduced graphene oxide (H-rGO) gradually become paramagnetic behavior at room temperature. Scanning transmission X-ray microscopy and corresponding X-ray absorption near-edge structure spectroscopy were utilized to investigate thoroughly the variation of the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups, as well as the C 2p(σ*)-derived states in flat and wrinkle regions to clarify the relationship between the spatially-resolved chemical states and the magnetism of GO, M-rGO and H-rGO. The results of X-ray magnetic circular dichroism further support the finding that C 2p(σ*)-derived states are the main origin of the magnetism of GO. Based on experimental results and first-principles calculations, the variation in magnetic behavior from GO to M-rGO and to H-rGO is interpreted, and the origin of ferromagnetism is identified as the C 2p(σ*)-derived states that involve defects/vacancies rather than the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups on GO sheets.

Hydrogen sulfide increases nitric oxide production from endothelial cells by an Akt-dependent mechanism

Directory of Open Access Journals (Sweden)

Arturo J Cardounel

2011-12-01

Full Text Available Hydrogen sulfide (H2S and nitric oxide (NO are both gasotransmitters that can elicit synergistic vasodilatory responses in the in the cardiovascular system, but the mechanisms behind this synergy are unclear. In the current study we investigated the molecular mechanisms through which H2S regulates endothelial NO production. Initial studies were performed to establish the temporal and dose-dependent effects of H2S on NO generation using EPR spin trapping techniques. H2S stimulated a two-fold increase in NO production from endothelial nitric oxide synthase (eNOS, which was maximal 30 min after exposure to 25-150 µM H2S. Following 30 min H2S exposure, eNOS phosphorylation at Ser 1177 was significantly increased compared to control, consistent with eNOS activation. Pharmacological inhibition of Akt, the kinase responsible for Ser 1177 phosphorylation, attenuated the stimulatory effect of H2S on NO production. Taken together, these data demonstrate that H2S up-regulates NO production from eNOS through an Akt-dependent mechanism. These results implicate H2S in the regulation of NO in endothelial cells, and suggest that deficiencies in H2S signaling can directly impact processes regulated by NO.

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

Science.gov (United States)

Blewett, Tamzin A; Wood, Chris M

2015-02-01

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

Oxidative stress markers in hypertensive states of pregnancy: preterm and term disease.

Directory of Open Access Journals (Sweden)

Lesia Olha Kurlak

2014-08-01

Full Text Available Discussion continues as to whether de novo hypertension in pregnancy with significant proteinuria (pre-eclampsia; PE and non-proteinuric new hypertension (gestational hypertension; GH are parts of the same disease spectrum or represent different conditions. Non-pregnant hypertension, pregnancy and PE are all associated with oxidative stress. We have established a 6 weeks post-partum clinic for women who experienced a hypertensive pregnancy. We hypothesized that PE and GH could be distinguished by markers of oxidative stress; thiobarbituric acid reactive substances (TBARS and antioxidants (ferric ion reducing ability of plasma; FRAP. Since the severity of PE and GH is greater pre-term, we also compared pre-term and term disease. Fifty-eight women had term PE, 23 pre-term PE, 60 had term GH and 6 pre-term GH, 11 pre-existing (essential hypertension (EH without PE. Limited data were available from normotensive pregnancies (n=7 and non-pregnant controls (n=14. There were no differences in postpartum TBARS or FRAP between hypertensive states; TBARS (P=0.001 and FRAP (P=0.009 were lower in plasma of non-pregnant controls compared to recently-pregnant women. Interestingly FRAP was higher in preterm than term GH (P=0.013. In PE and GH, TBARS correlated with low density lipoprotein (LDL-cholesterol (P=0.036; this association strengthened with inclusion of EH ((P=0.011. The 10 year Framingham index for cardiovascular risk was positively associated with TBARS (P=0.003.Oxidative stress profiles do not differ between hypertensive states but appear to distinguish between recently-pregnant and non-pregnant states. This suggests that pregnancy may alter vascular integrity with changes remaining 6 weeks postpartum. LDL-cholesterol is a known determinant of oxidative stress in cardiovascular disease and we have shown this association to be present in hypertensive pregnancy further emphasizing that such a pregnancy may be revealing a pre-existing cardiovascular

Ultrathin reduced graphene oxide films as transparent top-contacts for light switchable solid-state molecular junctions

DEFF Research Database (Denmark)

Li, Tao; Jevric, Martyn; Hauptmann, Jonas Rahlf

2013-01-01

A new type of solid-state molecular junction is introduced, which employs reduced graphene oxide as a transparent top contact that permits a self-assembled molecular monolayer to be photoswitched in situ, while simultaneously enabling charge-transport measurements across the molecules. The electr......A new type of solid-state molecular junction is introduced, which employs reduced graphene oxide as a transparent top contact that permits a self-assembled molecular monolayer to be photoswitched in situ, while simultaneously enabling charge-transport measurements across the molecules...

Determination of Pu Oxidation states in the HCl Media Using with UV-Visible Absorption Spectroscopic Techniques

International Nuclear Information System (INIS)

Lee, Myung Ho; Suh, Mu Yeol; Park, Kyoung Kyun; Park, Yeong Jae; Kim, Won Ho

2006-01-01

The spectroscopic characteristics of Pu (III, IV, V, VI) in the HCl media were investigated by measuring Pu oxidation states using a UV-Vis-NIR spectrophotometer (400-1200 nm) after adjusting Pu oxidation states with oxidation/reduction reagents. Pu in stock solution was reduced to Pu(III) with NH 2 OH · HCl, and oxidized to Pu(IV) and Pu(VI) with NaNO 2 and HCIO 4 , respectively. Also, Pu(V) was adjusted in the Pu(VI) solution with NH 2 OH · HCl. The major absorption peaks of Pu (IV) and Pu(III) were measured in the 470 nm and 600 nm, respectively. The major absorption peaks of Pu (VI) and Pu(V) were measured in the 830 nm and 1135 nm, respectively. There was not found to be significant changes of UV-V is absorption spectra for Pu(III), Pu(IV) and Pu(VI) with aging time, except that an unstable Pu(V) immediately reduced to Pu(III).

Subgeometric Ergodicity Analysis of Continuous-Time Markov Chains under Random-Time State-Dependent Lyapunov Drift Conditions

Directory of Open Access Journals (Sweden)

Mokaedi V. Lekgari

2014-01-01

Full Text Available We investigate random-time state-dependent Foster-Lyapunov analysis on subgeometric rate ergodicity of continuous-time Markov chains (CTMCs. We are mainly concerned with making use of the available results on deterministic state-dependent drift conditions for CTMCs and on random-time state-dependent drift conditions for discrete-time Markov chains and transferring them to CTMCs.

The effect on phase separation of the oxidation state of molybdenum in a Na2O-B2O3-SiO2 glass

International Nuclear Information System (INIS)

Kawamoto, Y.; Clemens, K.; Tomozawa, M.; Warden, J.T.

1981-01-01

The effect of oxidation state on phase separation was studied for 13Na 2 O, 49B 2 O 3 , 38SiO 2 (mol%) glasses containing 1 mol% Mo oxide. The glasses were melted under various conditions to vary the oxidation states of Mo ions. The oxidation states of Mo ions were determined by chemical analysis and ESR. The crystallisation tendency, the immiscibility temperature, and the phase separation morphology of the glasses were examined by DTA, x-ray diffraction, opalescence method, and replica electron microscopy. Glasses containing Mo 4+ ions have a great tendency to precipitate MoO 2 crystals. The immiscibility temperature of glass goes through a minimum when the oxidation states of Mo ions are changed. It was suggested that there is an optimum oxidation state to prevent crystallisation and to suppress the phase separation tendency of this system. (author)

Obesity-Associated Oxidative Stress: Strategies Finalized to Improve Redox State

Directory of Open Access Journals (Sweden)

Valeria Gasperi

2013-05-01

Full Text Available Obesity represents a major risk factor for a plethora of severe diseases, including diabetes, cardiovascular disease, non-alcoholic fatty liver disease, and cancer. It is often accompanied by an increased risk of mortality and, in the case of non-fatal health problems, the quality of life is impaired because of associated conditions, including sleep apnea, respiratory problems, osteoarthritis, and infertility. Recent evidence suggests that oxidative stress may be the mechanistic link between obesity and related complications. In obese patients, antioxidant defenses are lower than normal weight counterparts and their levels inversely correlate with central adiposity; obesity is also characterized by enhanced levels of reactive oxygen or nitrogen species. Inadequacy of antioxidant defenses probably relies on different factors: obese individuals may have a lower intake of antioxidant- and phytochemical-rich foods, such as fruits, vegetables, and legumes; otherwise, consumption of antioxidant nutrients is normal, but obese individuals may have an increased utilization of these molecules, likewise to that reported in diabetic patients and smokers. Also inadequate physical activity may account for a decreased antioxidant state. In this review, we describe current concepts in the meaning of obesity as a state of chronic oxidative stress and the potential interventions to improve redox balance.

Obesity-Associated Oxidative Stress: Strategies Finalized to Improve Redox State

Science.gov (United States)

Savini, Isabella; Catani, Maria Valeria; Evangelista, Daniela; Gasperi, Valeria; Avigliano, Luciana

2013-01-01

Obesity represents a major risk factor for a plethora of severe diseases, including diabetes, cardiovascular disease, non-alcoholic fatty liver disease, and cancer. It is often accompanied by an increased risk of mortality and, in the case of non-fatal health problems, the quality of life is impaired because of associated conditions, including sleep apnea, respiratory problems, osteoarthritis, and infertility. Recent evidence suggests that oxidative stress may be the mechanistic link between obesity and related complications. In obese patients, antioxidant defenses are lower than normal weight counterparts and their levels inversely correlate with central adiposity; obesity is also characterized by enhanced levels of reactive oxygen or nitrogen species. Inadequacy of antioxidant defenses probably relies on different factors: obese individuals may have a lower intake of antioxidant- and phytochemical-rich foods, such as fruits, vegetables, and legumes; otherwise, consumption of antioxidant nutrients is normal, but obese individuals may have an increased utilization of these molecules, likewise to that reported in diabetic patients and smokers. Also inadequate physical activity may account for a decreased antioxidant state. In this review, we describe current concepts in the meaning of obesity as a state of chronic oxidative stress and the potential interventions to improve redox balance. PMID:23698776

Facet-Dependent Oxidative Goethite Growth As a Function of Aqueous Solution Conditions.

Science.gov (United States)

Strehlau, Jennifer H; Stemig, Melissa S; Penn, R Lee; Arnold, William A

2016-10-04

Nitroaromatic compounds are groundwater pollutants that can be degraded through reactions with Fe(II) adsorbed on iron oxide nanoparticles, although little is known about the evolving reactivity of the minerals with continuous pollutant exposure. In this work, Fe(II)/goethite reactivity toward 4-chloronitrobenzene (4-ClNB) as a function of pH, organic matter presence, and reactant concentrations was explored using sequential-spike batch reactors. Reaction rate constants were smaller with lower pH, introduction of organic matter, and diluted reactant concentrations as compared to a reference condition. Reaction rate constants did not change with the number of 4-ClNB spikes for all reaction conditions. Under all conditions, oxidative goethite growth was demonstrated through X-ray diffraction, magnetic characterization, and transmission electron microscopy. Nonparametric statistics were applied to compare histograms of lengths and widths of goethite nanoparticles as a function of varied solution conditions. The conditions that slowed the reaction also resulted in statistically shorter and wider particles than for the faster reactions. Additionally, added organic matter interfered with particle growth on the favorable {021} faces to a greater extent, with statistically reduced rate of growth on the tip facets and increased rate of growth on the side facets. These data demonstrate that oxidative growth of goethite in aqueous systems is dependent on major groundwater variables, such as pH and the presence of organic matter, which could lead to the evolving reactivity of goethite particles in natural environments.

Exactly solvable quantum state reduction models with time-dependent coupling

International Nuclear Information System (INIS)

Brody, Dorje C; Constantinou, Irene C; Dear, James D C; Hughston, Lane P

2006-01-01

A closed-form solution to the energy-based stochastic Schroedinger equation with a time-dependent coupling is obtained. The solution is algebraic in character, and is expressed directly in terms of independent random data. The data consist of (i) a random variable H which has the distribution P(H=E i ) = π i , where π i is the transition probability vertical bar (ψ 0 vertical bar Φ i ) vertical bar 2 from the initial state vertical bar ψ 0 ) to the Lueders state vertical bar Φ i ) with energy E i , and (ii) an independent P-Brownian motion, where P is the physical probability measure associated with the dynamics of the reduction process. When the coupling is time independent, it is known that state reduction occurs asymptotically-that is to say, over an infinite time horizon. In the case of a time-dependent coupling, we show that if the magnitude of the coupling decreases sufficiently rapidly, then the energy variance will be reduced under the dynamics, but the state need not reach an energy eigenstate. This situation corresponds to the case of a 'partial' or 'incomplete' measurement of the energy. We also construct an example of a model where the opposite situation prevails, in which complete state reduction is achieved after the passage of a finite period of time

Oxidation states of Fe and Ti in blue sapphire

International Nuclear Information System (INIS)

Wongrawang, P; Wongkokua, W; Monarumit, N; Thammajak, N; Wathanakul, P

2016-01-01

X-ray absorption near-edge spectroscopy (XANES) can be used to study the oxidation state of a dilute system such as transition metal defects in solid-state samples. In blue sapphire, Fe and Ti are defects that cause the blue color. Inter-valence charge transfer (IVCT) between Fe 2+ and Ti 4+ has been proposed to describe the optical color’s origin. However, the existence of divalent iron cations has not been thoroughly investigated. Fluorescent XANES is therefore employed to study K-edge absorptions of Fe and Ti cations in various blue sapphire samples including natural, synthetic, diffused and heat-treated sapphires. All the samples showed an Fe absorption edge at 7124 eV, corresponding to the Fe 3+ state; and Ti at 4984 eV, corresponding to Ti 4+ . From these results, we propose Fe 3+ -Ti 4+ mixed acceptor states located at 1.75 eV and 2.14 eV above the valence band of corundum, that correspond to 710 nm and 580 nm bands of UV–vis absorption spectra, to describe the cause of the color of blue sapphire. (paper)

Detection-dependent six-photon Holland-Burnett state interference

Science.gov (United States)

Jin, Rui-Bo; Fujiwara, Mikio; Shimizu, Ryosuke; Collins, Robert J.; Buller, Gerald S.; Yamashita, Taro; Miki, Shigehito; Terai, Hirotaka; Takeoka, Masahiro; Sasaki, Masahide

2016-11-01

The NOON state, and its experimental approximation the Holland-Burnett state, have important applications in phase sensing measurement with enhanced sensitivity. However, most of the previous Holland-Burnett state interference (HBSI) experiments only investigated the area of the interference pattern in the region immediately around zero optical path length difference, while the full HBSI pattern over a wide range of optical path length differences has not yet been well explored. In this work, we experimentally and theoretically demonstrate up to six-photon HBSI and study the properties of the interference patterns over a wide range of optical path length differences. It was found that the shape, the coherence time and the visibility of the interference patterns were strongly dependent on the detection schemes. This work paves the way for applications which are based on the envelope of the HBSI pattern, such as quantum spectroscopy and quantum metrology.

Local Properties of Solutions to Non-Autonomous Parabolic PDEs with State-Dependent Delays

Czech Academy of Sciences Publication Activity Database

Rezunenko, Oleksandr

2012-01-01

Roč. 2, č. 2 (2012), s. 56-71 ISSN 2158-611X R&D Projects: GA ČR(CZ) GAP103/12/2431 Institutional support: RVO:67985556 Keywords : partial differential equations * state-dependent delay * invariance principle Subject RIV: BC - Control Systems Theory http://library.utia.cas.cz/separaty/2012/AS/rezunenko- local properties of solutions to non-autonomous parabolic PDEs with state-dependent delay s.pdf

Effects of self-esteem on state and trait components of interpersonal dependency and depression in the workplace.

Science.gov (United States)

Takagishi, Yukihiro; Sakata, Masatsugu; Kitamura, Toshinori

2011-09-01

This longitudinal study was undertaken to clarify the relationships among self-esteem, interpersonal dependency, and depression, focusing on a trait and state component of interpersonal dependency and depression. In a sample of 466 working people, self-esteem, interpersonal dependency, job stressor, and depression were assessed at 2 points of time. A structural equation model (SEM) was created to differentiate the trait component of interpersonal dependency, depression and the state component of interpersonal dependency, depression. The model revealed that self-esteem influenced trait interpersonal dependency and trait depression but not state interpersonal dependency or depression. Setting a latent variable as a trait component to differentiate trait and state in interpersonal dependency and depression in SEM was found to be effective both statistically and clinically. © 2011 Wiley Periodicals, Inc.

The role of age, gender, mood states and exercise frequency on exercise dependence.

Science.gov (United States)

Costa, Sebastiano; Hausenblas, Heather A; Oliva, Patrizia; Cuzzocrea, Francesca; Larcan, Rosalba

2013-12-01

The purpose of our study was to explore the prevalence, and the role of mood, exercise frequency, age, and gender differences of exercise dependence. Regular exercisers (N = 409) completed a socio-demographic questionnaire, the Exercise Dependence Scale, and the Profile of Mood States. For data analyses, the participants were stratified for sex and age (age ranges = young adults: 18-24 years, adults: 25-44 years, and middle-aged adults: 45-64 years). We found that: (a) 4.4% of the participants were classified as at-risk for exercise dependence; (b) the men and the two younger groups (i.e., young adults and adults) had higher exercise dependence scores; and (c) age, gender, exercise frequency, and mood state were related to exercise dependence. Our results support previous research on the prevalence of exercise dependence and reveal that adulthood may be the critical age for developing exercise dependence. These findings have practical implication for identifying individuals at-risk for exercise dependence symptoms, and may aid in targeting and guiding the implementation of prevention program for adults.

Role of state-dependent learning in the cognitive effects of caffeine in mice.

Science.gov (United States)

Sanday, Leandro; Zanin, Karina A; Patti, Camilla L; Fernandes-Santos, Luciano; Oliveira, Larissa C; Longo, Beatriz M; Andersen, Monica L; Tufik, Sergio; Frussa-Filho, Roberto

2013-08-01

Caffeine is the most widely used psychoactive substance in the world and it is generally believed that it promotes beneficial effects on cognitive performance. However, there is also evidence suggesting that caffeine has inhibitory effects on learning and memory. Considering that caffeine may have anxiogenic effects, thus changing the emotional state of the subjects, state-dependent learning may play a role in caffeine-induced cognitive alterations. Mice were administered 20 mg/kg caffeine before training and/or before testing both in the plus-maze discriminative avoidance task (an animal model that concomitantly evaluates learning, memory, anxiety-like behaviour and general activity) and in the inhibitory avoidance task, a classic paradigm for evaluating memory in rodents. Pre-training caffeine administration did not modify learning, but produced an anxiogenic effect and impaired memory retention. While pre-test administration of caffeine did not modify retrieval on its own, the pre-test administration counteracted the memory deficit induced by the pre-training caffeine injection in both the plus-maze discriminative and inhibitory avoidance tasks. Our data demonstrate that caffeine-induced memory deficits are critically related to state-dependent learning, reinforcing the importance of considering the participation of state-dependency on the interpretation of the cognitive effects of caffeine. The possible participation of caffeine-induced anxiety alterations in state-dependent memory deficits is discussed.

Thermal state of the general time-dependent harmonic oscillator

Indian Academy of Sciences (India)

Taking advantage of dynamical invariant operator, we derived quantum mechanical solution of general time-dependent harmonic oscillator. The uncertainty relation of the system is always larger than ħ=2 not only in number but also in the thermal state as expected. We used the diagonal elements of density operator ...

State-Dependent Decoding Algorithms Improve the Performance of a Bidirectional BMI in Anesthetized Rats

Directory of Open Access Journals (Sweden)

Vito De Feo

2017-05-01

Full Text Available Brain-machine interfaces (BMIs promise to improve the quality of life of patients suffering from sensory and motor disabilities by creating a direct communication channel between the brain and the external world. Yet, their performance is currently limited by the relatively small amount of information that can be decoded from neural activity recorded form the brain. We have recently proposed that such decoding performance may be improved when using state-dependent decoding algorithms that predict and discount the large component of the trial-to-trial variability of neural activity which is due to the dependence of neural responses on the network's current internal state. Here we tested this idea by using a bidirectional BMI to investigate the gain in performance arising from using a state-dependent decoding algorithm. This BMI, implemented in anesthetized rats, controlled the movement of a dynamical system using neural activity decoded from motor cortex and fed back to the brain the dynamical system's position by electrically microstimulating somatosensory cortex. We found that using state-dependent algorithms that tracked the dynamics of ongoing activity led to an increase in the amount of information extracted form neural activity by 22%, with a consequently increase in all of the indices measuring the BMI's performance in controlling the dynamical system. This suggests that state-dependent decoding algorithms may be used to enhance BMIs at moderate computational cost.

State-Dependent Decoding Algorithms Improve the Performance of a Bidirectional BMI in Anesthetized Rats.

Science.gov (United States)

De Feo, Vito; Boi, Fabio; Safaai, Houman; Onken, Arno; Panzeri, Stefano; Vato, Alessandro

2017-01-01

Brain-machine interfaces (BMIs) promise to improve the quality of life of patients suffering from sensory and motor disabilities by creating a direct communication channel between the brain and the external world. Yet, their performance is currently limited by the relatively small amount of information that can be decoded from neural activity recorded form the brain. We have recently proposed that such decoding performance may be improved when using state-dependent decoding algorithms that predict and discount the large component of the trial-to-trial variability of neural activity which is due to the dependence of neural responses on the network's current internal state. Here we tested this idea by using a bidirectional BMI to investigate the gain in performance arising from using a state-dependent decoding algorithm. This BMI, implemented in anesthetized rats, controlled the movement of a dynamical system using neural activity decoded from motor cortex and fed back to the brain the dynamical system's position by electrically microstimulating somatosensory cortex. We found that using state-dependent algorithms that tracked the dynamics of ongoing activity led to an increase in the amount of information extracted form neural activity by 22%, with a consequently increase in all of the indices measuring the BMI's performance in controlling the dynamical system. This suggests that state-dependent decoding algorithms may be used to enhance BMIs at moderate computational cost.

State-dependent bulk-boundary maps and black hole complementarity

NARCIS (Netherlands)

Papadodimas, Kyriakos; Raju, Suvrat

2014-01-01

We provide a simple and explicit construction of local bulk operators that describe the interior of a black hole in the AdS/CFT correspondence. The existence of these operators is predicated on the assumption that the mapping of CFT operators to local bulk operators depends on the state of the CFT.

Temperature dependent selective detection of hydrogen and acetone using Pd doped WO3/reduced graphene oxide nanocomposite

Science.gov (United States)

Kaur, Jasmeet; Anand, Kanica; Kohli, Nipin; Kaur, Amanpreet; Singh, Ravi Chand

2018-06-01

Reduced graphene oxide (RGO) and Pd doped WO3 nanocomposites were fabricated by employing electrostatic interactions between poly (diallyldimethylammonium chloride) (PDDA) modified Pd doped WO3 nanostructures and graphite oxide (GO) and studied for their gas sensing application. XRD, Raman, FTIR, FESEM-EDX, TEM, TGA, XPS and Photoluminescence techniques were used for characterization of as-synthesized samples. Gas sensing studies revealed that the sensor with optimized doping of 1.5 mol% Pd and 1 wt% GO shows temperature dependent selectivity towards hydrogen and acetone. The role of WO3, Pd and RGO has been discussed in detail for enhanced sensing performance.

Solid-state electrochromic cell with anodic iridium oxide film electrodes

International Nuclear Information System (INIS)

Dautremont-Smith, W.C.; Beni, G.; Schiavone, L.M.; Shay, J.L.

1979-01-01

A new solid-state electrochromic cell has been fabricated using an anodic iridium oxide film (AIROF) display electrode. The cell has the symmetric sandwich structure AIROFvertical-barNafionvertical-barAIROF, with the Nafion solid electrolyte opacified by an in situ precipitation technique. A symmetric square-wave voltage of 1.5 V amplitude produces clearly perceivable color changes from pale to dark blue-gray in approx. =1 sec when viewed in diffuse reflection. Good open-circuit optical memory is exhibited:

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

Science.gov (United States)

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

2001-02-01

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

Intestinal Oxidative State Can Alter Nutrient and Drug Bioavailability

Directory of Open Access Journals (Sweden)

Faria Ana

2009-01-01

Full Text Available Organic cations (OCs are substances of endogenous (e.g., dopamine, choline or exogenous (e.g., drugs like cimetidine origin that are positively charged at physiological ph. since many of these compounds can not pass the cell membrane freely, their transport in or out of cells must be mediated by specific transport systems. Transport by organic cation transporters (OCTs can be regulated rapidly by altering their trafficking and/or affinities in response to stimuli. However, for example, a specific disease could lead to modifications in the expression of OCTs. Chronic exposure to oxidative stress has been suggested to alter regulation and functional activity of proteins through several pathways. According to results from a previous work, oxidation-reduction pathways were thought to be involved in intestinal organic cation uptake modulation. The present work was performed in order to evaluate the influence of oxidative stressors, especially glutathione, on the intestinal organic cation absorption. For this purpose, the effect of compounds with different redox potential (glutathione, an endogenous antioxidant, and procyanidins, diet antioxidants was assessed on MPP+ (1-methyl-4-phenylpyridinium iodide uptake in an enterocyte cell line (Caco-2. Caco-2 cells were subcultured with two different media conditions (physiological: 5 mM glucose, referred as control cells; and high-glucose: 25 mM glucose, referred as HG cells. In HG cells, the uptake was significantly lower than in control cells. Redox changing interventions affected Mpp+ uptake, both in control and in high-glucose Caco-2 cells. Cellular glutathione levels could have an important impact on membrane transporter activity. The results indicate that modifications in the cellular oxidative state modulate MPP+ uptake by Caco-2 cells. Such modifications may reflect in changes of nutrient and drug bioavailability.

Solid-state dewetting of single- and bilayer Au-W thin films: Unraveling the role of individual layer thickness, stacking sequence and oxidation on morphology evolution

Directory of Open Access Journals (Sweden)

A. Herz

2016-03-01

Full Text Available Self-assembly of ultrathin Au, W, and Au-W bilayer thin films is investigated using a rapid thermal annealing technique in an inert ambient. The solid-state dewetting of Au films is briefly revisited in order to emphasize the role of initial film thickness. W films deposited onto SiO2 evolve into needle-like nanocrystals rather than forming particle-like agglomerates upon annealing at elevated temperatures. Transmission electron microscopy reveals that such nanocrystals actually consist of tungsten (VI oxide (WO3 which is related to an anisotropic oxide crystal growth out of the thin film. The evolution of W films is highly sensitive to the presence of any residual oxygen. Combination of both the dewetting of Au and the oxide crystal growth of WO3 is realized by using various bilayer film configurations of the immiscible Au and W. At low temperature, Au dewetting is initiated while oxide crystal growth is still suppressed. Depending on the stacking sequence of the Au-W bilayer thin film, W acts either as a substrate or as a passivation layer for the dewetting of Au. Being the ground layer, W changes the wettability of Au which clearly modifies its initial state for the dewetting. Being the top layer, W prevents Au from dewetting regardless of Au film thickness. Moreover, regular pattern formation of Au-WO3 nanoparticles is observed at high temperature demonstrating how bilayer thin film dewetting can create unique nanostructure arrangements.

Solid-state dewetting of single- and bilayer Au-W thin films: Unraveling the role of individual layer thickness, stacking sequence and oxidation on morphology evolution

Energy Technology Data Exchange (ETDEWEB)

Herz, A., E-mail: andreas.herz@tu-ilmenau.de, E-mail: dong.wang@tu-ilmenau.de; Franz, A.; Theska, F.; Hentschel, M.; Kups, Th.; Wang, D., E-mail: andreas.herz@tu-ilmenau.de, E-mail: dong.wang@tu-ilmenau.de; Schaaf, P. [Department of Materials for Electronics and Electrical Engineering, Institute of Materials Science and Engineering and Institute of Micro- and Nanotechnologies MacroNano, TU Ilmenau, D-98693 Ilmenau (Germany)

2016-03-15

Self-assembly of ultrathin Au, W, and Au-W bilayer thin films is investigated using a rapid thermal annealing technique in an inert ambient. The solid-state dewetting of Au films is briefly revisited in order to emphasize the role of initial film thickness. W films deposited onto SiO{sub 2} evolve into needle-like nanocrystals rather than forming particle-like agglomerates upon annealing at elevated temperatures. Transmission electron microscopy reveals that such nanocrystals actually consist of tungsten (VI) oxide (WO{sub 3}) which is related to an anisotropic oxide crystal growth out of the thin film. The evolution of W films is highly sensitive to the presence of any residual oxygen. Combination of both the dewetting of Au and the oxide crystal growth of WO{sub 3} is realized by using various bilayer film configurations of the immiscible Au and W. At low temperature, Au dewetting is initiated while oxide crystal growth is still suppressed. Depending on the stacking sequence of the Au-W bilayer thin film, W acts either as a substrate or as a passivation layer for the dewetting of Au. Being the ground layer, W changes the wettability of Au which clearly modifies its initial state for the dewetting. Being the top layer, W prevents Au from dewetting regardless of Au film thickness. Moreover, regular pattern formation of Au-WO{sub 3} nanoparticles is observed at high temperature demonstrating how bilayer thin film dewetting can create unique nanostructure arrangements.

Teaching the Properties of Chromium's Oxidation States with a Case Study Method

Science.gov (United States)

Ozdilek, Zehra

2015-01-01

The purpose of this study was to investigate how a mixed-method case study affects pre-service science teachers' awareness of hexavalent chromium pollution and content knowledge about the properties of chromium's different oxidation states. The study was conducted in Turkey with 55 sophomores during the fall semester of 2013-2014. The students…

Control of Thermodynamical System with Input-Dependent State Delays

DEFF Research Database (Denmark)

Bendtsen, Jan Dimon; Krstic, Miroslav

2013-01-01

We consider control of a cooling system with several consumers that require cooling from a common source. The flow feeding coolant to the consumers can be controlled, but due to significant physical distances between the common source and the consumers, the coolant flow takes a non......-negligible amount of time to travel to the consumers, giving rise to input-dependent state delays. We first present a simple bilinear model of the system, followed by a state feedback control design that is able to stabilize the system at a chosen equilibrium in spite of the delays. We also present a heuristic...

Steady-State Growth under Inorganic Carbon Limitation Conditions Increases Energy Consumption for Maintenance and Enhances Nitrous Oxide Production in Nitrosomonas europaea.

Science.gov (United States)

Mellbye, Brett L; Giguere, Andrew; Chaplen, Frank; Bottomley, Peter J; Sayavedra-Soto, Luis A

2016-06-01

Nitrosomonas europaea is a chemolithoautotrophic bacterium that oxidizes ammonia (NH3) to obtain energy for growth on carbon dioxide (CO2) and can also produce nitrous oxide (N2O), a greenhouse gas. We interrogated the growth, physiological, and transcriptome responses of N. europaea to conditions of replete (>5.2 mM) and limited inorganic carbon (IC) provided by either 1.0 mM or 0.2 mM sodium carbonate (Na2CO3) supplemented with atmospheric CO2 IC-limited cultures oxidized 25 to 58% of available NH3 to nitrite, depending on the dilution rate and Na2CO3 concentration. IC limitation resulted in a 2.3-fold increase in cellular maintenance energy requirements compared to those for NH3-limited cultures. Rates of N2O production increased 2.5- and 6.3-fold under the two IC-limited conditions, increasing the percentage of oxidized NH3-N that was transformed to N2O-N from 0.5% (replete) up to 4.4% (0.2 mM Na2CO3). Transcriptome analysis showed differential expression (P ≤ 0.05) of 488 genes (20% of inventory) between replete and IC-limited conditions, but few differences were detected between the two IC-limiting treatments. IC-limited conditions resulted in a decreased expression of ammonium/ammonia transporter and ammonia monooxygenase subunits and increased the expression of genes involved in C1 metabolism, including the genes for RuBisCO (cbb gene cluster), carbonic anhydrase, folate-linked metabolism of C1 moieties, and putative C salvage due to oxygenase activity of RuBisCO. Increased expression of nitrite reductase (gene cluster NE0924 to NE0927) correlated with increased production of N2O. Together, these data suggest that N. europaea adapts physiologically during IC-limited steady-state growth, which leads to the uncoupling of NH3 oxidation from growth and increased N2O production. Nitrification, the aerobic oxidation of ammonia to nitrate via nitrite, is an important process in the global nitrogen cycle. This process is generally dependent on ammonia-oxidizing

Existence results for impulsive evolution differential equations with state-dependent delay

OpenAIRE

Eduardo Hernandez M.; Rathinasamy Sakthivel; Sueli Tanaka Aki

2008-01-01

We study the existence of mild solution for impulsive evolution abstract differential equations with state-dependent delay. A concrete application to partial delayed differential equations is considered.

Dependence of extinction cross-section on incident polarization state and particle orientation

International Nuclear Information System (INIS)

Yang Ping; Wendisch, Manfred; Bi Lei; Kattawar, George; Mishchenko, Michael; Hu, Yongxiang

2011-01-01

This note reports on the effects of the polarization state of an incident quasi-monochromatic parallel beam of radiation and the orientation of a hexagonal ice particle with respect to the incident direction on the extinction process. When the incident beam is aligned with the six-fold rotational symmetry axis, the extinction is independent of the polarization state of the incident light. For other orientations, the extinction cross-section for linearly polarized light can be either larger or smaller than its counterpart for an unpolarized incident beam. Therefore, the attenuation of a quasi-monochromatic radiation beam by an ice cloud depends on the polarization state of the beam if ice crystals within the cloud are not randomly oriented. Furthermore, a case study of the extinction of light by a quartz particle is also presented to illustrate the dependence of the extinction cross-section on the polarization state of the incident light.

Energy dependency and sustainable regional development in the Baltic states: A review

Directory of Open Access Journals (Sweden)

Štreimikienė Dalia

2016-01-01

Full Text Available Energy security is one of the most important indicators of sustainable regional development and 'green' growth in implementation of EU strategy Europe 2020. It can provide the harmonized development and cohesion of 'old' and 'new' EU member states. Our paper conducts a comparative study of energy dependency and energy security indicators in the Baltic States. The Baltic countries achieved enormous progress in the use of renewable energy sources and energy efficiency since their EU accession in 2004. The increase of renewable energy capacities in Baltic States also contributed to the reduction of energy intensity and carbon intensity of economy and energy import dependency. Our results show that amongst all three states, it was Estonia that had achieved the best results in increased use of renewables and energy efficiency improvements and had distinguished itself with the best indicators and economic and regional policy outcomes.

Molecular beam epitaxy growth of niobium oxides by solid/liquid state oxygen source and lithium assisted metal-halide chemistry

Science.gov (United States)

Tellekamp, M. Brooks; Greenlee, Jordan D.; Shank, Joshua C.; Doolittle, W. Alan

2015-09-01

In order to consistently grow high quality niobium oxides and lithium niobium oxides, a novel solid/liquid state oxygen source, LiClO4, has been implemented in a molecular beam epitaxy (MBE) system. LiClO4 is shown to decompose into both molecular and atomic oxygen upon heating. This allows oxidation rates similar to that of molecular oxygen but at a reduced overall beam flux, quantified by in situ Auger analysis. LiClO4 operation is decomposition limited to less than 400 °C, and other material limitations are identified. The design of a custom near-ambient NbCl5 effusion cell is presented, which improves both short and long term stability. Films of Nb oxidation state +2, +3, and +5 are grown using these new tools, including the multi-functional sub-oxide LiNbO2.

Ionization and Coulomb explosion of small uranium oxide clusters

International Nuclear Information System (INIS)

Ross, Matt W; Castleman, A W Jr

2012-01-01

Femtosecond pulses are used to study the strong-field ionization and subsequent Coulomb explosion of small uranium oxide clusters. The resulting high atomic charge states are explored as a function of laser intensity and compared to ionization rates calculated using semi-classical tunneling theory with sequential ionization potential values. The gap in laser intensity between saturation intensity values for the 7s, 6d, and 5f orbitals are identified and quantified. Extreme charge states of oxygen up to O 4+ are observed indicating multiple ionization enhancement processes occurring within the clusters. The peak splittings of the atomic charge states are explored and compared to previous results on transition metal oxide species. Participation of the 5f orbitals in bonding is clearly identified based on the saturation intensity dependence of oxygen to uranium metal.

Enhancement of nitrite on heme-induced oxidative reactions: A potential toxicological implication.

Science.gov (United States)

Lu, Naihao; Chen, Wei; Zhu, Jingjie; Peng, Yi-Yuan

2012-02-01

Evidence to support the role of heme as major inducers of oxidative damage is increasingly present. Nitrite (NO(2)(-)) is one of the major end products of NO metabolism. Although the biological significance of heme/NO(2)(-)-mediated protein tyrosine nitration is a subject of great interest, the important roles of NO(2)(-) on heme-dependent redox reaction have been greatly underestimated. In this study, we investigated the influence of NO(2)(-) on heme -dependent oxidative reactions. It was found that NO(2)(-) had the capacity to act as a reducing agent to remove high oxidation states of heme iron. In the reduction of ferryl heme to ferric heme, NO(2)(-) was oxidized to a nitrating agent NO(2), and subsequently, tyrosine residues in bovine serum albumin (BSA) were nitrated. However, the presence of NO(2)(-) surprisingly exerted pro-oxidant effect on heme-H(2)O(2)-induced formation of BSA carbonyls at lower concentrations and enhanced the loss of HepG2 cell viability dose-dependently, which was probably due to the ability of this inorganic compound to efficiently enhance the peroxidase activity and oxidative degradation of heme. These data provide novel evidence that the dietary intake and experimental use of NO(2)(-) in vivo and in vitro would possess the pro-oxidant activity through interfering in heme-dependent oxidative reactions. Besides the classic role in protein tyrosine nitration, the deleterious effects on heme redox reactions may provide new insights into the toxicological implications of NO(2)(-) with cellular heme proteins. Copyright © 2011 Elsevier Ltd. All rights reserved.

Raman spectroscopic study of the oxidation state of Eu in molten LiCl-KCl

Energy Technology Data Exchange (ETDEWEB)

Park, Seung; Yun, Jong-Il [KAIST, Daejeon(Korea, Republic of)

2016-10-15

Spectroscopy can provide high reliability for the quantitative analysis of such system. The molar absorptivity of Eu(II) at 325 nm is reported as about 1645 M{sup -1}cm{sup -1}, which is too high to apply to higher concentration. A high-temperature Raman spectroscopy has been set and employed for analyzing the molecular structure and coordination complex and investigating the oxidation state of europium in molten LiCl-KCl. Europium can be present in divalent state while many other lanthanides exist in trivalent state. The thermodynamic properties of europium ions have been studied using electrochemical methods, spectroscopic methods, and EPR technique. Although there has been discrepancy of the reduced amount of europium in previous works, the majority of Eu(III) is thought to be reduced to Eu(II) in molten LiCl-KCl spontaneously at relatively low concentration (< 7.5 × 10{sup -4} M). Raman spectroscopy was employed to investigate the oxidation state of EuClx in LiCl-KCl at 500 .deg. C. The Raman scattering results suggest the majority of trivalent europium is reduced to divalent state with the composition change by vaporization. The Raman bands show highly asymmetric structure, quite different from regular octahedral structure.

Heterogeneous Partial (ammOxidation and Oxidative Dehydrogenation Catalysis on Mixed Metal Oxides

Directory of Open Access Journals (Sweden)

Jacques C. Védrine

2016-01-01

Full Text Available This paper presents an overview of heterogeneous partial (ammoxidation and oxidative dehydrogenation (ODH of hydrocarbons. The review has been voluntarily restricted to metal oxide-type catalysts, as the partial oxidation field is very broad and the number of catalysts is quite high. The main factors of solid catalysts for such reactions, designated by Grasselli as the “seven pillars”, and playing a determining role in catalytic properties, are considered to be, namely: isolation of active sites (known to be composed of ensembles of atoms, Me–O bond strength, crystalline structure, redox features, phase cooperation, multi-functionality and the nature of the surface oxygen species. Other important features and physical and chemical properties of solid catalysts, more or less related to the seven pillars, are also emphasized, including reaction sensitivity to metal oxide structure, epitaxial contact between an active phase and a second phase or its support, synergy effect between several phases, acid-base aspects, electron transfer ability, catalyst preparation and activation and reaction atmospheres, etc. Some examples are presented to illustrate the importance of these key factors. They include light alkanes (C1–C4 oxidation, ethane oxidation to ethylene and acetic acid on MoVTe(SbNb-O and Nb doped NiO, propene oxidation to acrolein on BiMoCoFe-O systems, propane (ammoxidation to (acrylonitrile acrylic acid on MoVTe(SbNb-O mixed oxides, butane oxidation to maleic anhydride on VPO: (VO2P2O7-based catalyst, and isobutyric acid ODH to methacrylic acid on Fe hydroxyl phosphates. It is shown that active sites are composed of ensembles of atoms whose size and chemical composition depend on the reactants to be transformed (their chemical and size features and the reaction mechanism, often of Mars and van Krevelen type. An important aspect is the fact that surface composition and surface crystalline structure vary with reaction on stream until

Chemical state analysis of oxidation products on steel surface by conversion electron Moessbauer spectrometry

International Nuclear Information System (INIS)

Ujihira, Yusuke; Nomura, Kiyoshi

1978-01-01

The polished NT-70H steel (Fe: 95.97%, C: 0.56%, diameter: 5 cm, thickness: 0.5 cm) was immersed in deionized water or in solutions containing (0.25 -- 0.5) M of chloride, sulfate and nitrate ions. The chemical states of oxidation products of iron on the surface were identified through the analysis of conversion electron Moessbauer spectra (CEMS). CEMS of the steel surface, which had been dipped in deionized water, revealed that γ-FeOOH was formed on the surface. The thickness of γ-FeOOH layer increased with the increase of the duration of dipping. Dissolved oxygen in the solution played an essential role in the oxidation of iron to γ-FeOOH. Oxidation product of iron dipped in the 0.5 M sodium chloride solution was identified as γ-FeOOH. Amorphous paramagnetic iron (III) compound tended to form in the presence of hydrogen peroxide or ammonium ions in the solutions. The increase of alkalinity of the solution up to pH 12 suppressed the oxidation rate and assisted the formation of green rust, which was confirmed by the appearance of the quadrupole splitting peaks of the green rust. In the 0.25 M sodium sulfate solution, oxidation of the steel surface proceeded slowly and the quadrupole splitting peaks of Fe(OH) 2 were seen in the CEMS. The peak intensity of Fe(OH) 2 gradually decreased and that of γ-FeOOH increased by the extension of immersion of steel in the solution. Magnetite (Fe 3 O 4 ) layer was developed beneath the γ-FeOOH layer, when steel was dipped in 0.5 M sodium nitrate solution. However, the peaks of Fe 3 O 4 were not seen on CEMS of steel surface immersed in 0.5 M ammonium nitrate solution. Thus, applying the feasibility of CEMS for the characterization of oxidated compounds of iron on the steel surface formed by the immersion in solutions, the oxidation mechanism of the steel surface was discussed based upon the results of chemical state analyses. (author)

Solid state chemistry of rare earth oxides. Final report, September 1, 1950--July 31, 1977

International Nuclear Information System (INIS)

Eyring, L.

1977-07-01

Work under Contract E(11-1)-1109 and its antecedents has been primarily for the purpose of obtaining detailed thermodynamic, kinetic and structural information on the complex rare earth oxides of praseodymium and terbium. These systems exhibit homologous series of ordered phases, order-disorder transformations, wide-range nonstoichiometric phases, chemical hysteresis in two-phase regions and many other solid state reaction phenomena. Fluorite-related materials of importance to ERDA occur as nuclear fuels, radiation power sources, insulators and solid electrolytes. The rare earth oxides serve directly as model systems for such similar materials and, in a more general sense, they serve as models of solids in general since they exhibit nearly the full range of solid state properties

Assigning Oxidation States to Organic Compounds via Predictions from X-Ray Photoelectron Spectroscopy: A Discussion of Approaches and Recommended Improvements

Science.gov (United States)

Gupta, Vipul; Ganegoda, Hasitha; Engelhard, Mark H.; Terry, Jeff; Linford, Matthew R.

2014-01-01

The traditional assignment of oxidation states to organic molecules is problematic. Accordingly, in 1999, Calzaferri proposed a simple and elegant solution that is based on the similar electronegativities of carbon and hydrogen: hydrogen would be assigned an oxidation state of zero when bonded to carbon. Here, we show that X-ray photoelectron…

Quantum State-Resolved Collision Dynamics of Nitric Oxide at Ionic Liquid and Molten Metal Surfaces

Science.gov (United States)

Zutz, Amelia Marie

Detailed molecular scale interactions at the gas-liquid interface are explored with quantum state-to-state resolved scattering of a jet-cooled beam of NO(2pi1/2; N = 0) from ionic liquid and molten metal surfaces. The scattered distributions are probed via laser-induced fluorescence methods, which yield rotational and spin-orbit state populations that elucidate the dynamics of energy transfer at the gas-liquid interface. These collision dynamics are explored as a function of incident collision energy, surface temperature, scattering angle, and liquid identity, all of which are found to substantially affect the degree of rotational, electronic and vibrational excitation of NO via collisions at the liquid surface. Rotational distributions observed reveal two distinct scattering pathways, (i) molecules that trap, thermalize and eventually desorb from the surface (trapping-desorption, TD), and (ii) those that undergo prompt recoil (impulsive scattering, IS) prior to complete equilibration with the liquid surface. Thermally desorbing NO molecules are found to have rotational temperatures close to, but slightly cooler than the surface temperature, indicative of rotational dependent sticking probabilities on liquid surfaces. Nitric oxide is a radical with multiple low-lying electronic states that serves as an ideal candidate for exploring nonadiabatic state-changing collision dynamics at the gas-liquid interface, which induce significant excitation from ground (2pi1/2) to excited (2pi 3/2) spin-orbit states. Molecular beam scattering of supersonically cooled NO from hot molten metals (Ga and Au, Ts = 300 - 1400 K) is also explored, which provide preliminary evidence for vibrational excitation of NO mediated by thermally populated electron-hole pairs in the hot, conducting liquid metals. The results highlight the presence of electronically nonadiabatic effects and build toward a more complete characterization of energy transfer dynamics at gas-liquid interfaces.

SOLID STATE ENERGY CONVERSION ALLIANCE (SECA) SOLID OXIDE FUEL CELL PROGRAM

Energy Technology Data Exchange (ETDEWEB)

Unknown

2003-06-01

This report summarizes the progress made during the September 2001-March 2002 reporting period under Cooperative Agreement DE-FC26-01NT41245 for the U. S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled ''Solid State Energy Conversion Alliance (SECA) Solid Oxide Fuel Cell Program''. The program focuses on the development of a low-cost, high-performance 3-to-10-kW solid oxide fuel cell (SOFC) system suitable for a broad spectrum of power-generation applications. The overall objective of the program is to demonstrate a modular SOFC system that can be configured to create highly efficient, cost-competitive, and environmentally benign power plants tailored to specific markets. When fully developed, the system will meet the efficiency, performance, life, and cost goals for future commercial power plants.

Hydroxylamine-dependent Anaerobic Ammonium Oxidation (Anammox) by “ Candidatus Brocadia sinica”

KAUST Repository

Oshiki, Mamoru; Ali, Muhammad; Shinyako-Hata, Kaori; Satoh, Hisashi; Okabe, Satoshi

2016-01-01

Although metabolic pathways and associated enzymes of anaerobic ammonium oxidation (anammox) of “Ca. Kuenenia stuttgartiensis” have been studied, those of other anammox bacteria are still poorly understood. NO2- reduction to NO is considered to be the first step in the anammox metabolism of “Ca. K. stuttgartiensis”, however, “Ca. Brocadia” lacks the genes that encode canonical NO-forming nitrite reductases (NirS or NirK) in its genome, which is different from “Ca. K. stuttgartiensis”. Here, we studied the anammox metabolism of “Ca. Brocadia sinica”. 15N-tracer experiments demonstrated that “Ca. B. sinica” cells could reduce NO2- to NH2OH, instead of NO, with as yet unidentified nitrite reductase(s). Furthermore, N2H4 synthesis, downstream reaction of NO2- reduction, was investigated using a purified “Ca. B. sinica” hydrazine synthase (Hzs) and intact cells. Both the “Ca. B. sinica” Hzs and cells utilized NH2OH and NH4+, but not NO and NH4+, for N2H4 synthesis and further oxidized N2H4 to N2 gas. Taken together, the metabolic pathway of “Ca. B. sinica” is NH2OH-dependent and different from the one of “Ca. K. stuttgartiensis”, indicating metabolic diversity of anammox bacteria. This article is protected by copyright. All rights reserved.

Hydroxylamine-dependent Anaerobic Ammonium Oxidation (Anammox) by “ Candidatus Brocadia sinica”

KAUST Repository

Oshiki, Mamoru

2016-04-26

Although metabolic pathways and associated enzymes of anaerobic ammonium oxidation (anammox) of “Ca. Kuenenia stuttgartiensis” have been studied, those of other anammox bacteria are still poorly understood. NO2- reduction to NO is considered to be the first step in the anammox metabolism of “Ca. K. stuttgartiensis”, however, “Ca. Brocadia” lacks the genes that encode canonical NO-forming nitrite reductases (NirS or NirK) in its genome, which is different from “Ca. K. stuttgartiensis”. Here, we studied the anammox metabolism of “Ca. Brocadia sinica”. 15N-tracer experiments demonstrated that “Ca. B. sinica” cells could reduce NO2- to NH2OH, instead of NO, with as yet unidentified nitrite reductase(s). Furthermore, N2H4 synthesis, downstream reaction of NO2- reduction, was investigated using a purified “Ca. B. sinica” hydrazine synthase (Hzs) and intact cells. Both the “Ca. B. sinica” Hzs and cells utilized NH2OH and NH4+, but not NO and NH4+, for N2H4 synthesis and further oxidized N2H4 to N2 gas. Taken together, the metabolic pathway of “Ca. B. sinica” is NH2OH-dependent and different from the one of “Ca. K. stuttgartiensis”, indicating metabolic diversity of anammox bacteria. This article is protected by copyright. All rights reserved.

Correlation of the oxidation state of cerium in sol-gel glasses as a function of thermal treatment via optical spectroscopy and XANES studies.

Science.gov (United States)

Assefa, Zerihun; Haire, R G; Caulder, D L; Shuh, D K

2004-07-01

Sol-gel glass matrices containing lanthanides have numerous technological applications and their formation involves several chemical facets. In the case of cerium, its ability to exist in two different oxidation states or in mixed valence state provides additional complexities for the sol-gel process. The oxidation state of cerium present during different facets of preparation of sol-gel glasses, and also as a function of the starting oxidation state of cerium added, were studied both by optical spectroscopy and X-ray absorption near-edge structures (XANES). The findings acquired by each approach were compared. The primary focus was on the redox chemistries associated with sample preparation, gelation, and thermal treatment. When Ce3+ is introduced into the starting sols, the trivalent state normally prevails in the wet and room temperature-dried gels. Heating in air at >100 degrees C can generate a light yellow coloration with partial oxidation to the tetravalent state. Above 200 degrees C and up to approximately 1000 degrees C, cerium is oxidized to its tetravalent state. In contrast, when tetravalent cerium is introduced into the sol, both the wet and room temperature-dried gels lose the yellow-brown color of the initial ceric ammonium nitrate solution. When the sol-gel is heated to 110 degrees C it turns yellowish as the cerium tends to be re-oxidized. The yellow color is believed to represent the effect of oxidation and oligomerization of the cerium-silanol units in the matrix. The luminescence properties are also affected by these changes, the details of which are reported herein.

Investigation on Fluorescence Quenching Mechanism of Perylene Diimide Dyes by Graphene Oxide

Directory of Open Access Journals (Sweden)

Yuzhen Zhao

2016-11-01

Full Text Available Perylene diimide derivatives were used as probes to investigate the effect of the molecular structures on the fluorescence quenching mechanism in a perylene diimide/graphene oxide system. The electrons transferred from the excited state of dyes to the conductive band of graphene oxide with different concentrations were determined by fluorescence spectra. The results indicated that the quenching efficiency of perylene diimides by graphene oxide was not only dependent on the difference between the lowest unoccupied molecular orbital level of dyes and the conduction band of the graphene oxide, but also mainly on the difference in the molecular structures.

Angiopoietin-like 4 mediates PPAR delta effect on lipoprotein lipase-dependent fatty acid uptake but not on beta-oxidation in myotubes.

Directory of Open Access Journals (Sweden)

Marius R Robciuc

Full Text Available Peroxisome proliferator-activated receptor (PPAR delta is an important regulator of fatty acid (FA metabolism. Angiopoietin-like 4 (Angptl4, a multifunctional protein, is one of the major targets of PPAR delta in skeletal muscle cells. Here we investigated the regulation of Angptl4 and its role in mediating PPAR delta functions using human, rat and mouse myotubes. Expression of Angptl4 was upregulated during myotubes differentiation and by oleic acid, insulin and PPAR delta agonist GW501516. Treatment with GW501516 or Angptl4 overexpression inhibited both lipoprotein lipase (LPL activity and LPL-dependent uptake of FAs whereas uptake of BSA-bound FAs was not affected by either treatment. Activation of retinoic X receptor (RXR, PPAR delta functional partner, using bexarotene upregulated Angptl4 expression and inhibited LPL activity in a PPAR delta dependent fashion. Silencing of Angptl4 blocked the effect of GW501516 and bexarotene on LPL activity. Treatment with GW501516 but not Angptl4 overexpression significantly increased palmitate oxidation. Furthermore, Angptl4 overexpression did not affect the capacity of GW501516 to increase palmitate oxidation. Basal and insulin stimulated glucose uptake, glycogen synthesis and glucose oxidation were not significantly modulated by Angptl4 overexpression. Our findings suggest that FAs-PPARdelta/RXR-Angptl4 axis controls the LPL-dependent uptake of FAs in myotubes, whereas the effect of PPAR delta activation on beta-oxidation is independent of Angptl4.

High-temperature oxidation behavior of dense SiBCN monoliths: Carbon-content dependent oxidation structure, kinetics and mechanisms

International Nuclear Information System (INIS)

Li, Daxin; Yang, Zhihua; Jia, Dechang; Wang, Shengjin; Duan, Xiaoming; Zhu, Qishuai; Miao, Yang; Rao, Jiancun; Zhou, Yu

2017-01-01

Highlights: •The scale growth for all investigated monoliths at 1500 °C cannot be depicted by a linear or parabolic rate law. •The carbon-rich monoliths oxidize at 1500 °C according to a approximately linear weight loss equation. •The excessive carbon in SiBCN monoliths deteriorates the oxidation resistance. •The oxidation resistance stems from the characteristic oxide structures and increased oxidation resistance of BN(C). -- Abstract: The high temperature oxidation behavior of three SiBCN monoliths: carbon-lean SiBCN with substantial Si metal, carbon-moderate SiBCN and carbon-rich SiBCN with excessive carbon, was investigated at 1500 °C for times up to15 h. Scale growth for carbon-lean and −moderate monoliths at 1500 °C cannot be described by a linear or parabolic rate law, while the carbon-rich monoliths oxidize according to a approximately linear weight loss equation. The microstructures of the oxide scale compose of three distinct layers. The passivating layer of carbon and boron containing amorphous SiO 2 and increased oxidation resistance of BN(C) both benefit the oxidation resistance.

Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States

Science.gov (United States)

Díaz-de-Cerio, Elixabet; Verardo, Vito; Gómez-Caravaca, Ana María; Fernández-Gutiérrez, Alberto; Segura-Carretero, Antonio

2016-01-01

Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high). The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production. PMID:27187352

Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States

Directory of Open Access Journals (Sweden)

Elixabet Díaz-de-Cerio

2016-05-01

Full Text Available Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high. The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production.

Exploratory Characterization of Phenolic Compounds with Demonstrated Anti-Diabetic Activity in Guava Leaves at Different Oxidation States.

Science.gov (United States)

Díaz-de-Cerio, Elixabet; Verardo, Vito; Gómez-Caravaca, Ana María; Fernández-Gutiérrez, Alberto; Segura-Carretero, Antonio

2016-05-11

Psidium guajava L. is widely used like food and in folk medicine all around the world. Many studies have demonstrated that guava leaves have anti-hyperglycemic and anti-hyperlipidemic activities, among others, and that these activities belong mainly to phenolic compounds, although it is known that phenolic composition in guava tree varies throughout seasonal changes. Andalusia is one of the regions in Europe where guava is grown, thus, the aim of this work was to study the phenolic compounds present in Andalusian guava leaves at different oxidation states (low, medium, and high). The phenolic compounds in guava leaves were determined by HPLC-DAD-ESI-QTOF-MS. The results obtained by chromatographic analysis reported that guava leaves with low degree of oxidation had a higher content of flavonols, gallic, and ellagic derivatives compared to the other two guava leaf samples. Contrary, high oxidation state guava leaves reported the highest content of cyanidin-glucoside that was 2.6 and 15 times higher than guava leaves with medium and low oxidation state, respectively. The QTOF platform permitted the determination of several phenolic compounds with anti-diabetic properties and provided new information about guava leaf phenolic composition that could be useful for nutraceutical production.

Elevated oxidative stress monitored via the albumin-thiol redox state is correlated with matrix metalloproteinase-3 elevation in patients with rheumatoid arthritis.

Science.gov (United States)

Kizaki, Kazuha; Yoshizumi, Yusuke; Takahashi, Teppei; Era, Seiichi

2015-01-01

In rheumatoid arthritis (RA), matrix metalloproteinase-3 (MMP-3) and oxidative stress contribute to joint destruction. However, little is known about the relationship between MMP-3 and oxidative stress in RA. We measured the albumin-thiol redox state as a marker of oxidative stress, MMP-3, and the DAS-28 score calculated using CRP values among forty-seven patients (9 males and 38 females) with RA. According to the serum MMP-3 levels, they were divided into two groups (group A: within normal ranges of 36.9-121.0 ng/mL for men and 17.3-59.7 ng/mL for women; group B: above normal ranges). The albumin-thiol redox state in group B was significantly oxidized compared with that in group A (p < 0.01). The percentage of oxidized albumin-thiol showed a positive correlation with serum MMP-3 (r = 0.52). DAS-28 and CRP were also correlated with the percentage of oxidized albumin-thiol (r = 0.46, r = 0.44). The albumin-thiol redox state was significantly oxidized in correlation with serum MMP-3 elevation in RA.

The angular dependence of spin-state energy splittings in the ? core

Science.gov (United States)

Groß, Lynn; Steenbock, Torben; Herrmann, Carmen

2013-07-01

Spin-state energy splittings are highly relevant for catalysis, molecular magnetism, and materials science, yet continue to pose a challenge for electronic structure methods. For a Fe2O2+ 2 core, we evaluate the bridging angle dependence of energy splittings between ferromagnetically and antiferromagnetically coupled states for different exchange-correlation functionals, and compare with complete active space self-consistent field (CASSCF) values, also including second-order perturbative corrections (CASPT2). CASSCF and CASPT2 yield strong antiferromagnetic coupling, with the smallest coupling at 100°, and a smooth dependence on the angle for Fe-O-Fe angles of 70° to 120°. Interestingly, this is qualitatively the same behaviour as often found for stable dinuclear transition metal complexes. While all functionals show the same angular dependence as CASPT2, they favour the antiferromagnetic state less strongly. Pure functionals such as BP86, BLYP, SSB-D, and TPSS come closer to the CASPT2 results (with energy splittings by about 60 kJ/mol smaller than the CASPT2 ones) than hybrid functionals. The hybrid functionals B3LYP, B3LYP⋆, and PBE0 favour the antiferromagnetic state even less strongly, resulting in ferromagnetic coupling for angles around 100°. The good qualitative agreement between CASPT2 and CASSCF on the one hand and CASPT2 and density functional theory on the other hand for angles between 70° and 110° suggests that the chosen active space of 18 electrons in 14 orbitals may be adequate for spin-state energy splitting of Fe2O2+ 2 in that region (possibly due to error cancellation), while angles of 60° or 120° may require larger active spaces. This study is complemented by an analysis of local spins, local charges, and CASSCF natural orbitals.

Stability of Ruddlesden–Popper-structured oxides in humid conditions

Energy Technology Data Exchange (ETDEWEB)

Lehtimäki, M.; Yamauchi, H.; Karppinen, M., E-mail: maarit.karppinen@aalto.fi

2013-08-15

Some of layered transition-metal oxides are known to react with atmospheric humidity to form through topotactic intercalation reactions new water-containing layered structures. Here we investigate the influence of oxygen content (7−δ) of the Ruddlesden–Popper-structured Sr{sub 3}FeMO{sub 7−δ} (M=Ni, Mn, Ti) oxides on the water-intercalation reaction. It is found that their oxygen contents influence greatly the reactivity of the phases with water. Other factors possibly affecting the reactivity are discussed on the basis of the present data in combination with a comprehensive review of previous works on Ruddlesden–Popper and related layered oxide phases. - Graphical abstract: Many of the Ruddlesden–Popper-structured A{sub 3}B{sub 2}O{sub 7−δ} oxides readily react with water via intercalation reactions. Three possible factors affecting the water intercalation are identified: oxygen content of the phase, ionic radius of cation A and valence state of cation B. The resultant layered water-derivative phases can be categorised into two groups, depending on the crystal symmetry of the phase. Highlights: • Ruddlesden–Popper oxides A{sub 3}B{sub 2}O{sub 7−δ} often accommodate water via intercalation reaction. • The lower the oxygen content 7−δ is the more readily the intercalation reaction occurs. • The second factor promoting the reaction is the large size of cation A. • The third possible factor is the high valence state of cation B. • Resultant water-derivatives can be categorised into two groups depending on symmetry.

Stability of Ruddlesden–Popper-structured oxides in humid conditions

International Nuclear Information System (INIS)

Lehtimäki, M.; Yamauchi, H.; Karppinen, M.

2013-01-01

Some of layered transition-metal oxides are known to react with atmospheric humidity to form through topotactic intercalation reactions new water-containing layered structures. Here we investigate the influence of oxygen content (7−δ) of the Ruddlesden–Popper-structured Sr 3 FeMO 7−δ (M=Ni, Mn, Ti) oxides on the water-intercalation reaction. It is found that their oxygen contents influence greatly the reactivity of the phases with water. Other factors possibly affecting the reactivity are discussed on the basis of the present data in combination with a comprehensive review of previous works on Ruddlesden–Popper and related layered oxide phases. - Graphical abstract: Many of the Ruddlesden–Popper-structured A 3 B 2 O 7−δ oxides readily react with water via intercalation reactions. Three possible factors affecting the water intercalation are identified: oxygen content of the phase, ionic radius of cation A and valence state of cation B. The resultant layered water-derivative phases can be categorised into two groups, depending on the crystal symmetry of the phase. Highlights: • Ruddlesden–Popper oxides A 3 B 2 O 7−δ often accommodate water via intercalation reaction. • The lower the oxygen content 7−δ is the more readily the intercalation reaction occurs. • The second factor promoting the reaction is the large size of cation A. • The third possible factor is the high valence state of cation B. • Resultant water-derivatives can be categorised into two groups depending on symmetry

The induction of the oxidative burst in Elodea densa by sulfhydryl reagent does not depend on de novo protein synthesis

Energy Technology Data Exchange (ETDEWEB)

Amicucci, Enrica [Milan, Univ. (Italy). Dipt. di Fisiologia e Biochimica delle Piante

1997-12-31

In Elodea densa Planchon leaves, N-ethylmaleimide (NEM) and other sulfhydryl-binding reagents induce a marked and temporary increase of respiration that is insensitive to cyanide, hydroxamate and propylgallate and completely inhibited by diphenylene iodonium (DPI) and by quinacrine. In this paper the author investigates whether the mechanism that causes the oxidative burst depends on the activation of preexisting oxidative systems or on the activation of de novo protein synthesis. The inhibitors used were cycloheximide (CHI) which inhibits protein synthesis in plant cells by depressing the incorporation of aminoacids into proteins and cordycepin, an effective inhibitor of mRNA synthesis. The data support the idea that the mechanism investigated depends on the activation of a long lived protein(s) and not on de novo protein synthesis.

Electrochemical determination of the oxidation potentials and the thermodynamic stability of the valence states of the transuranium elements in aqueous alkaline media

International Nuclear Information System (INIS)

Peretrukhin, V.F.; Spitsyn, V.I.

1982-01-01

The oxidation potentials of neptunium, plutonium, and americium in the valance states from (III) to (VII) have been determined experimentally in 0.1-15 M NaOH. Heptavalent plutonium and americium are thermodynamically able to oxidize water with the evolution of oxygen in 0.1-15 M NaOH, neptunium(VII) in 0.1-7 M NaOH. All valance states of plutonium resist disproportionation in alkaline solutions; in the case of neptunium and americium only one disproportionation reaction is possible; of the hexavalent state in to penta- and heptavalent states. The degree of completion of the reaction can be calculated accurately from the oxidation potentials determined

Direct Yaw Control of Vehicle using State Dependent Riccati Equation with Integral Terms

Directory of Open Access Journals (Sweden)

SANDHU, F.

2016-05-01

Full Text Available Direct yaw control of four-wheel vehicles using optimal controllers such as the linear quadratic regulator (LQR and the sliding mode controller (SMC either considers only certain parameters constant in the nonlinear equations of vehicle model or totally neglect their effects to obtain simplified models, resulting in loss of states for the system. In this paper, a modified state-dependent Ricatti equation method obtained by the simplification of the vehicle model is proposed. This method overcomes the problem of the lost states by including state integrals. The results of the proposed system are compared with the sliding mode slip controller and state-dependent Ricatti equation method using high fidelity vehicle model in the vehicle simulation software package, Carsim. Results show 38% reduction in the lateral velocity, 34% reduction in roll and 16% reduction in excessive yaw by only increasing the fuel consumption by 6.07%.

The Behavior of the Ru-bda Water Oxidation Catalysts at Low Oxidation States.

Science.gov (United States)

Matheu, Roc; Ghaderian, Abolfazl; Francas, Laia; Chernev, Petko; Ertem, Mehmed; Benet-Buchholz, Jordi; Batista, Victor; Haumann, Michael; Gimbert-Suriñach, Carolina; Sala, Xavier; Llobet, Antoni

2018-06-13

The Ru complex [RuII(bda-κ-N2O2)(N-NH2)2], 1, (bda2- = (2,2'-bipyridine)-6,6'-dicarboxylate; N-NH2 = 4-(pyridin-4-yl)aniline) is used as a synthetic intermediate to prepare Ru-bda complexes that contain the NO+, acetonitrile (MeCN) or H2O ligands at oxidation states II and III. Complex 1 reacts with excess NO+ to form a Ru complex where the aryl amine ligands N-NH2 in 1 are transformed into diazonium salts (N-N2+ = 4-(pyridin-4-yl)benzenediazonium)) together with the formation of a new Ru-NO group at the equatorial zone, to generate [RuII(bda-κ-N2O)(NO)(N-N2)2]3+, 23+. Similarly, complex 1 can also react with a coordinating solvent, such as MeCN, at room temperature leading to complex [RuII(bda-κ-N2O)(MeCN)(N-NH2)2], 3. Finally in acidic aqueous solutions solvent water coordinates the Ru center forming {[RuII(bda-κ-(NO)3)(H2O)(N-NH3)2](H2O)n}2+, 42+, that is strongly hydrogen bonded with additional water molecules at the second coordination sphere. We have additionally characterized the one electron oxidized complex {[RuIII(bda-κ-(NO)3.5)(H2O)(N-NH3)2](H2O)n}3+, 53+. The coordination mode of the complexes has been studied both in the solid state and in solution through single-crystal XRD, X-ray absorption spectroscopy, variable-temperature NMR and DFT calculations. While the κ-N2O is the main coordination mode for 23+ and 3, an equilibrium that involves isomers with κ-N2O and κ-NO2 coordination modes and neighboring hydrogen bonded water molecules is observed for 42+ and 53+. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evidence for forcing-dependent steady states in a turbulent swirling flow.

Science.gov (United States)

Saint-Michel, B; Dubrulle, B; Marié, L; Ravelet, F; Daviaud, F

2013-12-06

We study the influence on steady turbulent states of the forcing in a von Karman flow, at constant impeller speed, or at constant torque. We find that the different forcing conditions change the nature of the stability of the steady states and reveal dynamical regimes that bear similarities to low-dimensional systems. We suggest that this forcing dependence may be applicable to other turbulent systems.

Capacity region of the 3 receiver state dependent multilevel BC with noncausal state information

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Viswanathan Ramachandran

2017-09-01

Full Text Available We consider a three receiver state dependent multilevel broadcast channel (BC, where the state information is known non-causally at the encoder as well as all the decoders. This is an extension of Nair and El Gamal’s three receiver multilevel BC (Nair and El Gamal, 2009, wherein two of the receivers decode only a common message while a third receiver decodes a private message as well. The objective is to characterize the rate tuples that are simultaneously achievable while ensuring negligible probability of error at each of the receivers. We characterize the capacity region of this setup in the paper.

Interface Controlled Oxidation States in Layered Cobalt Oxide Nanoislands on Gold

DEFF Research Database (Denmark)

Walton, Alexander; Fester, Jakob; Bajdich, Michal

2015-01-01

Layered cobalt oxides have been shown to be highly active catalysts for the oxygen evolution reaction (OER; half of the catalytic “water splitting” reaction), particularly when promoted with gold. However, the surface chemistry of cobalt oxides and in particular the nature of the synergistic effect...

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

Science.gov (United States)

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

2016-07-01

Nitric oxide (NO) is a ubiquitous signaling molecule involved in the regulation of a large number of cellular functions. The regulatory mechanism of NO generation in unicellular eukaryotic yeast cells is poorly understood due to the lack of mammalian and bacterial NO synthase (NOS) orthologues, even though yeast produces NO under oxidative stress conditions. Recently, we reported that the flavoprotein Tah18, which was previously shown to transfer electrons to the iron-sulfur cluster protein Dre2, is involved in NOS-like activity in the yeast Saccharomyces cerevisiae. On the other hand, Tah18 was reported to promote apoptotic cell death after exposure to hydrogen peroxide (H2O2). Here, we showed that NOS-like activity requiring Tah18 induced cell death upon treatment with H2O2. Our experimental results also indicate that Tah18-dependent NO production and cell death are suppressed by enhancement of the interaction between Tah18 and its molecular partner Dre2. Our findings indicate that the Tah18-Dre2 complex regulates cell death as a molecular switch via Tah18-dependent NOS-like activity in response to environmental changes. Copyright © 2016 Elsevier Inc. All rights reserved.

The fate of arsenic adsorbed on iron oxides in the presence of arsenite-oxidizing bacteria.

Science.gov (United States)

Zhang, Zhennan; Yin, Naiyi; Du, Huili; Cai, Xiaolin; Cui, Yanshan

2016-05-01

Arsenic (As) is a redox-active metalloid whose toxicity and mobility in soil depend on its oxidation state. Arsenite [As(III)] can be oxidized by microbes and adsorbed by minerals in the soil. However, the combined effects of these abiotic and biotic processes are not well understood. In this study, the fate of arsenic in the presence of an isolated As(III)-oxidizing bacterium (Pseudomonas sp. HN-1, 10(9) colony-forming units (CFUs)·ml(-1)) and three iron oxides (goethite, hematite, and magnetite at 1.6 g L(-1)) was determined using batch experiments. The total As adsorption by iron oxides was lower with bacteria present and was higher with iron oxides alone. The total As adsorption decreased by 78.6%, 36.0% and 79.7% for goethite, hematite and magnetite, respectively, due to the presence of bacteria. As(III) adsorbed on iron oxides could also be oxidized by Pseudomonas sp. HN-1, but the oxidation rate (1.3 μmol h(-1)) was much slower than the rate in the aqueous phase (96.2 μmol h(-1)). Therefore, the results of other studies with minerals only might overestimate the adsorptive capacity of solids in natural systems; the presence of minerals might hinder As(III) oxidation by microbes. Under aerobic conditions, in the presence of iron oxides and As(III)-oxidizing bacteria, arsenic is adsorbed onto iron oxides within the adsorption capacity, and As(V) is the primary form in the solid and aqueous phases. Copyright © 2016 Elsevier Ltd. All rights reserved.

Remarks on the necessity and implications of state-dependence in the black hole interior

Science.gov (United States)

Papadodimas, Kyriakos; Raju, Suvrat

2016-04-01

We revisit the "state-dependence" of the map that we proposed recently between bulk operators in the interior of a large anti-de Sitter black hole and operators in the boundary CFT. By refining recent versions of the information paradox, we show that this feature is necessary for the CFT to successfully describe local physics behind the horizon—not only for single-sided black holes but even in the eternal black hole. We show that state-dependence is invisible to an infalling observer who cannot differentiate these operators from those of ordinary quantum effective field theory. Therefore the infalling observer does not observe any violations of quantum mechanics. We successfully resolve a large class of potential ambiguities in our construction. We analyze states where the CFT is entangled with another system and show that the ER =EPR conjecture emerges from our construction in a natural and precise form. We comment on the possible semiclassical origins of state-dependence.

Remarks on the necessity and implications of state-dependence in the black hole interior

CERN Document Server

Papadodimas, Kyriakos

2016-01-01

We revisit the "state-dependence" of the map that we proposed recently between bulk operators in the interior of a large AdS black hole and operators in the boundary CFT. By refining recent versions of the information paradox, we show that this feature is necessary for the CFT to successfully describe local physics behind the horizon --- not only for single-sided black holes but even in the eternal black hole. We show that state-dependence is invisible to an infalling observer who cannot differentiate these operators from those of ordinary quantum effective field theory. Therefore the infalling observer does not observe any violations of quantum mechanics. We successfully resolve a large class of potential ambiguities in our construction. We analyze states where the CFT is entangled with another system and show that the ER=EPR conjecture emerges from our construction in a natural and precise form. We comment on the possible semi-classical origins of state-dependence.

Triplet-State Dissolved Organic Matter Quantum Yields and Lifetimes from Direct Observation of Aromatic Amine Oxidation.

Science.gov (United States)

Schmitt, Markus; Erickson, Paul R; McNeill, Kristopher

2017-11-21

Excited triplet state chromophoric dissolved organic matter ( 3 CDOM*) is a short-lived mixture of excited-state species that plays important roles in aquatic photochemical processes. Unlike the study of the triplet states of well-defined molecules, which are amenable to transient absorbance spectroscopy, the study of 3 CDOM* is hampered by it being a complex mixture and its low average intersystem crossing quantum yield (Φ ISC ). This study is an alternative approach to investigating 3 CDOM* using transient absorption laser spectroscopy. The radical cation of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), formed through oxidation by 3 CDOM*, was directly observable by transient absorption spectroscopy and was used to probe basic photophysical properties of 3 CDOM*. Quenching and control experiments verified that TMPD •+ was formed from 3 CDOM* under anoxic conditions. Model triplet sensitizers with a wide range of excited triplet state reduction potentials and CDOM oxidized TMPD at near diffusion-controlled rates. This gives support to the idea that a large cross-section of 3 CDOM* moieties are able to oxidize TMPD and that the complex mixture of 3 CDOM* can be simplified to a single signal. Using the TMPD •+ transient, the natural triplet lifetime and Φ ISC for different DOM isolates and natural waters were quantified; values ranged from 12 to 26 μs and 4.1-7.8%, respectively.

Shelf-life modeling of bakery products by using oxidation indices.

Science.gov (United States)

Calligaris, Sonia; Manzocco, Lara; Kravina, Giuditta; Nicoli, Maria Cristina

2007-03-07

The aim of this work was to develop a shelf-life prediction model of lipid-containing bakery products. To this purpose (i) the temperature dependence of the oxidation rate of bakery products was modeled, taking into account the changes in lipid physical state; (ii) the acceptance limits were assessed by sensory analysis; and (iii) the relationship between chemical oxidation index and acceptance limit was evaluated. Results highlight that the peroxide number, the changes of which are linearly related to consumer acceptability, is a representative index of the quality depletion of biscuits during their shelf life. In addition, the evolution of peroxides can be predicted by a modified Arrhenius equation accounting for the changes in the physical state of biscuit fat. Knowledge of the relationship between peroxides and sensory acceptability together with the temperature dependence of peroxide formation allows a mathematical model to be set up to simply and quickly calculate the shelf life of biscuits.

The Effect of Nitric Oxide Synthetase Inhibitor (L-NAME on Prevention of Morphine Dependence in Rats

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A. Rafati

2004-10-01

Full Text Available Prevention of dependency to morphine or delaying to it and decreasing of tendency to morphine craving and also decreasing in morphine induced hyperalgesia(tolerance were the aims of this study. Nitric oxide is one of the neurotransmitters, which involves in the Dopamine reuptake in striatum. Dopamine is one of the most important neurotransmitters in reward system in central nervous system and it has a critical role in morphine addiction and dependency, tendency and tolerance to it, so in this study we survied the role of L- NAME as a nitric oxide synthetase (NOS inhibitor on the prevention of morphine addiction in rats. In this study we evaluated behavioral changes such as morphine craving by self - administration as a criterion for tendency, dependency by observation of withdrawal syndrom signs (e.g Jumping, wet dog shaking and also responses to nociceptive condenced bim of light by using tail flick analgesia metric device in sham (consuming tap water, control (consuming increasing doses of morphine sulfate solution from 0.1mg/ml up to 0.4mg/ml and test (treated with 45 mg/kg of L- NAME 30 minutes before consuming of morphine sulfate solution per day groups. The results showed that pretreatment with L- NAME in test group lead to a significant decline in tendency to morphine craving, withdrawal signs and also a significant reversal of morphine induced hyperalgesia. We concluded that L- NAME is a potent agent in the prevention of morphine addiction.

Effect of particle size on iron nanoparticle oxidation state

International Nuclear Information System (INIS)

Lombardo, Jeffrey J.; Lysaght, Andrew C.; Goberman, Daniel G.; Chiu, Wilson K.S.

2012-01-01

Selecting catalyst particles is a very important part of carbon nanotube growth, although the properties of these nanoscale particles are unclear. In this article iron nanoparticles are analyzed through the use of atomic force microscopy and x-ray photoelectron spectroscopy in order to understand how the size affects the chemical composition of nanoparticles and thus their physical structure. Initially, atomic force microscopy was used to confirm the presence of iron particles, and to determine the average size of the particles. Next an analytical model was developed to estimate particle size as a function of deposition time using inputs from atomic force microscopy measurement. X-ray photoelectron spectroscopy analysis was then performed with a focus on the spectra relating to the 2p Fe electrons to study the chemical state of the particles as a function of time. It was shown that as the size of nanoparticles decreased, the oxidation state of the particles changed due to a high proportion of atoms on the surface.

Lung injury-dependent oxidative status and chymotrypsin-like activity of skeletal muscles in hamsters with experimental emphysema.

Science.gov (United States)

Tonon, Jair; Cecchini, Alessandra Lourenço; Brunnquell, Cláudia Roberta; Bernardes, Sara Santos; Cecchini, Rubens; Guarnier, Flávia Alessandra

2013-01-23

Peripheral skeletal muscle is altered in patients suffering from emphysema and chronic obstructive pulmonary disease (COPD). Oxidative stress have been demonstrated to participate on skeletal muscle loss of several states, including disuse atrophy, mechanical ventilation, and chronic diseases. No evidences have demonstrated the occurance in a severity manner. We evaluated body weight, muscle loss, oxidative stress, and chymotrypsin-like proteolytic activity in the gastrocnemius muscle of emphysemic hamsters. The experimental animals had 2 different severities of lung damage from experimental emphysema induced by 20 mg/mL (E20) and 40 mg/mL (E40) papain. The severity of emphysema increased significantly in E20 (60.52 ± 2.8, p < 0.05) and E40 (52.27 ± 4.7; crossed the alveolar intercepts) groups. As compared to the control group, there was a reduction on body (171.6 ± 15.9 g) and muscle weight (251.87 ± 24.87 mg) in the E20 group (157.5 ± 10.3 mg and 230.12 ± 23.52 mg, for body and muscle weight, respectively), which was accentuated in the E40 group (137.4 ± 7.2 g and 197.87 ± 10.49 mg, for body and muscle weight, respectively). Additionally, the thiobarbituric acid reactive substances (TBARS), tert-butyl hydroperoxide-initiated chemiluminescence (CL), carbonylated proteins, and chymotrypsin-like proteolytic activity were elevated in the E40 group as compared to the E20 group (p < 0.05 for all comparisons). The severity of emphysema significantly correlated with the progressive increase in CL (r = -0.95), TBARS (r = -0.98), carbonyl proteins (r = -0.99), and chymotrypsin-like proteolytic activity (r = -0.90). Furthermore, augmentation of proteolytic activity correlated significantly with CL (r = 0.97), TBARS (r = 0.96), and carbonyl proteins (r = 0.91). Taken together, the results of the present study suggest that muscle atrophy observed in this model of emphysema is mediated by increased muscle chymotrypsin-like activity, with possible involvement of

High-Pressure Reactivity of Kr and F2—Stabilization of Krypton in the +4 Oxidation State

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Dominik Kurzydłowski

2017-10-01

Full Text Available Since the synthesis of the first krypton compound, several other Kr-bearing connections have been obtained. However, in all of them krypton adopts the +2 oxidation state, in contrast to xenon which forms numerous compounds with an oxidation state as high as +8. Motivated by the possibility of thermodynamic stabilization of exotic compounds with the use of high pressure (exceeding 1 GPa = 10 kbar, we present here theoretical investigations into the chemistry of krypton and fluorine at such large compression. In particular we focus on krypton tetrafluoride, KrF4, a molecular crystal in which krypton forms short covalent bonds with neighboring fluorine atoms thus adopting the +4 oxidation state. We find that this hitherto unknown compound can be stabilized at pressures below 50 GPa. Our results indicate also that, at larger compressions, a multitude of other KrmFn fluorides should be stable, among them KrF which exhibits covalent Kr–Kr bonds. Our results set the stage for future high-pressure synthesis of novel krypton compounds.

Operando XAS Study of the Surface Oxidation State on a Monolayer IrO_x on RuO_x and Ru Oxide Based Nanoparticles for Oxygen Evolution in Acidic Media

DEFF Research Database (Denmark)

Pedersen, Anders Filsøe; Escribano, Maria Escudero; Sebok, Bela

2018-01-01

that the average Ir oxidation state change is strongly affected by the coverage of atomic O. The observed shifts in oxidation state suggest that the surface has a high coverage of O at potentials just below the potential where oxygen evolution is exergonic in free energy. This observation is consistent...

Irradiation temperature dependence of production efficiency of lattice defects in some neutron-irradiated oxides

International Nuclear Information System (INIS)

Okada, Moritami; Atobe, Kozo; Nakagawa, Masuo

2004-01-01

Temperature dependence of production efficiency of irradiation-induced defects in neutron-irradiated oxides has been investigated. Some oxide single crystals, MgO, α-Al 2 O 3 (sapphire) and TiO 2 (rutile), were irradiated at several controlled temperatures, 10, 20, 50, 100, 150 and 200 K, using the low-temperature irradiation facility of Kyoto University Reactor (KUR-LTL), and at ambient temperature (∼370 K) in the same facility. Irradiation temperature dependence of production efficiency of a 1 μm band in TiO 2 differs greatly from that of anion vacancy (F-type centers) in MgO and α-Al 2 O 3 . Results for MgO and α-Al 2 O 3 show steep negative gradients from 10 to 370 K, whereas that for TiO 2 includes a valley between 40 and 60 K and a hump at about 130 K, and then disappear at about 200 K. In MgO and α-Al 2 O 3 , this behavior can be explained by the recombination of Frenkel pairs, which is activated at higher temperature. In TiO 2 , in addition to the recombination mechanism, a covalent bonding property is thought to be exerted strong influence, and it is suggested that a disappearance of the 1 μm band at above 200 K is due to the recombination process of Frenkel pairs which is caused by the irradiation-induced crystallization

Irradiation temperature dependence of production efficiency of lattice defects in some neutron-irradiated oxides

Energy Technology Data Exchange (ETDEWEB)

Okada, Moritami [Research Reactor Institute, Kyoto University, Kumatori-cho, Sennan-gun, Osaka 5900494 (Japan)]. E-mail: okada@rri.kyoto-u.ac.jp; Atobe, Kozo [Faculty of Science, Naruto University of Education, Naruto, Tokushima 7728502 (Japan); Nakagawa, Masuo [Faculty of Education, Kagawa University, Takamatsu, Kagawa 7608522 (Japan)

2004-11-01

Temperature dependence of production efficiency of irradiation-induced defects in neutron-irradiated oxides has been investigated. Some oxide single crystals, MgO, {alpha}-Al{sub 2}O{sub 3} (sapphire) and TiO{sub 2} (rutile), were irradiated at several controlled temperatures, 10, 20, 50, 100, 150 and 200 K, using the low-temperature irradiation facility of Kyoto University Reactor (KUR-LTL), and at ambient temperature ({approx}370 K) in the same facility. Irradiation temperature dependence of production efficiency of a 1 {mu}m band in TiO{sub 2} differs greatly from that of anion vacancy (F-type centers) in MgO and {alpha}-Al{sub 2}O{sub 3}. Results for MgO and {alpha}-Al{sub 2}O{sub 3} show steep negative gradients from 10 to 370 K, whereas that for TiO{sub 2} includes a valley between 40 and 60 K and a hump at about 130 K, and then disappear at about 200 K. In MgO and {alpha}-Al{sub 2}O{sub 3}, this behavior can be explained by the recombination of Frenkel pairs, which is activated at higher temperature. In TiO{sub 2}, in addition to the recombination mechanism, a covalent bonding property is thought to be exerted strong influence, and it is suggested that a disappearance of the 1 {mu}m band at above 200 K is due to the recombination process of Frenkel pairs which is caused by the irradiation-induced crystallization.

The inverse Gamma process: A family of continuous stochastic models for describing state-dependent deterioration phenomena

International Nuclear Information System (INIS)

Guida, M.; Pulcini, G.

2013-01-01

This paper proposes the family of non-stationary inverse Gamma processes for modeling state-dependent deterioration processes with nonlinear trend. The proposed family of processes, which is based on the assumption that the “inverse” time process is Gamma, is mathematically more tractable than previously proposed state-dependent processes, because, unlike the previous models, the inverse Gamma process is a time-continuous and state-continuous model and does not require discretization of time and state. The conditional distribution of the deterioration growth over a generic time interval, the conditional distribution of the residual life and the residual reliability of the unit, given the current state, are provided. Point and interval estimation of the parameters which index the proposed process, as well as of several quantities of interest, are also discussed. Finally, the proposed model is applied to the wear process of the liners of some Diesel engines which was previously analyzed and proved to be a purely state-dependent process. The comparison of the inferential results obtained under the competitor models shows the ability of the Inverse Gamma process to adequately model the observed state-dependent wear process

Manganese oxidation state mediates toxicity in PC12 cells

International Nuclear Information System (INIS)

Reaney, S.H.; Smith, D.R.

2005-01-01

The role of the manganese (Mn) oxidation state on cellular Mn uptake and toxicity is not well understood. Therefore, undifferentiated PC12 cells were exposed to 0-200 μM Mn(II)-chloride or Mn(III)-pyrophosphate for 24 h, after which cellular manganese levels were measured along with measures of cell viability, function, and cytotoxicity (trypan blue exclusion, medium lactate dehydrogenase (LDH), 8-isoprostanes, cellular ATP, dopamine, serotonin, H-ferritin, transferrin receptor (TfR), Mn-superoxide dismutase (MnSOD), and copper-zinc superoxide dismutase (CuZnSOD) protein levels). Exposures to Mn(III) >10 μM produced 2- to 5-fold higher cellular manganese levels than equimolar exposures to Mn(II). Cell viability and ATP levels both decreased at the highest Mn(II) and Mn(III) exposures (150-200 μM), while Mn(III) exposures produced increases in LDH activity at lower exposures (≥50 μM) than did Mn(II) (200 μM only). Mn(II) reduced cellular dopamine levels more than Mn(III), especially at the highest exposures (50% reduced at 200 μM Mn(II)). In contrast, Mn(III) produced a >70% reduction in cellular serotonin at all exposures compared to Mn(II). Different cellular responses to Mn(II) exposures compared to Mn(III) were also observed for H-ferritin, TfR, and MnSOD protein levels. Notably, these differential effects of Mn(II) versus Mn(III) exposures on cellular toxicity could not simply be accounted for by the different cellular levels of manganese. These results suggest that the oxidation state of manganese exposures plays an important role in mediating manganese cytotoxicity

Effect of aluminum oxide doping on the structural, electrical, and optical properties of zinc oxide (AOZO) nanofibers synthesized by electrospinning

International Nuclear Information System (INIS)

Lotus, A.F.; Kang, Y.C.; Walker, J.I.; Ramsier, R.D.; Chase, G.G.

2010-01-01

Zinc oxide nanofibers doped with aluminum oxide were prepared by sol-gel processing and electrospinning techniques using polyvinylpyrrolidone (PVP), zinc acetate and aluminum acetate as precursors. The resulting nanofibers were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-Vis spectroscopy, and current-voltage (I-V) properties. The nanofibers had diameters in the range of 60-150 nm. The incorporation of aluminum oxide resulted in a decrease in the crystallite sizes of the zinc oxide nanofibers. Aluminum oxide doped zinc oxide (AOZO) nanofibers exhibited lower bandgap energies compared to undoped zinc oxide nanofibers. However, as the aluminum content (Al/(Al + Zn) x 100%) was increased from 1.70 at.% to 3.20 at.% in the electrospinning solution, the bandgap energy increased resulting in lower conductivity. The electrical conductivity of the AOZO samples was found to depend on the amount of aluminum dopant in the matrix as reflected in the changes in oxidation state elucidated from XPS data. Electrospinning was found to be a productive, simple, and easy method for tuning the bandgap energy and conductivity of zinc oxide semiconducting nanofibers.

Oxidation kinetics of Si and SiGe by dry rapid thermal oxidation, in-situ steam generation oxidation and dry furnace oxidation

Science.gov (United States)

Rozé, Fabien; Gourhant, Olivier; Blanquet, Elisabeth; Bertin, François; Juhel, Marc; Abbate, Francesco; Pribat, Clément; Duru, Romain

2017-06-01

The fabrication of ultrathin compressively strained SiGe-On-Insulator layers by the condensation technique is likely a key milestone towards low-power and high performances FD-SOI logic devices. However, the SiGe condensation technique still requires challenges to be solved for an optimized use in an industrial environment. SiGe oxidation kinetics, upon which the condensation technique is founded, has still not reached a consensus in spite of various studies which gave insights into the matter. This paper aims to bridge the gaps between these studies by covering various oxidation processes relevant to today's technological needs with a new and quantitative analysis methodology. We thus address oxidation kinetics of SiGe with three Ge concentrations (0%, 10%, and 30%) by means of dry rapid thermal oxidation, in-situ steam generation oxidation, and dry furnace oxidation. Oxide thicknesses in the 50 Å to 150 Å range grown with oxidation temperatures between 850 and 1100 °C were targeted. The present work shows first that for all investigated processes, oxidation follows a parabolic regime even for thin oxides, which indicates a diffusion-limited oxidation regime. We also observe that, for all investigated processes, the SiGe oxidation rate is systematically higher than that of Si. The amplitude of the variation of oxidation kinetics of SiGe with respect to Si is found to be strongly dependent on the process type. Second, a new quantitative analysis methodology of oxidation kinetics is introduced. This methodology allows us to highlight the dependence of oxidation kinetics on the Ge concentration at the oxidation interface, which is modulated by the pile-up mechanism. Our results show that the oxidation rate increases with the Ge concentration at the oxidation interface.

Proteomic indicators of oxidation and hydration state in colorectal cancer

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Jeffrey M. Dick

2016-07-01

Full Text Available New integrative approaches are needed to harness the potential of rapidly growing datasets of protein expression and microbial community composition in colorectal cancer. Chemical and thermodynamic models offer theoretical tools to describe populations of biomacromolecules and their relative potential for formation in different microenvironmental conditions. The average oxidation state of carbon (ZC can be calculated as an elemental ratio from the chemical formulas of proteins, and water demand per residue ( ${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$ n ¯ H 2 O is computed by writing the overall formation reactions of proteins from basis species. Using results reported in proteomic studies of clinical samples, many datasets exhibit higher mean ZC or ${\\overline{n}}_{{\\mathrm{H}}_{2}\\mathrm{O}}$ n ¯ H 2 O of proteins in carcinoma or adenoma compared to normal tissue. In contrast, average protein compositions in bacterial genomes often have lower ZC for bacteria enriched in fecal samples from cancer patients compared to healthy donors. In thermodynamic calculations, the potential for formation of the cancer-related proteins is energetically favored by changes in the chemical activity of H2O and fugacity of O2 that reflect the compositional differences. The compositional analysis suggests that a systematic change in chemical composition is an essential feature of cancer proteomes, and the thermodynamic descriptions show that the observed proteomic transformations in host tissue could be promoted by relatively high microenvironmental oxidation and hydration states.

Unravelling the dependence of hydrogen oxidation kinetics on the size of Pt nanoparticles by in operando nanoplasmonic temperature sensing

DEFF Research Database (Denmark)

Wettergren, Kristina; Hellman, Anders; Cavalca, Filippo Carlo

2015-01-01

We use a noninvasive nanoscale optical-temperature measurement method based on localized surface plasmon resonance to investigate the particle size-dependence of the hydrogen oxidation reaction kinetics on model supported Pt nanocatalysts at atmospheric pressure in operando. With decreasing average...

Witness memory and alcohol: The effects of state-dependent recall.

Science.gov (United States)

Schreiber Compo, Nadja; Carol, Rolando N; Evans, Jacqueline R; Pimentel, Pamela; Holness, Howard; Nichols-Lopez, Kristin; Rose, Stefan; Furton, Kenneth G

2017-04-01

Many real-world eyewitnesses are under the influence of alcohol either at the time of the crime, the interview, or both. Only recently has empirical research begun to examine the effects of alcohol on witness memory, yielding mixed results. The present study tested the importance of state-dependent memory in the context of alcohol's effects on encoding versus retrieval of a witnessed event, while simultaneously informing real-world investigative practices: Should witnesses sober up before an interview? Participants (N = 249) were randomized to a control, placebo, or alcohol condition at encoding and to either an immediate retrieval condition (in the same state) or a 1-week delay control, placebo, or alcohol retrieval condition. They recalled a witnessed mock crime using open ended and cued recall formats. After a delay, witnesses intoxicated at both encoding and retrieval provided less accurate information than witnesses in sober or placebo groups at both times. There was no advantage of state-dependent memory but intoxicated witnesses were best when recalling immediately compared to 1 week later (sober, placebo, or reintoxicated). Findings have direct implications for the timing of intoxicated witnesses' interviews such that moderately intoxicated witnesses may not benefit from a sobering delay but rather, should be interviewed immediately. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

Ropivacaine-Induced Contraction Is Attenuated by Both Endothelial Nitric Oxide and Voltage-Dependent Potassium Channels in Isolated Rat Aortae

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Seong-Ho Ok

2013-01-01

Full Text Available This study investigated endothelium-derived vasodilators and potassium channels involved in the modulation of ropivacaine-induced contraction. In endothelium-intact rat aortae, ropivacaine concentration-response curves were generated in the presence or absence of the following inhibitors: the nonspecific nitric oxide synthase (NOS inhibitor Nω-nitro-L-arginine methyl ester (L-NAME, the neuronal NOS inhibitor Nω-propyl-L-arginine hydrochloride, the inducible NOS inhibitor 1400W dihydrochloride, the nitric oxide-sensitive guanylyl cyclase (GC inhibitor ODQ, the NOS and GC inhibitor methylene blue, the phosphoinositide-3 kinase inhibitor wortmannin, the cytochrome p450 epoxygenase inhibitor fluconazole, the voltage-dependent potassium channel inhibitor 4-aminopyridine (4-AP, the calcium-activated potassium channel inhibitor tetraethylammonium (TEA, the inward-rectifying potassium channel inhibitor barium chloride, and the ATP-sensitive potassium channel inhibitor glibenclamide. The effect of ropivacaine on endothelial nitric oxide synthase (eNOS phosphorylation in human umbilical vein endothelial cells was examined by western blotting. Ropivacaine-induced contraction was weaker in endothelium-intact aortae than in endothelium-denuded aortae. L-NAME, ODQ, and methylene blue enhanced ropivacaine-induced contraction, whereas wortmannin, Nω-propyl-L-arginine hydrochloride, 1400W dihydrochloride, and fluconazole had no effect. 4-AP and TEA enhanced ropivacaine-induced contraction; however, barium chloride and glibenclamide had no effect. eNOS phosphorylation was induced by ropivacaine. These results suggest that ropivacaine-induced contraction is attenuated primarily by both endothelial nitric oxide and voltage-dependent potassium channels.

Surface State Capture Cross-Section at the Interface between Silicon and Hafnium Oxide

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Fu-Chien Chiu

2013-01-01

Full Text Available The interfacial properties between silicon and hafnium oxide (HfO2 are explored by the gated-diode method and the subthreshold measurement. The density of interface-trapped charges, the current induced by surface defect centers, the surface recombination velocity, and the surface state capture cross-section are obtained in this work. Among the interfacial properties, the surface state capture cross-section is approximately constant even if the postdeposition annealing condition is changed. This effective capture cross-section of surface states is about 2.4 × 10−15 cm2, which may be an inherent nature in the HfO2/Si interface.

Iron biomineralization by anaerobic neutrophilic iron-oxidizing bacteria

DEFF Research Database (Denmark)

Miot, Jennyfer; Benzerara, Karim; Morin, Guillaume

2009-01-01

Minerals formed by bio-oxidation of ferrous iron (Fe(II)) at neutral pH, their association with bacterial ultrastructures as well as their impact on the metabolism of iron-oxidizing bacteria remain poorly understood. Here, we investigated iron biomineralization by the anaerobic nitrate-dependent ......Minerals formed by bio-oxidation of ferrous iron (Fe(II)) at neutral pH, their association with bacterial ultrastructures as well as their impact on the metabolism of iron-oxidizing bacteria remain poorly understood. Here, we investigated iron biomineralization by the anaerobic nitrate...... precipitation in the periplasm (in a few tens of minutes), followed by the formation of surface-bound globules. Moreover, we frequently observed an asymmetric mineral thickening at the cell poles. In parallel, the evolution of iron oxidation was quantified by STXM: iron both contained in the bacteria...... and in the extracellular precipitates reached complete oxidation within 6 days. While a progressive oxidation of Fe in the bacteria and in the medium could be observed, spatial redox (oxido-reduction state) heterogeneities were detected at the cell poles and in the extracellular precipitates after 1 day. All...

Role of the pH in state-dependent blockade of hERG currents

Science.gov (United States)

Wang, Yibo; Guo, Jiqing; Perissinotti, Laura L.; Lees-Miller, James; Teng, Guoqi; Durdagi, Serdar; Duff, Henry J.; Noskov, Sergei Yu.

2016-10-01

Mutations that reduce inactivation of the voltage-gated Kv11.1 potassium channel (hERG) reduce binding for a number of blockers. State specific block of the inactivated state of hERG block may increase risks of drug-induced Torsade de pointes. In this study, molecular simulations of dofetilide binding to the previously developed and experimentally validated models of the hERG channel in open and open-inactivated states were combined with voltage-clamp experiments to unravel the mechanism(s) of state-dependent blockade. The computations of the free energy profiles associated with the drug block to its binding pocket in the intra-cavitary site display startling differences in the open and open-inactivated states of the channel. It was also found that drug ionization may play a crucial role in preferential targeting to the open-inactivated state of the pore domain. pH-dependent hERG blockade by dofetilie was studied with patch-clamp recordings. The results show that low pH increases the extent and speed of drug-induced block. Both experimental and computational findings indicate that binding to the open-inactivated state is of key importance to our understanding of the dofetilide’s mode of action.

A multiconfigurational time-dependent Hartree-Fock method for excited electronic states. I. General formalism and application to open-shell states.

Science.gov (United States)

Miranda, R P; Fisher, A J; Stella, L; Horsfield, A P

2011-06-28

The solution of the time-dependent Schrödinger equation for systems of interacting electrons is generally a prohibitive task, for which approximate methods are necessary. Popular approaches, such as the time-dependent Hartree-Fock (TDHF) approximation and time-dependent density functional theory (TDDFT), are essentially single-configurational schemes. TDHF is by construction incapable of fully accounting for the excited character of the electronic states involved in many physical processes of interest; TDDFT, although exact in principle, is limited by the currently available exchange-correlation functionals. On the other hand, multiconfigurational methods, such as the multiconfigurational time-dependent Hartree-Fock (MCTDHF) approach, provide an accurate description of the excited states and can be systematically improved. However, the computational cost becomes prohibitive as the number of degrees of freedom increases, and thus, at present, the MCTDHF method is only practical for few-electron systems. In this work, we propose an alternative approach which effectively establishes a compromise between efficiency and accuracy, by retaining the smallest possible number of configurations that catches the essential features of the electronic wavefunction. Based on a time-dependent variational principle, we derive the MCTDHF working equation for a multiconfigurational expansion with fixed coefficients and specialise to the case of general open-shell states, which are relevant for many physical processes of interest.