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Sample records for 70oc h2 producing

  1. Chemiluminescent Detection of Enzymatically Produced H2S

    PubMed Central

    Bailey, T. Spencer; Pluth, Michael D.

    2015-01-01

    Hydrogen sulfide (H2S) has emerged as an important biological signaling molecule. To better understand the multifaceted biological roles of H2S, the development of selective and sensitive biocompatible assays for H2S is becoming increasingly important. Motivated by these challenges, our laboratory is developing new methods to further detect and monitor biological H2S. Here, we describe in detail our recent advances in the development and the use of chemiluminescence-based H2S sensors to assist other investigators with use of these chemical tools. We highlight the use of these tools use by displaying their selectivity and high sensitivity toward H2S and provide examples of assays we have developed to detect enzymatically produced H2S. PMID:25725517

  2. Identification of H2S3 and H2S produced by 3-mercaptopyruvate sulfurtransferase in the brain

    PubMed Central

    Kimura, Yuka; Toyofuku, Yukiko; Koike, Shin; Shibuya, Norihiro; Nagahara, Noriyuki; Lefer, David; Ogasawara, Yuki; Kimura, Hideo

    2015-01-01

    Hydrogen polysulfides (H2Sn) have a higher number of sulfane sulfur atoms than hydrogen sulfide (H2S), which has various physiological roles. We recently found H2Sn in the brain. H2Sn induced some responses previously attributed to H2S but with much greater potency than H2S. However, the number of sulfur atoms in H2Sn and its producing enzyme were unknown. Here, we detected H2S3 and H2S, which were produced from 3-mercaptopyruvate (3 MP) by 3-mercaptopyruvate sulfurtransferase (3MST), in the brain. High performance liquid chromatography with fluorescence detection (LC-FL) and tandem mass spectrometry (LC-MS/MS) analyses showed that H2S3 and H2S were produced from 3 MP in the brain cells of wild-type mice but not 3MST knockout (3MST-KO) mice. Purified recombinant 3MST and lysates of COS cells expressing 3MST produced H2S3 from 3 MP, while those expressing defective 3MST mutants did not. H2S3 was localized in the cytosol of cells. H2S3 was also produced from H2S by 3MST and rhodanese. H2S2 was identified as a minor H2Sn, and 3 MP did not affect the H2S5 level. The present study provides new insights into the physiology of H2S3 and H2S, as well as novel therapeutic targets for diseases in which these molecules are involved. PMID:26437775

  3. The stable isotopic signature of biologically produced molecular hydrogen (H2)

    NASA Astrophysics Data System (ADS)

    Walter, S.; Laukenmann, S.; Stams, A. J. M.; Vollmer, M. K.; Gleixner, G.; Röckmann, T.

    2011-12-01

    Biologically produced molecular hydrogen (H2) is characterized by a very strong depletion in deuterium. Although the biological source to the atmosphere is small compared to photochemical or combustion sources, it makes an important contribution to the global isotope budget of molecular hydrogen (H2). Large uncertainties exist in the quantification of the individual production and degradation processes that contribute to the atmospheric budget, and isotope measurements are a tool to distinguish the contributions from the different sources. Measurements of δD from the various H2 sources are scarce and for biologically produced H2 only very few measurements exist. Here the first systematic study of the isotopic composition of biologically produced H2 is presented. We investigated δD of H2 produced in a biogas plant, covering different treatments of biogas production, and from several H2 producing microorganisms such as bacteria or green algae. A Keeling plot analysis provides a robust overall source signature of δD = -712‰ (±13‰) for the samples from the biogas reactor (at 38 °C, δDH2O = 73.4‰), with a fractionation constant ϵH2-H2O of -689‰ (±20‰). The pure culture samples from different microorganisms give a mean source signature of δD = -728‰ (±39‰), and a fractionation constant ϵH2-H2O of -711‰ (±45‰) between H2 and the water, respectively. The results confirm the massive deuterium depletion of biologically produced H2 as was predicted by calculation of the thermodynamic fractionation factors for hydrogen exchange between H2 and water vapor. As expected for a thermodynamic equilibrium, the fractionation factor is largely independent of the substrates used and the H2 production conditions. The predicted equilibrium fractionation coefficient is positively correlated with temperature and we measured a change of 2.2‰/°C between 45 °C and 60 °C. This is in general agreement with the theoretical predictions. Our

  4. The H2S Donor NaHS Changes the Expression Pattern of H2S-Producing Enzymes after Myocardial Infarction.

    PubMed

    Li, Na; Wang, Ming-Jie; Jin, Sheng; Bai, Ya-Dan; Hou, Cui-Lan; Ma, Fen-Fen; Li, Xing-Hui; Zhu, Yi-Chun

    2016-01-01

    Aims. To examine the expression patterns of hydrogen sulphide- (H2S-) producing enzymes in ischaemic heart tissue and plasma levels of H2S after 2 weeks of NaHS treatment after myocardial infarction (MI) and to clarify the role of endogenous H2S in the MI process. Results. After MI surgery, 2 weeks of treatment with the H2S donor NaHS alleviated ischaemic injury. Meanwhile, in ischemia myocardium, three H2S-producing enzymes, cystathionine γ-lyase (CSE), cystathionine-β-synthase (CBS), and 3-mercaptopyruvate sulfurtransferase (3-MST) significantly increased. Plasma H2S levels were also elevated. In vitro, NaHS treatment protected cardiomyocytes from hypoxic injury and raised CBS levels in a concentration-dependent manner. Different from in vivo results, however, CSE or 3-MST expression did not change. NaHS treatment increased the activity of CSE/CBS but not of 3-MST. When CSE was either knocked down (in vitro) or knocked out (in vivo), H2S levels significantly decreased, which subsequently exacerbated the ischaemic injury. Meanwhile, the expressions of CBS and 3-MST increased due to compensation. Conclusions. Exogenous H2S treatment changed the expressions of three H2S-producing enzymes and H2S levels after MI, suggesting a new and indirect regulatory mechanism for H2S production and its contribution to cardiac protection. Endogenous H2S plays an important role in protecting ischaemic tissue after MI. PMID:27057284

  5. An analytical model of the free H2 produced by serpentinization within oceanic lithosphere

    NASA Astrophysics Data System (ADS)

    Worman, S. L.; Pratson, L.; Darrah, T. H.; Karson, J. A.; Klein, E. M.

    2014-12-01

    The free H2 produced by serpentinization within oceanic lithosphere figures prominently in theories regarding (1) the origin and early evolution of life of earth, (2) the basal fuel-source sustaining the sub-seafloor biosphere, (3) the formation of abiogenic hydrocarbons as well as (4) native metal alloys, (5) the geochemical cycles of various elements, and (5) the future use of H2 as a substitute for fossil fuels. Here we present an analytical model that ties H2 production to seafloor spreading rates and the cooling of oceanic lithosphere. If the assumptions underpinning our simplistic model are largely correct, we estimate that global H2 production by the serpentinization of peridoitite within oceanic-lithosphere may be as large as ~9.7x1012 moles H2/year, which is within one or two orders of magnitude of any previous estimates. The model, however, also predicts where globally H2 production should be greatest as well as how far from the axis of a mid-oceanic ridge H2 production should remain significant. We could not rigorously test our model due to sparse and varied measurements of H2 globally however the model suggests a number of systematic relationships and testable predications for future field-based studies. To demonstrate the potential validity and implications our results, we evaluate where all the free-H2 predicted by the model may go given the limited amount known about the H2 budget within the oceans.

  6. The stable isotopic signature of biologically produced molecular hydrogen (H2)

    NASA Astrophysics Data System (ADS)

    Walter, S.; Laukenmann, S.; Stams, A. J. M.; Vollmer, M. K.; Gleixner, G.; Röckmann, T.

    2012-10-01

    Biologically produced molecular hydrogen (H2) is characterised by a very strong depletion in deuterium. Although the biological source to the atmosphere is small compared to photochemical or combustion sources, it makes an important contribution to the global isotope budget of H2. Large uncertainties exist in the quantification of the individual production and degradation processes that contribute to the atmospheric budget, and isotope measurements are a tool to distinguish the contributions from the different sources. Measurements of δ D from the various H2 sources are scarce and for biologically produced H2 only very few measurements exist. Here the first systematic study of the isotopic composition of biologically produced H2 is presented. In a first set of experiments, we investigated δ D of H2 produced in a biogas plant, covering different treatments of biogas production. In a second set of experiments, we investigated pure cultures of several H2 producing microorganisms such as bacteria or green algae. A Keeling plot analysis provides a robust overall source signature of δ D = -712‰ (±13‰) for the samples from the biogas reactor (at 38 °C, δ DH2O= +73.4‰), with a fractionation constant ϵH2-H2O of -689‰ (±20‰) between H2 and the water. The five experiments using pure culture samples from different microorganisms give a mean source signature of δ D = -728‰ (±28‰), and a fractionation constant ϵH2-H2O of -711‰ (±34‰) between H2 and the water. The results confirm the massive deuterium depletion of biologically produced H2 as was predicted by the calculation of the thermodynamic fractionation factors for hydrogen exchange between H2 and water vapour. Systematic errors in the isotope scale are difficult to assess in the absence of international standards for δ D of H2. As expected for a thermodynamic equilibrium, the fractionation factor is temperature dependent, but largely independent of the substrates used and

  7. Concentrated solar energy for thermochemically producing liquid fuels from CO2 and H2O

    NASA Astrophysics Data System (ADS)

    Loutzenhiser, Peter G.; Stamatiou, Anastasia; Villasmil, Willy; Meier, Anton; Steinfeld, Aldo

    2011-01-01

    A two-step solar thermochemical cycle for producing syngas from H2O and CO2 via Zn/ZnO redox reactions is considered. The first, endothermic step is the thermolysis of ZnO to Zn and O2 using concentrated solar radiation as the source of process heat. The second, non-solar, exothermic step is the reaction of Zn with mixtures of H2O and CO2 yielding high-quality syngas (mainly H2 and CO) and ZnO; the latter is recycled to the first solar step, resulting in net reactions CO2 = CO+0.5O2 and H2O= H2 +0.5O2. Syngas is further processed to liquid fuels via Fischer-Tropsch or other catalytic reforming processes. State-of-the-art reactor technologies and experimental results are provided for both steps of the cycle.

  8. Three-dimensional WS2 nanosheet networks for H2O2 produced for cell signaling

    NASA Astrophysics Data System (ADS)

    Tang, Jing; Quan, Yingzhou; Zhang, Yueyu; Jiang, Min; Al-Enizi, Abdullah M.; Kong, Biao; An, Tiance; Wang, Wenshuo; Xia, Limin; Gong, Xingao; Zheng, Gengfeng

    2016-03-01

    Hydrogen peroxide (H2O2) is an important molecular messenger for cellular signal transduction. The capability of direct probing of H2O2 in complex biological systems can offer potential for elucidating its manifold roles in living systems. Here we report the fabrication of three-dimensional (3D) WS2 nanosheet networks with flower-like morphologies on a variety of conducting substrates. The semiconducting WS2 nanosheets with largely exposed edge sites on flexible carbon fibers enable abundant catalytically active sites, excellent charge transfer, and high permeability to chemicals and biomaterials. Thus, the 3D WS2-based nano-bio-interface exhibits a wide detection range, high sensitivity and rapid response time for H2O2, and is capable of visualizing endogenous H2O2 produced in living RAW 264.7 macrophage cells and neurons. First-principles calculations further demonstrate that the enhanced sensitivity of probing H2O2 is attributed to the efficient and spontaneous H2O2 adsorption on WS2 nanosheet edge sites. The combined features of 3D WS2 nanosheet networks suggest attractive new opportunities for exploring the physiological roles of reactive oxygen species like H2O2 in living systems.Hydrogen peroxide (H2O2) is an important molecular messenger for cellular signal transduction. The capability of direct probing of H2O2 in complex biological systems can offer potential for elucidating its manifold roles in living systems. Here we report the fabrication of three-dimensional (3D) WS2 nanosheet networks with flower-like morphologies on a variety of conducting substrates. The semiconducting WS2 nanosheets with largely exposed edge sites on flexible carbon fibers enable abundant catalytically active sites, excellent charge transfer, and high permeability to chemicals and biomaterials. Thus, the 3D WS2-based nano-bio-interface exhibits a wide detection range, high sensitivity and rapid response time for H2O2, and is capable of visualizing endogenous H2O2 produced in

  9. Three-dimensional WS2 nanosheet networks for H2O2 produced for cell signaling.

    PubMed

    Tang, Jing; Quan, Yingzhou; Zhang, Yueyu; Jiang, Min; Al-Enizi, Abdullah M; Kong, Biao; An, Tiance; Wang, Wenshuo; Xia, Limin; Gong, Xingao; Zheng, Gengfeng

    2016-03-01

    Hydrogen peroxide (H2O2) is an important molecular messenger for cellular signal transduction. The capability of direct probing of H2O2 in complex biological systems can offer potential for elucidating its manifold roles in living systems. Here we report the fabrication of three-dimensional (3D) WS2 nanosheet networks with flower-like morphologies on a variety of conducting substrates. The semiconducting WS2 nanosheets with largely exposed edge sites on flexible carbon fibers enable abundant catalytically active sites, excellent charge transfer, and high permeability to chemicals and biomaterials. Thus, the 3D WS2-based nano-bio-interface exhibits a wide detection range, high sensitivity and rapid response time for H2O2, and is capable of visualizing endogenous H2O2 produced in living RAW 264.7 macrophage cells and neurons. First-principles calculations further demonstrate that the enhanced sensitivity of probing H2O2 is attributed to the efficient and spontaneous H2O2 adsorption on WS2 nanosheet edge sites. The combined features of 3D WS2 nanosheet networks suggest attractive new opportunities for exploring the physiological roles of reactive oxygen species like H2O2 in living systems. PMID:26909564

  10. Global rate and distribution of H2 gas produced by serpentinization within oceanic lithosphere

    NASA Astrophysics Data System (ADS)

    Worman, Stacey L.; Pratson, Lincoln F.; Karson, Jeffrey A.; Klein, Emily M.

    2016-06-01

    It has recently been estimated that serpentinization within continental lithosphere produces H2 at rates comparable to oceanic lithosphere (both are ~1011 mol H2/yr). Here we present a simple model that suggests that H2 production rates along the mid-oceanic ridge alone (i.e., excluding other marine settings) may exceed continental production by an order of magnitude (~1012 mol H2/yr). In our model, H2 production rates increase with spreading rate and the net thickness of serpentinizing peridotite (S-P) in a column of lithosphere. Lithosphere with a faster spreading rate therefore requires a relatively smaller net thickness of S-P to produce H2 at the same rate as lithosphere with a slower rate and greater thickness of S-P. We apply our model globally, incorporating an inverse relationship between spreading rate and net thickness of S-P to be consistent with observations that serpentinization is more common within lithosphere spreading at slower rates.

  11. H2-producing bacterial communities from a heat-treated soil inoculum.

    PubMed

    Iyer, Prabha; Bruns, Mary Ann; Zhang, Husen; Van Ginkel, Steve; Logan, Bruce E

    2004-12-01

    Hydrogen gas (approximately 60% H(2)) was produced in a continuous flow bioreactor inoculated with heat-treated soil, and fed synthetic wastewater containing glucose (9.5 g l(-1)). The pH in the bioreactor was maintained at 5.5 to inhibit consumption of H(2) by methanogens. The objective of this study was to characterize bacterial communities in the reactor operated under two different hydraulic retention times (HRTs of 30-h and 10-h) and temperatures (30 degrees C and 37 degrees C). At 30-h HRT, the H(2) production rate was 80 ml h(-1) and yield was 0.91 mol H(2)/mol glucose. At 10-h HRT, the H(2) production rate was more than 5 times higher at 436 ml h(-1), and yield was 1.61 mol H(2)/mol glucose. Samples were removed from the reactor under steady-state conditions for PCR-based detection of bacterial populations by ribosomal intergenic spacer analysis (RISA). Populations detected at 30-h HRT were more diverse than at 10-h HRT and included representatives of Bacillaceae, Clostridiaceae, and Enterobacteriaceae. At 10-h HRT, only Clostridiaceae were detected. When the temperature of the 10-h HRT reactor was increased from 30 degrees C to 37 degrees C, the steady-state H(2) production rate increased slightly to 463 ml h(-1) and yield was 1.8 mol H(2)/mol glucose. Compared to 30 degrees C, RISA fingerprints at 37 degrees C from the 10-h HRT bioreactor exhibited a clear shift from populations related to Clostridium acidisoli (subcluster Ic) to populations related to Clostridium acetobutylicum (subcluster Ib). PMID:15558274

  12. Increasing extracellular H2O2 produces a bi-phasic response in intracellular H2O2, with peroxiredoxin hyperoxidation only triggered once the cellular H2O2-buffering capacity is overwhelmed.

    PubMed

    Tomalin, Lewis Elwood; Day, Alison Michelle; Underwood, Zoe Elizabeth; Smith, Graham Robert; Dalle Pezze, Piero; Rallis, Charalampos; Patel, Waseema; Dickinson, Bryan Craig; Bähler, Jürg; Brewer, Thomas Francis; Chang, Christopher Joh-Leung; Shanley, Daryl Pierson; Veal, Elizabeth Ann

    2016-06-01

    Reactive oxygen species, such as H2O2, can damage cells but also promote fundamental processes, including growth, differentiation and migration. The mechanisms allowing cells to differentially respond to toxic or signaling H2O2 levels are poorly defined. Here we reveal that increasing external H2O2 produces a bi-phasic response in intracellular H2O2. Peroxiredoxins (Prx) are abundant peroxidases which protect against genome instability, ageing and cancer. We have developed a dynamic model simulating in vivo changes in Prx oxidation. Remarkably, we show that the thioredoxin peroxidase activity of Prx does not provide any significant protection against external rises in H2O2. Instead, our model and experimental data are consistent with low levels of extracellular H2O2 being efficiently buffered by other thioredoxin-dependent activities, including H2O2-reactive cysteines in the thiol-proteome. We show that when extracellular H2O2 levels overwhelm this buffering capacity, the consequent rise in intracellular H2O2 triggers hyperoxidation of Prx to thioredoxin-resistant, peroxidase-inactive form/s. Accordingly, Prx hyperoxidation signals that H2O2 defenses are breached, diverting thioredoxin to repair damage. PMID:26944189

  13. Remote processing, delivery and injection of H2[15O] produced from a N2/H2 gas target using a simple and compact apparatus.

    PubMed

    Ferrieri, R A; Alexoff, D L; Schlyer, D J; Wolf, A P

    1994-12-01

    We report here a simple apparatus for remote trapping and processing of H2[15O] produced from the N2/H2 target. The system performs a three step operation for H2[15O] delivery at the PET imaging facility which includes the following: (i) collecting the radiotracer in sterile water; (ii) adjusting preparation pH through removal of radiolytically produced ammonia, while at the same time adjusting solution isotonicity; and (iii) delivery of the radiotracer preparation to the injection syringe in a sterile and pyrogen-free form suitable for human studies. The processing apparatus is simple, can be remotely operated and fits inside a Capintec Dose Monitoring Chamber for direct measurement of accumulated radioactivity. Using this system, 300 mCi of H2[15O] (15 microA of 8 MeV D+ on target) is transferred from target through 120 m x 3.18 mm o.d. Impolene tubing to yield 100 mCi of H2[15O] which is isotonic, neutral and suitable for human studies. A remote hydraulically driven system for i.v. injection of the H2[15O] is also described. The device allows for direct measurement of syringe dose while filling, and for easy, as well as safe transport of the injection syringe assembly to the patient's bedside via a shielded delivery cart. This cart houses a hydraulic piston that allows the physician to "manually" inject the radiotracer without directly handling the syringe. PMID:7894394

  14. Serpentinization of the Martian early lithosphere to produce magnetite, CO2 and H2

    NASA Astrophysics Data System (ADS)

    Quesnel, Y.; Sotin, C.; Langlais, B.; Mandea, M.

    2007-08-01

    The magnetic measurements made on board the Mars Global Surveyor (MGS) probe revealed the intense nature of the lithospheric magnetic field at Mars. Since most of the strong anomalies at satellite altitudes (between 100 and 400 km) were measured over Noachian surfaces, crustal magnetization and / or demagnetization in the presence of an early axial, global and dipolar magnetic field is the most likely scenario to explain the anomaly distribution. Martian lithospheric magnetization contrasts derived by numerous studies range from 10 to more than 60 A/m, much larger than classical terrestrial values. In this study, we show that the chemical remanent magnetization (CRM) through the serpentinization can produce such large values. This produces magnetite as well as CO2 and H2. The Noachian period gathers all the necessary ingredients for this process to be emplaced: a strong magnetic field, a basaltic crust, large amounts of water causing hydrothermalism, and local heating due to the internal mantle convection. Predicted magnetization values are computed according to different hypotheses on the intensity of the main paleofield and the serpentinization process. This latter aspect is investigated with respect to the initial iron content of the mafic mineral, the water abundance and the reacting rock volume. The amounts of released H2 and CO2, possibly combining in CH4, are also studied.

  15. Clonal diversity of Shiga toxin-producing Escherichia coli O103:H2/H(-) in Germany.

    PubMed

    Prager, Rita; Liesegang, Almut; Voigt, W; Rabsch, W; Fruth, Angelika; Tschäpe, H

    2002-07-01

    Shiga toxin producing Escherichia coli O103:H2/H(-) belong to the third most frequently isolated EHEC serotypes in Germany following isolates of O157:H7/H(-) and O26:H11/H(-). A total of 145 respective E. coli 103 isolates from single cases of diarrhoea and haemolytic uremic syndrome (HUS) in 1997-2000 were characterised by a range of molecular subtyping methods (PFGE, P-gene profiling, ribotyping, electrotyping) and phage typing in order to analyse their genetic relatedness and the practicability for new epidemiological tracing back. All isolates cluster into a distinct EHEC subgroup and reveal a high clonal diversity together with a considerable stability. Since strains of this serotype rank up to the third most frequently isolated EHEC in Germany a large population of this serotype, and therefore, a great supply of such strains may exist in this country. PMID:12798005

  16. Bacterial communities in thermophilic H2-producing reactors investigated using 16S rRNA 454 pyrosequencing.

    PubMed

    Ratti, Regiane Priscila; Delforno, Tiago Palladino; Okada, Dagoberto Yukio; Varesche, Maria Bernadete Amâncio

    2015-04-01

    In this study, the composition and diversity of the bacterial community in thermophilic H2-producing reactors fed with glucose were investigated using pyrosequencing. The H2-producing experiments in batch were conducted using 0.5 and 2.0 g l(-1) glucose at 550 °C. Under the two conditions, the H2 production and yield were 1.3 and 1.6 mol H2 mol glucose(-1), respectively. Acetic, butyric, iso-butyric, lactic and propionic acids were detected in the two reactors. The increase in substrate concentration favored a high H2 yield. In this reactor, a predominance of acetic and iso-butyric acids, 27.7% and 40%, were measured, respectively. By means of pyrosequencing, a total of 323 and 247 operational taxonomic units were obtained, with a predominance of the phylum Firmicutes (68.73-67.61%) for reactors with 0.5 and 2.0 g l(-1) glucose, respectively. Approximately 40.55% and 62.34% of sequences were affiliated with Thermoanaerobacterium and Thermohydrogenium, microorganisms that produce H2 under thermophilic conditions. PMID:25801966

  17. A survey of genes encoding H2O2-producing GMC oxidoreductases in 10 Polyporales genomes.

    PubMed

    Ferreira, Patricia; Carro, Juan; Serrano, Ana; Martínez, Angel T

    2015-01-01

    The genomes of three representative Polyporales (Bjerkandera adusta, Phlebia brevispora and a member of the Ganoderma lucidum complex) recently were sequenced to expand our knowledge on the diversity and distribution of genes involved in degradation of plant polymers in this Basidiomycota order, which includes most wood-rotting fungi. Oxidases, including members of the glucose-methanol-choline (GMC) oxidoreductase superfamily, play a central role in the above degradative process because they generate extracellular H2O2 acting as the ultimate oxidizer in both white-rot and brown-rot decay. The survey was completed by analyzing the GMC genes in the available genomes of seven more species to cover the four Polyporales clades. First, an in silico search for sequences encoding members of the aryl-alcohol oxidase, glucose oxidase, methanol oxidase, pyranose oxidase, cellobiose dehydrogenase and pyranose dehydrogenase families was performed. The curated sequences were subjected to an analysis of their evolutionary relationships, followed by estimation of gene duplication/reduction history during fungal evolution. Second, the molecular structures of the near one hundred GMC oxidoreductases identified were modeled to gain insight into their structural variation and expected catalytic properties. In contrast to ligninolytic peroxidases, whose genes are present in all white-rot Polyporales genomes and absent from those of brown-rot species, the H2O2-generating oxidases are widely distributed in both fungal types. This indicates that the GMC oxidases provide H2O2 for both ligninolytic peroxidase activity (in white-rot decay) and Fenton attack on cellulose (in brown-rot decay), after the transition between both decay patterns in Polyporales occurred. PMID:26297778

  18. Using H2O and trace element ratios to produce a spatial map of magmatic H2O contents throughout the Trans-Mexican Volcanic Belt

    NASA Astrophysics Data System (ADS)

    Johnson, E. R.; Wallace, P. J.; Manea, V. C.

    2007-12-01

    Along with fluids, trace elements are released during dehydration of subducting sediment and altered oceanic crust. Large ion lithophile elements are typically fluid mobile, and thus may be used as tracers for fluid fluxing. We used melt inclusion H2O and trace element data from nine cinder cones across the subduction-related Michoacan-Guanajuato Volcanic Field (MGVF) of central Mexico to assess the fluid mobility of trace element species. We found correlations between H2O and Sr/La, Ba/Nb, Ba/Y, Pb/Y, Sr/Ti, suggesting that Sr, Ba, and Pb are present in fluids released from the downgoing slab. Additionally, we used regression lines for these correlations to estimate magmatic H2O for cinder cones across Mexico. We have applied the Sr/La and Sr/Ti relationships to the extensive dataset of cinder cone lava and scoria analyses from the MGVF by Hasenaka and Carmichael (1985). In order to see 2-D spatial patterns in H2O across the MGVF, we plotted the localities and the calculated H2O contents on a digital elevation model of Mexico. Initial results from this modeling show that, like our melt inclusion data, magmatic H2O contents are generally high (>3 wt%) across a broad region from the volcanic front to ~100 km behind the front. High H2O concentrations (4-6 wt%) are most abundant along the volcanic front, whereas much lower values (1-2 wt%) occur in an extensional region far behind the front. The relationship between H2O and trace element ratios can also be extended to other regions of Mexico, as the correlation between H2O/La and Sr/La is consistent to the east in the Chichinautzin Volcanic Field (Cervantes and Wallace, 2003) and to the west in the Colima Graben. Using analyses from these and other regions, we have created a spatial map of H2O contents across the Trans- Mexican Volcanic Belt, enabling us to see trends both along and across the arc. We can then use these spatial maps to relate patterns in H2O content to subduction processes such as arc migration over

  19. Influence of chemically produced singlet delta oxygen molecules on thermal ignition of O2-H2 mixtures

    NASA Astrophysics Data System (ADS)

    Vagin, N. P.; Kochetov, I. V.; Napartovich, A. P.; Yuryshev, N. N.

    2016-02-01

    Thermal ignition of the H2-O2 mixture with O2(a 1Δ g ) addition is studied experimentally and theoretically. The singlet delta oxygen was produced in a chemical generator. In this way, the competing chemical processes involving plasma produced chemically active O atoms and оzone (O3) were excluded. A satisfactory agreement is achieved between experimentally observed and numerically predicted values of the ignition time at the initial gas temperature (900-950) K and gas pressure (9-10) Torr. The percentage of the reactive channel in the binary collisions O2(a 1Δ g )  +  H is evaluated on the level (10-20)% for the H2-O2 mixture.

  20. Vacuum ultraviolet photolysis of hydrogenated amorphous carbons. III. Diffusion of photo-produced H2 as a function of temperature

    NASA Astrophysics Data System (ADS)

    Martín-Doménech, R.; Dartois, E.; Muñoz Caro, G. M.

    2016-06-01

    Context. Hydrogenated amorphous carbon (a-C:H) has been proposed as one of the carbonaceous solids detected in the interstellar medium. Energetic processing of the a-C:H particles leads to the dissociation of the C-H bonds and the formation of hydrogen molecules and small hydrocarbons. Photo-produced H2 molecules in the bulk of the dust particles can diffuse out to the gas phase and contribute to the total H2 abundance. Aims: We have simulated this process in the laboratory with plasma-produced a-C:H and a-C:D analogs under astrophysically relevant conditions to investigate the dependence of the diffusion as a function of temperature. Methods: Experimental simulations were performed in a high-vacuum chamber, with complementary experiments carried out in an ultra-high-vacuum chamber. Plasma-produced a-C:H and a-C:D analogs were UV-irradiated using a microwave-discharged hydrogen flow lamp. Molecules diffusing to the gas-phase were detected by a quadrupole mass spectrometer, providing a measurement of the outgoing H2 or D2 flux. By comparing the experimental measurements with the expected flux from a one-dimensional diffusion model, a diffusion coefficient D could be derived for experiments carried out at different temperatures. Results: Dependence on the diffusion coefficient D with the temperature followed an Arrhenius-type equation. The activation energy for the diffusion process was estimated (ED(H2) = 1660 ± 110 K, ED(D2) = 2090 ± 90 K), as well as the pre-exponential factor (D0(H2) = 0.0007 cm2 s-1, D0(D2) = 0.0045 cm2 s-1). Conclusions: The strong decrease of the diffusion coefficient at low dust particle temperatures exponentially increases the diffusion times in astrophysical environments. Therefore, transient dust heating by cosmic rays needs to be invoked for the release of the photo-produced H2 molecules in cold photon-dominated regions, where destruction of the aliphatic component in hydrogenated amorphous carbons most probably takes place.

  1. Pd-catalytic hydrodechlorination of chlorinated hydrocarbons in groundwater using H2 produced by a dual-anode system.

    PubMed

    Xie, Shiwei; Yuan, Songhu; Liao, Peng; Jia, Mengqi; Wang, Yin

    2015-12-01

    Water electrolysis has been employed for in situ supplying H2 to Pd-catalytic treatment of groundwater, but the treatment efficiency is greatly inhibited by the concomitant production of O2. In this study, a new dual-anode system is proposed to improve the efficiency. An inert anode and an iron anode are used simultaneously to produce O2 and Fe(II), respectively. The quick oxidative precipitation of Fe(II) by O2 removes both Fe(II) and O2, improving the utilization of cathodic H2 for the subsequent Pd-catalytic hydrodechlorination. Feasibility tests in the lab show that Pd-catalytic hydrodechlorination of trichloroethylene (TCE) was considerably increased by the addition of an iron anode to the conventional two-electrode system. Scale-up tests at an abandoned chemical site demonstrated that chlorobenzenes in the groundwater were largely hydrodechlorinated to benzene, showing a maximum efficiency with the currents of 0.24 and 0.16 A applied to the inert and iron anodes, respectively, at the flow rate of 6 L/h. In a 3-month intermittent field test, Pd normalized rate constants of hydrodechlorinating three chlorobenzenes are comparable to the conventional means of H2 supply, while the cost for hydrodechlorination normalized by one mole [H] is much lower. The dual-anode system is an effective means to supplying H2 in situ for Pd-catalytic treatment. PMID:26212567

  2. Solid organic residues produced by irradiation of hydrocarbon-containing H2O and H2O/NH3 ices - Infrared spectroscopy and astronomical implications

    NASA Technical Reports Server (NTRS)

    Khare, B. N.; Thompson, W. R.; Murray, B. G. J. P. T.; Chyba, C. F.; Sagan, C.

    1989-01-01

    Plasma-discharge irradiations were conducted for the methane clathrate expected in outer solar system satellites and cometary nuclei; also irradiated were ices prepared from other combinations of H2O with CH4, C2H6, or C2H2. Upon evaporation of the yellowish-to-tan irradiated ices, it is found that a colored solid film adheres to the walls of the reaction vessel at room temperature. These organic films are found to exhibit IR band identifiable with alkane, aldehide, alcohol, and perhaps alkene, as well as substituted aromatic functional groups. These spectra are compared with previous studies of UV- or photon-irradiated nonclathrated hydrocarbon-containing ices.

  3. Emergence and Prevalence of Non-H2S-Producing Salmonella enterica Serovar Senftenberg Isolates Belonging to Novel Sequence Type 1751 in China

    PubMed Central

    Yi, Shengjie; Xie, Jing; Liu, Nan; Li, Peng; Xu, Xuebin; Li, Hao; Sun, Jichao; Wang, Jian; Liang, Beibei; Yang, Chaojie; Wang, Xu; Hao, Rongzhang; Wang, Ligui; Wu, Zhihao; Zhang, Jianmin; Wang, Yong; Huang, Liuyu; Sun, Yansong; Klena, John D.; Meng, Jianghong

    2014-01-01

    Salmonella enterica serovar Senftenberg is a common nontyphoidal Salmonella serotype which causes human Salmonella infections worldwide. In this study, 182 S. Senftenberg isolates, including 17 atypical non-hydrogen sulfide (H2S)-producing isolates, were detected in China from 2005 to 2011. The microbiological and genetic characteristics of the non-H2S-producing and selected H2S-producing isolates were determined by using pulsed-field gel electrophoresis (PFGE), multilocus sequence typing (MLST), and clustered regularly interspaced short palindromic repeat (CRISPR) analysis. The phs operons were amplified and sequenced. The 17 non-H2S-producing and 36 H2S-producing isolates belonged to 7 sequence types (STs), including 3 new STs, ST1751, ST1757, and ST1758. Fourteen of the 17 non-H2S-producing isolates belonged to ST1751 and had very similar PFGE patterns. All 17 non-H2S-producing isolates had a nonsense mutation at position 1621 of phsA. H2S-producing and non-H2S-producing S. Senftenberg isolates were isolated from the same stool sample from three patients; isolates from the same patients displayed the same antimicrobial susceptibility, ST, and PFGE pattern but could be discriminated based on CRISPR spacers. Non-H2S-producing S. Senftenberg isolates belonging to ST1751 have been prevalent in Shanghai, China. It is possible that these emerging organisms will disseminate further, because they are difficult to detect. Thus, we should strengthen the surveillance for the spread of this atypical S. Senftenberg variant. PMID:24829240

  4. Development and function of invariant natural killer T cells producing T(h)2- and T(h)17-cytokines.

    PubMed

    Watarai, Hiroshi; Sekine-Kondo, Etsuko; Shigeura, Tomokuni; Motomura, Yasutaka; Yasuda, Takuwa; Satoh, Rumi; Yoshida, Hisahiro; Kubo, Masato; Kawamoto, Hiroshi; Koseki, Haruhiko; Taniguchi, Masaru

    2012-02-01

    There is heterogeneity in invariant natural killer T (iNKT) cells based on the expression of CD4 and the IL-17 receptor B (IL-17RB), a receptor for IL-25 which is a key factor in T(H)2 immunity. However, the development pathway and precise function of these iNKT cell subtypes remain unknown. IL-17RB⁺iNKT cells are present in the thymic CD44⁺/⁻ NK1.1⁻ population and develop normally even in the absence of IL-15, which is required for maturation and homeostasis of IL-17RB⁻iNKT cells producing IFN-γ. These results suggest that iNKT cells contain at least two subtypes, IL-17RB⁺ and IL-17RB⁻ subsets. The IL-17RB⁺iNKT subtypes can be further divided into two subtypes on the basis of CD4 expression both in the thymus and in the periphery. CD4⁺ IL-17RB⁺iNKT cells produce T(H)2 (IL-13), T(H)9 (IL-9 and IL-10), and T(H)17 (IL-17A and IL-22) cytokines in response to IL-25 in an E4BP4-dependent fashion, whereas CD4⁻ IL-17RB⁺iNKT cells are a retinoic acid receptor-related orphan receptor (ROR)γt⁺ subset producing T(H)17 cytokines upon stimulation with IL-23 in an E4BP4-independent fashion. These IL-17RB⁺iNKT cell subtypes are abundantly present in the lung in the steady state and mediate the pathogenesis in virus-induced airway hyperreactivity (AHR). In this study we demonstrated that the IL-17RB⁺iNKT cell subsets develop distinct from classical iNKT cell developmental stages in the thymus and play important roles in the pathogenesis of airway diseases. PMID:22346732

  5. Modelling bio-electrosynthesis in a reverse microbial fuel cell to produce acetate from CO2 and H2O.

    PubMed

    Kazemi, M; Biria, D; Rismani-Yazdi, H

    2015-05-21

    Bio-electrosynthesis is one of the significant developments in reverse microbial fuel cell technology which is potentially capable of creating organic compounds by combining CO2 with H2O. Accordingly, the main objective in the current study was to present a model of microbial electrosynthesis for producing organic compounds (acetate) based on direct conduction of electrons in biofilms. The proposed model enjoys a high degree of rigor because it can predict variations in the substrate concentration, electrical potential, current density and the thickness of the biofilm. Additionally, coulombic efficiency was investigated as a function of substrate concentration and cathode potential. For a system containing CO2 as the substrate and Sporomusa ovata as the biofilm forming microorganism, an increase in the substrate concentration at a constant potential can lead to a decrease in coulombic efficiency as well as an increase in current density and biofilm thickness. On the other hand, an increase in the surface cathodic voltage at a constant substrate concentration may result in an increase in the coulombic efficiency and a decrease in the current density. The maximum coulombic efficiency was revealed to be 75% at a substrate concentration of 0.025 mmol cm(-3) and 55% at a surface cathodic voltage of -0.3 V producing a high range of acetate production by creating an optimal state in the concentration and potential intervals. Finally, the validity of the model was verified by comparing the obtained results with related experimental findings. PMID:25898971

  6. Reversion of stressed and unstressed hydrogen sulfide (H2S) producing strains of Salmonella in different media.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Salmonella can be difficult to assess and isolate in poultry feed due to uneven distribution and poor growth. Previous studies have shown that several strains of Salmonella can be affected by changes in environment, resulting in the growth of H2S-negative colonies. This is concerning, as H2S produ...

  7. Profiling Chlamydomonas metabolism under dark, anoxic H2-producing conditions using a combined proteomic, transcriptomic, and metabolomic approach.

    PubMed

    Subramanian, Venkataramanan; Dubini, Alexandra; Astling, David P; Laurens, Lieve M L; Old, William M; Grossman, Arthur R; Posewitz, Matthew C; Seibert, Michael

    2014-12-01

    Chlamydomonas reinhardtii is well adapted to survive under different environmental conditions due to the unique flexibility of its metabolism. Here we report metabolic pathways that are active during acclimation to anoxia, but were previously not thoroughly studied under dark, anoxic H2-producing conditions in this model green alga. Proteomic analyses, using 2D-differential in-gel electrophoresis in combination with shotgun mass fingerprinting, revealed increased levels of proteins involved in the glycolytic pathway downstream of 3-phosphoglycerate, the glyoxylate pathway, and steps of the tricarboxylic acid (TCA) reactions. Upregulation of the enzyme, isocitrate lyase (ICL), was observed, which was accompanied by increased intracellular succinate levels, suggesting the functioning of glyoxylate pathway reactions. The ICL-inhibitor study revealed presence of reverse TCA reactions under these conditions. Contributions of the serine-isocitrate lyase pathway, glycine cleavage system, and c1-THF/serine hydroxymethyltransferase pathway in the acclimation to dark anoxia were found. We also observed increased levels of amino acids (AAs) suggesting nitrogen reorganization in the form of de novo AA biosynthesis during anoxia. Overall, novel routes for reductant utilization, in combination with redistribution of carbon and nitrogen, are used by this alga during acclimation to O2 deprivation in the dark. PMID:25333711

  8. Cantilever enhanced photoacoustic spectrometry: Quantitative analysis of the trace H2S produced by SF6 decomposition

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaoxing; Cheng, Zheng; Li, Xin

    2016-09-01

    As one of the key characteristic components that result from sulfur hexafluoride (SF6) decomposition in SF6 gas-insulated equipment, hydrogen sulfide (H2S) can reflect the severity of the internal insulation faults and indicate whether or not such faults involve solid insulation material effectively. The decomposition of SF6 and its reaction with other impurities to form H2S are simulated in this study via Materials Studio. The simulation verifies that H2S is generated only when serious faults occur in the equipment; thus, the online monitoring of the trace H2S is highly necessary. To achieve a high detection accuracy and avoid cross interference, the spectral line R (8) of the H2S ν1 + ν2 + ν3 co-frequency absorption band is taken as the absorption line for the gas detection by online simulation based on the HITRAN on the Web. In addition, this study develops a cantilever-enhanced photoacoustic spectrometry trace gas detection platform and conducts experimental research on the quantitative detection of trace H2S/SF6 and H2S/N2. Experimental results show that the detection sensitivity of the detection platform to trace H2S under the background gas N2 and SF6 is 0.84 and 1.75 μL/L, respectively, and a strong linear relationship exists between the trace H2S concentration and its corresponding PA signal. Moreover, based on both the theoretical simulation and experiment, the influence of temperature and pressure on the detection platform is discussed and analyzed. The results indicate that the change in the PA signal amplitude decreases with an increase in the pressure or temperature of the PA cell, and the detection platform is more sensitive to pressure.

  9. The H2S-producing enzyme CSE is dispensable for the processing of inflammatory and neuropathic pain.

    PubMed

    Syhr, Katharina M J; Boosen, Meike; Hohmann, Stephan W; Longen, Sebastian; Köhler, Yvette; Pfeilschifter, Josef; Beck, Karl-Friedrich; Geisslinger, Gerd; Schmidtko, Achim; Kallenborn-Gerhardt, Wiebke

    2015-10-22

    Accumulating lines of evidence indicate that hydrogen sulfide (H2S) contributes to the processing of chronic pain. However, the sources of H2S production in the nociceptive system are poorly understood. Here we investigated the expression of the H2S releasing enzyme cystathionine γ-lyase (CSE) in the nociceptive system and characterized its role in chronic pain signaling using CSE deficient mice. We show that paw inflammation and peripheral nerve injury led to upregulation of CSE expression in dorsal root ganglia. However, conditional knockout mice lacking CSE in sensory neurons as well as global CSE knockout mice demonstrated normal pain behaviors in inflammatory and neuropathic pain models as compared to WT littermates. Thus, our results suggest that CSE is not critically involved in chronic pain signaling in mice and that sources different from CSE mediate the pain relevant effects of H2S. PMID:26271715

  10. Linking genome content to biofuel production yields: a meta-analysis of major catabolic pathways among select H2 and ethanol-producing bacteria

    PubMed Central

    2012-01-01

    Background Fermentative bacteria offer the potential to convert lignocellulosic waste-streams into biofuels such as hydrogen (H2) and ethanol. Current fermentative H2 and ethanol yields, however, are below theoretical maxima, vary greatly among organisms, and depend on the extent of metabolic pathways utilized. For fermentative H2 and/or ethanol production to become practical, biofuel yields must be increased. We performed a comparative meta-analysis of (i) reported end-product yields, and (ii) genes encoding pyruvate metabolism and end-product synthesis pathways to identify suitable biomarkers for screening a microorganism’s potential of H2 and/or ethanol production, and to identify targets for metabolic engineering to improve biofuel yields. Our interest in H2 and/or ethanol optimization restricted our meta-analysis to organisms with sequenced genomes and limited branched end-product pathways. These included members of the Firmicutes, Euryarchaeota, and Thermotogae. Results Bioinformatic analysis revealed that the absence of genes encoding acetaldehyde dehydrogenase and bifunctional acetaldehyde/alcohol dehydrogenase (AdhE) in Caldicellulosiruptor, Thermococcus, Pyrococcus, and Thermotoga species coincide with high H2 yields and low ethanol production. Organisms containing genes (or activities) for both ethanol and H2 synthesis pathways (i.e. Caldanaerobacter subterraneus subsp. tengcongensis, Ethanoligenens harbinense, and Clostridium species) had relatively uniform mixed product patterns. The absence of hydrogenases in Geobacillus and Bacillus species did not confer high ethanol production, but rather high lactate production. Only Thermoanaerobacter pseudethanolicus produced relatively high ethanol and low H2 yields. This may be attributed to the presence of genes encoding proteins that promote NADH production. Lactate dehydrogenase and pyruvate:formate lyase are not conducive for ethanol and/or H2 production. While the type(s) of encoded hydrogenases appear

  11. Effects of extracellular pH on the metabolic pathways in sulfur-deprived, H2-producing Chlamydomonas reinhardtii cultures.

    PubMed

    Kosourov, Sergey; Seibert, Michael; Ghirardi, Maria L

    2003-02-01

    Sustained photoproduction of H(2) by the green alga, Chlamydomonas reinhardtii, can be obtained by incubating cells in sulfur-deprived medium [Ghirardi et al. (2000b) Trends Biotechnol. 18: 506; Melis et al. (2000) Plant Physiol. 122: 127]. The current work focuses on (a) the effects of different initial extracellular pHs on the inactivation of photosystem II (PSII) and O(2)-sensitive H(2)-production activity in sulfur-deprived algal cells and (b) the relationships among H(2)-production, photosynthetic, aerobic and anaerobic metabolisms under different pH regimens. The maximum rate and yield of H(2) production occur when the pH at the start of the sulfur deprivation period is 7.7 and decrease when the initial pH is lowered to 6.5 or increased to 8.2. The pH profile of hydrogen photoproduction correlates with that of the residual PSII activity (optimum pH 7.3-7.9), but not with the pH profiles of photosynthetic electron transport through photosystem I or of starch and protein degradation. In vitro hydrogenase activity over this pH range is much higher than the actual in situ rates of H(2) production, indicating that hydrogenase activity per se is not limiting. Starch and protein catabolisms generate formate, acetate and ethanol; contribute some reductant for H(2) photoproduction, as indicated by 3-(3,4-dichlorophenyl)-1,1-dimethylurea and 2,5-dibromo-6-isopropyl-3-methyl-1,4-benzoquinone inhibition results; and are the primary sources of reductant for respiratory processes that remove photosynthetically generated O(2). Carbon balances demonstrate that alternative metabolic pathways predominate at different pHs, and these depend on whether residual photosynthetic activity is present or not. PMID:12610217

  12. Experimental evidence suggesting that H2O2 is produced within the thylakoid membrane in a reaction between plastoquinol and singlet oxygen.

    PubMed

    Khorobrykh, Sergey A; Karonen, Maarit; Tyystjärvi, Esa

    2015-03-12

    Plastoquinol (PQH2-9) and plastoquinone (PQ-9) mediate photosynthetic electron transfer. We isolated PQH2-9 from thylakoid membranes, purified it with HPLC, subjected the purified PQH2-9 to singlet oxygen ((1)O2) and analyzed the products. The main reaction of (1)O2 with PQH2-9 in methanol was found to result in formation of PQ-9 and H2O2, and the amount of H2O2 produced was essentially the same as the amount of oxidized PQH2-9. Formation of H2O2 in the reaction between (1)O2 and PQH2-9 may be an important source of H2O2 within the lipophilic thylakoid membrane. PMID:25701589

  13. Radiolytic corrosion of uranium dioxide induced by He2+ localized irradiation of water: Role of the produced H2O2 distance

    NASA Astrophysics Data System (ADS)

    Traboulsi, Ali; Vandenborre, Johan; Blain, Guillaume; Humbert, Bernard; Haddad, Ferid; Fattahi, Massoud

    2015-12-01

    The short-range (few μm in water) of the α-emitting from the spent fuel involves that the radiolytic corrosion of this kind of sample occurs at the solid/solution interface. In order to establish the role of localization of H2O2 species produced by the He2+ particle beam in water from the surface, we perform UO2 radiolytic corrosion experiment with different distance between H2O2 production area and UO2 surface. Then, in this work, the radiolytic corrosion of UO2 particles by oxidative species produced by 4He2+ radiolysis of water was investigated in open to air atmosphere. The dose rate, the localization of H2O2 produced by water radiolysis and the grain boundaries present on the surface of the particles were investigated. UO2 corrosion was investigated by in situ (during irradiation) characterization of the solid surface, analysis of H2O2 produced by water radiolysis and quantification of the uranium species released into the solution during irradiation. Characterization of the UO2 particles, surface and volume, was realized by Raman spectroscopy. UV-vis spectrophotometry was used to monitor H2O2 produced by water radiolysis and in parallel the soluble uranium species released into the solution were quantified by inductively coupled plasma mass spectrometry. During the He2+ irradiation of ultra-pure water in contact with the UO2 particles, metastudtite phase was formed on the solid surface indicating an oxidation process of the particles by the oxidative species produced by water radiolysis. This oxidation occurred essentially on the grain boundaries and was accompanied by migration of soluble uranium species (U(VI)) into the irradiated solution. Closer to the surface the localization of H2O2 formation, higher the UO2 oxidation process occurs, whereas the dose rate had no effect on it. Simultaneously, closer to the surface the localization of H2O2 formation lower the H2O2 concentration measured in solution. Moreover, the metastudtite was the only secondary

  14. Subtilase cytotoxin encoding genes are present in human, sheep and deer intimin-negative, Shiga toxin-producing Escherichia coli O128:H2.

    PubMed

    Sánchez, Sergio; Beristain, Xabier; Martínez, Remigio; García, Alfredo; Martín, Carmen; Vidal, Dolors; Díaz-Sánchez, Sandra; Rey, Joaquín; Alonso, Juan M; Herrera-León, Silvia

    2012-10-12

    Shiga toxin-producing Escherichia coli (STEC) O128:H2 is recognised worldwide to be an important non-O157 STEC associated with human illness and in particular with causing haemolytic uraemic syndrome. This serotype is commonly isolated from sheep and is being increasingly isolated from deer. We determined the virulence profile and genetic relationships of one human, six sheep and five deer intimin-negative STEC O128:H2 strains isolated in Spain over a 7-year period. Our goals were to establish the presence of other virulence-associated factors, such as SubAB, in intimin-negative STEC O128:H2 strains involved in human disease and in that case, to determine if sheep and/or deer represent a reservoir of SubAB-positive STEC O128:H2. All the strains lacked the eae gene and carried subtilase cytotoxin (SubAB) encoding genes (subAB) and tia genes, but not saa gene, suggesting the presence of the recently identified new variant of SubAB, encoded on a putative pathogenicity island together with tia. We report for the first time the presence of subtilase cytotoxin encoding genes in intimin-negative STEC O128:H2 strains pathogenic for humans and how this finding might explain their clinical relevance despite neither carrying eae nor stx subtypes associated with severe clinical outcomes, but only stx1c and stx2b. Multilocus sequence typing analysis revealed that STEC O128:H2 strains from sheep and deer belong to the clonal lineage of STEC O128:H2 strains involved in diarrhoeal and haemorrhagic diseases in humans. Our results indicate that sheep and deer represent a reservoir of SubAB-positive STEC O128:H2 strains and thus a potential source of human infection. PMID:22622337

  15. Purification and characterization of a surfactin-like molecule produced by Bacillus sp. H2O-1 and its antagonistic effect against sulfate reducing bacteria

    PubMed Central

    2012-01-01

    Background Bacillus sp. H2O-1, isolated from the connate water of a Brazilian reservoir, produces an antimicrobial substance (denoted as AMS H2O-1) that is active against sulfate reducing bacteria, which are the major bacterial group responsible for biogenic souring and biocorrosion in petroleum reservoirs. Thus, the use of AMS H2O-1 for sulfate reducing bacteria control in the petroleum industry is a promising alternative to chemical biocides. However, prior to the large-scale production of AMS H2O-1 for industrial applications, its chemical structure must be elucidated. This study also analyzed the changes in the wetting properties of different surfaces conditioned with AMS H2O-1 and demonstrated the effect of AMS H2O-1 on sulfate reducing bacteria cells. Results A lipopeptide mixture from AMS H2O-1 was partially purified on a silica gel column and identified via mass spectrometry (ESI-MS). It comprises four major components that range in size from 1007 to 1049 Da. The lipid moiety contains linear and branched β-hydroxy fatty acids that range in length from C13 to C16. The peptide moiety contains seven amino acids identified as Glu-Leu-Leu-Val-Asp-Leu-Leu. Transmission electron microscopy revealed cell membrane alteration of sulfate reducing bacteria after AMS H2O-1 treatment at the minimum inhibitory concentration (5 μg/ml). Cytoplasmic electron dense inclusions were observed in treated cells but not in untreated cells. AMS H2O-1 enhanced the osmosis of sulfate reducing bacteria cells and caused the leakage of the intracellular contents. In addition, contact angle measurements indicated that different surfaces conditioned by AMS H2O-1 were less hydrophobic and more electron-donor than untreated surfaces. Conclusion AMS H2O-1 is a mixture of four surfactin-like homologues, and its biocidal activity and surfactant properties suggest that this compound may be a good candidate for sulfate reducing bacteria control. Thus, it is a potential alternative to the

  16. Role of H2O2 in RET/PTC1 chromosomal rearrangement produced by ionizing radiation in human thyroid cells.

    PubMed

    Ameziane-El-Hassani, Rabii; Boufraqech, Myriem; Lagente-Chevallier, Odile; Weyemi, Urbain; Talbot, Monique; Métivier, Didier; Courtin, Françoise; Bidart, Jean-Michel; El Mzibri, Mohammed; Schlumberger, Martin; Dupuy, Corinne

    2010-05-15

    During childhood, the thyroid gland is one of the most sensitive organs to the carcinogenetic effects of ionizing radiation that may lead to papillary thyroid carcinoma (PTC) associated with RET/PTC oncogene rearrangement. Exposure to ionizing radiation induces a transient "oxidative burst" through radiolysis of water, which can cause DNA damage and mediates part of the radiation effects. H(2)O(2) is a potent DNA-damaging agent that induces DNA double-strand breaks, and consequently, chromosomal aberrations. Irradiation by 5 Gy X-ray increased extracellular H(2)O(2). Therefore, we investigated the implication of H(2)O(2) in the generation of RET/PTC1 rearrangement after X-ray exposure. We developed a highly specific and sensitive nested reverse transcription-PCR method. By using the human thyroid cell line HTori-3, previously found to produce RET/PTC1 after gamma-irradiation, we showed that H(2)O(2), generated during a 5 Gy X-ray irradiation, causes DNA double-strand breaks and contributes to RET/PTC1 formation. Pretreatment of cells with catalase, a scavenger of H(2)O(2), significantly decreased RET/PTC1 rearrangement formation. Finally, RET/PTC chromosomal rearrangement was detected in HTori-3.1 cells after exposure of cells to H(2)O(2) (25 micromol/L), at a dose that did not affect the cell viability. This study shows for the first time that H(2)O(2) is able to cause RET/PTC1 rearrangement in thyroid cells and consequently highlights that oxidative stress could be responsible for the occurrence of RET/PTC1 rearrangement found in thyroid lesions even in the absence of radiation exposure. PMID:20424115

  17. Draft Genome Sequence of Calothrix Strain 336/3, a Novel H2-Producing Cyanobacterium Isolated from a Finnish Lake

    PubMed Central

    Isojärvi, Janne; Shunmugam, Sumathy; Sivonen, Kaarina; Allahverdiyeva, Yagut; Aro, Eva-Mari

    2015-01-01

    We announce the draft genome sequence of Calothrix strain 336/3, an N2-fixing heterocystous filamentous cyanobacterium isolated from a natural habitat. Calothrix 336/3 produces higher levels of hydrogen than Nostoc punctiforme PCC 73102 and Anabaena strain PCC 7120 and, therefore, is of interest for potential technological applications. PMID:25614574

  18. Fusing catalase to an alkane-producing enzyme maintains enzymatic activity by converting the inhibitory byproduct H2O2 to the cosubstrate O2

    PubMed Central

    Andre, Carl; Kim, Sung Won; Yu, Xiao-Hong; Shanklin, John

    2013-01-01

    Biologically produced alkanes represent potential renewable alternatives to petroleum-derived chemicals. A cyanobacterial pathway consisting of acyl–Acyl Carrier Protein reductase and an aldehyde-deformylating oxygenase (ADO) converts acyl–Acyl Carrier Proteins into corresponding n-1 alkanes via aldehyde intermediates in an oxygen-dependent manner (Km for O2, 84 ± 9 µM). In vitro, ADO turned over only three times, but addition of more ADO to exhausted assays resulted in additional product formation. While evaluating the peroxide shunt to drive ADO catalysis, we discovered that ADO is inhibited by hydrogen peroxide (H2O2) with an apparent Ki of 16 ± 6 µM and that H2O2 inhibition is of mixed-type with respect to O2. Supplementing exhausted assays with catalase (CAT) restored ADO activity, demonstrating that inhibition was reversible and dependent on H2O2, which originated from poor coupling of reductant consumption with alkane formation. Kinetic analysis showed that long-chain (C14–C18) substrates follow Michaelis–Menten kinetics, whereas short and medium chains (C8–C12) exhibit substrate inhibition. A bifunctional protein comprising an N-terminal CAT coupled to a C-terminal ADO (CAT–ADO) prevents H2O2 inhibition by converting it to the cosubstrate O2. Indeed, alkane production by the fusion protein is observed upon addition of H2O2 to an anaerobic reaction mix. In assays, CAT–ADO turns over 225 times versus three times for the native ADO, and its expression in Escherichia coli increases catalytic turnovers per active site by fivefold relative to the expression of native ADO. We propose the term “protection via inhibitor metabolism” for fusion proteins designed to metabolize inhibitors into noninhibitory compounds. PMID:23391732

  19. H2-Producing Bacterial Community during Rice Straw Decomposition in Paddy Field Soil: Estimation by an Analysis of [FeFe]-Hydrogenase Gene Transcripts

    PubMed Central

    Baba, Ryuko; Asakawa, Susumu; Watanabe, Takeshi

    2016-01-01

    The transcription patterns of [FeFe]-hydrogenase genes (hydA), which encode the enzymes responsible for H2 production, were investigated during rice straw decomposition in paddy soil using molecular biological techniques. Paddy soil amended with and without rice straw was incubated under anoxic conditions. RNA was extracted from the soil, and three clone libraries of hydA were constructed using RNAs obtained from samples in the initial phase of rice straw decomposition (day 1 with rice straw), methanogenic phase of rice straw decomposition (day 14 with rice straw), and under a non-amended condition (day 14 without rice straw). hydA genes related to Proteobacteria, Firmicutes, Bacteroidetes, Chloroflexi, and Thermotogae were mainly transcribed in paddy soil samples; however, their proportions markedly differed among the libraries. Deltaproteobacteria-related hydA genes were predominantly transcribed on day 1 with rice straw, while various types of hydA genes related to several phyla were transcribed on day 14 with rice straw. Although the diversity of transcribed hydA was significantly higher in the library on day 14 with rice straw than the other two libraries, the composition of hydA transcripts in the library was similar to that in the library on day 14 without rice straw. These results indicate that the composition of active H2 producers and/or H2 metabolic patterns dynamically change during rice straw decomposition in paddy soil. PMID:27319579

  20. H2O beams for zinc oxide film growth produced by a Pt-catalyzed H2-O2 reaction at various divergent aperture angles of a de Laval nozzle

    NASA Astrophysics Data System (ADS)

    Teraguchi, Yusuke; Ishidzuka, Yuki; Nakamura, Tomoki; Takahashi, Kazumasa; Tamayama, Yasuhiro; Harada, Nobuhiro; Yasui, Kanji

    2016-02-01

    High-energy H2O beams generated by a de Laval nozzle, meant for the growth of zinc oxide thin films through chemical vapor deposition, were assessed based on compressible flow theory at various divergent aperture angles. In this process, high temperature H2O was generated by a catalytic reaction between H2 and O2 on Pt nanoparticles and effused through the nozzle into the reaction zone. The theoretical beam temperature distributions, reduced scaling parameters and mean cluster sizes of the H2O beams generated at angles between 50 and 90° were evaluated. The reduced scaling parameters of the H2O beams for all angles were calculated to be less than 200 and the mean cluster sizes were estimated to be less than one irrespective of the divergent aperture angle of the nozzle, suggesting that clusters are not formed in the H2O beam in our apparatus. The crystallinity and electrical properties of the zinc oxide films grown using various divergent aperture angles were also evaluated.

  1. Hexagonal plate-like magnetite nanocrystals produced in komatiite-H2O-CO2 reaction system at 450°C

    NASA Astrophysics Data System (ADS)

    Hao, Xi-Luo; Li, Yi-Liang

    2015-10-01

    Batch experiments of komatiite-H2O-CO2 system with temperatures from 200 to 450°C were performed to simulate the interactions between the newly formed ultramafic crust and the proto-atmosphere on Earth before the formation of its earliest ocean. Particularly, magnetite nanocrystals were observed in the experiment carried out at 450°C that are characterized by their hexagonal platelet-like morphology and porous structure. Exactly the same set of lattice fringes on the two opposite sides of one pore suggests post-crystallization erosion. The results demonstrate that magnetite could be produced by the direct interactions between the ultramafic rocky crust and the atmosphere before the formation of the ocean on the Hadean Earth. These magnetite nanoparticles could serve as a catalyst in the synthesis of simple organic molecules during the organochemical evolution towards life.

  2. H2 blockers

    MedlinePlus

    Peptic ulcer disease - H2 blockers; PUD - H2 blockers; Gastroesophageal reflux - H2 blockers ... H2 blockers are used to: Relieve symptoms of acid reflux, or gastroesophageal reflux disease (GERD). This is a ...

  3. BioCO2 - a multidisciplinary, biological approach using solar energy to capture CO2 while producing H2 and high value products.

    PubMed

    Skjånes, Kari; Lindblad, Peter; Muller, Jiri

    2007-10-01

    Many areas of algae technology have developed over the last decades, and there is an established market for products derived from algae, dominated by health food and aquaculture. In addition, the interest for active biomolecules from algae is increasing rapidly. The need for CO(2) management, in particular capture and storage is currently an important technological, economical and global political issue and will continue to be so until alternative energy sources and energy carriers diminish the need for fossil fuels. This review summarizes in an integrated manner different technologies for use of algae, demonstrating the possibility of combining different areas of algae technology to capture CO(2) and using the obtained algal biomass for various industrial applications thus bringing added value to the capturing and storage processes. Furthermore, we emphasize the use of algae in a novel biological process which produces H(2) directly from solar energy in contrast to the conventional CO(2) neutral biological methods. This biological process is a part of the proposed integrated CO(2) management scheme. PMID:17662653

  4. Staphylococcus aureus Adapts to Oxidative Stress by Producing H2O2-Resistant Small-Colony Variants via the SOS Response

    PubMed Central

    Painter, Kimberley L.; Strange, Elizabeth; Bamford, Kathleen B.; Armstrong-James, Darius

    2015-01-01

    The development of chronic and recurrent Staphylococcus aureus infections is associated with the emergence of slow-growing mutants known as small-colony variants (SCVs), which are highly tolerant of antibiotics and can survive inside host cells. However, the host and bacterial factors which underpin SCV emergence during infection are poorly understood. Here, we demonstrate that exposure of S. aureus to sublethal concentrations of H2O2 leads to a specific, dose-dependent increase in the population frequency of gentamicin-resistant SCVs. Time course analyses revealed that H2O2 exposure caused bacteriostasis in wild-type cells during which time SCVs appeared spontaneously within the S. aureus population. This occurred via a mutagenic DNA repair pathway that included DNA double-strand break repair proteins RexAB, recombinase A, and polymerase V. In addition to triggering SCV emergence by increasing the mutation rate, H2O2 also selected for the SCV phenotype, leading to increased phenotypic stability and further enhancing the size of the SCV subpopulation by reducing the rate of SCV reversion to the wild type. Subsequent analyses revealed that SCVs were significantly more resistant to the toxic effects of H2O2 than wild-type bacteria. With the exception of heme auxotrophs, gentamicin-resistant SCVs displayed greater catalase activity than wild-type bacteria, which contributed to their resistance to H2O2. Taken together, these data reveal a mechanism by which S. aureus adapts to oxidative stress via the production of a subpopulation of H2O2-resistant SCVs with enhanced catalase production. PMID:25690100

  5. Staphylococcus aureus adapts to oxidative stress by producing H2O2-resistant small-colony variants via the SOS response.

    PubMed

    Painter, Kimberley L; Strange, Elizabeth; Parkhill, Julian; Bamford, Kathleen B; Armstrong-James, Darius; Edwards, Andrew M

    2015-05-01

    The development of chronic and recurrent Staphylococcus aureus infections is associated with the emergence of slow-growing mutants known as small-colony variants (SCVs), which are highly tolerant of antibiotics and can survive inside host cells. However, the host and bacterial factors which underpin SCV emergence during infection are poorly understood. Here, we demonstrate that exposure of S. aureus to sublethal concentrations of H2O2 leads to a specific, dose-dependent increase in the population frequency of gentamicin-resistant SCVs. Time course analyses revealed that H2O2 exposure caused bacteriostasis in wild-type cells during which time SCVs appeared spontaneously within the S. aureus population. This occurred via a mutagenic DNA repair pathway that included DNA double-strand break repair proteins RexAB, recombinase A, and polymerase V. In addition to triggering SCV emergence by increasing the mutation rate, H2O2 also selected for the SCV phenotype, leading to increased phenotypic stability and further enhancing the size of the SCV subpopulation by reducing the rate of SCV reversion to the wild type. Subsequent analyses revealed that SCVs were significantly more resistant to the toxic effects of H2O2 than wild-type bacteria. With the exception of heme auxotrophs, gentamicin-resistant SCVs displayed greater catalase activity than wild-type bacteria, which contributed to their resistance to H2O2. Taken together, these data reveal a mechanism by which S. aureus adapts to oxidative stress via the production of a subpopulation of H2O2-resistant SCVs with enhanced catalase production. PMID:25690100

  6. Infrared absorption of t-HOCO(+), H(+)(CO2)2, and HCO2 (-) produced in electron bombardment of CO2 in solid para-H2.

    PubMed

    Das, Prasanta; Tsuge, Masashi; Lee, Yuan-Pern

    2016-07-01

    We have employed electron bombardment during matrix deposition of CO2 (or (13)CO2, C(18)O2) and para-hydrogen (p-H2) at 3.2 K and recorded infrared (IR) spectra of t-HOCO(+), H(+)(CO2)2, HCO2 (-), CO2 (-), t-HOCO, and other species isolated in solid p-H2. After the matrix was maintained in darkness for 13 h, intensities of absorption features of t-HOCO(+) at 2403.5 (ν1), 2369.9 (ν2), 1018.1 (ν4), and 606.5 (ν6) cm(-1) and those of H(+)(CO2)2 at 1341.1, 883.6, and 591.5 cm(-1) decreased. Corresponding lines of isotopologues were observed when (13)CO2 or C(18)O2 replaced CO2. In contrast, lines of HCO2 (-) at 2522.4 (ν1), 1616.1 (ν5), 1327.9 (ν2), and 745.6 (ν3) cm(-1) increased in intensity; corresponding lines of H(13)CO2 (-) or HC(18)O2 (-) were also observed. Lines of t-DOCO(+) and DCO2 (-) were observed in an electron bombarded CO2 /normal-deuterium (n-D2) matrix. Data of ν6 of t-HOCO(+) and all observed modes of H(18)OC(18)O(+) and HC(18)O2 (-) are new. The assignments were made according to expected chemical behavior, observed isotopic shifts, and comparisons with vibrational wavenumbers and relative intensities of previous reports and calculations with the B3PW91/aug-cc-pVQZ method. The ν1 line of t-HOCO(+) in solid p-H2 (2403.5 cm(-1)), similar to the line at 2673 cm(-1) of t-HOCO(+) tagged with an Ar atom, is significantly red-shifted from that reported for gaseous t-HOCO(+) (3375.37 cm(-1)) due to partial proton sharing between CO2 and H2 or Ar. The ν1 line of HCO2 (-) in solid p-H2 (2522.4 cm(-1)) is blue shifted from that reported for HCO2 (-) in solid Ne (2455.7 cm(-1)) and that of HCO2 (-) tagged with Ar (2449 cm(-1)); this can be explained by the varied solvation effects by Ne, Ar, or H2 on the mixing of H(+) + CO2 and H + CO2 (-) surfaces. Possible formation mechanisms of t-HOCO(+), H(+)(CO2)2, HCO2 (-), CO2 (-), t-HOCO, H2O, and t-HCOOH are discussed. PMID:27394107

  7. Infrared absorption of t-HOCO+, H+(CO2)2, and HCO2- produced in electron bombardment of CO2 in solid para-H2

    NASA Astrophysics Data System (ADS)

    Das, Prasanta; Tsuge, Masashi; Lee, Yuan-Pern

    2016-07-01

    We have employed electron bombardment during matrix deposition of CO2 (or 13CO2, C18O2) and para-hydrogen (p-H2) at 3.2 K and recorded infrared (IR) spectra of t-HOCO+, H+(CO2)2, HCO2-, CO2-, t-HOCO, and other species isolated in solid p-H2. After the matrix was maintained in darkness for 13 h, intensities of absorption features of t-HOCO+ at 2403.5 (ν1), 2369.9 (ν2), 1018.1 (ν4), and 606.5 (ν6) cm-1 and those of H+(CO2)2 at 1341.1, 883.6, and 591.5 cm-1 decreased. Corresponding lines of isotopologues were observed when 13CO2 or C18O2 replaced CO2. In contrast, lines of HCO2- at 2522.4 (ν1), 1616.1 (ν5), 1327.9 (ν2), and 745.6 (ν3) cm-1 increased in intensity; corresponding lines of H13CO2- or HC18O2- were also observed. Lines of t-DOCO+ and DCO2- were observed in an electron bombarded CO2 /normal-deuterium (n-D2) matrix. Data of ν6 of t-HOCO+ and all observed modes of H18OC18O+ and HC18O2- are new. The assignments were made according to expected chemical behavior, observed isotopic shifts, and comparisons with vibrational wavenumbers and relative intensities of previous reports and calculations with the B3PW91/aug-cc-pVQZ method. The ν1 line of t-HOCO+ in solid p-H2 (2403.5 cm-1), similar to the line at 2673 cm-1 of t-HOCO+ tagged with an Ar atom, is significantly red-shifted from that reported for gaseous t-HOCO+ (3375.37 cm-1) due to partial proton sharing between CO2 and H2 or Ar. The ν1 line of HCO2- in solid p-H2 (2522.4 cm-1) is blue shifted from that reported for HCO2- in solid Ne (2455.7 cm-1) and that of HCO2- tagged with Ar (2449 cm-1); this can be explained by the varied solvation effects by Ne, Ar, or H2 on the mixing of H+ + CO2 and H + CO2- surfaces. Possible formation mechanisms of t-HOCO+, H+(CO2)2, HCO2-, CO2-, t-HOCO, H2O, and t-HCOOH are discussed.

  8. Nucleobases and prebiotic molecules in organic residues produced from the ultraviolet photo-irradiation of pyrimidine in NH(3) and H(2)O+NH(3) ices.

    PubMed

    Nuevo, Michel; Milam, Stefanie N; Sandford, Scott A

    2012-04-01

    Although not yet identified in the interstellar medium (ISM), N-heterocycles including nucleobases-the information subunits of DNA and RNA-are present in carbonaceous chondrites, which indicates that molecules of biological interest can be formed in non-terrestrial environments via abiotic pathways. Recent laboratory experiments and ab initio calculations have already shown that the irradiation of pyrimidine in pure H(2)O ices leads to the formation of a suite of oxidized pyrimidine derivatives, including the nucleobase uracil. In the present work, NH(3):pyrimidine and H(2)O:NH(3):pyrimidine ice mixtures with different relative proportions were irradiated with UV photons under astrophysically relevant conditions. Liquid- and gas-chromatography analysis of the resulting organic residues has led to the detection of the nucleobases uracil and cytosine, as well as other species of prebiotic interest such as urea and small amino acids. The presence of these molecules in organic residues formed under abiotic conditions supports scenarios in which extraterrestrial organics that formed in space and were subsequently delivered to telluric planets via comets and meteorites could have contributed to the inventory of molecules that triggered the first biological reactions on their surfaces. PMID:22519971

  9. Nucleobases and Prebiotic Molecules in Organic Residues Produced from the Ultraviolet Photo-Irradiation of Pyrimidine in NH3 and H2O+NH3 Ices

    NASA Technical Reports Server (NTRS)

    Nuevo, Michel; Milam, Stefanie N.; Sandford, Scott

    2012-01-01

    Although not yet identified in the interstellar medium (ISM), N-heterocycles including nucleobases the information subunits of DNA and RNA are present in carbonaceous chondrites, which indicates that molecules of biological interest can be formed in non-terrestrial environments via abiotic pathways. Recent laboratory experiments and ab-initio calculations have already shown that the irradiation of pyrimidine in pure H2O ices leads to the formation of a suite of oxidized pyrimidine derivatives, including the nucleobase uracil. In the present work, NH3:pyrimidine and H2O:NH3:pyrimidine ice mixtures with different relative proportions were irradiated with UV photons under astrophysically relevant conditions. Liquid- and gas-chromatography analysis of the resulting organic residues has led to the detection of the nucleobases uracil and cytosine, as well as other species of prebiotic interest such as urea and small amino acids. The presence of these molecules in organic residues formed under abiotic conditions supports scenarios in which extraterrestrial organics that formed in space and were subsequently delivered to telluric planets via comets and meteorites could have contributed to the inventory of molecules that triggered the first biological reactions on their surfaces.

  10. Potential of BAC combined with UVC/H2O2 for reducing organic matter from highly saline reverse osmosis concentrate produced from municipal wastewater reclamation.

    PubMed

    Lu, Jie; Fan, Linhua; Roddick, Felicity A

    2013-10-01

    The organic matter present in the concentrate streams generated from reverse osmosis (RO) based municipal wastewater reclamation processes poses environmental and health risks on its disposal to the receiving environment (e.g., estuaries, bays). The potential of a biological activated carbon (BAC) process combined with pre-oxidation using a UVC/H2O2 advanced oxidation process for treating a high salinity (TDS~10000 mg L(-1)) municipal wastewater RO concentrate (ROC) was evaluated at lab scale during 90 d of operation. The combined treatment reduced the UVA254 and colour of the ROC to below those for the influent of the RO process (i.e., biologically treated secondary effluent), and the reductions in DOC and COD were approximately 60% and 50%, respectively. UVC/H2O2 was demonstrated to be an effective means of converting the recalcitrant organic compounds in the ROC into biodegradable substances which were readily removed by the BAC process, leading to a synergistic effect of the combined treatment in degrading the organic matter. The tests using various BAC feed concentrations suggested that the biological treatment was robust and consistent for treating the high salinity ROC. Using Microtox analysis no toxicity was detected for the ROC after the combined treatment, and the trihalomethane formation potential was reduced from 3.5 to 2.8 mg L(-1). PMID:23820538

  11. N- and O-heterocycles Produced from the Irradiation of Benzene and Naphthalene in H2O/NH3-containing Ices

    NASA Astrophysics Data System (ADS)

    Materese, Christopher K.; Nuevo, Michel; Sandford, Scott A.

    2015-02-01

    Aromatic heterocyclic molecules are an important class of molecules of astrophysical and biological significance that include pyridine, pyrimidine, and their derivatives. Such compounds are believed to exist in interstellar and circumstellar environments, though they have never been observed in the gas phase. Regardless of their presence in the gas phase in space, numerous heterocycles have been reported in carbonaceous meteorites, which indicates that they are formed under astrophysical conditions. The experimental work described here shows that N- and O-heterocyclic molecules can form from the ultraviolet (UV) irradiation of the homocyclic aromatic molecules benzene (C6H6) or naphthalene (C10H8) mixed in ices containing H2O and NH3. This represents an alternative way to generate aromatic heterocycles to those considered before and may have important implications for astrochemistry and astrobiology.

  12. Ultrastructural and Immunocytochemical Studies on the H2O2-Producing Enzyme Pyranose Oxidase in Phanerochaete chrysosporium Grown under Liquid Culture Conditions

    PubMed Central

    Daniel, Geoffrey; Volc, Jindrich; Kubatova, Elena; Nilsson, Thomas

    1992-01-01

    The ultrastructural distribution of the sugar-oxidizing enzyme pyranose 2-oxidase (POD) in hyphae of Phanerochaete chrysosporium K-3 grown under liquid culture conditions optimal for the enzyme's production was studied by transmission electron microscopy immunocytochemistry. Using the 3-dimethylaminobenzoic acid-3-methyl-2-benzothiazolinone hydrazone hydrochloride H2O2 peroxidase spectrophotometric assay, POD was detected in mycelial extracts from days 7 to 18, with maximum activity recorded on day 12. Onset of POD activity occurred in the secondary phase of hyphal development at a time of stationary growth, glucose limitation, and pH increase. POD was also detected extracellularly in the culture fluid from days 7 to 18, with maximum activity recorded on day 13. At early stages of development (3 to 4 days), using anti-POD antibodies and immunogold labeling, POD was localized in multivesicular and electron-dense bodies and in cell membrane regions. After 10 to 12 days of growth, at maximum POD activity, POD was concentrated within the periplasmic space where it was associated with membrane-bound vesicles and other membrane structures. At later stages of development (17 to 18 days), when the majority of hyphae were lysed, POD was observed associated with residual intracellular membrane systems and vesicles. Transmission electron microscopy immunocytochemical studies also demonstrated an extracellular distribution of the enzyme at the stationary growth phase, showing its association with fungal extracellular slime. In studies of ligninolytic cultures of the same fungus, POD was found to have a similar intracellular and extracellular distribution in slime as that recorded for cultures grown with cornsteep. POD's peripheral cytoplasmic distribution shows similarities to the cellular distribution of that reported previously for H2O2-dependent lignin and manganese peroxidases in P. chrysosporium. Images PMID:16348809

  13. Akbu-LAAO exhibits potent anti-tumor activity to HepG2 cells partially through produced H2O2 via TGF-β signal pathway

    PubMed Central

    Guo, Chunmei; Liu, Shuqing; Dong, Panpan; Zhao, Dongting; Wang, Chengyi; Tao, Zhiwei; Sun, Ming-Zhong

    2015-01-01

    Previously, we characterized the biological properties of Akbu-LAAO, a novel L-amino acid oxidase from Agkistrodon blomhoffii ussurensis snake venom (SV). Current work investigated its in vitro anti-tumor activity and underlying mechanism on HepG2 cells. Akbu-LAAO inhibited HepG2 growth time and dose-dependently with an IC50 of ~38.82 μg/mL. It could induce the apoptosis of HepG2 cells. Akbu-LAAO exhibited cytotoxicity by inhibiting growth and inducing apoptosis of HepG2 as it showed no effect on its cell cycle. The inhibition of Akbu-LAAO to HepG2 growth partially relied on enzymatic-released H2O2 as catalase only partially antagonized this effect. cDNA microarray results indicated TGF-β signaling pathway was linked to the cytotoxicity of Akbu-LAAO on HepG2. TGF-β pathway related molecules CYR61, p53, GDF15, TOB1, BTG2, BMP2, BMP6, SMAD9, JUN, JUNB, LOX, CCND1, CDK6, GADD45A, CDKN1A were deregulated in HepG2 following Akbu-LAAO stimulation. The presence of catalase only slightly restored the mRNA changes induced by Akbu-LAAO for differentially expressed genes. Meanwhile, LDN-193189, a TGF-β pathway inhibitor reduced Akbu-LAAO cytotoxicity on HepG2. Collectively, we reported, for the first time, SV-LAAO showed anti-tumor cell activity via TGF-β pathway. It provides new insight of SV-LAAO exhibiting anti-tumor effect via a novel signaling pathway. PMID:26655928

  14. Novel Sorption Enhanced Reaction Process for Simultaneous Production of CO2 and H2 from Synthesis Gas Produced by Coal Gasification

    SciTech Connect

    Shivaji Sircar; Hugo S. Caram; Kwangkook Jeong; Michael G. Beaver; Fan Ni; Agbor Tabi Makebe

    2010-06-04

    The goal of this project is to evaluate the extensive feasibility of a novel concept called Thermal Swing Sorption Enhanced Reaction (TSSER) process to simultaneously produce H{sub 2} and CO{sub 2} as a single unit operation in a sorber-reactor. The successful demonstration of the potential feasibility of the TSSER concept implies that it is worth pursuing further development of the idea. This can be done by more extensive evaluation of the basic sorptive properties of the CO{sub 2} chemisorbents at realistic high pressures and by continuing the experimental and theoretical study of the TSSER process. This will allow us to substantiate the assumptions made during the preliminary design and evaluation of the process and firm up the initial conclusions. The task performed under this project consists of (i) retrofitting an existing single column sorption apparatus for measurement of high pressure CO{sub 2} sorption characteristics, (ii) measurement of high pressure CO{sub 2} chemisorption equilibria, kinetics and sorption-desorption column dynamic characteristics under the conditions of thermal swing operation of the TSSER process, (iii) experimental evaluation of the individual steps of the TSSER process (iv) development of extended mathematical model for simulating cyclic continuous operation of TSSER to aid in process scale-up and for guiding future work, (v) simulate and test SER concept using realistic syngas composition, (vi) extensive demonstration of the thermal stability of sorbents using a TGA apparatus, (vii) investigation of the surfaces of the adsorbents and adsorbed CO{sub 2} ,and (viii) test the effects of sulfur compounds found in syngas on the CO{sub 2} sorbents.

  15. Polarization degrees of 3p 2P3/2-3s 2S1/2 transition in O5+(1s 23p) produced in collisions of O6+ with He and H2

    NASA Astrophysics Data System (ADS)

    Zhao, Y. Q.; Liu, L.; Xue, P.; Wang, J. G.; Janev, R. K.

    2010-09-01

    Electron capture processes in collisions of O6+ with ground state He and H2 are investigated using the two-centre atomic orbital close-coupling method. Total and state-selective one-electron capture cross sections are obtained for collision energies between 0.5 and 300 keV/u. The comparison with the available experimental state-selective capture data in the overlapping energy range (0.5-100 keV/u for O6++He and 0.5-8 keV/u for O6++H2) shows a good overall agreement. The polarization degrees of 3p 2P3/2-3s 2S1/2 radiation from O5+(3p 2P3/2) produced in O6++He and O6++H2 collisions are calculated from the magnetic substate-selective cross sections with inclusion of cascade contributions from higher n = 4 and n = 5 states. Good agreement is obtained with the experimental data available in the energy range 3-8 keV/u. Below ~10 keV/u, the polarization degrees of O5+(3p 2P3/2) in both collision systems exhibit an oscillatory structure and above this energy they steadily increase with the increase of collision energy, reaching the values of about 0.37 at 300 keV/u. The energy behaviour of the polarization degree of O5+(3p 2P3/2) in the O6++He collision system is determined almost exclusively by the direct electron capture to 3p0 and 3p1 states of O5+, while in the case of the O6++H2 collision system in the energy region below ~40 keV/u it is strongly affected by the cascade contributions from the 4l states, which are the dominant capture states in this system.

  16. H2 blockers

    MedlinePlus

    H2 blockers are medicines that work by reducing the amount of stomach acid secreted by glands in the lining of your stomach. ... symptoms of acid reflux, or gastroesophageal reflux disease ... from the mouth to the stomach). Treat a peptic or stomach ulcer.

  17. γH2AX and cancer

    PubMed Central

    Bonner, William M.; Redon, Christophe E.; Dickey, Jennifer S.; Nakamura, Asako J.; Sedelnikova, Olga A.; Solier, Stéphanie; Pommier, Yves

    2011-01-01

    Histone H2AX phosphorylation on a serine four residues from the carboxyl terminus (producing γH2AX) is a sensitive marker for DNA double-strand breaks (DSBs). DSBs may lead to cancer but, paradoxically, are also used to kill cancer cells. Using γH2AX detection to determine the extent of DSB induction may help to detect precancerous cells, to stage cancers, to monitor the effectiveness of cancer therapies and to develop novel anticancer drugs. PMID:19005492

  18. Biogeochemistry of dihydrogen (H2).

    PubMed

    Hoehler, Tori M

    2005-01-01

    of water-rock interaction could have supported an early chemosynthetic biosphere. Such processes offer the continued potential for a deep, rock-hosted biosphere on Earth or other bodies in the solar system. The continued evolution of metabolic and community-level versatility among microbes led to an expanded ability to completely exploit the energy available in complex organic matter. Under the anoxic conditions that prevailed on the early Earth, this was accomplished through the linked and sequential action of several metabolic classes of organisms. By transporting electrons between cells, H2 provides a means of linking the activities of these organisms into a highly functional and interactive network. At the same time, H2 concentrations exert a powerful thermodynamic control on many aspects of metabolism and biogeochemical function in these systems. Anaerobic communities based on the consumption of organic matter continue to play an important role in global biogeochemistry even into the present day. As the principal arbiters of chemistry in most aquatic sediments and animal digestive systems, these microbes affect the redox and trace-gas chemistry of our oceans and atmosphere, and constitute the ultimate biological filter on material passing into the rock record. It is in such communities that the significance of H2 in mediating biogeochemical function is most strongly expressed. The advent of phototrophic metabolism added another layer of complexity to microbial communities, and to the role of H2 therein. Anoxygenic and oxygenic phototrophs retained and expanded on the utilization of H2 in metabolic processes. Both groups produce and consume H2 through a variety of mechanisms. In the natural world, phototrophic organisms are often closely juxtaposed with a variety of other metabolic types, through the formation of biofilms and microbial mats. In the few examples studied, phototrophs contribute an often swamping term to the H2 economy of these communities, with

  19. H2 Reconstitution

    NASA Astrophysics Data System (ADS)

    Skipper, Mike

    2002-02-01

    The high power microwave program at the Air Force Research Laboratory (AFRL) includes high power source development in narrow band and wideband technologies. The H2 source is an existing wideband source that was developed at the AFRL. A recent AFRL requirement for a wideband impulse generator to use in materials tests has provided the need to update the H2 source for the current test requirements. The H2 source is composed of a dual resonant transformer that charges a short length of coaxial transmission line. The transmission line is then discharged into an output coaxial transmission line with a self-break hydrogen switch. The dual resonant transformer is driven by a low inductance primary capacitor bank operating through a self-break gas switch. The upgrade of the coaxial hydrogen output switch is the focus of this report. The hydrogen output switch was developed through extensive electrical and mechanical simulations. The switch insulator is made of Ultem 2300 and is designed to operate with a mechanical factor of safety equal to 4.0 at 1,000 psi. The design criteria, design data and operational data will be presented.

  20. Infrared Absorption of CH_3O/CD_3O Radicals Produced upon Photolysis of CH_3ONO/CD_3ONO in a {p}-H2 Matrix

    NASA Astrophysics Data System (ADS)

    Lee, Yu-Fang; Chou, Wei-Te; Johnson, Britta; Sibert, Edwin; Lee, Yuan-Pern

    2014-06-01

    The methoxy radical, CH_3O, has attracted much attention because of its important molecular structure and also as a reaction intermediate in combustion and atmospheric chemistry. Previous investigations include laser-induced fluorescence, laser magnetic resonance, and stimulated emission pumping. High-resolution infrared spectrum of jet-cooled CH_3O, produced by laser photolysis of CH_3ONO, in the C-H stretching region 2850-2940 cm-1 has been reported. However, direct infrared absorption spectrum of CH_3O other than the C-H stretching region remains unreported. Irradiation of a {p}-H2 matrix containing CH_3ONO at 3.2 K with UV light produced main features at 1365.4, 1427.5 (21-, 21+), 1041.8 (31-), 1346.8, 1427.5, 1520.9, 1520.9 (51-, 51+, 51-, 51+), and 689.3/694.9, 945.9/951.7, 1233.5, 1235.9 cm-1 (61-, 61+, 61-, 61+); labels 2-6 in parentheses indicate transitions to vibrational states attributable to the umbrella, C-O stretching, CH_2 scissoring, and HCO deformation modes of CH_3O, respectively. These features appeared upon photolysis and diminished after five minutes; formation of CH_2OH was observed as CH_3O decayed. The assignments were based on comparison of observed vibrational wavenumbers with those predicted with the quadratic potential energy force field and quadratic dipole moment expansion calculated with the CCSD(T)/cc-pVTZ method. Jahn-Teller and anharmonic vibrational contributions were included in the full Hamiltonian to estimate the correlation diagram connecting the harmonic eigenvalues to those of the fully coupled problem. Similarly, lines of CD_3O were observed upon UV photolysis of CD_3ONO, but became diminished within five minutes. These observations demonstrates the advantage of diminished cage effect of solid {p}-H2; CH_3O and CD_3O are produced via {in situ} UV photodissociation of CH_3ONO isolated in {p}-H2, but not in Ar or Ne. J.-X. Han, Y. G. Utkin, H.-B. Chen, L. A. Burns and R. F. Curl, J. Chem. Phys., 117, 6538 (2009). J. Nagesh

  1. MELCOR-H2

    Energy Science and Technology Software Center (ESTSC)

    2009-11-10

    Before this LDRD research, no single tool could simulate a very high temperature reactor (VHTR) that is coupled to a secondary system and the sulfur iodine (SI) thermochemistry. Furthermore, the SI chemistry could only be modeled in steady state, typically via flow sheets. Additionally, the MELCOR nuclear reactor analysis code was suitable only for the modeling of light water reactors, not gas-cooled reactors. We extended MELCOR in order to address the above deficiencies. In particular,more » we developed three VHTR input models, added generalized, modular secondary system components, developed reactor point kinetics, included transient thermochemistry for the most important cycles [SI and the Westinghouse hybrid sulfur], and developed an interactive graphical user interface for full plant visualization. The new tool is called MELCOR-H2, and it allows users to maximize hydrogen and electrical production, as well as enhance overall plant safety. We conducted validation and verification studies on the key models, and showed that the MELCOR-H2 results typically compared to within less than 5% from experimental data, code-to-code comparisons, and/or analytical solutions.« less

  2. MELCOR-H2

    SciTech Connect

    2009-11-10

    Before this LDRD research, no single tool could simulate a very high temperature reactor (VHTR) that is coupled to a secondary system and the sulfur iodine (SI) thermochemistry. Furthermore, the SI chemistry could only be modeled in steady state, typically via flow sheets. Additionally, the MELCOR nuclear reactor analysis code was suitable only for the modeling of light water reactors, not gas-cooled reactors. We extended MELCOR in order to address the above deficiencies. In particular, we developed three VHTR input models, added generalized, modular secondary system components, developed reactor point kinetics, included transient thermochemistry for the most important cycles [SI and the Westinghouse hybrid sulfur], and developed an interactive graphical user interface for full plant visualization. The new tool is called MELCOR-H2, and it allows users to maximize hydrogen and electrical production, as well as enhance overall plant safety. We conducted validation and verification studies on the key models, and showed that the MELCOR-H2 results typically compared to within less than 5% from experimental data, code-to-code comparisons, and/or analytical solutions.

  3. Infrared absorption of CH3OSO and CD3OSO radicals produced upon photolysis of CH3OS(O)Cl and CD3OS(O)Cl in p-H2 matrices

    NASA Astrophysics Data System (ADS)

    Lee, Yu-Fang; Kong, Lin-Jun; Lee, Yuan-Pern

    2012-03-01

    Irradiation at 239 ± 20 nm of a p-H2 matrix containing methoxysulfinyl chloride, CH3OS(O)Cl, at 3.2 K with filtered light from a medium-pressure mercury lamp produced infrared (IR) absorption lines at 3028.4 (attributable to ν1, CH2 antisymmetric stretching), 2999.5 (ν2, CH3 antisymmetric stretching), 2950.4 (ν3, CH3 symmetric stretching), 1465.2 (ν4, CH2 scissoring), 1452.0 (ν5, CH3 deformation), 1417.8 (ν6, CH3 umbrella), 1165.2 (ν7, CH3 wagging), 1152.1 (ν8, S=O stretching mixed with CH3 rocking), 1147.8 (ν9, S=O stretching mixed with CH3 wagging), 989.7 (ν10, C-O stretching), and 714.5 cm-1 (ν11, S-O stretching) modes of syn-CH3OSO. When CD3OS(O)Cl in a p-H2 matrix was used, lines at 2275.9 (ν1), 2251.9 (ν2), 2083.3 (ν3), 1070.3 (ν4), 1056.0 (ν5), 1085.5 (ν6), 1159.7 (ν7), 920.1 (ν8), 889.0 (ν9), 976.9 (ν10), and 688.9 (ν11) cm-1 appeared and are assigned to syn-CD3OSO; the mode numbers correspond to those used for syn-CH3OSO. The assignments are based on the photolytic behavior and a comparison of observed vibrational wavenumbers, infrared intensities, and deuterium isotopic shifts with those predicted with the B3P86/aug-cc-pVTZ method. Our results extend the previously reported four transient IR absorption bands of gaseous syn-CH3OSO near 2991, 2956, 1152, and 994 cm-1 to 11 lines, including those associated with C-O, O-S, and S=O stretching modes. Vibrational wavenumbers of syn-CD3OSO are new. These results demonstrate the advantage of a diminished cage effect of solid p-H2 such that the Cl atom, produced via UV photodissociation of CH3OS(O)Cl in situ, might escape from the original cage to yield isolated CH3OSO radicals.

  4. Prevalence of carriage of Shiga toxin-producing Escherichia coli serotypes O157:H7, O26:H11, O103:H2, O111:H8, and O145:H28 among slaughtered adult cattle in France.

    PubMed

    Bibbal, Delphine; Loukiadis, Estelle; Kérourédan, Monique; Ferré, Franck; Dilasser, Françoise; Peytavin de Garam, Carine; Cartier, Philippe; Oswald, Eric; Gay, Emilie; Auvray, Frédéric; Brugère, Hubert

    2015-02-01

    The main pathogenic enterohemorrhagic Escherichia coli (EHEC) strains are defined as Shiga toxin (Stx)-producing E. coli (STEC) belonging to one of the following serotypes: O157:H7, O26:H11, O103:H2, O111:H8, and O145:H28. Each of these five serotypes is known to be associated with a specific subtype of the intimin-encoding gene (eae). The objective of this study was to evaluate the prevalence of bovine carriers of these “top five” STEC in the four adult cattle categories slaughtered in France. Fecal samples were collected from 1,318 cattle, including 291 young dairy bulls, 296 young beef bulls, 337 dairy cows, and 394 beef cows. A total of 96 E. coli isolates, including 33 top five STEC and 63 atypical enteropathogenic E. coli (aEPEC) isolates, with the same genetic characteristics as the top five STEC strains except that they lacked an stx gene, were recovered from these samples.O157:H7 was the most frequently isolated STEC serotype. The prevalence of top five STEC (all serotypes included) was 4.5% in young dairy bulls, 2.4% in young beef bulls, 1.8% in dairy cows, and 1.0% in beef cows. It was significantly higher in young dairy bulls (P<0.05) than in the other 3 categories. The basis for these differences between categories remains to be elucidated. Moreover,simultaneous carriage of STEC O26:H11 and STEC O103:H2 was detected in one young dairy bull. Lastly, the prevalence of bovine carriers of the top five STEC, evaluated through a weighted arithmetic mean of the prevalence by categories, was estimated to 1.8% in slaughtered adult cattle in France. PMID:25527532

  5. Short communication: Behavior of different Shiga toxin-producing Escherichia coli serotypes (O26:H11, O103:H2, O145:H28, O157:H7) during the manufacture, ripening, and storage of a white mold cheese.

    PubMed

    Miszczycha, S D; Bel, N; Gay-Perret, P; Michel, V; Montel, M C; Sergentet-Thevenot, D

    2016-07-01

    Ruminants are healthy carriers of Shiga toxin-producing Escherichia coli (STEC). If good hygienic and agricultural practices at the farm level, especially during the milking process, are not adequately followed, milk and dairy products made with raw milk could become contaminated. Sporadic cases and rare food outbreaks have been linked with dairy products. Consequently, understanding STEC behavior in cheeses would help to evaluate risks for human health. The behavior of 4 different STEC strains belonging to the serotypes O26:H11, O103:H2, O145:H28, and O157:H7 were monitored during the manufacture, ripening, and storage of a white mold soft cheese. These strains, originating from dairy products, were inoculated individually in raw milk from cow at 10(2) cfu/mL. During the first 24 to 36h of the manufacturing stage, the STEC level increased by 2 to 3 log10 cfu/g. Over the course of the ripening stage, the concentration of the non-O157 STEC remained relatively constant, whereas a decrease of the E. coli O157:H7 concentration was observed. During the storage stage, the level of the different non-O157 STEC strains decreased slowly in the core and in the rind of cheeses. The non-O157 STEC level reached between 3.1 and 4.1 log10 cfu/g at d 56. Interestingly, the concentration of the E. coli O157:H7 strain decreased dramatically: the strains remained detectable only after enrichment. During ripening and storage, STEC levels were generally higher in rinds than in cheese cores. In contrast to what was seen in cheese cores, the E. coli O157:H7 strain remained enumerable in rinds during these steps. These results highlight that STEC can grow during the manufacture and survive during the ripening and storage of a white mold soft cheese. PMID:27157567

  6. H2 Detection via Polarography

    NASA Technical Reports Server (NTRS)

    Dominquez, Jesus; Barile, Ron

    2006-01-01

    Polarography is the measurement of the current that flows in solution as a function of an applied voltage. The actual form of the observed polarographic current depends upon the manner in which the voltage is applied and on the characteristics of the working electrode. The new gas polarographic H2 sensor shows a current level increment with concentration of the gaseous H2 similar to those relating to metal ions in liquid electrolytes in well-known polarography. This phenomenon is caused by the fact that the diffusion of the gaseous H2 through a gas diffusion hole built in the sensor is a rate-determining step in the gaseous-hydrogen sensing mechanism. The diffusion hole artificially limits the diffusion of the gaseous H2 toward the electrode located at the sensor cavity. This gas polarographic H2 sensor is actually an electrochemical-pumping cell since the gaseous H2 is in fact pumped via the electrochemical driving force generated between the electrodes. Gaseous H2 enters the diffusion hole and reaches the first electrode (anode) located in the sensor cavity to be transformed into an H ions or protons; H ions pass through the electrolyte and reach the second electrode (cathode) to be reformed to gaseous H2. Gas polarographic O2 sensors are commercially available; a gas polarographic O2 sensor was used to prove the feasibility of building a new gas polarographic H2 sensor.

  7. Why are Outflows Under-Producing Water? A Study of the Abundances of the Key Species H2O, OH, CO, and OI as Seen by Herschel and the Changes to Shock Models They May Impose

    NASA Astrophysics Data System (ADS)

    Melnick, Gary

    The pervasiveness of shocks is evident in the broad pedestals seen routinely in spectra toward a variety of rapidly evolving astrophysical sources, such as colliding gas clouds, protostellar outflows, and supernova explosions. The high densities and temperatures that accompany these shocks not only excite ions, atoms, and molecules into emission, but also enable a host of chemical reactions not favored in colder, quiescent gas. While it is often possible to infer the temperature, density, and abundance of individual species from such emitting regions, it is only through an understanding of these shocks, including the profile of temperature and density in their wake and the compositional changes they produce, that we can construct a self-consistent model of the dynamics and chemistry within these sources. For more than 15 years, the non-dissociative shock models of Kaufman & Neufeld (1996a) have been the most cited models for interpreting broad-line spectra toward molecular outflows. However, during this time we have come to realize that many, if not most, of the sources toward which we apply these shock models possess stronger than average far-ultraviolet and X-ray radiation fields. The models of Kaufman and Neufeld were constructed under the assumption that these shocks occur within well- shielded gas; however, the presence of such external radiation can alter both the structure and chemistry within non-dissociative shocks. The difficulties currently being encountered in explaining the under abundance of water toward a large number of molecular outflows is just one manifestation of the shortcomings of applying the original shock models to conditions for which they were not designed. We propose to modify the existing shock code to include the effects of an external far-ultraviolet and X-ray radiation field and to apply the modified code to re-interpret archived Herschel measurements of H2O along with OH, CO, and O toward more than 20 protostellar outflow sources

  8. Thermodynamic and transport properties of frozen and reacting pH2-oH2 mixtures

    NASA Technical Reports Server (NTRS)

    Carter, H. G.; Bullock, R. E.

    1972-01-01

    Application of experimental state data and spectroscopic term values shows that the thermodynamic and transport properties of reacting pH2-oH2 mixtures are considerably different than those of chemically frozen pH2 at temperatures below 300 R. Calculated H-S data also show that radiation-induced pH2-oH2 equilibration at constant enthalpy produces a temperature drop of at least 28 R, corresponding to an ideal shaft work loss of 15% or more for a turbine operating downstream from the point of conversion. Aside from differences in thermodynamic and transport properties, frozen pH2-oH2 mixtures may differ from pure pH2 on a purely hydrodynamical basis.

  9. Identification of produced powerful radicals involved in the mineralization of bisphenol A using a novel UV-Na(2)S(2)O(8)/H(2)O(2)-Fe(II,III) two-stage oxidation process.

    PubMed

    Huang, Yi-Fong; Huang, Yao-Hui

    2009-03-15

    A two-stage oxidation (UV-Na(2)S(2)O(8)/H(2)O(2)-Fe(II,III)) process was applied to mineralize bisphenol A (BPA) at pH(i) (initial pH) 7. We take advantage of the high oxidation potential of sulfate radicals and use persulfate as the 1st-stage oxidant to oxidize BPA to less complex compounds (stoichiometric ratio: [S(2)O(8)(2-)](0)/[BPA](0)=1). Afterwards, the traditional photo-Fenton process was used to mineralize those compounds to CO(2). To the best of our knowledge, this is the first attempt to utilize the two processes in conjunction for the complete degradation of BPA. During the 2nd-stage reaction, other oxidants (H(2)O(2) and Iron alone) were also employed to observe the extent of enhancement of photo-Fenton. Further, qualitative identification of both hydroxyl and sulfate radicals was performed to evaluate their dominance under different conditions. The BPA degradation in this UV/persulfate process formulated a pseudo-first-order kinetic model well, with a rate constant of approximately 0.038 min(-1) (25 degrees C), 0.057 min(-1) (35 degrees C), and 0.087 min(-1) (50 degrees C), respectively. The much lower activation energy (DeltaE = 26 kJ mol(-1)) was further calculated to clarify that the thermal-effect of an illuminated system differs from single heat-assisted systems described in other research. Final total organic carbon (TOC) removal levels of BPA by the use of such two-stage oxidation processes were 25-34%, 25%, and 87-91% for additional Fe(II,III) activation, H(2)O(2) promotion, and Fe(II,III)/H(2)O(2) promotions, respectively. PMID:18635314

  10. Covariance mapping of two-photon double core hole states in C2H2 and C2H6 produced by an x-ray free electron laser

    NASA Astrophysics Data System (ADS)

    Mucke, M.; Zhaunerchyk, V.; Frasinski, L. J.; Squibb, R. J.; Siano, M.; Eland, J. H. D.; Linusson, P.; Salén, P.; Meulen, P. v. d.; Thomas, R. D.; Larsson, M.; Foucar, L.; Ullrich, J.; Motomura, K.; Mondal, S.; Ueda, K.; Osipov, T.; Fang, L.; Murphy, B. F.; Berrah, N.; Bostedt, C.; Bozek, J. D.; Schorb, S.; Messerschmidt, M.; Glownia, J. M.; Cryan, J. P.; Coffee, R. N.; Takahashi, O.; Wada, S.; Piancastelli, M. N.; Richter, R.; Prince, K. C.; Feifel, R.

    2015-07-01

    Few-photon ionization and relaxation processes in acetylene (C2H2) and ethane (C2H6) were investigated at the linac coherent light source x-ray free electron laser (FEL) at SLAC, Stanford using a highly efficient multi-particle correlation spectroscopy technique based on a magnetic bottle. The analysis method of covariance mapping has been applied and enhanced, allowing us to identify electron pairs associated with double core hole (DCH) production and competing multiple ionization processes including Auger decay sequences. The experimental technique and the analysis procedure are discussed in the light of earlier investigations of DCH studies carried out at the same FEL and at third generation synchrotron radiation sources. In particular, we demonstrate the capability of the covariance mapping technique to disentangle the formation of molecular DCH states which is barely feasible with conventional electron spectroscopy methods.

  11. Covariance mapping of two-photon double core hole states in C 2 H 2 and C 2 H 6 produced by an x-ray free electron laser

    DOE PAGESBeta

    Mucke, M; Zhaunerchyk, V; Frasinski, L J; Squibb, R J; Siano, M; Eland, J H D; Linusson, P; Salén, P; Meulen, P v d; Thomas, R D; et al

    2015-07-01

    Few-photon ionization and relaxation processes in acetylene (C2H2) and ethane (C2H6) were investigated at the linac coherent light source x-ray free electron laser (FEL) at SLAC, Stanford using a highly efficient multi-particle correlation spectroscopy technique based on a magnetic bottle. The analysis method of covariance mapping has been applied and enhanced, allowing us to identify electron pairs associated with double core hole (DCH) production and competing multiple ionization processes including Auger decay sequences. The experimental technique and the analysis procedure are discussed in the light of earlier investigations of DCH studies carried out at the same FEL and at thirdmore » generation synchrotron radiation sources. In particular, we demonstrate the capability of the covariance mapping technique to disentangle the formation of molecular DCH states which is barely feasible with conventional electron spectroscopy methods.« less

  12. Non-Franck-Condon electron-impact dissociative-excitation cross sections of molecular hydrogen producing H(1s)+H(2l) through X 1Σ+g(v=0)-->\\{B 1Σ+u, B' 1Σ+u, C 1Πu\\}

    NASA Astrophysics Data System (ADS)

    Borges, Itamar, Jr.; Jalbert, Ginette; Bielschowsky, Carlos Eduardo

    1998-02-01

    Dissociation cross sections of H2 for high-energy electron impact (100-1000 eV) producing H(1s), H(2s), and H(2p) for excitation from the ground vibrational state (v=0) to the continuum of the B1Σ+u, B' 1Σ+u, and C 1Πu states were computed in the first Born approximation. Configuration-interaction electronic wave functions were used and vibrational degrees of freedom taken in account. The dissociative excitation cross sections as a function of the continuum energy for each final state were presented, and the accuracy of the wave function, including the importance of relaxation effects and the validity of the Franck-Condon approximation, is analyzed in comparison to available previous theoretical results. The computed dissociation cross sections were compared to experimental results making use of the separation of the various breakup channels proposed by Ajello, Shemansky, and James [Astrophys. J. 371, 422 (1991)]. The obtained cross sections to produce H(2p)+H(1s) fragments via dissociative excitation to the B and C states have agreed well with the decomposed experimental results within the error bars. The dissociation cross sections to produce H(2s)+H(1s) through the B' state were in most cases somewhat larger than the reported experimental error bars. In the most favorable case our theoretical B' dissociation cross section was 3.1% within the reported error bar at 300 eV electron impact energy. A possible experimental reason for this discrepancy was raised.

  13. Mice without MacroH2A Histone Variants

    PubMed Central

    Changolkar, Lakshmi N.; Costanzi, Carl; Leu, N. Adrian

    2014-01-01

    MacroH2A core histone variants have a unique structure that includes a C-terminal nonhistone domain. They are highly conserved in vertebrates and are thought to regulate gene expression. However, the nature of genes regulated by macroH2As and their biological significance remain unclear. Here, we examine macroH2A function in vivo by knocking out both macroH2A1 and macroH2A2 in the mouse. While macroH2As are not required for early development, the absence of macroH2As impairs prenatal and postnatal growth and can significantly reduce reproductive efficiency. The distributions of macroH2A.1- and macroH2A.2-containing nucleosomes show substantial overlap, as do their effects on gene expression. Our studies in fetal and adult liver indicate that macroH2As can exert large positive or negative effects on gene expression, with macroH2A.1 and macroH2A.2 acting synergistically on the expression of some genes and apparently having opposing effects on others. These effects are very specific and in the adult liver preferentially involve genes related to lipid metabolism, including the leptin receptor. MacroH2A-dependent gene regulation changes substantially in postnatal development and can be strongly affected by fasting. We propose that macroH2As produce adaptive changes to gene expression, which in the liver focus on metabolism. PMID:25312643

  14. Legumes, N2 fixation and the H2 cycle

    NASA Astrophysics Data System (ADS)

    Layzell, D. B.

    2004-12-01

    Legume plants such as soybean or pea can form symbiotic, N2 fixing associations with bacteria that exist in root nodules. For every N2 fixed, 1 to 3 H2 are produced as a by-product of the nitrogenase reaction. Therefore, a typical N2 fixing legume crop produces about 200,000 L H2 gas (at STP) per hectare per crop season. This paper will summarize our current understanding of the processes leading to H2 production in legumes, the magnitude of H2 production associated with global cropping systems, and the implications for its production and oxidation on both the legumes and the soils in which they grow. Specific points may include: ˜ In symbioses lacking uptake hydrogenase (HUP) activity (thought to be the majority of crop legumes), the H2 diffuses into the soil where it is oxidized by soil microbes that grow up around the legume nodules. The kinetic properties of these microbes are very different (higher Km and Vmax) from that of microbes in soils exposed to normal air (ca. 0.5 ppm H2); ˜ Laboratory studies indicate that 60% of the reducing power from H2 is coupled to O2 uptake, whereas 40% is coupled to autotrophic CO2 fixation. The latter process should increase soil carbon stocks by about 25 kg C/ha/yr; ˜ At the site of the nitrogenase enzyme, H2 production is autocatalytic such that the higher the H2 concentration, the more H2 is produced and the less N2 fixed. The variable O2 diffusion barrier in legumes can act to restrict H2 diffusion from the nodule, thereby increasing the relative magnitude of H2 production versus N2 fixation; ˜ Studies to understand why legume symbioses make such an energy investment in H2 production have led to the discovery that H2 treated soils have improved fertility, supporting the growth and yield of legume and non-legume crops. This observation may account for the benefits of legumes when used in rotation with cereal crops, a phenomenon that has been used by farmers for over 2000 years, but which has remained unexplained. An

  15. The H2O2-H2O Hypothesis: Extremophiles Adapted to Conditions on Mars?

    NASA Astrophysics Data System (ADS)

    Houtkooper, Joop M.; Schulze-Makuch, Dirk

    2007-08-01

    The discovery of extremophiles on Earth is a sequence of discoveries of life in environments where it had been deemed impossible a few decades ago. The next frontier may be the Martian surface environment: could life have adapted to this harsh environment? What we learned from terrestrial extremophiles is that life adapts to every available niche where energy, liquid water and organic materials are available so that in principle metabolism and propagation are possible. A feasible adaptation mechanism to the Martian surface environment would be the incorporation of a high concentration of hydrogen peroxide in the intracellular fluid of organisms. The H2O2-H2O hypothesis suggests the existence of Martian organisms that have a mixture of H2O2 and H2O instead of salty water as their intracellular liquid (Houtkooper and Schulze-Makuch, 2007). The advantages are that the freezing point is low (the eutectic freezes at 56.5°C) and that the mixture is hygroscopic. This would enable the organisms to scavenge water from the atmosphere or from the adsorbed layers of water molecules on mineral grains, with H2O2 being also a source of oxygen. Moreover, below its freezing point the H2O2-H2O mixture has the tendency to supercool. Hydrogen peroxide is not unknown to biochemistry on Earth. There are organisms for which H2O2 plays a significant role: the bombardier beetle, Brachinus crepitans, produces a 25% H2O2 solution and, when attacked by a predator, mixes it with a fluid containing hydroquinone and a catalyst, which produces an audible steam explosion and noxious fumes. Another example is Acetobacter peroxidans, which uses H2O2 in its metabolism. H2O2 plays various other roles, such as the mediation of physiological responses such as cell proliferation, differentiation, and migration. Moreover, most eukaryotic cells contain an organelle, the peroxisome, which mediates the reactions involving H2O2. Therefore it is feasible that in the course of evolution, water-based organisms

  16. H2S and Blood Vessels: An Overview.

    PubMed

    Yang, Guangdong; Wang, Rui

    2015-01-01

    The physiological and biomedical importance of hydrogen sulfide (H2S) has been fully recognized in the cardiovascular system as well as in the rest of the body. In blood vessels, cystathionine γ-lyase (CSE) is a major H2S-producing enzyme expressed in both smooth muscle and endothelium as well as periadventitial adipose tissues. Regulation of H2S production from CSE is controlled by a complex integration of transcriptional, posttranscriptional, and posttranslational mechanisms in blood vessels. In smooth muscle cells, H2S regulates cell apoptosis, phenotypic switch, relaxation and contraction, and calcification. In endothelial cells, H2S controls cell proliferation, cellular senescence, oxidative stress, inflammation, etc. H2S interacts with nitric oxide and acts as an endothelium-derived relaxing factor and an endothelium-derived hyperpolarizing factor. H2S generated from periadventitial adipose tissues acts as an adipocyte-derived relaxing factor and modulates the vascular tone. Extensive evidence has demonstrated the beneficial roles of the CSE/H2S system in various blood vessel diseases, such as hypertension, atherosclerosis, and aortic aneurysm. The important roles signaling in the cardiovascular system merit further intensive and extensive investigation. H2S-releasing agents and CSE activators will find their great applications in the prevention and treatment of blood vessel-related disorders. PMID:26162830

  17. Computational Investigation of the Oxidative Deboronation of Boroglycine, H2N-CH2-B(OH)2, Using H2O and H2O2

    NASA Astrophysics Data System (ADS)

    Larkin, Joseph D.; Markham, George D.; Milkevitch, Matt; Brooks, Bernard R.; Bock, Charles W.

    2009-09-01

    We report results from a computational investigation of the oxidative deboronation of boroglycine, H2N-CH2-B(OH)2, using H2O and H2O2 as the reactive oxygen species (ROS) to yield aminomethanol, H2N-CH2-OH; these results complement our study on the protodeboronation of boroglycine to produce methylamine, H2N-CH3 (Larkin et al. J. Phys. Chem. A 2007, 111, 6489-6500). Second-order Møller-Plesset (MP2) perturbation theory with Dunning-Woon correlation-consistent (cc) basis sets were used for the calculations with comparisons made to results from density functional theory (DFT) at the PBE1PBE/6-311++G(d,p)(cc-pVDZ) levels. The effects of a bulk aqueous environment were also incorporated into the calculations employing PCM and CPCM methodology. Using H2O as the ROS, the reaction H2O + H2N-CH2-B(OH)2 → H2N-CH2-OH + H-B(OH)2 was calculated to be endothermic; the value of ΔH2980 was +12.0 kcal/mol at the MP2(FC)/cc-pVTZ computational level in vacuo and +13.7 kcal/mol in PCM aqueous media; the corresponding value for the activation barrier, ΔH‡, was +94.3 kcal/mol relative to the separated reactants in vacuo and +89.9 kcal/mol in PCM aqueous media. In contrast, the reaction H2O2 + H2N-CH2-B(OH)2 → H2N-CH2-OH + B(OH)3 was calculated to be highly exothermic with an ΔH2980 value of -100.9 kcal/mol at the MP2(FC)/cc-pVTZ computational level in vacuo and -99.6 kcal/mol in CPCM aqueous media; the highest-energy transition state for the multistep process associated with this reaction involved the rearrangement of H2N-CH2-B(OH)(OOH) to H2N-CH2-O-B(OH)2 with a ΔH‡ value of +23.2 kcal/mol in vacuo relative to the separated reactants. These computational results for boroglycine are in accord with the experimental observations for the deboronation of the FDA approved anticancer drug bortezomib (Velcade, PS-341), where it was found to be the principle deactivation pathway (Labutti et al. Chem. Res. Toxicol. 2006, 19, 539-546).

  18. Improved photobiological H2 production in engineered green algal cells.

    PubMed

    Kruse, Olaf; Rupprecht, Jens; Bader, Klaus-Peter; Thomas-Hall, Skye; Schenk, Peer Martin; Finazzi, Giovanni; Hankamer, Ben

    2005-10-01

    Oxygenic photosynthetic organisms use solar energy to split water (H2O) into protons (H+), electrons (e-), and oxygen. A select group of photosynthetic microorganisms, including the green alga Chlamydomonas reinhardtii, has evolved the additional ability to redirect the derived H+ and e- to drive hydrogen (H2) production via the chloroplast hydrogenases HydA1 and A2 (H2 ase). This process occurs under anaerobic conditions and provides a biological basis for solar-driven H2 production. However, its relatively poor yield is a major limitation for the economic viability of this process. To improve H2 production in Chlamydomonas, we have developed a new approach to increase H+ and e- supply to the hydrogenases. In a first step, mutants blocked in the state 1 transition were selected. These mutants are inhibited in cyclic e- transfer around photosystem I, eliminating possible competition for e- with H2ase. Selected strains were further screened for increased H2 production rates, leading to the isolation of Stm6. This strain has a modified respiratory metabolism, providing it with two additional important properties as follows: large starch reserves (i.e. enhanced substrate availability), and a low dissolved O2 concentration (40% of the wild type (WT)), resulting in reduced inhibition of H2ase activation. The H2 production rates of Stm6 were 5-13 times that of the control WT strain over a range of conditions (light intensity, culture time, +/- uncoupler). Typically, approximately 540 ml of H2 liter(-1) culture (up to 98% pure) were produced over a 10-14-day period at a maximal rate of 4 ml h(-1) (efficiency = approximately 5 times the WT). Stm6 therefore represents an important step toward the development of future solar-powered H2 production systems. PMID:16100118

  19. H2S, a novel gasotransmitter, involves in gastric accommodation.

    PubMed

    Xiao, Ailin; Wang, Hongjuan; Lu, Xin; Zhu, Jianchun; Huang, Di; Xu, Tonghui; Guo, Jianqiang; Liu, Chuanyong; Li, Jingxin

    2015-01-01

    H2S is produced mainly by two enzymes:cystathionine-β-synthase (CBS) and cystathionine-γ-lyase (CSE), using L-cysteine (L-Cys) as the substrate. In this study, we investigated the role of H2S in gastric accommodation using CBS(+/-) mice, immunohistochemistry, immunoblot, methylene blue assay, intragastric pressure (IGP) recording and electrical field stimulation (EFS). Mouse gastric fundus expressed H2S-generating enzymes (CBS and CSE) and generated detectable amounts of H2S. The H2S donor, NaHS or L-Cys, caused a relaxation in either gastric fundus or body. The gastric compliance was significantly increased in the presence of L-Cys (1 mM). On the contrary, AOAA, an inhibitor for CBS, largely inhibited gastric compliance. Consistently, CBS(+/-) mice shows a lower gastric compliance. However, PAG, a CSE inhibitor, had no effect on gastric compliances. L-Cys enhances the non-adrenergic, non-cholinergic (NANC) relaxation of fundus strips, but AOAA reduces the magnitude of relaxations to EFS. Notably, the expression level of CBS but not CSE protein was elevated after feeding. Consistently, the production of H2S was also increased after feeding in mice gastric fundus. In addition, AOAA largely reduced food intake and body weight in mice. Furthermore, a metabolic aberration of H2S was found in patients with functional dyspepsia (FD). In conclusion, endogenous H2S, a novel gasotransmitter, involves in gastric accommodation. PMID:26531221

  20. H2S, a novel gasotransmitter, involves in gastric accommodation

    PubMed Central

    Xiao, Ailin; Wang, Hongjuan; Lu, Xin; Zhu, Jianchun; Huang, Di; Xu, Tonghui; Guo, Jianqiang; Liu, Chuanyong; Li, Jingxin

    2015-01-01

    H2S is produced mainly by two enzymes:cystathionine-β-synthase (CBS) and cystathionine-γ-lyase (CSE), using L-cysteine (L-Cys) as the substrate. In this study, we investigated the role of H2S in gastric accommodation using CBS+/− mice, immunohistochemistry, immunoblot, methylene blue assay, intragastric pressure (IGP) recording and electrical field stimulation (EFS). Mouse gastric fundus expressed H2S-generating enzymes (CBS and CSE) and generated detectable amounts of H2S. The H2S donor, NaHS or L-Cys, caused a relaxation in either gastric fundus or body. The gastric compliance was significantly increased in the presence of L-Cys (1 mM). On the contrary, AOAA, an inhibitor for CBS, largely inhibited gastric compliance. Consistently, CBS+/− mice shows a lower gastric compliance. However, PAG, a CSE inhibitor, had no effect on gastric compliances. L-Cys enhances the non-adrenergic, non-cholinergic (NANC) relaxation of fundus strips, but AOAA reduces the magnitude of relaxations to EFS. Notably, the expression level of CBS but not CSE protein was elevated after feeding. Consistently, the production of H2S was also increased after feeding in mice gastric fundus. In addition, AOAA largely reduced food intake and body weight in mice. Furthermore, a metabolic aberration of H2S was found in patients with functional dyspepsia (FD). In conclusion, endogenous H2S, a novel gasotransmitter, involves in gastric accommodation. PMID:26531221

  1. Polarization degree differences for the 3p2P3/2-3s2S1/2 transition of N4+(3p2P3/2) produced in N5+-He and N5+-H2 collisions

    NASA Astrophysics Data System (ADS)

    Liu, L.; Zhao, Y. Q.; Wang, J. G.; Janev, R. K.; Tanuma, H.

    2010-01-01

    The magnetic substate-selective single-electron-capture cross sections in collisions of N5+ with He and H2 are calculated using the two-center atomic orbital close-coupling method, and the polarization of emitted radiation from the excited state of N4+ is investigated for projectile energies between 1.2 and 7 keV/u. The polarization degrees for the 3p2P3/2-3s2S1/2 transition of N4+(3p2P3/2) produced in N5++He and N5++H2 electron-capture collisions are in general agreement with the experimental measurements. It is found both experimentally and theoretically that there exists a large difference between the polarization degrees of this radiation resulting from the N5++He and N5++H2 electron-capture collisions, namely, ~0.25 and ~0, respectively. By studying the time evolution of electron-capture dynamics in the two systems we have found that this difference is caused mainly by the difference in the interactions in the two systems at relatively small internuclear distances, consistent with the molecular picture of the collision dynamics.

  2. The ultraviolet photochemistry of diacetylene - Direct detection of primary products of the metastable C4H2* + C4H2 reaction

    NASA Technical Reports Server (NTRS)

    Bandy, Ralph E.; Lakshminarayan, Chitra; Frost, Rex K.; Zwier, Timothy S.

    1993-01-01

    The products of diacetylene's ultraviolet photochemistry over the 245-220 nm region were directly determined in experiments where C4H2 was excited within a small reaction tube attached to a pulsed nozzle. The products formed in the collisions of C4H2* with C4H2 were subsequently ionized by vacuum UV radiation (at 118 nm) in the ion source of a time-of-flight mass spectrometer. It was found that the reaction of C4H2* with C4H2 produces C6H2 (+C2H2), C8H2 (+2H,H2), and C8H3 (+H), confirming the results of Glicker and Okabe (1987). Under certain conditions, secondary products were observed. Mechanisms for the observed reactions are proposed.

  3. Histamine H2 receptor - Involvement in gastric ulceration

    NASA Technical Reports Server (NTRS)

    Brown, P. A.; Vernikos-Danellis, J.; Brown, T. H.

    1976-01-01

    The involvement of the H1 and H2 receptors for histamine in the pathogenesis of gastric ulcers was investigated in rats. Metiamide, an H2 receptor antagonist, reliably reduced ulceration produced by stress alone or by a combination of stress and aspirin. In contrast, pyrilamine, which blocks only the H1 receptor, was without effect under these same conditions. The results support the hypothesis that histamine mediates both stress and stress plus aspirin induced ulceration by a mechanism involving the H2 receptor.

  4. Crystal structures of heterotypic nucleosomes containing histones H2A.Z and H2A

    PubMed Central

    Horikoshi, Naoki; Arimura, Yasuhiro; Taguchi, Hiroyuki; Kurumizaka, Hitoshi

    2016-01-01

    H2A.Z is incorporated into nucleosomes located around transcription start sites and functions as an epigenetic regulator for the transcription of certain genes. During transcriptional regulation, the heterotypic H2A.Z/H2A nucleosome containing one each of H2A.Z and H2A is formed. However, previous homotypic H2A.Z nucleosome structures suggested that the L1 loop region of H2A.Z would sterically clash with the corresponding region of canonical H2A in the heterotypic nucleosome. To resolve this issue, we determined the crystal structures of heterotypic H2A.Z/H2A nucleosomes. In the H2A.Z/H2A nucleosome structure, the H2A.Z L1 loop structure was drastically altered without any structural changes of the canonical H2A L1 loop, thus avoiding the steric clash. Unexpectedly, the heterotypic H2A.Z/H2A nucleosome is more stable than the homotypic H2A.Z nucleosome. These data suggested that the flexible character of the H2A.Z L1 loop plays an essential role in forming the stable heterotypic H2A.Z/H2A nucleosome. PMID:27358293

  5. Solution structure of the isolated histone H2A-H2B heterodimer

    PubMed Central

    Moriwaki, Yoshihito; Yamane, Tsutomu; Ohtomo, Hideaki; Ikeguchi, Mitsunori; Kurita, Jun-ichi; Sato, Masahiko; Nagadoi, Aritaka; Shimojo, Hideaki; Nishimura, Yoshifumi

    2016-01-01

    During chromatin-regulated processes, the histone H2A-H2B heterodimer functions dynamically in and out of the nucleosome. Although detailed crystal structures of nucleosomes have been established, that of the isolated full-length H2A-H2B heterodimer has remained elusive. Here, we have determined the solution structure of human H2A-H2B by NMR coupled with CS-Rosetta. H2A and H2B each contain a histone fold, comprising four α-helices and two β-strands (α1–β1–α2–β2–α3–αC), together with the long disordered N- and C-terminal H2A tails and the long N-terminal H2B tail. The N-terminal αN helix, C-terminal β3 strand, and 310 helix of H2A observed in the H2A-H2B nucleosome structure are disordered in isolated H2A-H2B. In addition, the H2A α1 and H2B αC helices are not well fixed in the heterodimer, and the H2A and H2B tails are not completely random coils. Comparison of hydrogen-deuterium exchange, fast hydrogen exchange, and {1H}-15N hetero-nuclear NOE data with the CS-Rosetta structure indicates that there is some conformation in the H2A 310 helical and H2B Lys11 regions, while the repression domain of H2B (residues 27–34) exhibits an extended string-like structure. This first structure of the isolated H2A-H2B heterodimer provides insight into its dynamic functions in chromatin. PMID:27181506

  6. Solution structure of the isolated histone H2A-H2B heterodimer.

    PubMed

    Moriwaki, Yoshihito; Yamane, Tsutomu; Ohtomo, Hideaki; Ikeguchi, Mitsunori; Kurita, Jun-Ichi; Sato, Masahiko; Nagadoi, Aritaka; Shimojo, Hideaki; Nishimura, Yoshifumi

    2016-01-01

    During chromatin-regulated processes, the histone H2A-H2B heterodimer functions dynamically in and out of the nucleosome. Although detailed crystal structures of nucleosomes have been established, that of the isolated full-length H2A-H2B heterodimer has remained elusive. Here, we have determined the solution structure of human H2A-H2B by NMR coupled with CS-Rosetta. H2A and H2B each contain a histone fold, comprising four α-helices and two β-strands (α1-β1-α2-β2-α3-αC), together with the long disordered N- and C-terminal H2A tails and the long N-terminal H2B tail. The N-terminal αN helix, C-terminal β3 strand, and 310 helix of H2A observed in the H2A-H2B nucleosome structure are disordered in isolated H2A-H2B. In addition, the H2A α1 and H2B αC helices are not well fixed in the heterodimer, and the H2A and H2B tails are not completely random coils. Comparison of hydrogen-deuterium exchange, fast hydrogen exchange, and {(1)H}-(15)N hetero-nuclear NOE data with the CS-Rosetta structure indicates that there is some conformation in the H2A 310 helical and H2B Lys11 regions, while the repression domain of H2B (residues 27-34) exhibits an extended string-like structure. This first structure of the isolated H2A-H2B heterodimer provides insight into its dynamic functions in chromatin. PMID:27181506

  7. H2 distribution during the formation of multiphase molecular clouds

    NASA Astrophysics Data System (ADS)

    Valdivia, Valeska; Hennebelle, Patrick; Gérin, Maryvonne; Lesaffre, Pierre

    2016-03-01

    Context. H2 is the simplest and the most abundant molecule in the interstellar medium (ISM), and its formation precedes the formation of other molecules. Aims: Understanding the dynamical influence of the environment and the interplay between the thermal processes related to the formation and destruction of H2 and the structure of the cloud is mandatory to understand correctly the observations of H2. Methods: We performed high-resolution magnetohydrodynamical colliding-flow simulations with the adaptive mesh refinement code RAMSES in which the physics of H2 has been included. We compared the simulation results with various observations of the H2 molecule, including the column densities of excited rotational levels. Results: As a result of a combination of thermal pressure, ram pressure, and gravity, the clouds produced at the converging point of HI streams are highly inhomogeneous. H2 molecules quickly form in relatively dense clumps and spread into the diffuse interclump gas. This in particular leads to the existence of significant abundances of H2 in the diffuse and warm gas that lies in between clumps. Simulations and observations show similar trends, especially for the HI-to-H2 transition (H2 fraction vs. total hydrogen column density). Moreover, the abundances of excited rotational levels, calculated at equilibrium in the simulations, turn out to be very similar to the observed abundances inferred from FUSE results. This is a direct consequence of the presence of the H2 enriched diffuse and warm gas. Conclusions: Our simulations, which self-consistently form molecular clouds out of the diffuse atomic gas, show that H2 rapidly forms in the dense clumps and, due to the complex structure of molecular clouds, quickly spreads at lower densities. Consequently, a significant fraction of warm H2 exists in the low-density gas. This warm H2 leads to column densities of excited rotational levels close to the observed ones and probably reveals the complex intermix between

  8. Biosignature Gases in H2-dominated Atmospheres on Rocky Exoplanets

    NASA Astrophysics Data System (ADS)

    Seager, S.; Bains, W.; Hu, R.

    2013-11-01

    Super-Earth exoplanets are being discovered with increasing frequency and some will be able to retain stable H2-dominated atmospheres. We study biosignature gases on exoplanets with thin H2 atmospheres and habitable surface temperatures, using a model atmosphere with photochemistry and a biomass estimate framework for evaluating the plausibility of a range of biosignature gas candidates. We find that photochemically produced H atoms are the most abundant reactive species in H2 atmospheres. In atmospheres with high CO2 levels, atomic O is the major destructive species for some molecules. In Sun-Earth-like UV radiation environments, H (and in some cases O) will rapidly destroy nearly all biosignature gases of interest. The lower UV fluxes from UV-quiet M stars would produce a lower concentration of H (or O) for the same scenario, enabling some biosignature gases to accumulate. The favorability of low-UV radiation environments to accumulate detectable biosignature gases in an H2 atmosphere is closely analogous to the case of oxidized atmospheres, where photochemically produced OH is the major destructive species. Most potential biosignature gases, such as dimethylsulfide and CH3Cl, are therefore more favorable in low-UV, as compared with solar-like UV, environments. A few promising biosignature gas candidates, including NH3 and N2O, are favorable even in solar-like UV environments, as these gases are destroyed directly by photolysis and not by H (or O). A more subtle finding is that most gases produced by life that are fully hydrogenated forms of an element, such as CH4 and H2S, are not effective signs of life in an H2-rich atmosphere because the dominant atmospheric chemistry will generate such gases abiologically, through photochemistry or geochemistry. Suitable biosignature gases in H2-rich atmospheres for super-Earth exoplanets transiting M stars could potentially be detected in transmission spectra with the James Webb Space Telescope.

  9. H2O2: a dynamic neuromodulator.

    PubMed

    Rice, Margaret E

    2011-08-01

    Increasing evidence implicates hydrogen peroxide (H(2)O(2)) as an intracellular and intercellular signaling molecule that can influence processes from embryonic development to cell death. Most research has focused on relatively slow signaling, on the order of minutes to days, via second messenger cascades. However, H(2)O(2) can also mediate subsecond signaling via ion channel activation. This rapid signaling has been examined most thoroughly in the nigrostriatal dopamine (DA) pathway, which plays a key role in facilitating movement mediated by the basal ganglia. In DA neurons of the substantia nigra, endogenously generated H(2)O(2) activates ATP-sensitive K(+) (K-ATP) channels that inhibit DA neuron firing. In the striatum, H(2)O(2) generated downstream from glutamatergic AMPA receptor activation in medium spiny neurons acts as a diffusible messenger that inhibits axonal DA release, also via K-ATP channels. The source of dynamically generated H(2)O(2) is mitochondrial respiration; thus, H(2)O(2) provides a novel link between activity and metabolism via K-ATP channels. Additional targets of H(2)O(2) include transient receptor potential (TRP) channels. In contrast to the inhibitory effect of H(2)O(2) acting via K-ATP channels, TRP channel activation is excitatory. This review describes emerging roles of H(2)O(2) as a signaling agent in the nigrostriatal pathway and basal ganglia neurons. PMID:21666063

  10. Photolysis of H2O-H2O2 Mixtures: The Destruction of H2O2

    NASA Technical Reports Server (NTRS)

    Loeffler, M. J.; Fama, M.; Baragiola, R. A.; Carlson, R. W.

    2013-01-01

    We present laboratory results on the loss of H2O2 in solid H2O + H2O2 mixtures at temperatures between 21 and 145 K initiated by UV photolysis (193 nm). Using infrared spectroscopy and microbalance gravimetry, we measured the decrease of the 3.5 micrometer infrared absorption band during UV irradiation and obtained a photodestruction cross section that varies with temperature, being lowest at 70 K. We use our results, along with our previously measured H2O2 production rates via ionizing radiation and ion energy fluxes from the spacecraft to compare H2O2 creation and destruction at icy satellites by ions from their planetary magnetosphere and from solar UV photons. We conclude that, in many cases, H2O2 is not observed on icy satellite surfaces because the H2O2 photodestruction rate is much higher than the production rate via energetic particles, effectively keeping the H2O2 infrared signature at or below the noise level.

  11. H2 extraction and H2O and O2 production from lunar soil

    NASA Technical Reports Server (NTRS)

    Simonds, Charles H.; Christiansen, Eric L.

    1989-01-01

    Direct extraction and reaction of the 50 ppm H found in mature lunar soil with a small fraction of the 1 percent ilmenite found in even the most Ti-poor lunar soils is a viable method of producing H2O2 and H2O for propellants and life support. A plant with a mass of approximately 62 metric tons can produce about 8 metric tons of LOX and 1.2 metric tons of LH2 per month. The concept is viable in even Ti-poor regions if the soils have long exposure to solar wind. The plant processes over 29,000 tons of soil with about 50 ppm H per month. The mine that feeds the plant excavates over 8600 sq m per month with a fleet of three front-end loaders and five haulers. Trade studies demonstrate that nuclear power accompanied by a high process plant duty cycle results in a far smaller installation than a solar-powered unit.

  12. Graphene oxide and H2 production from bioelectrochemical graphite oxidation.

    PubMed

    Lu, Lu; Zeng, Cuiping; Wang, Luda; Yin, Xiaobo; Jin, Song; Lu, Anhuai; Jason Ren, Zhiyong

    2015-01-01

    Graphene oxide (GO) is an emerging material for energy and environmental applications, but it has been primarily produced using chemical processes involving high energy consumption and hazardous chemicals. In this study, we reported a new bioelectrochemical method to produce GO from graphite under ambient conditions without chemical amendments, value-added organic compounds and high rate H2 were also produced. Compared with abiotic electrochemical electrolysis control, the microbial assisted graphite oxidation produced high rate of graphite oxide and graphene oxide (BEGO) sheets, CO2, and current at lower applied voltage. The resultant electrons are transferred to a biocathode, where H2 and organic compounds are produced by microbial reduction of protons and CO2, respectively, a process known as microbial electrosynthesis (MES). Pseudomonas is the dominant population on the anode, while abundant anaerobic solvent-producing bacteria Clostridium carboxidivorans is likely responsible for electrosynthesis on the cathode. Oxygen production through water electrolysis was not detected on the anode due to the presence of facultative and aerobic bacteria as O2 sinkers. This new method provides a sustainable route for producing graphene materials and renewable H2 at low cost, and it may stimulate a new area of research in MES. PMID:26573014

  13. Graphene oxide and H2 production from bioelectrochemical graphite oxidation

    NASA Astrophysics Data System (ADS)

    Lu, Lu; Zeng, Cuiping; Wang, Luda; Yin, Xiaobo; Jin, Song; Lu, Anhuai; Jason Ren, Zhiyong

    2015-11-01

    Graphene oxide (GO) is an emerging material for energy and environmental applications, but it has been primarily produced using chemical processes involving high energy consumption and hazardous chemicals. In this study, we reported a new bioelectrochemical method to produce GO from graphite under ambient conditions without chemical amendments, value-added organic compounds and high rate H2 were also produced. Compared with abiotic electrochemical electrolysis control, the microbial assisted graphite oxidation produced high rate of graphite oxide and graphene oxide (BEGO) sheets, CO2, and current at lower applied voltage. The resultant electrons are transferred to a biocathode, where H2 and organic compounds are produced by microbial reduction of protons and CO2, respectively, a process known as microbial electrosynthesis (MES). Pseudomonas is the dominant population on the anode, while abundant anaerobic solvent-producing bacteria Clostridium carboxidivorans is likely responsible for electrosynthesis on the cathode. Oxygen production through water electrolysis was not detected on the anode due to the presence of facultative and aerobic bacteria as O2 sinkers. This new method provides a sustainable route for producing graphene materials and renewable H2 at low cost, and it may stimulate a new area of research in MES.

  14. Graphene oxide and H2 production from bioelectrochemical graphite oxidation

    PubMed Central

    Lu, Lu; Zeng, Cuiping; Wang, Luda; Yin, Xiaobo; Jin, Song; Lu, Anhuai; Jason Ren, Zhiyong

    2015-01-01

    Graphene oxide (GO) is an emerging material for energy and environmental applications, but it has been primarily produced using chemical processes involving high energy consumption and hazardous chemicals. In this study, we reported a new bioelectrochemical method to produce GO from graphite under ambient conditions without chemical amendments, value-added organic compounds and high rate H2 were also produced. Compared with abiotic electrochemical electrolysis control, the microbial assisted graphite oxidation produced high rate of graphite oxide and graphene oxide (BEGO) sheets, CO2, and current at lower applied voltage. The resultant electrons are transferred to a biocathode, where H2 and organic compounds are produced by microbial reduction of protons and CO2, respectively, a process known as microbial electrosynthesis (MES). Pseudomonas is the dominant population on the anode, while abundant anaerobic solvent-producing bacteria Clostridium carboxidivorans is likely responsible for electrosynthesis on the cathode. Oxygen production through water electrolysis was not detected on the anode due to the presence of facultative and aerobic bacteria as O2 sinkers. This new method provides a sustainable route for producing graphene materials and renewable H2 at low cost, and it may stimulate a new area of research in MES. PMID:26573014

  15. Assay Methods for H2S Biogenesis and Catabolism Enzymes

    PubMed Central

    Banerjee, Ruma; Chiku, Taurai; Kabil, Omer; Libiad, Marouane; Motl, Nicole; Yadav, Pramod K.

    2015-01-01

    H2S is produced from sulfur-containing amino acids, cysteine and homocysteine, or a catabolite, 3-mercaptopyruvate, by three known enzymes: cystathionine β-synthase, γ-cystathionase, and 3-mercaptopyruvate sulfurtransferase. Of these, the first two enzymes reside in the cytoplasm and comprise the transsulfuration pathway, while the third enzyme is found both in the cytoplasm and in the mitochondrion. The following mitochondrial enzymes oxidize H2S: sulfide quinone oxidoreductase, sulfur dioxygenase, rhodanese, and sulfite oxidase. The products of the sulfide oxidation pathway are thiosulfate and sulfate. Assays for enzymes involved in the production and oxidative clearance of sulfide to thiosulfate are described in this chapter. PMID:25725523

  16. Assay methods for H2S biogenesis and catabolism enzymes.

    PubMed

    Banerjee, Ruma; Chiku, Taurai; Kabil, Omer; Libiad, Marouane; Motl, Nicole; Yadav, Pramod K

    2015-01-01

    H2S is produced from sulfur-containing amino acids, cysteine and homocysteine, or a catabolite, 3-mercaptopyruvate, by three known enzymes: cystathionine β-synthase, γ-cystathionase, and 3-mercaptopyruvate sulfurtransferase. Of these, the first two enzymes reside in the cytoplasm and comprise the transsulfuration pathway, while the third enzyme is found both in the cytoplasm and in the mitochondrion. The following mitochondrial enzymes oxidize H2S: sulfide quinone oxidoreductase, sulfur dioxygenase, rhodanese, and sulfite oxidase. The products of the sulfide oxidation pathway are thiosulfate and sulfate. Assays for enzymes involved in the production and oxidative clearance of sulfide to thiosulfate are described in this chapter. PMID:25725523

  17. Vibrational relaxation of H2O(|04> ) in collisions with H2O, Ar, H2, N2 and O2: dynamical and atmospheric implications

    NASA Astrophysics Data System (ADS)

    Barnes, P. W.; Sims, I. R.; Smith, I. W.

    2003-04-01

    It has been suggested that sequential two-photon dissociation of water might provide a mechanism for the atmospheric production of OH radical. ^1 This mechanism requires that photodissociation of vibrationally excited molecules must occur at a rate competitive with their relaxation by collisions with atmospheric gases. In this paper, we shall describe new experiments on the collisional relaxation of H_2O molecules from the highly excited mid04>± vibrational state in collisions with H_2O, Ar, H_2, N_2 and O_2. In our experiments, the mid04>^- state is populated by direct absorption of radiation from a pulsed dye laser tuned to ca. 719 nm. Evolution of the population in the (mid04>±) levels is observed using the combination of a frequency-quadrupled Nd:YAG laser, which selectively photolyses H_2O(mid04>±), and a frequency-doubled dye laser, which observes the OH(v = 0) produced via laser-induced fluorescence (LIF). The delay between the pulse from the pump laser and those from the photolysis and probe lasers was systematically varied to generate kinetic decays. The rate coefficients for relaxation obtained from these experiments, in units of cm^3 molecule-1 s-1, are: k(H_2O) = (4.1 ± 1.2) x 10-10, k(Ar) = (4.9 ± 1.1) x 10-12, k(H_2) = (6.8 ± 1.1) x 10-12, k(N_2) = (7.7 ± 1.5) x 10-12, k(O_2) = (6.7 ± 1.4) x 10-12. The results will be discussed in two contexts. First, we shall consider the implications of our new results for the interpretation of our previous experiments on the reactions of vibrationally excited H_2O with H atoms.^2 Second, we shall consider the proposal of Goss et al.1 in the light of our finding that the collisional relaxation of H_2O(mid04>±) by N_2 and O_2 is rather rapid. ^1 L. M Goss, V. Vaida, J. W. Brault and R. T. Skodje, J. Phys. Chem. A, 05, 70 (2001). ^2 (a) G. Hawthorne, P. Sharkey and I. W. M. Smith, J. Chem. Phys., 108, 4693(1998); (b) P. W. Barnes, P. Sharkey, I. R. Sims and I. W. M. Smith, Faraday Discuss. Chem. Soc., 13, 167

  18. Cell-trappable fluorescent probes for endogenous hydrogen sulfide signaling and imaging H2O2-dependent H2S production

    PubMed Central

    Lin, Vivian S.; Lippert, Alexander R.; Chang, Christopher J.

    2013-01-01

    Hydrogen sulfide (H2S) is a reactive small molecule generated in the body that can be beneficial or toxic owing to its potent redox activity. In living systems, disentangling the pathways responsible for H2S production and their physiological and pathological consequences remains a challenge in part due to a lack of methods for monitoring changes in endogenous H2S fluxes. The development of fluorescent probes with appropriate selectivity and sensitivity for monitoring production of H2S at biologically relevant signaling levels offers opportunities to explore its roles in a variety of systems. Here we report the design, synthesis, and application of a family of azide-based fluorescent H2S indicators, Sulfidefluor-4, Sulfidefluor-5 acetoxymethyl ester, and Sulfidefluor-7 acetoxymethyl ester, which offer the unique capability to image H2S generated at physiological signaling levels. These probes are optimized for cellular imaging and feature enhanced sensitivity and cellular retention compared with our previously reported molecules. In particular, Sulfidefluor-7 acetoxymethyl ester allows for direct, real-time visualization of endogenous H2S produced in live human umbilical vein endothelial cells upon stimulation with vascular endothelial growth factor (VEGF). Moreover, we show that H2S production is dependent on NADPH oxidase–derived hydrogen peroxide (H2O2), which attenuates VEGF receptor 2 phosphorylation and establishes a link for H2S/H2O2 crosstalk. PMID:23589874

  19. Binding kinetics of histone chaperone Chz1 and variant histone H2A.Z-H2B by relaxation dispersion NMR spectroscopy

    PubMed Central

    Hansen, D. Flemming; Zhou, Zheng; Feng, Haniqiao; Miller Jenkins, Lisa M.; Bai, Yawen; Kay, Lewis E.

    2009-01-01

    The genome of eukaryotic cells is packed into a compact structure called chromatin that consists of DNA as well as both histone and non-histone proteins. Histone-chaperones associate with histone proteins and play important roles in the assembly of chromatin structure and transport of histones in the cell. The recently discovered histone-chaperone Chz1 associates with the variant histone H2A.Z of budding yeast and plays a critical role in the exchange of the canonical histone pair H2A-H2B for the variant H2A.Z-H2B. Here, we present an NMR approach that provides accurate estimates for the rates of association and dissociation of Chz1 and H2A.Z-H2B. The methodology exploits the fact that in a 1:1 mixture of Chz1 and H2A.Z-H2B the small amounts of unbound proteins that are invisible in spectra produce line-broadening of signals from the complex that can be quantified in terms of the thermodynamics and kinetics of the exchange process. The dissociation rate constant measured, 22±2 s−1, provides an upper bound for the rate of transfer of H2A.Z-H2B to the chromatin remodeling complex and the faster than diffusion association rate, 108±107 M−1s−1, establishes the importance of attractive electrostatic interactions that form the chaperone:histone complex. PMID:19385041

  20. Flammability and explosion limits of H2 and H2/CO: A literature review. Technical report

    SciTech Connect

    Cohen, N.

    1992-09-10

    The literature related to the flammability and explosion limits of H2/O2,H2/O2/diluent, CO/H2/O2, and CO/H2/air mixtures is reviewed, with particular attention to those aspects relevant to space- and launch vehicle-related conditions. The discussion is hardly exhaustive but is meant to be reasonably self-contained. Applications to a recent Atlas II AC-101 booster system exhaust leak are considered.

  1. TES/Aura L2 Water Vapor (H2O) Limb (TL2H2OL)

    Atmospheric Science Data Center

    2015-02-06

    TES/Aura L2 Water Vapor (H2O) Limb (TL2H2OL) News:  TES News ... Level:  L2 Platform:  TES/Aura L2 Water Vapor Spatial Coverage:  27 x 23 km Limb ... Access: OPeNDAP Parameters:  H2O Water Volume Mixing Radio Precision Vertical Resolution Order ...

  2. An H2A Histone Isotype, H2ac, Associates with Telomere and Maintains Telomere Integrity

    PubMed Central

    Tzeng, Tsai-Yu; Lin, I-Hsuan; Hsu, Ming-Ta

    2016-01-01

    Telomeres are capped at the ends of eukaryotic chromosomes and are composed of TTAGGG repeats bound to the shelterin complex. Here we report that a replication-dependent histone H2A isotype, H2ac, was associated with telomeres in human cells and co-immunoprecipitates with telomere repeat factor 2 (TRF2) and protection of telomeres protein 1 (POT1), whereas other histone H2A isotypes and mutations of H2ac did not bind to telomeres or these two proteins. The amino terminal basic domain of TRF2 was necessary for the association with H2ac and for the recruitment of H2ac to telomeres. Depletion of H2ac led to loss of telomeric repeat sequences, the appearance of dysfunctional telomeres, and chromosomal instability, including chromosomal breaks and anaphase bridges, as well as accumulation of telomere-associated DNA damage factors in H2ac depleted cells. Additionally, knockdown of H2ac elicits an ATM-dependent DNA damage response at telomeres and depletion of XPF protects telomeres against H2ac-deficiency-induced G-strand overhangs loss and DNA damage response, and prevents chromosomal instability. These findings suggest that the H2A isotype, H2ac, plays an essential role in maintaining telomere functional integrity. PMID:27228173

  3. A laser flash photolysis kinetics study of the reaction OH + H2O2 yields HO2 + H2O

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Semmes, D. H.; Ravishankara, A. R.

    1981-01-01

    Absolute rate constants for the reaction are reported as a function of temperature over the range 273-410 K. OH radicals are produced by 266 nm laser photolysis of H2O2 and detected by resonance fluorescence. H2O2 concentrations are determined in situ in the slow flow system by UV photometry. The results confirm the findings of two recent discharge flow-resonance fluorescence studies that the title reaction is considerably faster, particularly at temperatures below 300 K, than all earlier studies had indicated. A table giving kinetic data from the reaction is included.

  4. Interstellar clouds containing optically thin H2

    NASA Technical Reports Server (NTRS)

    Jura, M.

    1975-01-01

    The theory of Black and Delgarno that the relative populations of the excited rotational levels of H2 can be understood in terms of cascading following absorption in the Lyman and Werner bands is employed to infer the gas densities and radiation fields within diffuse interstellar clouds containing H2 that is optically thin in those bands. The procedure is described for computing the populations of the different rotation levels, the relative distribution among the different rotation levels of newly formed H2 is determined on the basis of five simplified models, and the rate of H2 formation is estimated. The results are applied to delta Ori, two components of iota Ori, the second components of rho Leo and zeta Ori, tau Sco, gamma Vel, and zeta Pup. The inferred parameters are summarized for each cloud.

  5. Electrochemical, H2O2-Boosted Catalytic Oxidation System

    NASA Technical Reports Server (NTRS)

    Akse, James R.; Thompson, John O.; Schussel, Leonard J.

    2004-01-01

    An improved water-sterilizing aqueous-phase catalytic oxidation system (APCOS) is based partly on the electrochemical generation of hydrogen peroxide (H2O2). This H2O2-boosted system offers significant improvements over prior dissolved-oxygen water-sterilizing systems in the way in which it increases oxidation capabilities, supplies H2O2 when needed, reduces the total organic carbon (TOC) content of treated water to a low level, consumes less energy than prior systems do, reduces the risk of contamination, and costs less to operate. This system was developed as a variant of part of an improved waste-management subsystem of the life-support system of a spacecraft. Going beyond its original intended purpose, it offers the advantage of being able to produce H2O2 on demand for surface sterilization and/or decontamination: this is a major advantage inasmuch as the benign byproducts of this H2O2 system, unlike those of systems that utilize other chemical sterilants, place no additional burden of containment control on other spacecraft air- or water-reclamation systems.

  6. Role of Metabolic H2O2 Generation

    PubMed Central

    Sies, Helmut

    2014-01-01

    Hydrogen peroxide, the nonradical 2-electron reduction product of oxygen, is a normal aerobic metabolite occurring at about 10 nm intracellular concentration. In liver, it is produced at 50 nmol/min/g of tissue, which is about 2% of total oxygen uptake at steady state. Metabolically generated H2O2 emerged from recent research as a central hub in redox signaling and oxidative stress. Upon generation by major sources, the NADPH oxidases or Complex III of the mitochondrial respiratory chain, H2O2 is under sophisticated fine control of peroxiredoxins and glutathione peroxidases with their backup systems as well as by catalase. Of note, H2O2 is a second messenger in insulin signaling and in several growth factor-induced signaling cascades. H2O2 transport across membranes is facilitated by aquaporins, denoted as peroxiporins. Specialized protein cysteines operate as redox switches using H2O2 as thiol oxidant, making this reactive oxygen species essential for poising the set point of the redox proteome. Major processes including proliferation, differentiation, tissue repair, inflammation, circadian rhythm, and aging use this low molecular weight oxygen metabolite as signaling compound. PMID:24515117

  7. Novel cooperative interactions and structural ordering in H2S-H2

    SciTech Connect

    Kent, Paul R

    2011-01-01

    Hydrogen sulfide (H2S) and hydrogen (H2) crystallize into a 'guest-host' structure at 3.5 GPa and, at the initial formation pressure, the rotationally disordered component molecules exhibit weak van der Waals type interactions. With increasing pressure, hydrogen bonding develops and strengthens between neighboring H2S molecules, reflected in a pronounced drop in S-H vibrational stretching frequency and also observed in first-principles calculations. At 17 GPa, an ordering process occurs where H2S molecules orient themselves to maximize hydrogen bonding and H2 molecules simultaneously occupy a chemically distinct lattice site. Intermolecular forces in the H2S+H2 system may be tuned with pressure from the weak hydrogen-bonding limit to the ordered hydrogen-bonding regime, resulting in a novel clathrate structure stabilized by cooperative interactions.

  8. Novel Cooperative Interactions and Structural Ordering in H2S-H2

    NASA Astrophysics Data System (ADS)

    Strobel, Timothy A.; Ganesh, P.; Somayazulu, Maddury; Kent, P. R. C.; Hemley, Russell J.

    2011-12-01

    Hydrogen sulfide (H2S) and hydrogen (H2) crystallize into a ‘guest-host’ structure at 3.5 GPa and, at the initial formation pressure, the rotationally disordered component molecules exhibit weak van der Waals-type interactions. With increasing pressure, hydrogen bonding develops and strengthens between neighboring H2S molecules, reflected in a pronounced drop in S-H vibrational stretching frequency and also observed in first-principles calculations. At 17 GPa, an ordering process occurs where H2S molecules orient themselves to maximize hydrogen bonding and H2 molecules simultaneously occupy a chemically distinct lattice site. Intermolecular forces in the H2S+H2 system may be tuned with pressure from the weak hydrogen-bonding limit to the ordered hydrogen-bonding regime, resulting in a novel clathrate structure stabilized by cooperative interactions.

  9. Hydrogen and carbon isotope systematics in hydrogenotrophic methanogenesis under H2-limited and H2-enriched conditions: implications for the origin of methane and its isotopic diagnosis

    NASA Astrophysics Data System (ADS)

    Okumura, Tomoyo; Kawagucci, Shinsuke; Saito, Yayoi; Matsui, Yohei; Takai, Ken; Imachi, Hiroyuki

    2016-12-01

    Hydrogen and carbon isotope systematics of H2O-H2-CO2-CH4 in hydrogenotrophic methanogenesis and their relation to H2 availability were investigated. Two H2-syntrophic cocultures of fermentatively hydrogenogenic bacteria and hydrogenotrophic methanogens under conditions of <102 Pa-H2 and two pure cultures of hydrogenotrophic methanogens under conditions of 105 Pa-H2 were tested. Carbon isotope fractionation between CH4 and CO2 during hydrogenotrophic methanogenesis was correlated with pH2, as indicated in previous studies. The hydrogen isotope ratio of CH4 produced during rapid growth of the thermophilic methanogen Methanothermococcus okinawensis under high pH2 conditions ( 105 Pa) was affected by the isotopic composition of H2, as concluded in a previous study of Methanothermobacter thermautotrophicus. This " {δ D}_{{H}_2} effect" is a possible cause of the diversity of previously reported values for hydrogen isotope fractionation between CH4 and H2O examined in H2-enriched culture experiments. Hydrogen isotope fractionation between CH4 and H2O, defined by (1000 + {δ D}_{{CH}_4} )/(1000 + {δ D}_{{H}_2O} ), during hydrogenotrophic methanogenesis of the H2-syntrophic cocultures was in the range 0.67-0.69. The hydrogen isotope fractionation of our H2-syntrophic dataset overlaps with those obtained not only from low- pH2 experiments reported so far but also from natural samples of "young" methane reservoirs (0.66-0.74). Conversely, such hydrogen isotope fractionation is not consistent with that of "aged" methane in geological samples (≥0.79), which has been regarded as methane produced via hydrogenotrophic methanogenesis from the carbon isotope fractionation. As a possible process inducing the inconsistency in hydrogen isotope signatures between experiments and geological samples, we hypothesize that the hydrogen isotope signature of CH4 imprinted at the time of methanogenesis, as in the experiments and natural young methane, may be altered by diagenetic hydrogen

  10. Simulating the H2 content of high-redshift galaxies

    NASA Astrophysics Data System (ADS)

    Tomassetti, Matteo; Porciani, Cristiano; Romano-Díaz, Emilio; Ludlow, Aaron D.

    2015-02-01

    We introduce a sub-grid model for the non-equilibrium abundance of molecular hydrogen in cosmological simulations of galaxy formation. We improve upon previous work by accounting for the unresolved structure of molecular clouds in a phenomenological way which combines both observational and numerical results on the properties of the turbulent interstellar medium. We apply the model to a cosmological simulation of the formation of a Milky Way-sized galaxy at z = 2, and compare the results to those obtained using other popular prescriptions that compute the equilibrium abundance of H2. In these runs, we introduce an explicit link between star formation and the local H2 abundance, and perform an additional simulation in which star formation is linked directly to the density of cold gas. In better agreement with observations, we find that the simulated galaxy produces less stars and harbours a larger gas reservoir when star formation is regulated by molecular hydrogen. In this case, the galaxy is composed of a younger stellar population as early star formation is inhibited in small, metal-poor dark-matter haloes which cannot efficiently produce H2. The number of luminous satellites orbiting within the virial radius of the galaxy at z = 2 is reduced by 10-30 per cent in models with H2-regulated star formation.

  11. Nonenzymatic biotinylation of histone H2A

    PubMed Central

    Healy, Shannon; Heightman, Tom D; Hohmann, Laura; Schriemer, David; Gravel, Roy A

    2009-01-01

    Holocarboxylase synthetase (HCS, eukaryotic enzyme) and BirA (prokaryotic) are biotin protein ligases that catalyze the ATP-dependent attachment of biotin to apocarboxylases via the reactive intermediate, bio-5′-AMP. In this study, we examined the in vitro mechanism of biotin attachment to histone H2A in the presence of HCS and BirA. The experiment derives from our observations that HCS is found in the nucleus of cells in addition to the cytoplasm, and it has the ability to attach biotin to histones in vitro (Narang et al., Hum Mol Genet 2004; 13:15–23). Using recombinant HCS or BirA, the rate of biotin attachment was considerably slower with histone H2A than with the biotin binding domain of an apocarboxylase. However, on incubation of recombinant H2A with chemically synthesized bio-5′-AMP, H2A was observed to be rapidly labeled with biotin in the absence of enzyme. Nonenzymatic biotinylation of a truncated apocarboxylase (BCCP87) has been previously reported (Streaker and Beckett, Protein Sci 2006; 15:1928–1935), though at a much slower rate than we observe for H2A. The specific attachment sites of nonenzymatically biotinylated recombinant H2A at different time points were identified using mass spectrometry, and were found to consist of a similar pattern of biotin attachment as seen in the presence of HCS, with preference for lysines in the highly basic N-terminal region of the histone. None of the lysine sites within H2A resembles the biotin attachment consensus sequence seen in carboxylases, suggesting a novel mechanism for histone biotinylation. PMID:19160459

  12. Interstellar H2 toward HD 147888

    NASA Astrophysics Data System (ADS)

    Gnaciński, P.

    2013-01-01

    The ultraviolet and far-ultraviolet spectra of HD 147888 allows the H2 vibrational level ν = 0 to be accessed along with higher vibrational levels of the ground H2 electronic level. The large number of H2 absorption lines in the HST spectra allows column densities to be determined even from a noisy spectra. We have determined column densities of the H2 molecule on vibrational levels ν = 0-5 and rotational levels J = 0-6 using the profile fitting method. No variations in the column densities of H2 on vibrationally excited levels were observed from 2000 through 2009. The ortho to para H2 ratio (O/P)* for the excited vibrational states ν = 1-4 equals to 1.13. For the lowest vibrational state ν = 0 and rotational level J = 1 the ortho to para H2 ratio is only 0.15. The temperature of ortho-para thermodynamical equilibrium is TOP = 42 ± 3 K. The measurements of H2 column densities on excited vibrational levels (from the HST spectra) leads to constraints on the radiation field in photon-dominated region (PDR) models of the interstellar cloud towards HD 147888. The Meudon PDR model locates the cloud 0.62 pc from the star. The modeled hydrogen cloud density (89-336 cm-3) agrees with independent density estimations based on the C2 molecule and the chemical model. The observed (O/P)J = 1 and (O/P)* H2 ratios cannot be explained by a simple model. Based on observations made with the NASA/ESA Hubble Space Telescope and with NASA/Johns Hopkins University Far Ultraviolet Spectroscopic Explorer, obtained from the data archive at the Space Telescope Science Institute. STScI is operated by the Association of Universities for Research in Astronomy, Inc. under NASA contract NAS 5-26555. Support for FUSE data is provided by the NASA Office of Space Science via grant NAG5-7584 and by other grants and contracts.

  13. Thermal modeling of NiH2 batteries

    NASA Technical Reports Server (NTRS)

    Ponthus, Agnes-Marie; Alexandre, Alain

    1994-01-01

    The following are discussed: NiH2 battery mission and environment; NiH2 cell heat dissipation; Nodal software; model development general philosophy; NiH2 battery model development; and NiH2 experimental developments.

  14. Comparative ecology of H2 cycling in sedimentary and phototrophic ecosystems

    NASA Technical Reports Server (NTRS)

    Hoehler, Tori M.; Albert, Daniel B.; Alperin, Marc J.; Bebout, Brad M.; Martens, Christopher S.; Des Marais, David J.

    2002-01-01

    The simple biochemistry of H2 is critical to a large number of microbial processes, affecting the interaction of organisms with each other and with the environment. The sensitivity of each of these processes to H2 can be described collectively, through the quantitative language of thermodynamics. A necessary prerequisite is to understand the factors that, in turn, control H2 partial pressures. These factors are assessed for two distinctly different ecosystems. In anoxic sediments from Cape Lookout Bight (North Carolina, USA), H2 partial pressures are strictly maintained at low, steady-state levels by H2-consuming organisms, in a fashion that can be quantitatively predicted by simple thermodynamic calculations. In phototrophic microbial mats from Baja California (Mexico), H2 partial pressures are controlled by the activity of light-sensitive H2-producing organisms, and consequently fluctuate over orders of magnitude on a daily basis. The differences in H2 cycling can subsequently impact any of the H2-sensitive microbial processes in these systems. In one example, methanogenesis in Cape Lookout Bight sediments is completely suppressed through the efficient consumption of H2 by sulfate-reducing bacteria; in contrast, elevated levels of H2 prevail in the producer-controlled phototrophic system, and methanogenesis occurs readily in the presence of 40 mM sulfate.

  15. The Effect of H2O on Ice Photochemistry

    NASA Astrophysics Data System (ADS)

    Öberg, Karin I.; van Dishoeck, Ewine F.; Linnartz, Harold; Andersson, Stefan

    2010-08-01

    UV irradiation of simple ices is proposed to efficiently produce complex organic species during star formation and planet formation. Through a series of laboratory experiments, we investigate the effects of the H2O concentration, the dominant ice constituent in space, on the photochemistry of more volatile species, especially CH4, in ice mixtures. In the experiments, thin (~40 ML) ice mixtures, kept at 20-60 K, are irradiated under ultra-high vacuum conditions with a broadband UV hydrogen discharge lamp. Photodestruction cross sections of volatile species (CH4 and NH3) and production efficiencies of new species (C2H6, C2H4, CO, H2CO, CH3OH, CH3CHO, and CH3CH2OH) in water-containing ice mixtures are determined using reflection-absorption infrared spectroscopy during irradiation and during a subsequent slow warm-up. The four major effects of increasing the H2O concentration are: (1) an increase of the destruction efficiency of the volatile mixture constituent by up to an order of magnitude due to a reduction of back reactions following photodissociation, (2) a shift to products rich in oxygen, e.g., CH3OH and H2CO, (3) trapping of up to a factor of 5 more of the formed radicals in the ice, and (4) a disproportional increase in the diffusion barrier for the OH radical compared with the CH3 and HCO radicals. The radical diffusion temperature dependencies are consistent with calculated H2O-radical bond strengths. All the listed effects are potentially important for the production of complex organics in H2O-rich icy grain mantles around protostars and should thus be taken into account when modeling ice chemistry.

  16. CO-dependent H2 production by genetically engineered Thermococcus onnurineus NA1.

    PubMed

    Kim, Min-Sik; Bae, Seung Seob; Kim, Yun Jae; Kim, Tae Wan; Lim, Jae Kyu; Lee, Seong Hyuk; Choi, Ae Ran; Jeon, Jeong Ho; Lee, Jung-Hyun; Lee, Hyun Sook; Kang, Sung Gyun

    2013-03-01

    Hydrogenogenic CO oxidation (CO + H(2)O → CO(2) + H(2)) has the potential for H(2) production as a clean renewable fuel. Thermococcus onnurineus NA1, which grows on CO and produces H(2), has a unique gene cluster encoding the carbon monoxide dehydrogenase (CODH) and the hydrogenase. The gene cluster was identified as essential for carboxydotrophic hydrogenogenic metabolism by gene disruption and transcriptional analysis. To develop a strain producing high levels of H(2), the gene cluster was placed under the control of a strong promoter. The resulting mutant, MC01, showed 30-fold-higher transcription of the mRNA encoding CODH, hydrogenase, and Na(+)/H(+) antiporter and a 1.8-fold-higher specific activity for CO-dependent H(2) production than did the wild-type strain. The H(2) production potential of the MC01 mutant in a bioreactor culture was 3.8-fold higher than that of the wild-type strain. The H(2) production rate of the engineered strain was severalfold higher than those of any other CO-dependent H(2)-producing prokaryotes studied to date. The engineered strain also possessed high activity for the bioconversion of industrial waste gases created as a by-product during steel production. This work represents the first demonstration of H(2) production from steel mill waste gas using a carboxydotrophic hydrogenogenic microbe. PMID:23335765

  17. Hydrogen bonding in neutral and cation dimers of H2Se with H2O, H2S, and H2Se.

    PubMed

    Joshi, Ravi; Ghanty, Tapan K; Mukherjee, Tulsi; Naumov, Sergej

    2012-12-01

    Structures, hydrogen bonding, and binding energies of H(4)SeA (A = O, S, Se) dimers and their cation radicals have been studied using DFT-B3LYP, MP2, and CCSD methods with 6-31++G(d,p), cc-pVTZ, and aug-cc-pVTZ basis sets. The binding energy (BE) order of the most stable neutral and cationic dimers have been found to be (H(2)Se···HOH) > (H(2)Se···HSH) > (H(2)Se···HSeH), and (H(2)Se···SeH(2))(+) > (H(2)Se···SH(2))(+) > (HSe···HOH(2))(+), respectively, by B3LYP/6-31++G(d,p) and MP2/aug-cc-pVTZ methods. Higher electronegativity of the heteroatom has been found to result in more stability of the neutral dimer but less of the cationic dimer. Among neutral dimers, structure with more electronegative heteroatom acting as proton donor has been found to be more stable. However, the hemibonded structure has been found to be more stable for the dimer cation radical unless the ionization potentials of the involved heteroatoms are very different, e.g., H(4)SeO(+). Vibrational frequency calculation suggests that an increase in electronegativity of A-atom results in a decrease in Se-H bond strength in H(4)SeA and H(4)SeA(+) dimers. The calculated values of Mulliken atomic charge/spin and hydrogen bond lengths of the dimers and their radical cations have also been discussed. PMID:23134584

  18. Symmetric electron transfer reactions of state-selected ions: H 2+ + H 2H 2 + H 2+(ν= 0-10)

    NASA Astrophysics Data System (ADS)

    Cole, S. Keith; Baer, Tomas; Guyon, Paul M.; Govers, Thomas R.

    1984-08-01

    Total symmetric electron transfer cross sections for state-selected H 2+ ions were measured for vibrational levels of the ion from ν = 0 to 10 at a relative translational energy of 16 eV. The internal energy of the H 2+ ions was selected by threshold photoelectron—photoion coincidence using pulsed synchrotron radiation from the ACO storage ring at Orsay. The relative cross sections agree very well with the recent calculations of Lee and DePristo using a semiclassical energy conserving trajectory approach with an accurate diabatic interaction potential between the ion and neutral diatoms.

  19. H2 molecules and the intercloud medium

    NASA Technical Reports Server (NTRS)

    Hill, J. K.; Hollenbach, D. J.

    1976-01-01

    The paper discusses expected column densities of H2 in the intercloud medium and the possible use of molecules as indicators of intercloud physical conditions. Molecule formation by the H(-) process and on graphite grains is treated, and it is shown that the Barlow-Silk hypothesis of a 1-eV semichemical hydrogen-graphite bond leads to a large enhancement of the intercloud molecule-formation rate. Rotational-excitation calculations are presented for both cloud and intercloud conditions which show, in agreement with Jura (1975), that the presently observed optically thin H2 absorption components are more likely to originate in cold clouds than in the intercloud medium.

  20. The reactions of HO2 with CO and NO and the reaction of O(1D) with H2O

    NASA Technical Reports Server (NTRS)

    Simonaitis, R.; Heicklen, J.

    1973-01-01

    HO2 radicals were generated by the photolysis of N2O at 2139 A in the presence of excess H2O or H2 and smaller amounts of CO and O2. The O(1D) atoms produced from the photolysis of N2O to give HO radicals or H2 to give HO + H. With H2O two HO radicals are produced for each O(1D) removed low pressures (i.e. approximately 20 torr H2O), but the HO yield drops as the pressure is raised. This drop is attributed to the insertion reaction: O(1D) + H2O + M yields H2O2 +M. The HO radicals generated can react with either CO or H2 to produce H atoms which then add to O2 to produce HO2. Two reactions are given for the reactions of the HO radicals, in the absence of NO.

  1. Possible sources of H2 to H2O enrichment at evaporation of parent chondritic material

    NASA Technical Reports Server (NTRS)

    Makalkin, A. B.; Dorofeyeva, V. A.; Vityazev, A. V.

    1993-01-01

    One of the results obtained from thermodynamic simulation of recondensation of the source chondritic material is that at 1500-1800 K it's possible to form iron-rich olivine by reaction between enstatite, metallic iron and water vapor in the case of (H2O)/(H2) approximately equal to 0.1. This could be reached if the gas depletion in hydrogen is 200-300 times relative to solar abundance. To get this range of depletion one needs some source material more rich in hydrogen than the carbonaceous CI material which is the richest in volatiles among chondrites. In the case of recondensation at impact heating and evaporation of colliding planetesimals composed of CI material, we obtain insufficiently high value of (H2)/(H2O) ratio. In the present paper we consider some possible source materials and physical conditions necessary to reach gas composition with (H2)/(H2O) approximately 10 at high temperature.

  2. Near Infrared Spectra of H2O/HCN Mixtures

    NASA Technical Reports Server (NTRS)

    Mastrapa, R. M.; Bernstein, M. P.; Sanford, S. A.

    2006-01-01

    Cassini's VIMS has already returned exciting results interpreting spectra of Saturn's icy satellites. The discovery of unidentified features possibly due to CN compounds inspired the work reported here. We wanted to test HCN as a possibility for explaining these features, and also explore how the features of HCN change when mixed with H2O. We have previously noted that mixing H20 and CO2 produces new spectral features and that those features change with temperature and mixing ratio.

  3. TES/Aura L2 Water Vapor (H2O) Limb (TL2H2OLS)

    Atmospheric Science Data Center

    2015-01-30

    TES/Aura L2 Water Vapor (H2O) Limb (TL2H2OLS) News:  TES News ... Level:  L2 Platform:  TES/Aura L2 Water Vapor Spatial Coverage:  27 x 23 km Limb ... Access:  OPeNDAP Parameters:  H2O Water Volume Mixing Radio Precision Vertical Resolution Order ...

  4. Comparison of genes required for H2O2 resistance in Streptococcus gordonii and Streptococcus sanguinis

    PubMed Central

    Xu, Yifan; Itzek, Andreas

    2014-01-01

    Hydrogen peroxide (H2O2) is produced by several members of the genus Streptococcus mainly through the pyruvate oxidase SpxB under aerobic growth conditions. The acute toxic nature of H2O2 raises the interesting question of how streptococci cope with intrinsically produced H2O2, which subsequently accumulates in the microenvironment and threatens the closely surrounding population. Here, we investigate the H2O2 susceptibility of oral Streptococcus gordonii and Streptococcus sanguinis and elucidate potential mechanisms of how they protect themselves from the deleterious effect of H2O2. Both organisms are considered primary colonizers and occupy the same intraoral niche making them potential targets for H2O2 produced by other species. We demonstrate that S. gordonii produces relatively more H2O2 and has a greater ability for resistance to H2O2 stress. Functional studies show that, unlike in Streptococcus pneumoniae, H2O2 resistance is not dependent on a functional SpxB and confirms the important role of the ferritin-like DNA-binding protein Dps. However, the observed increased H2O2 resistance of S. gordonii over S. sanguinis is likely to be caused by an oxidative stress protection machinery present even under anaerobic conditions, while S. sanguinis requires a longer period of time for adaptation. The ability to produce more H2O2 and be more resistant to H2O2 might aid S. gordonii in the competitive oral biofilm environment, since it is lower in abundance yet manages to survive quite efficiently in the oral biofilm. PMID:25280752

  5. Ni(II) affects ubiquitination of core histones H2B and H2A

    SciTech Connect

    Karaczyn, Aldona A.; Golebiowski, Filip; Kasprzak, Kazimierz S. . E-mail: kasprkaz@mail.ncifcrf.gov

    2006-10-15

    The molecular mechanisms of nickel-induced malignant cell transformation include effects altering the structure and covalent modifications of core histones. Previously, we found that exposure of cells to Ni(II) resulted in truncation of histones H2A and H2B and thus elimination of some modification sites. Here, we investigated the effect of Ni(II) on one such modification, ubiquitination, of histones H2B and H2A in nuclei of cultured 1HAEo- and HPL1D human lung cells. After 1-5 days of exposure, Ni(II) up to 0.25 mM stimulated mono-ubiquitination of both histones, while at higher concentrations a suppression was found. Di-ubiquitination of H2A was not affected except for a drop after 5 days at 0.5 mM Ni(II). The decrease in mono-ubiquitination coincided with the appearance of truncated H2B that lacks the K120 ubiquitination site. However, prevention of truncation did not avert the decrease of H2B ubiquitination, indicating mechanistic independence of these effects. The changes in H2B ubiquitination did not fully coincide with concurrent changes in the nuclear levels of the ubiquitin-conjugating enzymes Rad6 and UbcH6. Overall, our results suggest that dysregulation of H2B ubiquitination is a part of Ni(II) adverse effects on gene expression and DNA repair which may assist in cell transformation.

  6. Search for H2COH+ and H2(13)CO in dense interstellar molecular clouds

    NASA Technical Reports Server (NTRS)

    Minh, Y. C.; Irvine, W. M.; McGonagle, D.

    1993-01-01

    We have searched for the 2 mm transitions of H2COH+ (2(02) - 1(01)) and H2(13)CO (2(02) - 1(01), 2(12) - 1(11), and 2(11) - 1(10)) toward the dense interstellar molecular clouds Orion A, TMC-1 and L134N using the FCRAO 14m telescope. None of the transitions have been detected except the H2(13)CO transitions toward Orion-KL. We set upper limits for the abundances of the protonated formaldehyde ion (H2COH+), which are close to the abundances expected from ion-molecule chemistry.

  7. A survey of extended H2 emission from massive YSOs

    NASA Astrophysics Data System (ADS)

    Navarete, F.; Damineli, A.; Barbosa, C. L.; Blum, R. D.

    2015-07-01

    We present the results from a survey, designed to investigate the accretion process of massive young stellar objects (MYSOs) through near-infrared narrow-band imaging using the H2 ν=1-0 S(1) transition filter. A sample of 353 MYSO candidates was selected from the Red MSX Source survey using photometric criteria at longer wavelengths (infrared and submillimetre) and chosen with positions throughout the Galactic plane. Our survey was carried out at the Southern Astrophysical Research Telescope Telescope in Chile and Canada-France-Hawaii Telescope in Hawaii covering both hemispheres. The data reveal that extended H2 emission is a good tracer of outflow activity, which is a signpost of accretion process on young massive stars. Almost half of the sample exhibit extended H2 emission and 74 sources (21 per cent) have polar morphology, suggesting collimated outflows. The polar-like structures are more likely to appear on radio-quiet sources, indicating these structures occur during the pre-UCH II phase. We also found an important fraction of sources associated with fluorescent H2 diffuse emission that could be due to a more evolved phase. The images also indicate only ˜23 per cent (80) of the sample is associated with extant (young) stellar clusters. These results support the scenario in which massive stars are formed by accretion discs, since the merging of low-mass stars would not produce outflow structures.

  8. Hot hydrogen atom reactions moderated by H2 and He

    NASA Technical Reports Server (NTRS)

    Aronowitz, S.; Scattergood, T.; Flores, J.; Chang, S.

    1986-01-01

    Photolysis experiments were performed on the H2-CD4-NH3 and He-CD4-NH3 systems. The photolysis (1849 A) involved only NH3. Mixtures of H2:CD4:NH3 included all combinations of the ratios (200,400,800):(10,20,40):4. Two He:CD4:NH3 mixtures were examined where the ratios equalled the combinations 100:(10,20):4. Abstraction of a D from CD4 by the photolytically produced hot hydrogen from ammonia was monitored by mass spectrometric determination of HD. Both experiment and semiempirical hot-atom theory show that H2 is a very poor thermalizer of hot hydrogens with excess kinetic energy of about 2 eV. Applications of the hard-sphere collision model to the H2-CD4-NH3 system resulted in predicted ratios of net HD production to NH3 decomposition that were two orders of magnitude smaller than the experimental ratios. On the other hand, helium is found to be a very efficient thermalizer; here, the classical model yields reasonable agreement with experiments. Application of a semiempirical hot-atom program gave quantitative agreement with experiment for either system.

  9. Advanced Colloids Experiment (ACE-H-2)

    NASA Technical Reports Server (NTRS)

    Meyer, William V.; Sicker, Ron; Chmiel, Alan J.; Eustace, John; LaBarbera, Melissa

    2015-01-01

    Increment 43 - 44 Science Symposium presentation of Advanced Colloids Experiment (ACE-H-2) to RPO. The purpose of this event is for Principal Investigators to present their science objectives, testing approach, and measurement methods to agency scientists, managers, and other investigators.

  10. EPA H2O User Manual

    EPA Science Inventory

    EPA H2O is a software tool designed to support research being conducted in the Tampa Bay watershed to provide information, data, and approaches and guidance that communities can use to examine alternatives when making strategic decisions to support a prosperous and environmentall...

  11. EPA H2O Software Tool

    EPA Science Inventory

    EPA H2O allows user to: Understand the significance of EGS in Tampa Bay watershed; visually analyze spatial distribution of the EGS in Tampa Bay watershed; obtain map and summary statistics of EGS values in Tampa Bay watershed; analyze and compare potential impacts of development...

  12. Constraining the ortho-to-para ratio of H2 with anomalous H_2CO absorption

    NASA Astrophysics Data System (ADS)

    Troscompt, N.; Faure, A.; Maret, S.; Ceccarelli, C.; Hily-Blant, P.; Wiesenfeld, L.

    2009-11-01

    Context: The ortho-to-para ratio (OPR) of molecular hydrogen is a fundamental parameter in understanding the physics and chemistry of molecular clouds. In dark and cold regions, however, H2 is not directly observable and the OPR of H2 in these sources has so far remained elusive. Aims: We show that the 6 cm absorption line of ortho-formaldehyde (H2CO) can be employed to constrain both the density and the OPR of H2 in dark clouds. Methods: Green Bank Telescope (GBT) observations of ortho-H2CO toward the molecular cloud Barnard 68 (B68) are reported. Non-LTE radiative transfer calculations combined with the well-constrained structure of B68 are then employed to derive the physical conditions in the absorption region. Results: We provide the first firm confirmation of the Townes & Cheung mechanism: propensity rules for the collisions of H2CO with H2 molecules are responsible for the sub-2.7 K cooling of the 6 cm doublet. Non-LTE calculations show that in the absorption region of B68, the kinetic temperature is ˜ 10 K, the ortho-H2CO column density amounts to ˜ 2.2× 1013 cm-2, the H2 density is in the range 1.4{-}2.4× 10 4 cm-3, and the OPR of H2 is close to zero. Our observations thus provide fresh evidence that H2 is mostly in its para form in the cold gas, as expected from theoretical considerations. Our results also suggest that formaldehyde absorption originates in the edge of B68, at visual extinctions A_V⪉ 0.5 mag. This work has been inspired by our colleague and friend Pierre Valiron, who passed away in August 2008. This paper is dedicated to his memory.

  13. Comparative Ecology of H2 Cycling in Organotrophic and Phototrophic Ecosystems

    NASA Technical Reports Server (NTRS)

    Hoehler, Tori M.; Alperin, Marc J.; Albert, Daniel B.; Bebout, Brad M.; Martens, Christopher S.; DesMarais, David J.; DeVincenzi, Don (Technical Monitor)

    2001-01-01

    The simple biochemistry of H2 is critical to a large number of microbial processes, affecting the interaction of organisms with each other and with the environment. The sensitivity of these many processes to H2 can be described quantitatively, at a basic thermodynamic level. This shared dependence on H2 may provide a means for interpreting the ecology and system-level biogeochemistry of widely variant microbial ecosystems on a common (and quantitative) level. Understanding the factors that control H2 itself is a critical prerequisite. Here, we examine two ecosystems that vary widely with respect to H2 cycling. In anoxic, 'organotrophic' sediments from Cape Lookout Bight (North Carolina, USA), H2 partial pressures are strictly maintained at low, steady-state levels by H2-consuming organisms, in a fashion that can be quantitatively predicted by simple thermodynamic calculations. In phototrophic microbial mats from Baja, Mexico, H2 partial pressures are instead controlled by the activity of light-sensitive H2-producing organisms. In consequence, H2 partial pressures within the system fluctuate by orders of magnitude on hour-long time scales. The differences in H2 cycling subsequently impact H2-sensitive microbial processes, such as methanogenesis. For example, the presence of sulfate in the organotrophic system always yielded low levels of H2 that were inhibitory to methanogenesis; however, the elevated levels of H2 in the phototrophic system favored methane production at significant levels, even in the presence of high sulfate concentrations. The myriad of other H2-sensitive microbial processes are expected to exhibit similar behavior.

  14. Reduced Glutathione Mediates Resistance to H2S Toxicity in Oral Streptococci.

    PubMed

    Ooi, Xi Jia; Tan, Kai Soo

    2016-01-01

    Periodontal disease is associated with changes in the composition of the oral microflora, where health-associated oral streptococci decrease while Gram-negative anaerobes predominate in disease. A key feature of periodontal disease-associated anaerobes is their ability to produce hydrogen sulfide (H2S) abundantly as a by-product of anaerobic metabolism. So far, H2S has been reported to be either cytoprotective or cytotoxic by modulating bacterial antioxidant defense systems. Although oral anaerobes produce large amounts of H2S, the potential effects of H2S on oral streptococci are currently unknown. The aim of this study was to determine the effects of H2S on the survival and biofilm formation of oral streptococci. The growth and biofilm formation of Streptococcus mitis and Streptococcus oralis were inhibited by H2S. However, H2S did not significantly affect the growth of Streptococcus gordonii or Streptococcus sanguinis. The differential susceptibility of oral streptococci to H2S was attributed to differences in the intracellular concentrations of reduced glutathione (GSH). In the absence of GSH, H2S elicited its toxicity through an iron-dependent mechanism. Collectively, our results showed that H2S exerts antimicrobial effects on certain oral streptococci, potentially contributing to the decrease in health-associated plaque microflora. PMID:26801579

  15. Test summary for advanced H2 cycle NI-CD cell

    NASA Technical Reports Server (NTRS)

    Miller, Lee

    1987-01-01

    To improve operational tolerances and mass, the H2 gas recombination design provisions of the Ni-H2 system were incorporated into the sealed Ni-Cd system. Produced is a cell design capable of operating on the H2 cycle versus the normal O2 cycle. Three test cells have now completed approximately 4,330 LEO (90 minute) cycles at 20 percent depth of discharge (DOD). Performance remains stable although one cell exhibited a temporary pressure anomaly.

  16. TES/Aura L2 Water Vapor (H2O) Nadir (TL2H2ON)

    Atmospheric Science Data Center

    2015-01-30

    TES/Aura L2 Water Vapor (H2O) Nadir (TL2H2ON) News:  TES News ... Title:  TES Discipline:  Tropospheric Chemistry Level:  L2 Instrument:  TES/Aura L2 Water Vapor Spatial Coverage:  5.3 x 8.5 km nadir ...

  17. TES/Aura L2 Water Vapor (H2O) Nadir (TL2H2ONS)

    Atmospheric Science Data Center

    2015-01-30

    TES/Aura L2 Water Vapor (H2O) Nadir (TL2H2ONS) News:  TES News ... Title:  TES Discipline:  Tropospheric Chemistry Level:  L2 Platform:  TES/Aura L2 Water Vapor Spatial Coverage:  5.3 8.5 km nadir ...

  18. Formation of low-temperature cirrus from H2SO4/H2O aerosol droplets.

    PubMed

    Bogdan, A; Molina, M J; Sassen, K; Kulmala, M

    2006-11-23

    We present experimental results obtained with a differential scanning calorimeter (DSC) that indicate the small ice particles in low-temperature cirrus clouds are not completely solid but rather coated with an unfrozen H2SO4/H2O overlayer. Our results provide a new look on the formation, development, and microphysical properties of low-temperature cirrus clouds. PMID:17107102

  19. Enhancement of atmospheric H2SO4 / H2O nucleation: organic oxidation products versus amines

    NASA Astrophysics Data System (ADS)

    Berndt, T.; Sipilä, M.; Stratmann, F.; Petäjä, T.; Vanhanen, J.; Mikkilä, J.; Patokoski, J.; Taipale, R.; Mauldin, R. L., III; Kulmala, M.

    2014-01-01

    Atmospheric H2SO4 / H2O nucleation influencing effects have been studied in the flow tube IfT-LFT (Institute for Tropospheric Research - Laminar Flow Tube) at 293 ± 0.5 K and a pressure of 1 bar using synthetic air as the carrier gas. The presence of a possible background amine concentration in the order of 107-108 molecule cm-3 throughout the experiments has to be taken into account. In a first set of investigations, ozonolysis of olefins (tetramethylethylene, 1-methyl-cyclohexene, α-pinene and limonene) for close to atmospheric concentrations, served as the source of OH radicals and possibly other oxidants initiating H2SO4 formation starting from SO2. The oxidant generation is inevitably associated with the formation of organic oxidation products arising from the parent olefins. These products (first generation mainly) showed no clear effect on the number of nucleated particles within a wide range of experimental conditions for H2SO4 concentrations higher than ~107 molecule cm-3. Also the early growth process of the nucleated particles was not significantly influenced by the organic oxidation products in line with the expected growth by organic products using literature data. An additional, H2SO4-independent process of particle (nano-CN) formation was observed in the case of α-pinene and limonene ozonolysis for H2SO4 concentrations smaller than ~107 molecule cm-3. Furthermore, the findings confirm the appearance of an additional oxidant for SO2 beside OH radicals, very likely stabilized Criegee Intermediates (sCI). A second set of experiments has been performed in the presence of added amines in the concentrations range of a few 107-1010 molecule cm-3 applying photolytic OH radical generation for H2SO4 production without addition of other organics. All amines showed significant nucleation enhancement with increasing efficiency in the order pyridine < aniline < dimethylamine < trimethylamine. This result supports the idea of H2SO4 cluster stabilization by

  20. The Successive H2O Binding Energies for Fe(H2O)n(+)

    NASA Technical Reports Server (NTRS)

    Ricca, Alessandra; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R. (Technical Monitor)

    1994-01-01

    The binding energy, computed using density functional theory (DFT), are in good agreement with experiment. The bonding is electrostatic (charge-dipole) in origin for all systems. The structures are therefore determined mostly by metal-ligand and ligand-ligand repulsion. The computed structure for FeH2O(+) is C(2v) where sp hybridization is important in reducing the Fe-H2O repulsion. Fe(H2O)2(+) has D2d symmetry where sdo hybridization is the primary factor leading to the linear O-Fe-O geometry. The bonding in Fe(H2O)3(+) and Fe(H2O)4(+) are very complex because ligand-ligand and metal-ligand repulsion, both for the in-plane and out-of-plane water lone-pair orbitals, are important.

  1. Reactive collisions of atomic antihydrogen with the H2 and H2+ molecules

    NASA Astrophysics Data System (ADS)

    Cohen, James S.

    2006-09-01

    The fermion molecular dynamics (FMD) method is used to determine the protonium (Pn) formation and total destruction cross sections for collisions of antihydrogen (\\bar{H}) with the H2 molecule and the H2+ molecular ion at collision energies above 0.1 au in the centre-of-mass system. The cross sections and initial quantum numbers are compared with the analogous cross sections for \\bar{H}+H, \\barp+H, \\barp+H_2 and \\barp+H_2^+ previously calculated. Like the \\barp projectile, the protonium-formation cross sections for the \\bar{H} projectile are much larger and extend to higher energies with the molecular targets than with the atomic target. The possibility is considered that a relatively long-lived state of the \\bar{H}H molecule may be formed in rearrangement scattering of \\bar{H}+H_2 at low energies.

  2. Intimin gene (eae) subtype-based real-time PCR strategy for specific detection of Shiga toxin-producing Escherichia coli serotypes O157:H7, O26:H11, O103:H2, O111:H8, and O145:H28 in cattle feces.

    PubMed

    Bibbal, Delphine; Loukiadis, Estelle; Kérourédan, Monique; Peytavin de Garam, Carine; Ferré, Franck; Cartier, Philippe; Gay, Emilie; Oswald, Eric; Auvray, Frédéric; Brugère, Hubert

    2014-02-01

    Shiga toxin-producing Escherichia coli (STEC) strains belonging to serotypes O157:H7, O26:H11, O103:H2, O111:H8, and O145:H28 are known to be associated with particular subtypes of the intimin gene (eae), namely, γ1, β1, ε, θ, and γ1, respectively. This study aimed at evaluating the usefulness of their detection for the specific detection of these five main pathogenic STEC serotypes in cattle feces. Using real-time PCR assays, 58.7% of 150 fecal samples were found positive for at least one of the four targeted eae subtypes. The simultaneous presence of stx, eae, and one of the five O group markers was found in 58.0% of the samples, and the five targeted stx plus eae plus O genetic combinations were detected 143 times. However, taking into consideration the association between eae subtypes and O group markers, the resulting stx plus eae subtype plus O combinations were detected only 46 times. The 46 isolation assays performed allowed recovery of 22 E. coli strains belonging to one of the five targeted STEC serogroups. In contrast, only 2 of 39 isolation assays performed on samples that were positive for stx, eae and an O group marker, but that were negative for the corresponding eae subtype, were successful. Characterization of the 24 E. coli isolates showed that 6 were STEC, including 1 O157:H7, 3 O26:H11, and 2 O145:H28. The remaining 18 strains corresponded to atypical enteropathogenic E. coli (aEPEC). Finally, the more discriminating eae subtype-based PCR strategy described here may be helpful for the specific screening of the five major STEC in cattle feces. PMID:24296503

  3. Orion's Veil. IV. H2 Excitation and Geometry

    NASA Astrophysics Data System (ADS)

    Abel, N. P.; Ferland, G. J.; O'Dell, C. R.; Troland, T. H.

    2016-03-01

    The foreground Veil of material that lies in front of the Orion Nebula is the best studied sample of the interstellar medium because we know where it is located, how it is illuminated, and the balance of thermal and magnetic energy. In this work, we present high-resolution STIS observations toward the Trapezium, with the goal of better understanding the chemistry and geometry of the two primary Veil layers, along with ionized gas along the line of sight. The most complete characterization of the rotational/vibrational column densities of H2 in the almost purely atomic components of the Veil are presented, including updates to the Cloudy model for H2 formation on grain surfaces. The observed H2 is found to correlate almost exclusively with Component B. The observed H2, observations of CI, CI*, and CI**, and theoretical calculations using Cloudy allow us to place the tightest constraints yet on the distance, density, temperature, and other physical characteristics for each cloud component. We find the H2 excitation spectrum observed in the Veil is incompatible with a recent study that argued that the Veil was quite close to the Trapezium. The nature of a layer of ionized gas lying between the Veil and the Trapezium is characterized through the emission and absorption lines it produces, which we find to be the blueshifted component observed in S iii and P iii absorption. We deduce that, within the next 30-60 thousand years, the blueshifted ionized layer and Component B will merge, which will subsequently merge with Component A in the next one million years.

  4. H2S during circulatory shock: some unresolved questions.

    PubMed

    McCook, Oscar; Radermacher, Peter; Volani, Chiara; Asfar, Pierre; Ignatius, Anita; Kemmler, Julia; Möller, Peter; Szabó, Csaba; Whiteman, Matthew; Wood, Mark E; Wang, Rui; Georgieff, Michael; Wachter, Ulrich

    2014-09-15

    Numerous papers have been published on the role of H2S during circulatory shock. Consequently, knowledge about vascular sulfide concentrations may assume major importance, in particular in the context of "acute on chronic disease", i.e., during circulatory shock in animals with pre-existing chronic disease. This review addresses the questions (i) of the "real" sulfide levels during circulatory shock, and (ii) to which extent injury and pre-existing co-morbidity may affect the expression of H2S producing enzymes under these conditions. In the literature there is a huge range on sulfide blood levels during circulatory shock, in part as a result of the different analytical methods used, but also due to the variable of the models and species studied. Clearly, some of the very high levels reported should be questioned in the context of the well-known H2S toxicity. As long as "real" sulfide levels during circulatory shock are unknown and/or undetectable "on line" due to the lack of appropriate techniques, it appears to be premature to correlate the measured blood levels of hydrogen sulfide with the severity of shock or the H2S therapy-related biological outcomes. The available data on the tissue expression of the H2S-releasing enzymes during circulatory shock suggest that a "constitutive" CSE expression may play a crucial role of for the maintenance of organ function, at least in the kidney. The data also indicate that increased CBS and CSE expression, in particular in the lung and the liver, represents an adaptive response to stress states. PMID:24650697

  5. H2S during circulatory shock: Some unresolved questions

    PubMed Central

    McCook, Oscar; Radermacher, Peter; Volani, Chiara; Asfar, Pierre; Ignatius, Anita; Kemmler, Julia; Möller, Peter; Szabó, Csaba; Whiteman, Matthew; Wood, Mark E.; Wang, Rui; Georgieff, Michael; Wachter, Ulrich

    2014-01-01

    Numerous papers have been published on the role of H2S during circulatory shock. Consequently, knowledge about vascular sulfide concentrations may assume major importance, in particular in the context of “acute on chronic disease”, i.e., during circulatory shock in animals with pre-existing chronic disease. This review addresses the questions i) of the “real” sulfide levels during circulatory shock, and, ii) to which extent injury and pre-existing co-morbidity may affect the expression of H2S producing enzymes under these conditions. In the literature there is a huge range on sulfide blood levels during circulatory shock, in part as a result of the different analytical methods used, but also due to the variable of the models and species studied. Clearly, some of the very high levels reported should be questioned in the context of the well-known H2S toxicity. As long as “real” sulfide levels during circulatory shock are unknown and/or undetectable “on line” due to the lack of appropriate techniques, it appears to be premature to correlate the measured blood levels of hydrogen sulfide with the severity of shock or the H2S therapy-related biological outcomes. The available data on the tissue expression of the H2S-releasing enzymes during circulatory shock suggest that a “constitutive” CSE expression may play a crucial role of for the maintenance of organ function, at least in the kidney. The data also indicate that increased CBS and CSE expression, in particular in the lung and the liver, represents an adaptive response to stress states. PMID:24650697

  6. Thermodynamics and H2 Transfer in a Methanogenic, Syntrophic Community

    PubMed Central

    Hamilton, Joshua J.; Calixto Contreras, Montserrat; Reed, Jennifer L.

    2015-01-01

    Microorganisms in nature do not exist in isolation but rather interact with other species in their environment. Some microbes interact via syntrophic associations, in which the metabolic by-products of one species serve as nutrients for another. These associations sustain a variety of natural communities, including those involved in methanogenesis. In anaerobic syntrophic communities, energy is transferred from one species to another, either through direct contact and exchange of electrons, or through small molecule diffusion. Thermodynamics plays an important role in governing these interactions, as the oxidation reactions carried out by the first community member are only possible because degradation products are consumed by the second community member. This work presents the development and analysis of genome-scale network reconstructions of the bacterium Syntrophobacter fumaroxidans and the methanogenic archaeon Methanospirillum hungatei. The models were used to verify proposed mechanisms of ATP production within each species. We then identified additional constraints and the cellular objective function required to match experimental observations. The thermodynamic S. fumaroxidans model could not explain why S. fumaroxidans does not produce H2 in monoculture, indicating that current methods might not adequately estimate the thermodynamics, or that other cellular processes (e.g., regulation) play a role. We also developed a thermodynamic coculture model of the association between the organisms. The coculture model correctly predicted the exchange of both H2 and formate between the two species and suggested conditions under which H2 and formate produced by S. fumaroxidans would be fully consumed by M. hungatei. PMID:26147299

  7. Fluorescent excitation of interstellar H2

    NASA Technical Reports Server (NTRS)

    Black, John H.; Van Dishoeck, Ewine F.

    1987-01-01

    The infrared emission spectrum of H2 excited by ultraviolet absorption, followed by fluorescence, was investigated using comprehensive models of interstellar clouds for computing the spectrum and to assess the effects on the intensity to various cloud properties, such as density, size, temperature, and the intensity of the UV radiation field. It is shown that the absolute H2 IR line intensities depend primarily on the density of the cloud and the strength of the incident UV radiation, and to a much lesser exent on the temperature of the gas, the total thickness of the cloud, and the optical properties of the grains. A variety of recent observational results are discussed with reference to theoretical models. It is shown that the rich H2 emission spectrum of the reflection nebula NGC 2023 can be reproduced by a model with density of about 10,000/cu cm, temperature of about 80 K, and UV flux approximately 300 times that of the Galactic background starlight.

  8. Modelling of OH production in cold atmospheric-pressure He-H2O plasma jets

    NASA Astrophysics Data System (ADS)

    Naidis, G. V.

    2013-06-01

    Results of the modelling of OH production in the plasma bullet mode of cold atmospheric-pressure He-H2O plasma jets are presented. It is shown that the dominant source of OH molecules is related to the Penning and charge transfer reactions of H2O molecules with excited and charged helium species produced by guided streamers (plasma bullets), in contrast to the case of He-H2O glow discharges where OH production is mainly due to the dissociation of H2O molecules by electron impact.

  9. Thermodynamics of formate-oxidizing metabolism and implications for H2 production.

    PubMed

    Lim, Jae Kyu; Bae, Seung Seob; Kim, Tae Wan; Lee, Jung-Hyun; Lee, Hyun Sook; Kang, Sung Gyun

    2012-10-01

    Formate-dependent proton reduction to H(2) (HCOO(-) + H(2)O → HCO(3)(-) + H(2)) has been reported for hyperthermophilic Thermococcus strains. In this study, a hyperthermophilic archaeon, Thermococcus onnurineus strain NA1, yielded H(2) accumulation to a partial pressure of 1 × 10(5) to 7 × 10(5) Pa until the values of Gibbs free energy change (ΔG) reached near thermodynamic equilibrium (-1 to -3 kJ mol(-1)). The bioenergetic requirement for the metabolism to conserve energy was demonstrated by ΔG values as small as -5 kJ mol(-1), which are less than the biological minimum energy quantum, -20 kJ mol(-1), as calculated by Schink (B. Schink, Microbiol. Mol. Biol. Rev. 61:262-280, 1997). Considering formate as a possible H(2) storage material, the H(2) production potential of the strain was assessed. The volumetric H(2) production rate increased linearly with increasing cell density, leading to 2,820 mmol liter(-1) h(-1) at an optical density at 600 nm (OD(600)) of 18.6, and resulted in the high specific H(2) production rates of 404 ± 6 mmol g(-1) h(-1). The H(2) productivity indicates the great potential of T. onnurineus strain NA1 for practical application in comparison with H(2)-producing microbes. Our result demonstrates that T. onnurineus strain NA1 has a highly efficient metabolic system to thrive on formate in hydrothermal systems. PMID:22885755

  10. Synthesis and Anti-Candida Activity of Cobalt(II) Complexes of Benzene-1,2-Dioxyacetic Acid (bdoaH2). X-Ray Crystal Structures of [Co(bdoa)(H2O)3] ⋅3.5H2O and {[CO(phen)3](bdoa)}2⋅24H2O (phen = 1,10-Phenanthroline)

    PubMed Central

    Geraghty, Majella; McCann, Malachy; Devereux, Michael; Cronin, Fergal; Curran, Martin; McKee, Vickie

    1999-01-01

    Co(CH3CO2)2⋅4H2O reacts with benzene-1,2-dioxyacetic acid (bdoaH2) to give the Co2+ complexes [Co(bdoa)(H2O)3]⋅H2O (1a) and [Co(bdoa)(H2O)3] ⋅3.5H2O (1b). Subsequent reaction of 1a with 1,10- phenanthroline produces [CO(phen)3] bdoa⋅10H2O (2a) and {[CO(phen)3](bdoa)}2⋅24H2O (2b). Molecular structures of 1b and 2b were determined crystallographically. In 1b the bdoa2-- ligates the metal by two carboxylate oxygens and two ethereal oxygens, whereas in 2b the bdoa2- is uncoordinated. The Mn2+ and Cu2+ complexes [Mn(bdoa)(phen)2]⋅H2O (3) and [Cu(pdoa)(imid)2] (4) were also synthesised, 1a-4 and other metal complexes of bdoa H2 (metal = Mn2+, Co2+ ,Cu2+, Cu+ ) were screened for their ability to inhibit the growth ofhe yeast Candida albicans. Complexes incorporating the 1,10-phenanthroline ligand were the most active. PMID:18475879

  11. Thermodynamics of Formate-Oxidizing Metabolism and Implications for H2 Production

    PubMed Central

    Lim, Jae Kyu; Bae, Seung Seob; Kim, Tae Wan; Lee, Jung-Hyun

    2012-01-01

    Formate-dependent proton reduction to H2 (HCOO− + H2O → HCO3− + H2) has been reported for hyperthermophilic Thermococcus strains. In this study, a hyperthermophilic archaeon, Thermococcus onnurineus strain NA1, yielded H2 accumulation to a partial pressure of 1 × 105 to 7 × 105 Pa until the values of Gibbs free energy change (ΔG) reached near thermodynamic equilibrium (−1 to −3 kJ mol−1). The bioenergetic requirement for the metabolism to conserve energy was demonstrated by ΔG values as small as −5 kJ mol−1, which are less than the biological minimum energy quantum, −20 kJ mol−1, as calculated by Schink (B. Schink, Microbiol. Mol. Biol. Rev. 61:262-280, 1997). Considering formate as a possible H2 storage material, the H2 production potential of the strain was assessed. The volumetric H2 production rate increased linearly with increasing cell density, leading to 2,820 mmol liter−1 h−1 at an optical density at 600 nm (OD600) of 18.6, and resulted in the high specific H2 production rates of 404 ± 6 mmol g−1 h−1. The H2 productivity indicates the great potential of T. onnurineus strain NA1 for practical application in comparison with H2-producing microbes. Our result demonstrates that T. onnurineus strain NA1 has a highly efficient metabolic system to thrive on formate in hydrothermal systems. PMID:22885755

  12. Hydrogen peroxide (H2O2) controls axon pathfinding during zebrafish development.

    PubMed

    Gauron, Carole; Meda, Francesca; Dupont, Edmond; Albadri, Shahad; Quenech'Du, Nicole; Ipendey, Eliane; Volovitch, Michel; Del Bene, Filippo; Joliot, Alain; Rampon, Christine; Vriz, Sophie

    2016-06-15

    It is now becoming evident that hydrogen peroxide (H2O2), which is constantly produced by nearly all cells, contributes to bona fide physiological processes. However, little is known regarding the distribution and functions of H2O2 during embryonic development. To address this question, we used a dedicated genetic sensor and revealed a highly dynamic spatio-temporal pattern of H2O2 levels during zebrafish morphogenesis. The highest H2O2 levels are observed during somitogenesis and organogenesis, and these levels gradually decrease in the mature tissues. Biochemical and pharmacological approaches revealed that H2O2 distribution is mainly controlled by its enzymatic degradation. Here we show that H2O2 is enriched in different regions of the developing brain and demonstrate that it participates to axonal guidance. Retinal ganglion cell axonal projections are impaired upon H2O2 depletion and this defect is rescued by H2O2 or ectopic activation of the Hedgehog pathway. We further show that ex vivo, H2O2 directly modifies Hedgehog secretion. We propose that physiological levels of H2O2 regulate RGCs axonal growth through the modulation of Hedgehog pathway. PMID:27158028

  13. H-2b bound to egg lecithin liposomes: biochemical and functional properties.

    PubMed Central

    Rogers, M J

    1982-01-01

    Purified H-2b and H-2a molecules were bound to egg lecithin liposomes by a detergent dialysis procedure. Analysis of the liposomes indicated that only 30-50% of bound H-2b is oriented with the hydrophilic, antigenic portion of the molecule toward the outside of the liposome. Saturation of the liposomes occurred at a ratio of 64 molecules of egg lecithin per molecule of H-2b. Liposomes containing H-2 molecules were capable of stimulating spleen cells from primed donors to produce specific, alloreactive, cytotoxic T lymphocytes in vitro. Stimulation was dependent on adherent cells present in the responder spleen cells. Optimal stimulation occurred with highly saturated liposomes and at a ratio of 4-8 micrograms of H-2b per 8 X 10(6) responder cells. Images Fig. 4 PMID:7116686

  14. Far-infrared absorption in H2 and H2-He mixtures

    NASA Technical Reports Server (NTRS)

    Birnbaum, G.

    1978-01-01

    Collision-induced absorption in the translation-rotation band of H2 and H2-He mixtures has been measured from 20 to 900 kaysers at 77.4, 195, and 292 K. To establish the accuracy of the results, various sources of error are investigated. The zeroth and first spectral moments are evaluated from experiment and theory for H2 at the various temperatures. To obtain theoretical moments consistent with the experimental values, the quantum pair-distribution function must be used. The major portion of the experimental moments can be accounted for by quadrupole-induced dipoles in H2 pairs. The remaining portion is attributable to an anisotropic overlap interaction, although its magnitude depends on the value of the molecular parameters required to calculate the quadrupole contribution.

  15. Wave-function inspired density functional applied to the H2/{{\\rm{H}}}_{2}^{+} challenge

    NASA Astrophysics Data System (ADS)

    Zhang, Igor Ying; Rinke, Patrick; Scheffler, Matthias

    2016-07-01

    We start from the Bethe–Goldstone equation (BGE) to derive a simple orbital-dependent correlation functional—BGE2—which terminates the BGE expansion at the second-order, but retains the self-consistent coupling of electron-pair correlations. We demonstrate that BGE2 is size consistent and one-electron ‘self-correlation’ free. The electron-pair correlation coupling ensures the correct H2 dissociation limit and gives a finite correlation energy for any system even if it has a no energy gap. BGE2 provides a good description of both H2 and {{{H}}}2+ dissociation, which is regarded as a great challenge in density functional theory (DFT). We illustrate the behavior of BGE2 analytically by considering H2 in a minimal basis. Our analysis shows that BGE2 captures essential features of the adiabatic connection path that current state-of-the-art DFT approximations do not.

  16. Comparison of the efficiency of *OH radical formation during ozonation and the advanced oxidation processes O3/H2O2 and UV/H2O2.

    PubMed

    Rosenfeldt, Erik J; Linden, Karl G; Canonica, Silvio; von Gunten, Urs

    2006-12-01

    Comparison of advanced oxidation processes (AOPs) can be difficult due to physical and chemical differences in the fundamental processes used to produce OH radicals. This study compares the ability of several AOPs, including ozone, ozone+H2O2, low pressure UV (LP)+H2O2, and medium pressure UV (MP)+H2O2 in terms of energy required to produce OH radicals. Bench scale OH radical formation data was generated for each AOP using para-chlorobenzoic acid (pCBA) as an OH radical probe compound in three waters, Lake Greifensee water, Lake Zurich water, and a simulated groundwater. Ozone-based AOPs were found to be more energy efficient than the UV/H2O2 process at all H2O2 levels, and the addition of H2O2 in equimolar concentration resulted in 35% greater energy consumption over the ozone only process. Interestingly, the relatively high UV/AOP operational costs were due almost exclusively to the cost of hydrogen peroxide while the UV portion of the UV/AOP process typically accounted for less than 10 percent of the UV/AOP cost and was always less than the ozone energy cost. As the *OH radical exposure increased, the energy gap between UV/H2O2 AOP and ozone processes decreased, becoming negligible in some water quality scenarios. PMID:17078993

  17. The contribution of the Precambrian continental lithosphere to global H2 production.

    PubMed

    Lollar, Barbara Sherwood; Onstott, T C; Lacrampe-Couloume, G; Ballentine, C J

    2014-12-18

    Microbial ecosystems can be sustained by hydrogen gas (H2)-producing water-rock interactions in the Earth's subsurface and at deep ocean vents. Current estimates of global H2 production from the marine lithosphere by water-rock reactions (hydration) are in the range of 10(11) moles per year. Recent explorations of saline fracture waters in the Precambrian continental subsurface have identified environments as rich in H2 as hydrothermal vents and seafloor-spreading centres and have suggested a link between dissolved H2 and the radiolytic dissociation of water. However, extrapolation of a regional H2 flux based on the deep gold mines of the Witwatersrand basin in South Africa yields a contribution of the Precambrian lithosphere to global H2 production that was thought to be negligible (0.009 × 10(11) moles per year). Here we present a global compilation of published and new H2 concentration data obtained from Precambrian rocks and find that the H2 production potential of the Precambrian continental lithosphere has been underestimated. We suggest that this can be explained by a lack of consideration of additional H2-producing reactions, such as serpentinization, and the absence of appropriate scaling of H2 measurements from these environments to account for the fact that Precambrian crust represents over 70 per cent of global continental crust surface area. If H2 production via both radiolysis and hydration reactions is taken into account, our estimate of H2 production rates from the Precambrian continental lithosphere of 0.36-2.27 × 10(11) moles per year is comparable to estimates from marine systems. PMID:25519136

  18. The contribution of the Precambrian continental lithosphere to global H2 production

    NASA Astrophysics Data System (ADS)

    Lollar, Barbara Sherwood; Onstott, T. C.; Lacrampe-Couloume, G.; Ballentine, C. J.

    2014-12-01

    Microbial ecosystems can be sustained by hydrogen gas (H2)-producing water-rock interactions in the Earth's subsurface and at deep ocean vents. Current estimates of global H2 production from the marine lithosphere by water-rock reactions (hydration) are in the range of 1011 moles per year. Recent explorations of saline fracture waters in the Precambrian continental subsurface have identified environments as rich in H2 as hydrothermal vents and seafloor-spreading centres and have suggested a link between dissolved H2 and the radiolytic dissociation of water. However, extrapolation of a regional H2 flux based on the deep gold mines of the Witwatersrand basin in South Africa yields a contribution of the Precambrian lithosphere to global H2 production that was thought to be negligible (0.009 × 1011 moles per year). Here we present a global compilation of published and new H2 concentration data obtained from Precambrian rocks and find that the H2 production potential of the Precambrian continental lithosphere has been underestimated. We suggest that this can be explained by a lack of consideration of additional H2-producing reactions, such as serpentinization, and the absence of appropriate scaling of H2 measurements from these environments to account for the fact that Precambrian crust represents over 70 per cent of global continental crust surface area. If H2 production via both radiolysis and hydration reactions is taken into account, our estimate of H2 production rates from the Precambrian continental lithosphere of 0.36-2.27 × 1011 moles per year is comparable to estimates from marine systems.

  19. Refinements in an Mg/MgH2/H2O-Based Hydrogen Generator

    NASA Technical Reports Server (NTRS)

    Kindler, Andrew; Huang, Yuhong

    2010-01-01

    Some refinements have been conceived for a proposed apparatus that would generate hydrogen (for use in a fuel cell) by means of chemical reactions among magnesium, magnesium hydride, and steam. The refinements lie in tailoring spatial and temporal distributions of steam and liquid water so as to obtain greater overall energy-storage or energy-generation efficiency than would otherwise be possible. A description of the prior art is prerequisite to a meaningful description of the present refinements. The hydrogen-generating apparatus in question is one of two versions of what was called the "advanced hydrogen generator" in "Fuel-Cell Power Systems Incorporating Mg-Based H2 Generators" (NPO-43554), NASA Tech Briefs, Vol. 33, No. 1 (January 2009), page 52. To recapitulate: The apparatus would include a reactor vessel that would be initially charged with magnesium hydride. The apparatus would exploit two reactions: The endothermic decomposition reaction MgH2-->Mg + H2, which occurs at a temperature greater than or equal to 300 C, and The exothermic oxidation reaction MgH2 + H2O MgO + 2H2, which occurs at a temperature greater than or equal to 330 C.

  20. Spontaneous H2 loss through the interaction of squaric acid derivatives and BeH2.

    PubMed

    Montero-Campillo, M Merced; Yáñez, Manuel; Lamsabhi, Al Mokhtar; Mó, Otilia

    2014-04-25

    The most stable complexes between squaric acid and its sulfur- and selenium-containing analogues (C4X4H2 ; X = O, S, Se) with BeY2 (Y = H, F) were studied by means of the Gaussian 04 (G4) composite ab initio theory. Squaric acid derivatives are predicted to be very strong acids in the gas phase; their acidity increases with the size of the chalcogen, with C4Se4H2 being the strongest acid of the series and stronger than sulfuric acid. The relative stability of the C4X4H2⋅BeY2 (X = O, S, Se; Y = H, F) complexes changes with the nature of the chalcogen atom; but more importantly, the formation of the C4X4H2⋅BeF2 complexes results in a substantial acidity enhancement of the squaric moiety owing to the dramatic electron-density redistribution undergone by the system when the beryllium bond is formed. The most significant consequence of this acidity enhancement is that when BeF2 is replaced by BeH2, a spontaneous exergonic loss of H2 is observed regardless of the nature of the chalcogen atom. This is another clear piece of evidence of the important role that closed-shell interactions play in the modulation of physicochemical properties of the Lewis acid and/or the Lewis base. PMID:24665080

  1. VUV photoionization cross sections of HO2, H2O2, and H2CO.

    PubMed

    Dodson, Leah G; Shen, Linhan; Savee, John D; Eddingsaas, Nathan C; Welz, Oliver; Taatjes, Craig A; Osborn, David L; Sander, Stanley P; Okumura, Mitchio

    2015-02-26

    The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical (HO2), hydrogen peroxide (H2O2), and formaldehyde (H2CO) have been measured from their first ionization thresholds to 12.008 eV. HO2, H2O2, and H2CO were generated from the oxidation of methanol initiated by pulsed-laser-photolysis of Cl2 in a low-pressure slow flow reactor. Reactants, intermediates, and products were detected by time-resolved multiplexed synchrotron photoionization mass spectrometry. Absolute concentrations were obtained from the time-dependent photoion signals by modeling the kinetics of the methanol oxidation chemistry. Photoionization cross sections were determined at several photon energies relative to the cross section of methanol, which was in turn determined relative to that of propene. These measurements were used to place relative photoionization spectra of HO2, H2O2, and H2CO on an absolute scale, resulting in absolute photoionization spectra. PMID:25621533

  2. Transport of electrons in Ar/H2 mixtures

    NASA Astrophysics Data System (ADS)

    Nikitović, Ž.; Stojanović, V.; Petrović, Z. Lj.

    2012-08-01

    In this work we present transport coefficients for electrons in Ar/H2 mixtures for the conditions used in plasma-assisted technologies for semiconductor production, i.e., in moderate and very high E/N. We used a two-term numerical solution of the Boltzmann equation at the lowest E/N (E is the electric field; N is the gas density) and correspondingly at the lowest mean energies. We also use the Monte Carlo simulation technique at moderate and high E/N. We show that a good agreement with experimental data exists for low and moderate E/N and that based on the tests for pure H2 and Ar we can model properly the swarm properties at high E/N. For the conditions of very high electric fields runaway peaks develop in the electron energy distribution function and appreciable contribution of backscattered high-energy electrons produces additional emission of Hα emission close to the anode (made of stainless steel). Results are obtained for abundances of H2 from 1% to 30%, which are necessary in kinetic models for this mixture in a number of applications.

  3. Enhancement of atmospheric H2SO4/H2O nucleation: organic oxidation products versus amines

    NASA Astrophysics Data System (ADS)

    Berndt, T.; Sipilä, M.; Stratmann, F.; Petäjä, T.; Vanhanen, J.; Mikkilä, J.; Patokoski, J.; Taipale, R.; Mauldin, R. Lee, III; Kulmala, M.

    2013-06-01

    Atmospheric H2SO4/H2O nucleation influencing effects have been studied in the flow tube IfT-LFT (Institute for Tropospheric Research - Laminar Flow Tube) at 293 ± 0.5 K and a pressure of 1 bar using synthetic air as the carrier gas. The presence of a~possible background amine concentration in the order of 107-108 molecule cm-3 throughout the experiments has to be taken into account. In a first set of investigations, ozonolysis of olefins (tetramethylethylene, 1-methyl-cyclohexene, α-pinene and limonene) for close to atmospheric concentrations, served as the source of OH radicals and possibly other oxidants initiating H2SO4 formation starting from SO2. The oxidant generation is inevitably associated with the formation of a series of organic oxidation products arising from the parent olefins. These products (first generation mainly) showed no clear effect on the number of nucleated particles within a wide range of experimental conditions for H2SO4 concentrations higher than ~107 molecule cm-3. A comparison of the results of two different particle counters (50% cut-off size: about 1.5 nm or 2.5-3 nm) suggested that the early growth process of the nucleated particles was not significantly influenced by the organic oxidation products. An additional, H2SO4-independent process of particle (nano-CN) formation was observed in the case of α-pinene and limonene ozonolysis for H2SO4 concentrations smaller than ~10 7 molecule cm-3. Furthermore, the findings confirm the existence of an additional oxidant for SO2 beside OH radicals, very likely stabilized Criegee Intermediate (sCI). In the case of the ozonolysis of tetramethylethylene, the H2SO4 measurements in the absence and presence of an OH radical scavenger were well described by modelling using recently obtained kinetic data for the sCI reactivity in this system. A second set of experiments has been performed in the presence of added amines (trimethylamine, dimethylamine, aniline and pyridine) in the concentration range

  4. Impact of a future H2 transportation on atmospheric pollution in Europe

    NASA Astrophysics Data System (ADS)

    Popa, Maria Elena; Segers, Arjo; Denier van der Gon, Hugo; Schaap, Martijn; Krol, Maarten; Visschedijk, Antoon; Röckmann, Thomas

    2014-05-01

    Traditionally fuelled road traffic is a major source of greenhouse gases and pollutants. Greenhouse gases (e.g. CO2 and CH4) affect the global atmosphere and contribute to global warming. The pollutants emitted by vehicles (e.g. CO, NOx, SO2, particulate matter, volatile organic compounds) are toxic for man and environment and decrease air quality especially in highly populated areas. Burning H2 produces only water, thus H2-powered vehicles are seen as a possibility to reduce greenhouse gas emissions and improve air quality; because of this, H2 usage as a fuel is foreseen to significantly increase in the future. Large scale usage of H2 as a fuel has the potential to affect the atmospheric composition in different ways. On one hand, emissions associated to fossil fuel burning will decrease. On the other hand, large quantities of H2 used will likely lead to increased H2 emissions from leakages during production, transport and storage. Additional H2 in the atmosphere will affect the chemistry of many species, in principal by decreasing the availability of OH radicals, with the result of increasing the lifetime of greenhouse gases and pollutants. Thus the net effect of H2 vehicles on the atmospheric composition depends on the relative strength of these two contrary effects. In order to evaluate the potential influence of a future H2 road transportation on local and regional air quality, we implemented H2 in the atmospheric transport and chemistry model LOTOS-EUROS. We simulated the future (2020) using emission scenarios with different proportions of H2 vehicles and different H2 leakage rates. The reference future scenario does not include H2 vehicles, and assumes that all present and planned European regulations for emissions are fully implemented. We find that in general the air quality in 2020 will be significantly better than at present in all scenarios, with and without H2 cars. In the future scenario without H2 cars, the pollution is reduced due to the strict

  5. Canonical histone H2Ba and H2A.X dimerize in an opposite genomic localization to H2A.Z/H2B.Z dimers in Toxoplasma gondii

    PubMed Central

    Bogado, Silvina S.; Dalmasso, Carolina; Ganuza, Agustina; Kim, Kami; Sullivan, William J.; Angel, Sergio O.; Vanagas, Laura

    2014-01-01

    Histone H2Ba of Toxoplasma gondii was expressed as recombinant protein (rH2Ba) and used to generate antibody in mouse that is highly specific. Antibody recognizing rH2Ba detects a single band in tachyzoite lysate of the expected molecular weight (12 kDa). By indirect immunofluorescence (IFA) in in vitro grown tachyzoites and bradyzoites, the signal was detected only in the parasite nucleus. The nucleosome composition of H2Ba was determined through co-immunoprecipitation assays. H2Ba was detected in the same immunocomplex as H2A.X, but not with H2A.Z. Through chromatin immunoprecipitation (ChIP) assays and qPCR, it was observed that H2Ba is preferentially located at promoters of inactive genes and silent regions, accompanying H2A.X and opposed to H2A.Z/H2B.Z dimers. PMID:25286383

  6. Functions of MgH2 in hydrogen storage reactions of the 6LiBH4-CaH2 reactive hydride composite.

    PubMed

    Zhou, Yifan; Liu, Yongfeng; Zhang, Yu; Gao, Mingxia; Pan, Hongge

    2012-08-28

    A significant improvement of hydrogen storage properties was achieved by introducing MgH(2) into the 6LiBH(4)-CaH(2) system. It was found that ~8.0 wt% of hydrogen could be reversibly stored in a 6LiBH(4)-CaH(2)-3MgH(2) composite below 400 °C and 100 bar of hydrogen pressure with a stepwise reaction, which is superior to the pristine 6LiBH(4)-CaH(2) and LiBH(4) samples. Upon dehydriding, MgH(2) first decomposed to convert to Mg and liberate hydrogen with an on-set temperature of ~290 °C. Subsequently, LiBH(4) reacted with CaH(2) to form CaB(6) and LiH in addition to further hydrogen release. Hydrogen desorption from the 6LiBH(4)-CaH(2)-3MgH(2) composite finished at ~430 °C in non-isothermal model, a 160 °C reduction relative to the 6LiBH(4)-CaH(2) sample. JMA analyses revealed that hydrogen desorption was a diffusion-controlled reaction rather than an interface reaction-controlled process. The newly produced Mg of the first-step dehydrogenation possibly acts as the heterogeneous nucleation center of the resultant products of the second-step dehydrogenation, which diminishes the energy barrier and facilitates nucleation and growth, consequently reducing the operating temperature and improving the kinetics of hydrogen storage. PMID:22842399

  7. H2 metabolism is widespread and diverse among human colonic microbes.

    PubMed

    Wolf, Patricia G; Biswas, Ambarish; Morales, Sergio E; Greening, Chris; Gaskins, H Rex

    2016-05-01

    Microbial molecular hydrogen (H2) cycling is central to metabolic homeostasis and microbial composition in the human gastrointestinal tract. Molecular H2 is produced as an endproduct of carbohydrate fermentation and is reoxidised primarily by sulfate-reduction, acetogenesis, and methanogenesis. However, the enzymatic basis for these processes is incompletely understood and the hydrogenases responsible have not been investigated. In this work, we surveyed the genomic and metagenomic distribution of hydrogenase-encoding genes in the human colon to infer dominant mechanisms of H2 cycling. The data demonstrate that 70% of gastrointestinal microbial species listed in the Human Microbiome Project encode the genetic capacity to metabolise H2. A wide variety of anaerobically-adapted hydrogenases were present, with [FeFe]-hydrogenases predominant. We subsequently analyzed the hydrogenase gene content of stools from 20 healthy human subjects. The hydrogenase gene content of all samples was overwhelmingly dominated by fermentative and electron-bifurcating [FeFe]-hydrogenases emerging from the Bacteroidetes and Firmicutes. This study supports that H2 metabolism in the human gut is driven by fermentative H2 production and interspecies H2 transfer. However, it suggests that electron-bifurcation rather than respiration is the dominant mechanism of H2 reoxidation in the human colon, generating reduced ferredoxin to sustain carbon-fixation (e.g. acetogenesis) and respiration (via the Rnf complex). This work provides the first comprehensive bioinformatic insight into the mechanisms of H2 metabolism in the human colon. PMID:27123663

  8. Electrochemical Measurements of Single H2 Nanobubble Nucleation and Stability at Pt Nanoelectrodes.

    PubMed

    Chen, Qianjin; Luo, Long; Faraji, Hamaseh; Feldberg, Stephen W; White, Henry S

    2014-10-16

    Single H2 nanobubble nucleation is studied at Pt nanodisk electrodes of radii less than 50 nm, where H2 is produced through electrochemical reduction of protons in a strong acid solution. The critical concentration of dissolved H2 required for nanobubble nucleation is measured to be ∼0.25 M. This value is ∼310 times larger than the saturation concentration at room temperature and pressure and was found to be independent of acid type (e.g., H2SO4, HCl, and H3PO4) and nanoelectrode size. The effects of different surfactants on H2 nanobubble nucleation are consistent with the classic nucleation theory. As the surfactant concentration in H2SO4 solution increases, the solution surface tension decreases, resulting in a lower nucleation energy barrier and consequently a lower supersaturation concentration required for H2 nanobubble nucleation. Furthermore, amphiphilic surfactant molecules accumulate at the H2/solution interface, hindering interfacial H2 transfer from the nanobubble into the solution; consequently, the residual current decreases with increasing surfactant concentration. PMID:26278606

  9. The reaction of H2O2 with NO2 and NO

    NASA Technical Reports Server (NTRS)

    Gray, D.; Lissi, E.; Heicklen, J.

    1972-01-01

    The reactions of NO and NO2 with H2O2 have been examined at 25 C. Reaction mixtures were monitored by continuously bleeding through a pinhole into a monopole mass spectrometer. NO2 was also monitored by its optical absorption in the visible part of the spectrum. Reaction mixtures containing initially 1.5 - 2.5 torr of NO2 and 0.8 - 1.4 torr of H2O2 or 1 - 12 torr of NO and 0.5 - 1.5 torr of H2O2 were studied. The H2O2 - NO reaction was complex. There was an induction period followed by a marked acceleration in reactant removal. The final products of the reaction, NO2, probably H2O, and possibly HONO2 were produced mainly after all the H2O2 was removed. The HONO intermediate was shown to disproportionate to NO2 + NO + H2O in a relatively slow first order reaction. The acceleration in H2O2 removal after the NO - H2O2 reaction is started is caused by NO2 catalysis.

  10. Reflected-Shock Ignition of H2-O2-Ar Mixtures with Addition of H2S

    NASA Astrophysics Data System (ADS)

    Mathieu, O.; Deguillaume, F.; Petersen, E. L.

    It is well known that some impurities, even in very low concentration, can induce strong changes in the combustion properties of a fuel. Amongst these impurities, H2S is a common one that can be found in syngas produced from biomass or coal and in natural gases, in addition to being a by-product of the oil industry. Unfortunately, due to both the limited available literature data and the large number of sensitive reactions with significant rate uncertainty [1], the high-temperature chemistry of sulfur species remains poorly understood.

  11. Phosphorylation of BK channels modulates the sensitivity to hydrogen sulfide (H2S)

    PubMed Central

    Sitdikova, Guzel F.; Fuchs, Roman; Kainz, Verena; Weiger, Thomas M.; Hermann, Anton

    2014-01-01

    Introduction: Gases, such as nitric oxide (NO), carbon monoxide (CO), or hydrogen sulfide (H2S), termed gasotransmitters, play an increasingly important role in understanding of how electrical signaling of cells is modulated. H2S is well-known to act on various ion channels and receptors. In a previous study we reported that H2S increased calcium-activated potassium (BK) channel activity. Aims: The goal of the present study is to investigate the modulatory effect of BK channel phosphorylation on the action of H2S on the channel as well as to recalculate and determine the H2S concentrations in aqueous sodium hydrogen sulfide (NaHS) solutions. Methods: Single channel recordings of GH3, GH4, and GH4 STREX cells were used to analyze channel open probability, amplitude, and open dwell times. H2S was measured with an anion selective electrode. Results: The concentration of H2S produced from NaHS was recalculated taking pH, temperature salinity of the perfusate, and evaporation of H2S into account. The results indicate that from a concentration of 300 μM NaHS, only 11–13%, i.e., 34–41 μM is effective as H2S in solution. GH3, GH4, and GH4 STREX cells respond differently to phosphorylation. BK channel open probability (Po) of all cells lines used was increased by H2S in ATP-containing solutions. PKA prevented the action of H2S on channel Po in GH4 and GH4 STREX, but not in GH3 cells. H2S, high significantly increased Po of all PKG pretreated cells. In the presence of PKC, which lowers channel activity, H2S increased channel Po of GH4 and GH4 STREX, but not those of GH3 cells. H2S increased open dwell times of GH3 cells in the absence of ATP significantly. A significant increase of dwell times with H2S was also observed in the presence of okadaic acid. Conclusions: Our results suggest that phosphorylation by PKG primes the channels for H2S activation and indicate that channel phosphorylation plays an important role in the response to H2S. PMID:25429270

  12. FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT Drought(s)-Elimination FOREVER!!!

    NASA Astrophysics Data System (ADS)

    Ertl, G.; Alefeld, G.; Youdelis, W.; Radd, H.; Oertle, G.; Siegel, Edward

    2011-03-01

    "H2O H2O everywhere; ne'er a drop to drink"[Coleridge(1798)]; now: "H2 H2 everywhere; STILL ne'er a drop to drink": ONLY H2 (or methane CH4) can be FLYING-WATER(F-W) chemical-rain-in-pipelines Hindenberg-effect (H2-UP;H2O-DOWN): {O/H2O}=[16]/[18] 90 % ; O already in air uphill; NO H2O pumping need! In global-warming driven H2O-starved glacial-melting world, rescue is possible ONLY by Siegel [{3rd Intl. Conf. Alt.-Energy }(1980)-vol.5/p.459!!!] Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating-system. Rosenfeld[Science 315,1396(3/9/2007)]-Biello [Sci.Am.(3/9/2007)] crucial geomorph-ology which ONLY maximal-buoyancy H2 can exploit, to again make "Mountains into Fountains", ``upthrust rocks trapping the clouds to precipitate their rain/snow/H2O'': "terraforming"(and ocean-rebasificaton!!!) Siegel proprietary magnetic-hydrogen-valve (MHV) permits H2 flow in already in-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Science 300,1740(2003)] dire warning of global-pandemics (cancers/ blindness/famine) Hydrogen-economy CATASTROPHIC H2 ozone-layer destruction sobering cavat to dangerous H2-automotion-economy panacea hype!!!

  13. Molecular Characterization of Salmonella enterica Serovar Aberdeen Negative for H2S Production in China.

    PubMed

    Wu, Fuli; Xu, Xuebin; Xie, Jing; Yi, Shengjie; Wang, Jian; Yang, Xiaoxia; Yang, Chaojie; Liang, Beibei; Ma, Qiuxia; Li, Hao; Song, Hongbin; Qiu, Shaofu

    2016-01-01

    Salmonella enterica infections continue to be a significant burden on public health worldwide. The ability of S. enterica to produce hydrogen sulfide (H2S) is an important phenotypic characteristic used to screen and identify Salmonella with selective medium; however, H2S-negative Salmonella have recently emerged. In this study, the H2S phenotype of Salmonella isolates was confirmed, and the selected isolates were subjected to antimicrobial susceptibility testing and molecular identification by multilocus sequence typing, pulsed-field gel electrophoresis, and clustered regularly interspaced short palindromic repeat (CRISPR) analysis. The phs genetic operon was also analyzed. A total of 160 S. enterica serovar Aberdeen isolates were detected between 2005 and 2013 in China. Of them, seven non-H2S-producing isolates were detected. Notably, four samples yielded four pairs of isolates with different H2S phenotypes, simultaneously. The data demonstrated that H2S-negative isolates were genetically closely related to H2S-positive isolates. Three new spacers (Abe1, Abe2, and Abe3) were identified in CRISPR locus 1 in four pairs of isolates with different H2S phenotypes from the same samples. Sequence analysis revealed a new nonsense mutation at position 208 in the phsA gene of all non-H2S-producing isolates. Additionally, we describe a new screening procedure to avoid H2S-negative Salmonella, which would normally be overlooked during laboratory and hospital screening. The prevalence of this pathogen may be underestimated; therefore, it is important to focus on improving surveillance of this organism to control its spread. PMID:27552230

  14. Molecular Characterization of Salmonella enterica Serovar Aberdeen Negative for H2S Production in China

    PubMed Central

    Yi, Shengjie; Wang, Jian; Yang, Xiaoxia; Yang, Chaojie; Liang, Beibei; Ma, Qiuxia; Li, Hao; Song, Hongbin; Qiu, Shaofu

    2016-01-01

    Salmonella enterica infections continue to be a significant burden on public health worldwide. The ability of S. enterica to produce hydrogen sulfide (H2S) is an important phenotypic characteristic used to screen and identify Salmonella with selective medium; however, H2S-negative Salmonella have recently emerged. In this study, the H2S phenotype of Salmonella isolates was confirmed, and the selected isolates were subjected to antimicrobial susceptibility testing and molecular identification by multilocus sequence typing, pulsed-field gel electrophoresis, and clustered regularly interspaced short palindromic repeat (CRISPR) analysis. The phs genetic operon was also analyzed. A total of 160 S. enterica serovar Aberdeen isolates were detected between 2005 and 2013 in China. Of them, seven non-H2S-producing isolates were detected. Notably, four samples yielded four pairs of isolates with different H2S phenotypes, simultaneously. The data demonstrated that H2S-negative isolates were genetically closely related to H2S-positive isolates. Three new spacers (Abe1, Abe2, and Abe3) were identified in CRISPR locus 1 in four pairs of isolates with different H2S phenotypes from the same samples. Sequence analysis revealed a new nonsense mutation at position 208 in the phsA gene of all non-H2S-producing isolates. Additionally, we describe a new screening procedure to avoid H2S-negative Salmonella, which would normally be overlooked during laboratory and hospital screening. The prevalence of this pathogen may be underestimated; therefore, it is important to focus on improving surveillance of this organism to control its spread. PMID:27552230

  15. Hydrogen atom abstraction from aldehydes - OH + H2CO and O + H2CO

    NASA Technical Reports Server (NTRS)

    Dupuis, M.; Lester, W. A., Jr.

    1984-01-01

    The essential features of the potential energy surfaces governing hydrogen abstraction from formaldehyde by oxygen atom and hydroxyl radical have been characterized with ab inito multiconfiguration Hartree-Fock (MCHF) and configuration interaction (CI) wave functions. The results are consistent with a very small activation energy for the OH + H2CO reaction, and an activation energy of a few kcal/mol for the O + H2CO reaction. In the transition state structure of both systems, the attacking oxygen atom is nearly collinear with the attacked CH bond.

  16. Matrix-isolation and computational study of H2CCCl and H2CCBr radicals.

    PubMed

    Zhu, Cheng; Duarte, Luís; Khriachtchev, Leonid

    2016-08-21

    We report on two new radicals, H2CCCl and H2CCBr, prepared in low-temperature noble-gas matrices and characterized using infrared spectroscopy. These radicals are made by UV photolysis of HCCCl and HCCBr and subsequent thermal annealing to mobilize hydrogen atoms in the matrices and promote their reaction with the residual precursor molecules. Three characteristic infrared bands are observed for each radical. The assignments are supported by quantum chemical calculations at the B3LYP and CCSD(T) levels of theory with the def2-TZVPPD basis set. PMID:27544110

  17. Antiprotonic atoms in gaseous H2 and He and in liquid H2

    NASA Astrophysics Data System (ADS)

    Lindemuth, J. R.; Eckhause, M.; Giovanetti, K. L.; Kane, J. R.; Pandey, M. S.; Rushton, A. M.; Vulcan, W. F.; Welsh, R. E.; Winter, R. G.; Barnes, P. D.; Craig, J. N.; Eisenstein, R. A.; Sherman, J. D.; Sutton, R. B.; Wharton, W. R.; Miller, J. P.; Roberts, B. L.; Kunselman, A. R.; Powers, R. J.

    1984-11-01

    Antiprotons were brought to rest in targets of gaseous H2 and gaseous He at temperatures of 30 K and also in a target of liquid H2. High-resolution x-ray detectors were used to measure the energies of x rays from p¯-He and to search for x rays from p¯-H. The p¯-He data are compared with similar measurements at different densities and with the theoretical predictions of Landua and Klempt. The p¯-H data provide upper limits for the yields of nP-->1S x rays in liquid and gaseous hydrogen.

  18. Phase transition and optoelectronic properties of MgH2

    NASA Astrophysics Data System (ADS)

    Nayak, Vikas; Verma, U. P.

    2016-05-01

    In this article, structural and electronic properties of MgH2 have been studied. The aim behind this study was to find out the ground state crystal structure of MgH2. For the purpose, density functional theory (DFT)-based full-potential linearized augmented plane wave (FP-LAPW) calculations have been performed in three different space groups: P42/mnm (α-MgH2), Pa3 (β-MgH2) and Pbcn (γ-MgH2). It has been found that the ground state structure of MgH2 is α-MgH2. The present study shows that α-MgH2 transforms into γ-MgH2 at a pressure of 0.41 GPa. After further increase in pressure, γ-MgH2 transforms into β-MgH2 at a pressure of 3.67 GPa. The obtained results are in good agreement with previously reported experimental data. In all the studied phases, the behavior of MgH2 is insulating and its optical conductivity is around 6.0 eV. The α-MgH2 and γ-MgH2 are anisotropic materials while β-MgH2 is isotropic in nature.

  19. Structural evidence for Nap1-dependent H2A-H2B deposition and nucleosome assembly.

    PubMed

    Aguilar-Gurrieri, Carmen; Larabi, Amédé; Vinayachandran, Vinesh; Patel, Nisha A; Yen, Kuangyu; Reja, Rohit; Ebong, Ima-O; Schoehn, Guy; Robinson, Carol V; Pugh, B Franklin; Panne, Daniel

    2016-07-01

    Nap1 is a histone chaperone involved in the nuclear import of H2A-H2B and nucleosome assembly. Here, we report the crystal structure of Nap1 bound to H2A-H2B together with in vitro and in vivo functional studies that elucidate the principles underlying Nap1-mediated H2A-H2B chaperoning and nucleosome assembly. A Nap1 dimer provides an acidic binding surface and asymmetrically engages a single H2A-H2B heterodimer. Oligomerization of the Nap1-H2A-H2B complex results in burial of surfaces required for deposition of H2A-H2B into nucleosomes. Chromatin immunoprecipitation-exonuclease (ChIP-exo) analysis shows that Nap1 is required for H2A-H2B deposition across the genome. Mutants that interfere with Nap1 oligomerization exhibit severe nucleosome assembly defects showing that oligomerization is essential for the chaperone function. These findings establish the molecular basis for Nap1-mediated H2A-H2B deposition and nucleosome assembly. PMID:27225933

  20. Synthesis of zinc sulfide nanoparticles during zinc oxidization by H2S and H2S/H2O supercritical fluids

    NASA Astrophysics Data System (ADS)

    Vostrikov, A. A.; Fedyaeva, O. N.; Sokol, M. Ya.; Shatrova, A. V.

    2014-12-01

    Formation of zinc sulfide nanoparticles was detected during interaction of bulk samples with hydrogen sulfide at supercritical parameters. Synthesis proceeds with liberation of H2 by the reaction nZn + nH2S = (ZnS) n + nH2. It has been found by the X-ray diffraction method, scanning electron microscopy, and mass spectrometry that the addition of water stimulates coupled reactions of nanoparticle synthesis nZn + nH2O = (ZnO) n + nH2 and (ZnO) n + nH2S = (ZnS) n + nH2O and brings about an increase in the synthesis rate and morphological changes of (ZnS) n nanoparticles.

  1. Herschel/HIFI Search for H_2^{17}O and H_2^{18}O in IRC+10216: Constraints on Models for the Origin of Water Vapor

    NASA Astrophysics Data System (ADS)

    Neufeld, David A.; Tolls, Volker; Agúndez, Marcelino; González-Alfonso, Eduardo; Decin, Leen; Daniel, Fabien; Cernicharo, José; Melnick, Gary J.; Schmidt, Miroslaw; Szczerba, Ryszard

    2013-04-01

    We report the results of a sensitive search for the minor isotopologues of water, H_2^{17}O and H_2^{18}O, toward the carbon-rich asymptotic giant branch star IRC+10216 (a.k.a. CW Leonis) using the HIFI instrument on the Herschel Space Observatory. This search was motivated by the fact that any detection of isotopic enhancement in the H_2^{17}O and H_2^{18}O abundances would have strongly implicated CO photodissociation as the source of the atomic oxygen needed to produce water in a carbon-rich circumstellar envelope. Our observations place an upper limit of 1/470 on the H_2^{17}O/H_2^{16}O abundance ratio. Given the isotopic 17O/16O ratio of 1/840 inferred previously for the photosphere of IRC+10216, this result places an upper limit of a factor 1.8 on the extent of any isotope-selective enhancement of H_2^{17}O in the circumstellar material, and provides an important constraint on any model that invokes CO photodissociation as the source of O for H2O production. In the context of the clumpy photodissociation model proposed previously for the origin of water in IRC+10216, our limit implies that 12C16O (not 13C16O or SiO) must be the dominant source of 16O for H2O production, and that the effects of self-shielding can only have reduced the 12C16O photodissociation rate by at most a factor ~2. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

  2. UV and IR Spectroscopy of Cold H2O(+)-Benzo-Crown Ether Complexes.

    PubMed

    Inokuchi, Yoshiya; Ebata, Takayuki; Rizzo, Thomas R

    2015-11-12

    The H2O(+) radical ion, produced in an electrospray ion source via charge transfer from Eu(3+), is encapsulated in benzo-15-crown-5 (B15C5) or benzo-18-crown-6 (B18C6). We measure UV photodissociation (UVPD) spectra of the (H2O·B15C5)(+) and (H2O·B18C6)(+) complexes in a cold, 22-pole ion trap. These complexes show sharp vibronic bands in the 35 700-37 600 cm(-1) region, similar to the case of neutral B15C5 or B18C6. These results indicate that the positive charge in the complexes is localized on H2O, giving the forms H2O(+)·B15C5 and H2O(+)·B18C6, in spite of the fact that the ionization energy of B15C5 and B18C6 is lower than that of H2O. The formation of the H2O(+) complexes and the suppression of the H3O(+) production through the reaction of H2O(+) and H2O can be attributed to the encapsulation of hydrated Eu(3+) clusters by B15C5 and B18C6. On the contrary, the main fragment ions subsequent to the UV excitation of these complexes are B15C5(+) and B18C6(+) radical ions; the charge transfer occurs from H2O(+) to B15C5 and B18C6 after the UV excitation. The position of the band origin for the H2O(+)·B18C6 complex (36323 cm(-1)) is almost the same as that for Rb(+)·B18C6 (36315 cm(-1)); the strength of the intermolecular interaction of H2O(+) with B18C6 is similar to that of Rb(+). The spectral features of the H2O(+)·B15C5 complex also resemble those of the Rb(+)·B15C5 ion. We measure IR-UV spectra of these complexes in the CH and OH stretching region. Four conformers are found for the H2O(+)·B15C5 complex, but there is one dominant form for the H2O(+)·B18C6 ion. This study demonstrates the production of radical ions by charge transfer from multivalent metal ions, their encapsulation by host molecules, and separate detection of their conformers by cold UV spectroscopy in the gas phase. PMID:26491792

  3. 20 CFR 655.132 - H-2A labor contractor (H-2ALC) filing requirements.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... obligations under the H-2A program by including with the Application for Temporary Employment Certification the original surety bond as required by 29 CFR 501.9. The bond document must clearly identify the... bond (as calculated pursuant to 29 CFR 501.9) and any identifying designation used by the surety...

  4. Developmental Sculpting of Intracortical Circuits by MHC Class I H2-Db and H2-Kb.

    PubMed

    Adelson, Jaimie D; Sapp, Richard W; Brott, Barbara K; Lee, Hanmi; Miyamichi, Kazunari; Luo, Liqun; Cheng, Sarah; Djurisic, Maja; Shatz, Carla J

    2016-04-01

    Synapse pruning is an activity-regulated process needed for proper circuit sculpting in the developing brain. Major histocompatibility class I (MHCI) molecules are regulated by activity, but little is known about their role in the development of connectivity in cortex. Here we show that protein for 2 MHCI molecules H2-Kb and H2-Db is associated with synapses in the visual cortex. Pyramidal neurons in mice lacking H2-Kb and H2-Db (KbDb KO) have more extensive cortical connectivity than normal. Modified rabies virus tracing was used to monitor the extent of pyramidal cell connectivity: Horizontal connectivity is greater in the visual cortex of KbDb KO mice. Basal dendrites of L2/3 pyramids, where many horizontal connections terminate, are more highly branched and have elevated spine density in the KO. Furthermore, the density of axonal boutons is elevated within L2/3 of mutant mice. These increases are accompanied by elevated miniature excitatory postsynaptic current frequency, consistent with an increase in functional synapses. This functional and anatomical increase in intracortical connectivity is also associated with enhanced ocular dominance plasticity that persists into adulthood. Thus, these MHCI proteins regulate sculpting of local cortical circuits and in their absence, the excess connectivity can function as a substrate for cortical plasticity throughout life. PMID:25316337

  5. Modeling Ice Giant Interiors Using Constraints on the H2-H2O Critical Curve

    NASA Astrophysics Data System (ADS)

    Bailey, E.; Stevenson, D. J.

    2015-12-01

    We present a range of models of Uranus and Neptune, taking into account recent experimental data (Bali, 2013) implying the location of the critical curve of the H2-H2O system at pressures up to 2.6 GPa. The models presented satisfy the observed total mass of each planet and the radius at the observed 1-bar pressure level. We assume the existence of three regions at different depths: an outer adiabatic envelope composed predominately of H2 and He, with a helium mass fraction 0.26, a water-rich layer including varied amounts of rock and hydrogen, and a chemically homogeneous rock core. Using measured rotation rates of Uranus and Neptune, and a density profile obtained for each model using constituent equations of state and the assumption of hydrostatic equilibrium, we calculate the gravitational harmonics J2 and J4 for comparison with observed values as an additional constraint. The H2-H2O critical curve provides information about the nature of the boundary between the outer, hydrogen-rich envelope and underlying water-rich layer. The extrapolated critical curve for hydrogen-water mixtures crosses the adiabat of the outer atmospheric shell in these models at two depths, implying a shallow outer region of limited miscibility, an intermediate region between ~90 and 98 percent of the total planet radius within which hydrogen and water can mix in all proportions, and another, deeper region of limited miscibility at less than ~90 percent of the total planet radius. The pressure and temperature of the gaseous adiabatic shell at the depth of the shallowest extent of the water-rich layer determines whether a gradual compositional transition or an ocean surface boundary may exist at depth in these planets. To satisfy the observed J2, the outer extent of the water-rich layer in these models must be located between approximately 80 and 85 percent of the total planet radius, within the deep region of limited H2-H2O miscibility, implying an ocean surface is possible within the

  6. H2O2 space shuttle APU

    NASA Technical Reports Server (NTRS)

    1975-01-01

    A cryogenic H2-O2 auxiliary power unit (APU) was developed and successfully demonstrated. It has potential application as a minimum weight alternate to the space shuttle baseline APU because of its (1) low specific propellant consumption and (2) heat sink capabilities that reduce the amount of expendable evaporants. A reference system was designed with the necessary heat exchangers, combustor, turbine-gearbox, valves, and electronic controls to provide 400 shp to two aircraft hydraulic pumps. Development testing was carried out first on the combustor and control valves. This was followed by development of the control subsystem including the controller, the hydrogen and oxygen control valves, the combustor, and a turbine simulator. The complete APU system was hot tested for 10 hr with ambient and cryogenic propellants. Demonstrated at 95 percent of design power was 2.25 lb/hp-hr. At 10 percent design power, specific propellant consumption was 4 lb/hp-hr with space simulated exhaust and 5.2 lb/hp-hr with ambient exhaust. A 10 percent specific propellant consumption improvement is possible with some seal modifications. It was demonstrated that APU power levels could be changed by several hundred horsepower in less than 100 msec without exceeding allowable turbine inlet temperatures or turbine speed.

  7. Full-dimensional, high-level ab initio potential energy surfaces for H2(H2O) and H2(H2O)2 with application to hydrogen clathrate hydrates.

    PubMed

    Homayoon, Zahra; Conte, Riccardo; Qu, Chen; Bowman, Joel M

    2015-08-28

    New, full-dimensional potential energy surfaces (PESs), obtained using precise least-squares fitting of high-level electronic energy databases, are reported for intrinsic H2(H2O) two-body and H2(H2O)2 three-body potentials. The database for H2(H2O) consists of approximately 44 000 energies at the coupled cluster singles and doubles plus perturbative triples (CCSD(T))-F12a/haQZ (aug-cc-pVQZ for O and cc-pVQZ for H) level of theory, while the database for the three-body interaction consists of more than 36 000 energies at the CCSD(T)-F12a/haTZ (aug-cc-pVTZ for O, cc-pVTZ for H) level of theory. Two precise potentials are based on the invariant-polynomial technique and are compared to computationally faster ones obtained via "purified" symmetrization. All fits use reduced permutational symmetry appropriate for these non-covalent interactions. These intrinsic potentials are employed together with existing ones for H2, H2O, and (H2O)2, to obtain full PESs for H2(H2O) and H2(H2O)2. Properties of these full PESs are presented, including a diffusion Monte Carlo calculation of the zero-point energy and wavefunction, and dissociation energy of the H2(H2O) dimer. These PESs together with an existing one for water clusters are used in a many-body representation of the PES of hydrogen clathrate hydrates, illustrated for H2@(H2O)20. An analysis of this hydrate is presented, including the electronic dissociation energy to remove H2 from the calculated equilibrium structure. PMID:26328838

  8. Full-dimensional, high-level ab initio potential energy surfaces for H2(H2O) and H2(H2O)2 with application to hydrogen clathrate hydrates

    NASA Astrophysics Data System (ADS)

    Homayoon, Zahra; Conte, Riccardo; Qu, Chen; Bowman, Joel M.

    2015-08-01

    New, full-dimensional potential energy surfaces (PESs), obtained using precise least-squares fitting of high-level electronic energy databases, are reported for intrinsic H2(H2O) two-body and H2(H2O)2 three-body potentials. The database for H2(H2O) consists of approximately 44 000 energies at the coupled cluster singles and doubles plus perturbative triples (CCSD(T))-F12a/haQZ (aug-cc-pVQZ for O and cc-pVQZ for H) level of theory, while the database for the three-body interaction consists of more than 36 000 energies at the CCSD(T)-F12a/haTZ (aug-cc-pVTZ for O, cc-pVTZ for H) level of theory. Two precise potentials are based on the invariant-polynomial technique and are compared to computationally faster ones obtained via "purified" symmetrization. All fits use reduced permutational symmetry appropriate for these non-covalent interactions. These intrinsic potentials are employed together with existing ones for H2, H2O, and (H2O)2, to obtain full PESs for H2(H2O) and H2(H2O)2. Properties of these full PESs are presented, including a diffusion Monte Carlo calculation of the zero-point energy and wavefunction, and dissociation energy of the H2(H2O) dimer. These PESs together with an existing one for water clusters are used in a many-body representation of the PES of hydrogen clathrate hydrates, illustrated for H2@(H2O)20. An analysis of this hydrate is presented, including the electronic dissociation energy to remove H2 from the calculated equilibrium structure.

  9. The QTL within the H2 Complex Involved in the Control of Tuberculosis Infection in Mice Is the Classical Class II H2-Ab1 Gene

    PubMed Central

    Logunova, Nadezhda; Korotetskaya, Maria; Polshakov, Vladimir; Apt, Alexander

    2015-01-01

    The level of susceptibility to tuberculosis (TB) infection depends upon allelic variations in numerous interacting genes. In our mouse model system, the whole-genome quantitative trait loci (QTLs) scan revealed three QTLs involved in TB control on chromosomes 3, 9, and in the vicinity of the H2 complex on chromosome 17. For the present study, we have established a panel of new congenic, MHC-recombinant mouse strains bearing differential small segments of chromosome 17 transferred from the TB-susceptible I/St (H2 j) strain onto the genetic background of TB-resistant C57BL/6 (B6) mice (H2 b). This allowed narrowing the QTL interval to 17Ch: 33, 77–34, 34 Mb, containing 36 protein-encoding genes. Cloning and sequencing of the H2 j allelic variants of these genes demonstrated profound polymorphic variations compare to the H2 b haplotype. In two recombinant strains, B6.I-249.1.15.100 and B6.I-249.1.15.139, recombination breakpoints occurred in different sites of the H2-Aβ 1 gene (beta-chain of the Class II heterodimer H2-A), providing polymorphic variations in the domain β1 of the Aβ-chain. These variations were sufficient to produce different TB-relevant phenotypes: the more susceptible B6.I-249.1.15.100 strain demonstrated shorter survival time, more rapid body weight loss, higher mycobacterial loads in the lungs and more severe lung histopathology compared to the more resistant B6.I-249.1.15.139 strain. CD4+ T cells recognized mycobacterial antigens exclusively in the context of the H2-A Class II molecule, and the level of IFN-γ-producing CD4+ T cells in the lungs was significantly higher in the resistant strain. Thus, we directly demonstrated for the first time that the classical H2- Ab1 Class II gene is involved in TB control. Molecular modeling of the H2-Aj product predicts that amino acid (AA) substitutions in the Aβ-chain modify the motif of the peptide–MHC binding groove. Moreover, unique AA substitutions in both α- and β-chains of the H2-Aj molecule

  10. Time-Course Global Expression Profiles of Chlamydomonas reinhardtii during Photo-Biological H2 Production

    PubMed Central

    Nguyen, Anh Vu; Toepel, Joerg; Burgess, Steven; Uhmeyer, Andreas; Blifernez, Olga; Doebbe, Anja; Hankamer, Ben; Nixon, Peter; Wobbe, Lutz; Kruse, Olaf

    2011-01-01

    We used a microarray study in order to compare the time course expression profiles of two Chlamydomonas reinhardtii strains, namely the high H2 producing mutant stm6glc4 and its parental WT strain during H2 production induced by sulfur starvation. Major cellular reorganizations in photosynthetic apparatus, sulfur and carbon metabolism upon H2 production were confirmed as common to both strains. More importantly, our results pointed out factors which lead to the higher H2 production in the mutant including a higher starch accumulation in the aerobic phase and a lower competition between the H2ase pathway and alternative electron sinks within the H2 production phase. Key candidate genes of interest with differential expression pattern include LHCSR3, essential for efficient energy quenching (qE). The reduced LHCSR3 protein expression in mutant stm6glc4 could be closely related to the high-light sensitive phenotype. H2 measurements carried out with the LHCSR3 knock-out mutant npq4 however clearly demonstrated that a complete loss of this protein has almost no impact on H2 yields under moderate light conditions. The nuclear gene disrupted in the high H2 producing mutant stm6glc4 encodes for the mitochondrial transcription termination factor (mTERF) MOC1, whose expression strongly increases during –S-induced H2 production in WT strains. Studies under phototrophic high-light conditions demonstrated that the presence of functional MOC1 is a prerequisite for proper LHCSR3 expression. Furthermore knock-down of MOC1 in a WT strain was shown to improve the total H2 yield significantly suggesting that this strategy could be applied to further enhance H2 production in other strains already displaying a high H2 production capacity. By combining our array data with previously published metabolomics data we can now explain some of the phenotypic characteristics which lead to an elevated H2 production in stm6glc4. PMID:22242116

  11. Desulfovibrio vulgaris Growth Coupled to Formate-Driven H2 Production.

    PubMed

    Martins, Mónica; Mourato, Cláudia; Pereira, Inês A C

    2015-12-15

    Formate is recognized as a superior substrate for biological H2 production by several bacteria. However, the growth of a single organism coupled to this energetic pathway has not been shown in mesophilic conditions. In the present study, a bioreactor with gas sparging was used, where we observed for the first time that H2 production from formate can be coupled with growth of the model sulfate-reducing bacterium Desulfovibrio vulgaris in the absence of sulfate or a syntrophic partner. In these conditions, D. vulgaris had a maximum growth rate of 0.078 h(-1) and a doubling time of 9 h, and the ΔG of the reaction ranged between -21 and -18 kJ mol(-1). This is the first report of a single mesophilic organism that can grow while catalyzing the oxidation of formate to H2 and bicarbonate. Furthermore, high volumetric and specific H2 production rates (125 mL L(-1) h(-1) and 2500 mL gdcw(-1) h(-1)) were achieved in a new bioreactor designed and optimized for H2 production. This high H2 production demonstrates that the nonconventional H2-producing organism D. vulgaris is a good biocatalyst for converting formate to H2. PMID:26579558

  12. High-throughput biosensor discriminates between different algal H2 -photoproducing strains.

    PubMed

    Wecker, Matt S A; Ghirardi, Maria L

    2014-07-01

    A number of species of microalgae and cyanobacteria photosynthetically produce H2 gas by coupling water oxidation with the reduction of protons to molecular hydrogen, generating renewable energy from sunlight and water. Photosynthetic H2 production, however, is transitory, and there is considerable interest in increasing and extending it for commercial applications. Here we report a Petri-plate version of our previous, microplate-based assay that detects photosynthetic H2 production by algae. The assay consists of an agar overlay of H2 -sensing Rhodobacter capsulatus bacteria carrying a green fluorescent protein that responds to H2 produced by single algal colonies in the bottom agar layer. The assay distinguishes between algal strains that photoproduce H2 at different levels under high light intensities, and it does so in a simple, inexpensive, and high-throughput manner. The assay will be useful for screening both natural populations and mutant libraries for strains having increased H2 production, and useful for identifying various genetic factors that physiologically or genetically alter algal hydrogen production. PMID:24578287

  13. Hydrogen constituents of the mesosphere inferred from positive ions - H2O, CH4, H2CO, H2O2, and HCN

    NASA Technical Reports Server (NTRS)

    Kopp, E.

    1990-01-01

    The concentrations in the mesosphere of H2O, CH4, H2CO, H2O2, and HCN were inferred from data on positive ion compositions, obtained from one mid-latitude and four high-latitude rocket flights. The inferred concentrations were found to agree only partially with the ground-based microwave measurements and/or model prediction by Garcia and Solomon (1985). The CH4 concentration was found to vary between 70 and 4 ppb in daytime and 900 and 100 ppbv at night, respectively. Unexpectedly high H2CO concentrations were obtained, with H2CO/H2O ratios between 0.0006 and 0.1, and a mean HCN volume mixing ratio of 6 x 10 to the -10th was inferred.

  14. H2, CO and Dust Emission Around Low Mass Stars

    NASA Technical Reports Server (NTRS)

    Hollenbach, David; DeVincenzi, D. (Technical Monitor)

    2002-01-01

    We model the thermal balance, the chemistry, and the radiative transfer in dusty disks orbiting young, low mass stars. These models are motivated by observations of infrared and ultraviolet transitions of H2 from protoplanetary disks, as well as millimeter and submillimeter observations of other molecules such as CO, and infrared continuum observations of the dust. The dust grains are heated primarily by the stellar radiation and the infrared radiation field produced by the dust itself. The gas is heated by collisions with warmer dust grains, X-rays from the region close to the stellar surface, UV (ultraviolet) pumping of hydrogen molecules, and the grain photoelectric heating mechanism initiated by UV photons from the central star. We treat cases where the gas to dust ratio is high, because the dust has settled to the midplane and coagulated into relatively large objects. We discuss situations in which the infrared emission from H2 can be detected, and how the comparison of the observations with our models can deduce physical parameters such as the mass and the density and temperature distribution of the gas.

  15. H2, CO and Dust Emission Around Low Mass Stars

    NASA Technical Reports Server (NTRS)

    Hollenbach, David; DeVincenzi, Donald (Technical Monitor)

    2002-01-01

    We model the thermal balance, the chemistry, and the radiative transfer in dusty disks orbiting young, low mass stars. These models are motivated by observations of infrared and ultraviolet transitions of H2 from protoplanetary disks, as well as millimeter and submillimeter observations of other molecules such as CO, and infrared continuum observations of the dust. The dust grains are heated primarily by the stellar radiation and the infrared radiation field produced by the dust itself. The gas is heated by collisions with warmer dust grains, X-rays from the region close to the stellar surface, UV pumping of hydrogen molecules, and the grain photoelectric heating mechanism initiated by UV photons from the central star. We treat cases where the gas to dust ratio is high, because the dust has settled to the midplane and coagulated into relatively large objects. We discuss situations in which the infrared emission from H2 can be detected, and how the comparison of the observations with our models can deduce physical parameters such as the mass and the density and temperature distribution of the gas.

  16. Heterogeneous degradation of precipitated hexamine from wastewater by catalytic function of silicotungstic acid in the presence of H2O2 and H2O2/Fe2+.

    PubMed

    Taghdiri, Mehdi; Saadatjou, Naghi; Zamani, Navid; Farrokhi, Reyhaneh

    2013-02-15

    The industrial wastewater produced by hexamine plants is considered as a major environmental polluting factor due to resistance to biodegradation. So the treatment of such wastewater is required. In this work, the removal of hexamine from wastewater and its degradation have been studied. Hexamine was precipitated through formation of an insoluble and stable compound with silicotungstic acid. The oxidative heterogeneous degradation of precipitated hexamine was carried out with hydrogen peroxide (H(2)O(2)) aqueous solution and H(2)O(2)/Fe(2+) under the catalysis of silicotungstic acid. The operating conditions including amount of precipitate, hydrogen peroxide and ferrous ion dosage, temperature, time and pH were optimized by evaluating the removal of total organic carbon from system. A total organic carbon conversion higher than 70% was achieved in the presence of H(2)O(2)/Fe(2+). The experimental results showed that hexamine can be effectively degraded with H(2)O(2) and H(2)O(2)/Fe(2+) under the catalysis of silicotungstic acid. It was interesting that the solution of dissolved precipitate with H(2)O(2) can re-react with hexamine after the removal of excess hydrogen peroxide. This observation indicates the catalysis role of silicotungstic acid in the degradation of hexamine. A kinetic analysis based on total organic carbon reduction was carried out. The two steps mechanism was proposed for the degradation of hexamine. PMID:23313893

  17. Core-mass nonadiabatic corrections to molecules: H2, H2+, and isotopologues.

    PubMed

    Diniz, Leonardo G; Alijah, Alexander; Mohallem, José Rachid

    2012-10-28

    For high-precision calculations of rovibrational states of light molecules, it is essential to include non-adiabatic corrections. In the absence of crossings of potential energy surfaces, they can be incorporated in a single surface picture through coordinate-dependent vibrational and rotational reduced masses. We present a compact method for their evaluation and relate in particular the vibrational mass to a well defined nuclear core mass derived from a Mulliken analysis of the electronic density. For the rotational mass we propose a simple, but very effective parametrization. The use of these masses in the nuclear Schrödinger equation yields numerical data for the corrections of a much higher quality than can be obtained with optimized constant masses, typically better than 0.1 cm(-1). We demonstrate the method for H(2), H(2)(+), and singly deuterated isotopologues. Isotopic asymmetry does not present any particular difficulty. Generalization to polyatomic molecules is straightforward. PMID:23126719

  18. SIRT1-metabolite binding histone macroH2A1.1 protects hepatocytes against lipid accumulation

    PubMed Central

    Pazienza, Valerio; Borghesan, Michela; Mazza, Tommaso; Sheedfar, Fareeba; Panebianco, Concetta; Williams, Roger; Mazzoccoli, Gianluigi; Andriulli, Angelo; Nakanishi, Tomoko; Vinciguerra, Manlio

    2014-01-01

    Non-alcoholic-fatty-liver-disease (NAFLD) encompasses conditions associated to fat deposition in the liver, which are generally deteriorated during the aging process. MacroH2A1, a variant of histone H2A, is a key transcriptional regulator involved in tumorigenic processes and cell senescence, and featuring two alternatively splicing isoforms, macroH2A1.1 and macroH2A1.2. MacroH2A1.1 binds with high affinity O-acetyl ADP ribose, a small metabolite produced by the reaction catalysed by NAD+-dependent deacetylase SIRT1, whereas macroH2A1.2 is unable to do so. The functional significance of this binding is unknown. We previously reported that the hepatic levels of macroH2A1.1 and macroH2A1.2 are differentially expressed in mice models of NAFLD. Here we show that over-expression of macroH2A1.1, but not of macroH2A1.2, is able to protect hepatocytes against lipid accumulation. MacroH2A1.1 over-expressing cells display ameliorated glucose metabolism, reduced expression of lipidogenic genes and fatty acids content. SIRT1/macroH2A1.1-dependent epigenetic regulation of lipid metabolism may be relevant to NAFLD development. PMID:24473773

  19. Xenobiotic metal-induced autoimmunity: mercury and silver differentially induce antinucleolar autoantibody production in susceptible H-2s, H-2q and H-2f mice

    PubMed Central

    Hansson, M; Abedi-Valugerdi, M

    2003-01-01

    Xenobiotic-metals such as mercury (Hg) and silver (Ag) induce an H-2 linked antinucleolar autoantibody (ANolA) production in susceptible mice. The mechanism for induction of ANolA synthesis is not well understood. However, it has been suggested that both metals interact with nucleolar proteins and reveal cryptic self-peptides to nontolerant autoreactive T cells, which in turn stimulate specific autoreactive B cells. In this study, we considered this suggestion and asked if mercury and silver display, if not identical, similar cryptic self-peptides, they would induce comparable ANolA responses in H-2 susceptible mice. We analysed the development of ANolA production in mercury- and/or silver-treated mice of H-2s, H-2q and H-2f genotypes. We found that while mercury stimulated ANolA synthesis in all strains tested, silver induced ANolA responses of lower magnitudes in only H-2s and H-2q mice, but not in H-2f mice. Resistance to silver in H-2f mice was independent of the dosage/time-period of silver-treatment and non-H-2 genes. Further studies showed that F1 hybrid crosses between silver-susceptible A.SW (H-2s) and -resistant A.CA (H-2f) mice were resistant to silver, but not mercury with regard to ANolA production. Additionally, the magnitudes of mercury-induced ANolA responses in the F1 hybrids were lower than those of their parental strains. The above differential ANolA responses to mercury and silver can be explained by various factors, including the different display of nucleolar cryptic peptides by these xenobiotics, determinant capture and coexistence of different MHC molecules. Our findings also suggest that the ability of a xenobiotic metal merely to create cryptic self-peptides may not be sufficient for the induction of an ANolA response. PMID:12605692

  20. Characterization of a real time H2O2 monitor for use in studies on H2O2 production by antibodies and cells.

    PubMed

    Sharma, Harish A; Balcavage, Walter X; Waite, Lee R; Johnson, Mary T; Nindl, Gabi

    2003-01-01

    It was recently shown that antibodies catalyze a reaction between water and ultraviolet light (UV) creating singlet oxygen and ultimately H2O2. Although the in vivo relevance of these antibody reactions is unclear, it is interesting that among a wide variety of non-antibody proteins tested, the T cell receptor is the only protein with similar capabilities. In clinical settings UV is believed to exert therapeutic effects by eliminating inflammatory epidermal T cells and we hypothesized that UV-triggered H2O2 production is involved in this process. To test the hypothesis we developed tools to study production of H2O2 by T cell receptors with the long-term goal of understanding, and improving, UV phototherapy. Here, we report the development of an inexpensive, real time H2O2 monitoring system having broad applicability. The detector is a Clark oxygen electrode (Pt, Ag/AgCl) modified to detect UV-driven H2O2 production. Modifications include painting the electrode black to minimize UV effects on the Ag/AgCl electrode and the use of hydrophilic, large pore Gelnots electrode membranes. Electrode current was converted to voltage and then amplified and recorded using a digital multimeter coupled to a PC. A reaction vessel with a quartz window was developed to maintain constant temperature while permitting UV irradiation of the samples. The sensitivity and specificity of the system and its use in cell-free and cell-based assays will be presented. In a cellfree system, production of H2O2 by CD3 antibodies was confirmed using our real time H2O2 monitoring method. Additionally we report the finding that splenocytes and Jurkat T cells also produce H2O2 when exposed to UV light. PMID:12724951

  1. Electron swarm coefficients for H2O and H2O-N2

    NASA Astrophysics Data System (ADS)

    Juarez, A. M.; Basurto, E.; Hernandez-Avila, J. L.; de Urquijo, J.

    2008-10-01

    We have used a pulsed Townsend technique to measure the electron drift velocity ve, the density normalized longitudinal diffusion coefficient NDL, and effective ionization coefficient (α-η)/N, in water vapour and water vapour-nitrogen mixtures over the density-reduced electric field range E/N, 16-650 x 10-17V cm^2. The ve values are in good agreement with previous ones, while those for NDL agree well with a previous calculation. The limiting value for E/N was found to be E/Nlim=137 x 10-17 V cm^2. For E/N<70x10-17 V cm^2, the ve curves lie below that for pure N2; however, the 10% H2O-N2 curve for ve shows the trend for negative differential conductivity. The (α-η)/N curve for H2O shows a shallow, negative minimum, in disagreement with a recent measurement using the steady-state Townsend technique. The H2O-N2 curves for (α-η)/N show a progressively smaller minima, together with a trend to lower values of (α-η)/N as the N2 content in the mixture increases. This research aims to provide a complete set of self-consistent electron swarm parameters for the simulation of flue-gas discharges.

  2. H2 dissociation of H2 on Co layers on Cu(111) from abinitio studies

    NASA Astrophysics Data System (ADS)

    Le, Duy; Stolbov, Sergey; Rahman, Talat

    2009-03-01

    Through first principles electronic calculations, based on the spin-polarized density functional theory using the generalized gradient approximation and the ultrasoft pseudopotential method in the plane wave representation, we studied the adsorption and the dissociation of H2 on two Co layers grown on Cu(111). As H2 approaches the surface with the H-H bond parallel to that surface, it dissociates at a distance of about 1.7? from the Co layer, and constituent H atoms proceed to occupy neighboring fcc and hcp sites. The ``adsorption'' energy barrier for H2 is 0.14 eV and the ``adsorption'' energy is about 0.80eV. On the Co surface, H diffuses from an fcc site to an hcp site, or vise versa, with diffusion barriers of 0.17eV and 0.12eV respectively. We find no evidence of subsurface H. By analyzing the local electronic density of state, we establish, in agreement with suggestion from experiments [1], that the surface electronic states and magnetic moment of Co atoms depend very much on the H coverage. [3pt] [1] M. Sicot et al, Phys. Rev. B 77, 035417 (2008)

  3. Serpentinization and the Formation of H2 and CH4 on Celestial Bodies (Planets, Moons, Comets).

    PubMed

    Holm, N G; Oze, C; Mousis, O; Waite, J H; Guilbert-Lepoutre, A

    2015-07-01

    Serpentinization involves the hydrolysis and transformation of primary ferromagnesian minerals such as olivine ((Mg,Fe)2SiO4) and pyroxenes ((Mg,Fe)SiO3) to produce H2-rich fluids and a variety of secondary minerals over a wide range of environmental conditions. The continual and elevated production of H2 is capable of reducing carbon, thus initiating an inorganic pathway to produce organic compounds. The production of H2 and H2-dependent CH4 in serpentinization systems has received significant interdisciplinary interest, especially with regard to the abiotic synthesis of organic compounds and the origins and maintenance of life in Earth's lithosphere and elsewhere in the Universe. Here, serpentinization with an emphasis on the formation of H2 and CH4 are reviewed within the context of the mineralogy, temperature/pressure, and fluid/gas chemistry present in planetary environments. Whether deep in Earth's interior or in Kuiper Belt Objects in space, serpentinization is a feasible process to invoke as a means of producing astrobiologically indispensable H2 capable of reducing carbon to organic compounds. PMID:26154779

  4. Serpentinization and the Formation of H2 and CH4 on Celestial Bodies (Planets, Moons, Comets)

    PubMed Central

    Oze, C.; Mousis, O.; Waite, J.H.; Guilbert-Lepoutre, A.

    2015-01-01

    Abstract Serpentinization involves the hydrolysis and transformation of primary ferromagnesian minerals such as olivine ((Mg,Fe)2SiO4) and pyroxenes ((Mg,Fe)SiO3) to produce H2-rich fluids and a variety of secondary minerals over a wide range of environmental conditions. The continual and elevated production of H2 is capable of reducing carbon, thus initiating an inorganic pathway to produce organic compounds. The production of H2 and H2-dependent CH4 in serpentinization systems has received significant interdisciplinary interest, especially with regard to the abiotic synthesis of organic compounds and the origins and maintenance of life in Earth's lithosphere and elsewhere in the Universe. Here, serpentinization with an emphasis on the formation of H2 and CH4 are reviewed within the context of the mineralogy, temperature/pressure, and fluid/gas chemistry present in planetary environments. Whether deep in Earth's interior or in Kuiper Belt Objects in space, serpentinization is a feasible process to invoke as a means of producing astrobiologically indispensable H2 capable of reducing carbon to organic compounds. Key Words: Serpentinization—Fischer-Tropsch-type synthesis—Hydrogen formation—Methane formation—Ultramafic rocks. Astrobiology 15, 587–600. PMID:26154779

  5. 45 CFR 1626.11 - H-2 agricultural workers.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 45 Public Welfare 4 2011-10-01 2011-10-01 false H-2 agricultural workers. 1626.11 Section 1626.11... ON LEGAL ASSISTANCE TO ALIENS § 1626.11 H-2 agricultural workers. (a) Nonimmigrant agricultural workers admitted under the provisions of 8 U.S.C. 1101(a)(15)(h)(ii), commonly called H-2 workers, may...

  6. 45 CFR 1626.11 - H-2 agricultural workers.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 45 Public Welfare 4 2013-10-01 2013-10-01 false H-2 agricultural workers. 1626.11 Section 1626.11... ON LEGAL ASSISTANCE TO ALIENS § 1626.11 H-2 agricultural workers. (a) Nonimmigrant agricultural workers admitted under the provisions of 8 U.S.C. 1101(a)(15)(h)(ii), commonly called H-2 workers, may...

  7. 45 CFR 1626.11 - H-2 agricultural workers.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 45 Public Welfare 4 2010-10-01 2010-10-01 false H-2 agricultural workers. 1626.11 Section 1626.11... ON LEGAL ASSISTANCE TO ALIENS § 1626.11 H-2 agricultural workers. (a) Nonimmigrant agricultural workers admitted under the provisions of 8 U.S.C. 1101(a)(15)(h)(ii), commonly called H-2 workers, may...

  8. H2 formation and excitation in the Stephan's Quintet galaxy-wide collision

    NASA Astrophysics Data System (ADS)

    Guillard, P.; Boulanger, F.; Pineau Des Forêts, G.; Appleton, P. N.

    2009-08-01

    Context: The Spitzer Space Telescope has detected a powerful (L_H_2˜1041 erg s-1) mid-infrared H{2} emission towards the galaxy-wide collision in the Stephan's Quintet (henceforth SQ) galaxy group. This discovery was followed by the detection of more distant H{2}-luminous extragalactic sources, with almost no spectroscopic signatures of star formation. These observations place molecular gas in a new context where one has to describe its role as a cooling agent of energetic phases of galaxy evolution. Aims: The SQ postshock medium is observed to be multiphase, with H{2} gas coexisting with a hot (˜5 × 106 K), X-ray emitting plasma. The surface brightness of H{2} lines exceeds that of the X-rays and the 0-0 S(1) H2 linewidth is ˜900 km s-1, of the order of the collision velocity. These observations raise three questions we propose to answer: (i) why is H{2} present in the postshock gas? (ii) How can we account for the H2 excitation? (iii) Why is H2 a dominant coolant? Methods: We consider the collision of two flows of multiphase dusty gas. Our model quantifies the gas cooling, dust destruction, H{2} formation and excitation in the postshock medium. Results: (i) The shock velocity, the post-shock temperature and the gas cooling timescale depend on the preshock gas density. The collision velocity is the shock velocity in the low density volume-filling intercloud gas. This produces a ˜5 × 10^6 K, dust-free, X-ray emitting plasma. The shock velocity is lower in clouds. We show that gas heated to temperatures of less than 10^6 K cools, keeps its dust content and becomes H2 within the SQ collision age (˜5 × 10^6 years). (ii) Since the bulk kinetic energy of the H2 gas is the dominant energy reservoir, we consider that the H2 emission is powered by the dissipation of kinetic turbulent energy. We model this dissipation with non-dissociative MHD shocks and show that the H2 excitation can be reproduced by a combination of low velocities shocks (5-20 km s-1) within

  9. In Vivo Monitoring of H2O2 with Polydopamine and Prussian Blue-coated Microelectrode.

    PubMed

    Li, Ruixin; Liu, Xiaomeng; Qiu, Wanling; Zhang, Meining

    2016-08-01

    In vivo monitoring of hydrogen peroxide (H2O2) in the brain is of importance for understanding the function of both reactive oxygen species (ROS) and signal transmission. Producing a robust microelectrode for in vivo measurement of H2O2 is challenging due to the complex brain environment and the instability of electrocatalysts employed for the reduction of H2O2. Here, we develop a new kind of microelectrode for in vivo monitoring of H2O2, which is prepared by, first, electrodeposition of Prussian blue (PB) onto carbon nanotube (CNT) assembled carbon fiber microelectrodes (CFEs) and then overcoating of the CFEs with a thin membrane of polydopamine (PDA) through self-polymerization. Scanning electron microscopic and X-ray proton spectroscopic results confirm the formation of PDA/PB/CNT/CFEs. The PDA membrane enables PB-based electrodes to show high stability in both in vitro and in vivo studies and to stably catalyze the electrochemical reduction of H2O2. The microelectrode is selective for in vivo measurements of H2O2, interference-free from O2 and other electroactive species coexisting in the brain. These properties, along with good linearity, high biocompatibility, and stability toward H2O2, substantially enable the microelectrode to track H2O2 changes in vivo during electrical stimulation and microinfusion of H2O2 and drug, which demonstrates that the microelectrode could be well suited for in vivo monitoring of dynamic changes of H2O2 in rat brain. PMID:27385361

  10. Detection of HF Toward PKS 1830–211, Search for Interstellar H2F+, and Laboratory Study of H2F+ and H2Cl+ Dissociative Recombination

    NASA Astrophysics Data System (ADS)

    Kawaguchi, K.; Muller, S.; Black, J. H.; Amano, T.; Matsushima, F.; Fujimori, R.; Okabayahsi, Y.; Nagahiro, H.; Miyamoto, Y.; Tang, J.

    2016-05-01

    We report extragalactic observations of two fluorine-bearing species, hydrogen fluoride (HF) and fluoronium (H2F+), in the z = 0.89 absorber in front of the lensed blazar PKS 1830‑211 with the Atacama Large Millimeter/submillimeter Array. HF was detected toward both southwest and northeast images of the blazar, with column densities >3.4 × 1014 cm‑2 and 0.18 × 1014 cm‑2, respectively. H2F+ was not detected, down to an upper limit (3σ) of 8.8 × 1011 cm‑2 and an abundance ratio of [H2F+]/[HF] ≤slant 1/386. We also searched for H2F+ toward the Galactic sources NGC 6334 I and W51C, and toward Galactic center clouds with the Herschel HIFI spectrometer.6 The upper limit on the column density was derived to be 2.5 × 1011 cm‑2 in NGC 6334 I, which is 1/68 of that for H2Cl+. In constrast, the ortho transition of H2Cl+ is detected toward PKS 1830–211. To understand the small abundance of interstellar H2F+, we carried out laboratory experiments to determine the rate constants for the ion–electron recombination reaction by infrared time-resolved spectroscopy. The constants determined are k e (209 K) = (1.1+/- 0.3)× {10}-7 cm3 s‑1 and (0.46+/- 0.05)× {10}-7 cm3 s‑1 for H2F+ and H2Cl+, respectively. The difference in the dissociative recombination rates between H2F+ and H2Cl+ by a factor ∼2 and the cosmic abundance ratio [F]/[Cl] ≈ 1/6 are not enough to explain the much smaller abundance of H2F+. The difference in the formation mechanism of H2F+ and H2Cl+ in interstellar space would be a major factor in the small abundance of H2F+.

  11. Isolation of Salmonella enterica Serovar Kentucky Strain ST 198 and Its H2S-Negative Variant from a Patient: Implications for Diagnosis

    PubMed Central

    Al Obaid, Khaled; Alfouzan, Wadha; Sheikh, Abdul Rashid; Udo, Edet; Izumiya, Hidemasa; Bulach, Dieter M.; Seemann, Torsten

    2014-01-01

    H2S-producing multiresistant Salmonella enterica serovar Kentucky strain sequence type (ST) 198 and its non-H2S-producing variant were isolated from a patient. Whole-genome comparison showed a base addition in the gene encoding molybdenum cofactor biosynthesis protein C, which could affect H2S production in the variant. Lack of H2S production has implications for diagnosis of salmonella. PMID:25143568

  12. Radiation-induced reactions of COH 2 gas mixtures over various solid catalysts

    NASA Astrophysics Data System (ADS)

    Nagai, S.; Arai, H.; Hatada, M.

    Studies have been carried out of radiation-induced reactions of COH 2 gas mixtures in the presence of various solid catalysts in order to find possibilities of synthesizing organic raw materials from COH 2 by radiation for the future. The solid catalysts studied include Fischer-Tropsch catalyst (FeCu supported by diatomaceous earth), titania(TiO 2), and silica gel. Analysis of the reaction products over Fischer-Tropsch catalyst or semiconductors such as TiO 2 and ZnOCr 2O 3 reveals that these solid catalysts do not sensitize the radiation chemical reaction of COH 2 but show the secondary effects on the reaction so as to induce the hydrogenation of olefins produced by the catalytic reaction and of aldehydes produced in gas phase by radiation. On the other hand, silica gel and other insulators such as alumina have been found to exhibit high catalytic activity in the formation of hydrocarbons from COH 2 under electron beam irradiation at 300°C. It has been shown experimentally that secondary reactions between H 2 and carbonaceous solid produced from CO make a substantial contribution to the formation of hydrocarbons from COH 2 over silica gel. In an attempt to find the role of silica gel in the reaction to produce hydrocarbons, radiation-induced reactions have been studied of H 2 with the carbonaceous solid that had been produced by irradiation of CO in the absence of solid catalyst, over TiO 2, or over silica gel. The results indicate that silica gel not only enhances the yields of CO 2 and carbonaceous solid from CO but also promotes hydrogenation reactions of the carbonaceous solid under electron beam irradiation.

  13. H2S regulation of nitric oxide metabolism

    PubMed Central

    Kolluru, Gopi K.; Yuan, Shuai; Shen, Xinggui; Kevil, Christopher G.

    2015-01-01

    Nitric oxide (NO) and hydrogen sulfide (H2S) are two major gaseous signaling molecules that regulate diverse physiological functions. Recent publications indicate the regulatory role of H2S on NO metabolism. In this chapter, we discuss the latest findings on H2S-NO interactions through formation of novel chemical derivatives, and experimental approaches to study these adducts. This chapter also addresses potential H2S interference on various NO detection techniques, along with precautions for analyzing biological samples from various sources. This information will facilitate critical evaluation and clearer insight into H2S regulation of NO signaling and its influence on various physiological functions. PMID:25725527

  14. The thioredoxin and glutathione-dependent H2O2 consumption pathways in muscle mitochondria: Involvement in H2O2 metabolism and consequence to H2O2 efflux assays.

    PubMed

    Munro, Daniel; Banh, Sheena; Sotiri, Emianka; Tamanna, Nahid; Treberg, Jason R

    2016-07-01

    The most common methods of measuring mitochondrial hydrogen peroxide production are based on the extramitochondrial oxidation of a fluorescent probe such as amplex ultra red (AUR) by horseradish peroxidase (HRP). These traditional HRP-based assays only detect H2O2 that has escaped the matrix, raising the potential for substantial underestimation of production if H2O2 is consumed by matrix antioxidant pathways. To measure this underestimation, we characterized matrix consumers of H2O2 in rat skeletal muscle mitochondria, and developed specific means to inhibit these consumers. Mitochondria removed exogenously added H2O2 (2.5µM) at rates of 4.7 and 5.0nmol min(-1) mg protein(-1) when respiring on glutamate+malate and succinate+rotenone, respectively. In the absence of respiratory substrate, or after disrupting membranes by cycles of freeze-thaw, rates of H2O2 consumption were negligible. We concluded that matrix consumers are respiration-dependent (requiring respiratory substrates), suggesting the involvement of either the thioredoxin (Trx) and/or glutathione (GSH)-dependent enzymatic pathways. The Trx-reductase inhibitor auranofin (2µM), and a pre-treatment of mitochondria with 35µM of 1-chloro-2,4-dintrobenzene (CDNB) to deplete GSH specifically compromise these two consumption pathways. These inhibition approaches presented no undesirable "off-target" effects during extensive preliminary tests. These inhibition approaches independently and additively decreased the rate of consumption of H2O2 exogenously added to the medium (2.5µM). During traditional HRP-based H2O2 efflux assays, these inhibition approaches independently and additively increased apparent efflux rates. When used in combination (double inhibition), these inhibition approaches allowed accumulation of (endogenously produced) H2O2 in the medium at a comparable rate whether it was measured with an end point assay where 2.5µM H2O2 is initially added to the medium or with traditional HRP-based efflux

  15. H2-rich fluids from serpentinization: geochemical and biotic implications.

    PubMed

    Sleep, N H; Meibom, A; Fridriksson, Th; Coleman, R G; Bird, D K

    2004-08-31

    Metamorphic hydration and oxidation of ultramafic rocks produces serpentinites, composed of serpentine group minerals and varying amounts of brucite, magnetite, and/or FeNi alloys. These minerals buffer metamorphic fluids to extremely reducing conditions that are capable of producing hydrogen gas. Awaruite, FeNi3, forms early in this process when the serpentinite minerals are Fe-rich. Olivine with the current mantle Fe/Mg ratio was oxidized during serpentinization after the Moon-forming impact. This process formed some of the ferric iron in the Earth's mantle. For the rest of Earth's history, serpentinites covered only a small fraction of the Earth's surface but were an important prebiotic and biotic environment. Extant methanogens react H2 with CO2 to form methane. This is a likely habitable environment on large silicate planets. The catalytic properties of FeNi3 allow complex organic compounds to form within serpentinite and, when mixed with atmospherically produced complex organic matter and waters that circulated through basalts, constitutes an attractive prebiotic substrate. Conversely, inorganic catalysis of methane by FeNi3 competes with nascent and extant life. PMID:15326313

  16. H2-rich fluids from serpentinization: Geochemical and biotic implications

    PubMed Central

    Sleep, N. H.; Meibom, A.; Fridriksson, Th.; Coleman, R. G.; Bird, D. K.

    2004-01-01

    Metamorphic hydration and oxidation of ultramafic rocks produces serpentinites, composed of serpentine group minerals and varying amounts of brucite, magnetite, and/or FeNi alloys. These minerals buffer metamorphic fluids to extremely reducing conditions that are capable of producing hydrogen gas. Awaruite, FeNi3, forms early in this process when the serpentinite minerals are Fe-rich. Olivine with the current mantle Fe/Mg ratio was oxidized during serpentinization after the Moon-forming impact. This process formed some of the ferric iron in the Earth's mantle. For the rest of Earth's history, serpentinites covered only a small fraction of the Earth's surface but were an important prebiotic and biotic environment. Extant methanogens react H2 with CO2 to form methane. This is a likely habitable environment on large silicate planets. The catalytic properties of FeNi3 allow complex organic compounds to form within serpentinite and, when mixed with atmospherically produced complex organic matter and waters that circulated through basalts, constitutes an attractive prebiotic substrate. Conversely, inorganic catalysis of methane by FeNi3 competes with nascent and extant life. PMID:15326313

  17. H2O-mediated trimerization of H2SO4: A computational study and comparison with experimental data

    NASA Astrophysics Data System (ADS)

    Nadykto, A. B.; Nazarenko, K. M.; Jakovleva, M. V.; Uvarova, L. A.; Yu, F.

    2016-06-01

    In the present paper, the formation of stable hydrated (H2SO4)3(H2O)n clusters has been studied using the Density Functional Theory (DFT) at PW91PW91/6-311++(3df,3pd) level. We have found that the hydration of H2SO4 trimers is stronger than that of H2SO4 dimers and tends to decrease at large hydration numbers. We have shown that the affinity of H2SO4 to (H2SO4)2(H2O)n is much higher than that H2SO4 to (H2SO4) (H2O)n. We have compared the equilibrium constants of H2O-mediated trimerization of H2SO4 obtained using PW91PW91/6-311++(3df,3pd) method with experimental data and found that theory and experimentation are in good agreement. The new thermochemical data can be used in a wide range of nucleation studies and can be utilized for the development of quantum-based models of nucleation rates.

  18. A Computational Investigation of the Oxidative Deboronation of BoroGlycine, H2N–CH2–B(OH)2, Using H2O and H2O2

    PubMed Central

    Larkin, Joseph D.; Markham, George D.; Milkevitch, Matt; Brooks, Bernard R.; Bock, Charles W.

    2014-01-01

    We report results from a computational investigation of the oxidative deboronation of BoroGlycine, H2N–CH2–B(OH)2, using H2O and H2O2 as the reactive oxygen species (ROS) to yield aminomethanol, H2N–CH2–OH; these results complement our study on the protodeboronation of BoroGlycine to produce methylamine, H2N–CH3 (Larkin et al. J. Phys. Chem. A, 111, 6489–6500, 2007). Second-order Møller-Plesset (MP2) perturbation theory with Dunning-Woon correlation-consistent (cc) basis sets were used for the calculations with comparisons made to results from Density Functional Theory (DFT) at the PBE1PBE/6-311++G(d,p)(cc-pVDZ) levels. The effects of a bulk aqueous environment were also incorporated into the calculations employing PCM and CPCM methodology. Using H2O as the ROS, the reaction H2O + H2N–CH2–B(OH)2 → H2N–CH2–OH + H–B(OH)2 was calculated to be endothermic, the value of ΔH2980 was +12.0 kcal/mol at the MP2(FC)/cc-pVTZ computational level in vacuo and +13.7 kcal/mol in PCM aqueous media; the corresponding value for the activation barrier, ΔH‡, was +94.3 kcal/mol relative to the separated reactants in vacuo and +89.9 kcal/mol in PCM aqueous media. In contrast, the reaction H2O2 + H2N–CH2–B(OH)2 → H2N–CH2–OH + B(OH)3 was calculated to be highly exothermic with a ΔH2980 value of −100.9 kcal/mol at the MP2(FC)/cc-pVTZ computational level in vacuo and −99.6 kcal/mol in CPCM aqueous media; the highest-energy transition state for the multi-step process associated with this reaction involved the rearrangement of H2N–CH2–B(OH)(OOH) to H2N–CH2–O–B(OH)2 with a ΔH‡ value of +23.2 kcal/mol in vacuo relative to the separated reactants. These computational results for BoroGlycine are in accord with the experimental observations for the deboronation of the FDA approved anti-cancer drug Bortezomib (Velcade™, PS-341) where it was found to be the principle deactivation pathway. (Labutti et al. Chem. Res. Toxicol., 19, 539–546

  19. Role of peroxynitrite induced structural changes on H2B histone by physicochemical method.

    PubMed

    Khan, M Asad; Alam, Khursheed; Dixit, Kiran; Rizvi, M Moshahid A

    2016-01-01

    Histones are small highly conserved cationic proteins which bind DNA and remain confined in the nucleus. These histones are quite vulnerable to oxidizing and nitrating agents. Peroxynitrite is a powerful oxidant and nitrating agent present in the biological system. In this study, peroxynitrite-induced nitration and oxidation of H2B was assessed by various physicochemical techniques. The carbonyl content and dityrosine were markedly elevated in peroxynitrite-modified H2B histone as compared to the native histone. Cross-linking of H2B was evident on polyacrylamide gel electrophoresis. 3-Nitrotyrosine was present only in peroxynitrite-modified H2B revealed by HPLC. The results showed that peroxynitrite-mediated nitration and oxidation in H2B histone exhibited hyperchromicity, decrease of tyrosine fluorescence accompanied by increase in ANS-binding specific fluorescence, loss of β-sheet structure, appearance of new peak in FT-IR, increase in melting temperature and also loss of α-helix to produce a partially folded structure in comparison to intrinsically disordered structure of native H2B histone. We concluded that the H2B histone, a constituent of core histones, is highly sensitive to peroxynitrite and can adopt different structures under nitrosative and oxidative stress in order to protect the packaged DNA from the deleterious insult of peroxynitrite. PMID:26536630

  20. Tyrosine Kinase Signal Modulation: A Matter of H2O2 Membrane Permeability?

    PubMed Central

    Bertolotti, Milena; Bestetti, Stefano; García-Manteiga, Jose M.; Medraño-Fernandez, Iria; Dal Mas, Andrea; Malosio, Maria Luisa

    2013-01-01

    Abstract H2O2 produced by extracellular NADPH oxidases regulates tyrosine kinase signaling inhibiting phosphatases. How does it cross the membrane to reach its cytosolic targets? Silencing aquaporin-8 (AQP8), but not AQP3 or AQP4, inhibited H2O2 entry into HeLa cells. Re-expression of AQP8 with silencing-resistant vectors rescued H2O2 transport, whereas a C173A-AQP8 mutant failed to do so. Lowering AQP8 levels affected H2O2 entry into the endoplasmic reticulum, but not into mitochondria. AQP8 silencing also inhibited the H2O2 spikes and phosphorylation of downstream proteins induced by epidermal growth factor. These observations lead to the hypothesis that H2O2 does not freely diffuse across the plasma membrane and AQP8 and other H2O2 transporters are potential targets for manipulating key signaling pathways in cancer and degenerative diseases. Antioxid. Redox Signal. 19, 1447–1451. PMID:23541115

  1. Ametryn degradation in the ultraviolet (UV) irradiation/hydrogen peroxide (H2O2) treatment.

    PubMed

    Gao, Nai-Yun; Deng, Yang; Zhao, Dandan

    2009-05-30

    Ultraviolet (UV) irradiation (253.7nm) in the presence of hydrogen peroxide (H(2)O(2)) was used to decompose aqueous ametryn. The concentrations of ametryn were measured with time under various experiment conditions. The investigated factors included H(2)O(2) dosages, initial pH, initial ametryn concentrations, and a variety of inorganic anions. Results showed that ametryn degradation in UV/H(2)O(2) process was a pseudo-first-order reaction. Removal rates of ametryn were greatly affected by H(2)O(2) dosage and initial concentrations of ametryn, but appeared to be slightly influenced by initial pH. Furthermore, we investigated the effects of four anions (SO(4)(2-), Cl(-), HCO(3)(-), and CO(3)(2-)) on ametryn degradation by UV/H(2)O(2). The impact of SO(4)(2-) seemed to be insignificant; however, Cl(-), HCO(3)(-), and CO(3)(2-) considerably slowed down the degradation rate because they could strongly scavenge hydroxyl radicals (OH) produced during the UV/H(2)O(2) process. Finally, a preliminary cost analysis revealed that UV/H(2)O(2) process was more cost-effective than the UV alone in removal of ametryn from water. PMID:18824296

  2. EERE-SBIR technology transfer opportunity. H2 Safety Sensors for H2

    SciTech Connect

    Johnston, Mariann R.

    2015-12-01

    The Office of Energy Efficiency and Renewable Energy’s Fuel Cell Technologies Office (FCTO) works in partnership with industry (including small businesses), academia, and DOE's national laboratories to establish fuel cell and hydrogen energy technologies as economically competitive contributors to U.S. transportation needs. The work that is envisioned between the SBIR/STTR grantee and Los Alamos National Laboratory would involve Technical Transfer of Los Alamos Intellectual Property (IP) on Thin-film Mixed Potential Sensor (U.S. Patent 7,264,700) and associated know-how for H2 sensor manufacturing and packaging.

  3. A Proposal for Climate Stability on H2-greenhouse Planets

    NASA Astrophysics Data System (ADS)

    Abbot, Dorian S.

    2015-12-01

    A terrestrial planet in an orbit far outside of the standard habitable zone could maintain surface liquid water as a result of H2-H2 collision-induced absorption by a thick H2 atmosphere. Without a stabilizing climate feedback, however, habitability would be accidental and likely brief. In this letter I propose stabilizing climate feedbacks for such a planet that require only that biological functions have an optimal temperature and operate less efficiently at other temperatures. For example, on a planet with a net source of H2 from its interior, H2-consuming life (such as methanogens) could establish a stable climate. If a positive perturbation is added to the equilibrium temperature, H2 consumption by life will increase (cooling the planet) until the equilibrium climate is reestablished. The potential existence of such feedbacks makes H2-warmed planets more attractive astrobiological targets.

  4. FRET ratiometric probes reveal the chiral-sensitive cysteine-dependent H2S production and regulation in living cells

    NASA Astrophysics Data System (ADS)

    Wei, Lv; Yi, Long; Song, Fanbo; Wei, Chao; Wang, Bai-Fan; Xi, Zhen

    2014-04-01

    Hydrogen sulfide (H2S) is an endogenously produced gaseous signalling molecule with multiple biological functions. In order to visualize and quantify the endogenous in situ production of H2S in living cells, here we developed two new sulphide ratiometric probes (SR400 and SR550) based on fluorescence resonance energy transfer (FRET) strategy for live capture of H2S. The FRET-based probes show excellent selectivity toward H2S in a high thiol background under physiological buffer. The probe can be used to in situ visualize cysteine-dependent H2S production in a chiral-sensitive manner in living cells. The ratiometric imaging studies indicated that D-Cys induces more H2S production than that of L-Cys in mitochondria of human embryonic kidney 293 cells (HEK293). The cysteine mimics propargylglycine (PPG) has also been found to inhibit the cysteine-dependent endogenous H2S production in a chiral-sensitive manner in living cells. D-PPG inhibited D-Cys-dependent H2S production more efficiently than L-PPG, while, L-PPG inhibited L-Cys-dependent H2S production more efficiently than D-PPG. Our bioimaging studies support Kimura's discovery of H2S production from D-cysteine in mammalian cells and further highlight the potential of D-cysteine and its derivatives as an alternative strategy for classical H2S-releasing drugs.

  5. FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT ETERNAL Drought(s)-Elimination FOREVER!!!

    NASA Astrophysics Data System (ADS)

    Wignall, J.; Lyons, Marv; Ertl, G.; Alefeld, Georg; Youdelis, W.; Radd, H.; Oertle, G.; Siegel, Edward

    2013-03-01

    ''H2O H2O everywhere; ne'er a drop to drink''[Coleridge(1798)] now: ''H2 H2 everywhere; STILL ne'er a drop to drink'': ONLY H2 (or methane CH4) can be FLYING-WATER(F-W) chemical-rain-in-pipelines Hindenberg-effect (H2-UP;H2O-DOWN): { ∖{}O/H2O{ ∖}} =[16]/[18] ∖sim 90{ ∖%} O already in air uphill; NO H2O pumping need! In global-warming driven H2O-starved glacial-melting world, rescue is possible ONLY by Siegel [ ∖underline {3rd Intl. Conf. Alt.-Energy }(1980)-vol.5/p.459!!!] Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating-system. Rosenfeld[Science 315,1396(3/9/2007)]-Biello [Sci.Am.(3/9 /2007)] crucial geomorphology which ONLY maximal-buoyancy H2 can exploit, to again make ''Mountains into Fountains'', ``upthrust rocks trapping the clouds to precipitate their rain/snow/H2O'': ''terraforming''(and ocean-rebasificaton!!!) ONLY VIA Siegel[APS March MTGS.:1960s-2000ss) DIFFUSIVE-MAGNETORESISTANCE (DMR) proprietary MAGNETIC-HYDROGEN-VALVE(MHV) ALL-IMPORTANT PRECLUDED RADIAL-diffusion, permitting ONLY AXIAL-H2-BALLISTIC-flow (``G.A''.''/DoE''/''Terrapower''/''Intellectual-Ventures''/ ''Gileland''/ ''Myhrvold''/''Gates'' ``ARCHIMEDES'') in ALREADY IN-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Science 300,1740(2003)] dire warning of global-pandemics (cancers/ blindness/ famine)

  6. Optimization of intermolecular potential parameters for the CO2/H2O mixture.

    PubMed

    Orozco, Gustavo A; Economou, Ioannis G; Panagiotopoulos, Athanassios Z

    2014-10-01

    Monte Carlo simulations in the Gibbs ensemble were used to obtain optimized intermolecular potential parameters to describe the phase behavior of the mixture CO2/H2O, over a range of temperatures and pressures relevant for carbon capture and sequestration processes. Commonly used fixed-point-charge force fields that include Lennard-Jones 12-6 (LJ) or exponential-6 (Exp-6) terms were used to describe CO2 and H2O intermolecular interactions. For force fields based on the LJ functional form, changes of the unlike interactions produced higher variations in the H2O-rich phase than in the CO2-rich phase. A major finding of the present study is that for these potentials, no combination of unlike interaction parameters is able to adequately represent properties of both phases. Changes to the partial charges of H2O were found to produce significant variations in both phases and are able to fit experimental data in both phases, at the cost of inaccuracies for the pure H2O properties. By contrast, for the Exp-6 case, optimization of a single parameter, the oxygen-oxygen unlike-pair interaction, was found sufficient to give accurate predictions of the solubilities in both phases while preserving accuracy in the pure component properties. These models are thus recommended for future molecular simulation studies of CO2/H2O mixtures. PMID:25198539

  7. Reactive collisions of atomic antihydrogen with H, He^+, He, H2^+, and H2

    NASA Astrophysics Data System (ADS)

    Cohen, James S.

    2006-05-01

    The fermion molecular dynamics (FMD) method has been used to determine the rearrangement and destruction cross sections for collisions of antihydrogen (H) with H, He^+, He, H2^+, and H2 at collision energies above 0.1 au. The results for the H and He^+ targets satisfactorily merge with previous calculations done for lower collision energies. There are no previous calculations for the other targets. Despite the absence of a critical distance, the destruction cross section for collisions of H with He is found to be comparable with the destruction cross sections for H collisions with H and He^+, for which there are critical distances. The three atomic cross sections are shown to be given quite reasonably by simple classical orbiting formulas at energies that are very low but still high enough for L>0 partial waves to be dominant. The cross sections for formation of the antiprotonic atoms (Pn or pHe) and their initial quantum numbers are found to be significantly different from the analogous cross sections for p projectiles. The cross sections for the molecular targets are significantly larger.

  8. H2SO4/HNO3/H2O Phase Diagram in Regions of Stratospheric Importance

    NASA Astrophysics Data System (ADS)

    Beyer, K. D.; Hansen, A. R.; Raddatz, N.

    2003-12-01

    We have investigated the region of the H2SO4/HNO3/H2O ternary liquid/solid phase diagram bounded by ice, nitric acid trihydrate (NAT), and sulfuric acid tetrahydrate (SAT) using differential scanning calorimetry (DSC) and infrared spectroscopy of thin films. We report measurements and analysis of the eutectic melting curves in the ternary system of the hydrates mentioned as well as the temperature of the eutectics: ice/SAT/NAT, ice/sulfuric acid hemihexahydrate (SAH)/NAT, and SAT/NAT. We report for the first time an analysis of the content of the solid phase of completely frozen samples and find that sulfuric acid octahydrate (SAO) is often present in frozen ternary samples and can be a significant portion of the solid phase. We provide a description of how the melting path of a frozen ternary sample can be predicted using the ternary phase diagram. We have parameterized our melting point data and provide equations to generate the ternary melting surface. Finally, we compare our results to the historic work of Carpenter & Lehrmann (Carpenter, C. D.; Lehrman, A. Trans. AIChE 1925, 17, 35) and to other more recent work.

  9. State-specific Dissociation Rates for H2(v, j) + H2(v‧, j‧)

    NASA Astrophysics Data System (ADS)

    Mandy, M. E.

    2016-08-01

    State-specific rate coefficients for the dissociation of H2 as the result of collisions with H2 were calculated for all combinations of (v, j) with an internal energy below 1 eV. Full-dimensional quasiclassical trajectories were calculated using the BMKP2 interaction potential with a minimum of 80,000 trajectories at each translational energy. Additional large batches of trajectories were carried out to calculate the cross sections near the threshold to dissociation to attain the desired precision of the rate coefficients. A piecewise linear excitation function was used to calculate the rate coefficient between 100 and 100,000 K. The resulting state-specific rate coefficients, γ, were parametrized as a function of temperature over the range 600–10,000 K using: {{log}}10 γ (t)=a+{bz}+{{cz}}2-d≤ft(\\displaystyle \\frac{1}{t}-1\\right) where t=T/4500 K and z={{log}}10 t. The values of the resulting rate coefficients were sensitive to the internal energy of both molecules, with initial vibrational energy having a slightly greater effect than rotational energy. This effect diminished as temperature increased.

  10. Removal of Boron in Silicon by H2-H2O Gas Mixtures

    NASA Astrophysics Data System (ADS)

    Tang, Kai; Andersson, Stefan; Nordstrand, Erlend; Tangstad, Merete

    2012-08-01

    The removal of boron in pure silicon by gas mixtures has been examined in the laboratory. Water-vapor-saturated hydrogen was used to remove boron doped in electronic-grade silicon in a vacuum frequency furnace. Boron concentrations in silicon were reduced from 52 ppm initially to 0.7 ppm and 3.4 ppm at 1450°C and 1500°C, respectively, after blowing a H2-3.2%H2O gas mixture for 180 min. The experimental results indicate that the boron removal as a function of gas-blowing time follows the law of exponential decay. After 99% of the boron is removed, approximately 90% of the silicon can be recovered. In order to better understand the gaseous refining mechanism, the quantum chemical coupled cluster with single and double excitations and a perturbative treatment of triple excitations method was used to accurately predict the enthalpy and entropy of formation of the HBO molecule. A simple refining model was then used to describe the boron refining process. This model can be used to optimize the refining efficiency.

  11. Solar-Driven H2 O2 Generation From H2 O and O2 Using Earth-Abundant Mixed-Metal Oxide@Carbon Nitride Photocatalysts.

    PubMed

    Wang, Ruirui; Pan, Kecheng; Han, Dandan; Jiang, Jingjing; Xiang, Chengxiang; Huang, Zhuangqun; Zhang, Lu; Xiang, Xu

    2016-09-01

    Light-driven generation of H2 O2 only from water and molecular oxygen could be an ideal pathway for clean production of solar fuels. In this work, a mixed metal oxide/graphitic-C3 N4 (MMO@C3 N4 ) composite was synthesized as a dual-functional photocatalyst for both water oxidation and oxygen reduction to generate H2 O2 . The MMO was derived from a NiFe-layered double hydroxide (LDH) precursor for obtaining a high dispersion of metal oxides on the surface of the C3 N4 matrix. The C3 N4 is in the graphitic phase and the main crystalline phase in MMO is cubic NiO. The XPS analyses revealed the doping of Fe(3+) in the dominant NiO phase and the existence of surface defects in the C3 N4 matrix. The formation and decomposition kinetics of H2 O2 on the MMO@C3 N4 and the control samples, including bare MMO, C3 N4 matrix, Ni- or Fe-loaded C3 N4 and a simple mixture of MMO and C3 N4 , were investigated. The MMO@C3 N4 composite produced 63 μmol L(-1) of H2 O2 in 90 min in acidic solution (pH 3) and exhibited a significantly higher rate of production for H2 O2 relative to the control samples. The positive shift of the valence band in the composite and the enhanced water oxidation catalysis by incorporating the MMO improved the light-induced hole collection relative to the bare C3 N4 and resulted in the enhanced H2 O2 formation. The positively shifted conduction band in the composite also improved the selectivity of the two-electron reduction of molecular oxygen to H2 O2 . PMID:27484581

  12. Synthesis and Biological Activity of Manganese (II) Complexes of Phthalic and Isophthalic Acid: X-Ray Crystal Structures of [Mn(ph)(Phen)(2)(H(2)O)]. 4H(2)O, [Mn(Phen)(2)(H(2)O)(2)](2)(Isoph)(2)(Phen). 12H(2)O and {[Mn(Isoph)(bipy)](4). 2.75biby}(n)(phH(2) = Phthalic Acid; isoph = Isophthalic Acid; phen = 1,10-Phenanthroline; bipy = 2,2-Bipyridine).

    PubMed

    Devereux, M; McCann, M; Leon, V; Geraghty, M; McKee, V; Wikaira, J

    2000-01-01

    Manganese(II) acetate reacts with phthalic acid (phH(2)) to give [Mn(ph)].0.5H(2)O (1). Reaction of 1 with 1,10-phenanthroline produces [Mn(ph)(phen)].2H(2)O (2) and [Mn(ph)(phen)(2)(H(2)O)].4H(2)O (3). Reaction of isophthalic acid (isophH(2)) with manganese(II) acetate results in the formation of [Mn(isoph)].2H(2)O (4). The addition of the N,N-donor ligands 1,10-phenanthroline or 2,2'-bipyridine to 4 leads to the formation of [Mn(2) (isoph)(2)(phen)(3))].4H(2)O (5), [(Mn(phen)(2)(H(2)O)(2)](2)(isoph)(2)(phen).12H(2)O (6) and {[Mn(isoph)(bipy)](4).2.75 biby}(n) (7), respectively. Molecular structures of 3, 6 and 7 were determined crystallographically. In 3 the phthalate ligand is bound to the manganese via just one of its carboxylate groups in a monodentate mode with the remaining coordination sites filled by four phenanthroline nitrogen and one water oxygen atoms. In 6 the isophthalates are uncoordinated with the octahedral manganese center ligated by two phenanthrolines and two waters. In 7 the Isophthalate ligands act as bridges resulting in a polymeric structure. One of the carboxylate groups is chelating a single manganese with the other binding two metal centres in a bridging bidentate mode. The phthalate and isophthalate complexes, the metal free ligands and a number of simple manganes salts were each tested for their ability, to inhibit the growth of Candida albicans. Only the "metal free" 1,10-phenanthroline and its manganese complexes were found to be active. PMID:18475957

  13. Synthesis and Biological Activity of Manganese (II) Complexes of Phthalic and Isophthalic Acid: X-Ray Crystal Structures of [Mn(ph)(Phen)2(H2O)]· 4H2O, [Mn(Phen)2(H2O)2]2(Isoph)2(Phen)· 12H2O and {[Mn(Isoph)(bipy)]4· 2.75biby}n(phH2 = Phthalic Acid; isoph = Isophthalic Acid; phen = 1,10-Phenanthroline; bipy = 2,2-Bipyridine)

    PubMed Central

    McCann, Malachy; Leon, Vanessa; Geraghty, Majella; McKee, Vickie; Wikaira, Jan

    2000-01-01

    Manganese(II) acetate reacts with phthalic acid (phH2) to give [Mn(ph)]·0.5H2O (1). Reaction of 1 with 1,10-phenanthroline produces [Mn(ph)(phen)]·2H2O (2) and [Mn(ph)(phen)2(H2O)]·4H2O (3). Reaction of isophthalic acid (isophH2) with manganese(II) acetate results in the formation of [Mn(isoph)]·2H2O (4). The addition of the N,N-donor ligands 1,10-phenanthroline or 2,2'-bipyridine to 4 leads to the formation of [Mn2 (isoph)2(phen)3)]·4H2O (5), [(Mn(phen)2(H2O)2]2(isoph)2(phen)·12H2O (6) and {[Mn(isoph)(bipy)]4·2.75 biby}n (7), respectively. Molecular structures of 3, 6 and 7 were determined crystallographically. In 3 the phthalate ligand is bound to the manganese via just one of its carboxylate groups in a monodentate mode with the remaining coordination sites filled by four phenanthroline nitrogen and one water oxygen atoms. In 6 the isophthalates are uncoordinated with the octahedral manganese center ligated by two phenanthrolines and two waters. In 7 the Isophthalate ligands act as bridges resulting in a polymeric structure. One of the carboxylate groups is chelating a single manganese with the other binding two metal centres in a bridging bidentate mode. The phthalate and isophthalate complexes, the metal free ligands and a number of simple manganes salts were each tested for their ability, to inhibit the growth of Candida albicans. Only the “metal free” 1,10-phenanthroline and its manganese complexes were found to be active. PMID:18475957

  14. Palladium-tin catalysts for the direct synthesis of H2O2 with high selectivity

    DOE PAGESBeta

    Freakley, Simon J.; He, Qian; Harrhy, Jonathan H.; Lu, Li; Crole, David A.; Morgan, David J.; Ntainjua, Edwin N.; Edwards, Jennifer K.; Carley, Albert F.; Borisevich, Albina Y.; et al

    2016-02-25

    The direct synthesis of hydrogen peroxide (H2O2 ) from H2 and O2 represents a potentially atom-efficient alternative to the current industrial indirect process. We show that the addition of tin to palladium catalysts coupled with an appropriate heat treatment cycle switches off the sequential hydrogenation and decomposition reactions, enabling selectivities of >95% toward H2O2 . This effect arises from a tin oxide surface layer that encapsulates small Pd-rich particles while leaving larger Pd-Sn alloy particles exposed. In conclusion, we show that this effect is a general feature for oxide-supported Pd catalysts containing an appropriate second metal oxide component, and wemore » set out the design principles for producing high-selectivity Pd-based catalysts for direct H2O2 production that do not contain gold.« less

  15. The rational design of a peptide-based hydrogel responsive to H2S.

    PubMed

    Peltier, Raoul; Chen, Ganchao; Lei, Haipeng; Zhang, Mei; Gao, Liqian; Lee, Su Seong; Wang, Zuankai; Sun, Hongyan

    2015-12-18

    The development of hydrogels that are responsive to external stimuli in a well-controlled manner is important for numerous biomedical applications. Herein we reported the first example of a hydrogel responsive to hydrogen sulphide (H2S). H2S is an important gasotransmitter whose deregulation has been associated with a number of pathological conditions. Our hydrogel design is based on the functionalization of an ultrashort hydrogelating peptide sequence with an azidobenzyl moiety, which was reported to react with H2S selectively under physiological conditions. The resulting peptide was able to produce hydrogels at a concentration as low as 0.1 wt%. It could then be fully degraded in the presence of excess H2S. We envision that the novel hydrogel developed in this study may provide useful tools for biomedical research. PMID:26463661

  16. 3-Methyl-1,2-BN-Cyclopentane: A Promising H2 Storage Material?

    SciTech Connect

    Luo, Wei; Neiner, Doinita; Karkamkar, Abhijeet J.; Parab, Kshitij; Garner, Edward B.; Dixon, David A.; Matson, Dean W.; Autrey, Thomas; Liu, Shih-Yuan

    2013-01-21

    We provide detailed characterization of properties for 3-methyl-1,2-BN-cyclopentane 1 that are relevant to H2 storage applications such as viscosity, thermal stability, H2 gas stream purity, and polarity. The viscosity of 1 at room temperature is 25±5 cP, about one fourth the viscosity of olive oil. TGA/MS analysis indicates that liquid carrier 1 is thermally stable at 30 °C but decomposes slowly at 50 °C. RGA data suggest that the H2 desorption from 1 is a clean process, producing relatively pure H2 gas. Compound 1 is a polar zwitterionic type liquid consistent with theoretical predictions and solvatochromic studies. "T.A. acknowledges support from the Fuel Cell Technology Program at U.S. DOE, Office of Energy Efficiency 65 and Renewable Energy. Pacific Northwest National Laboratory is operated by Battelle."

  17. Strain H2-419-4 of Haematococcus pluvialis induced by ethyl methanesulphonate and ultraviolet radiation

    NASA Astrophysics Data System (ADS)

    Sun, Yanhong; Liu, Jianguo; Zhang, Xiaoli; Lin, Wei

    2008-05-01

    Two strains H2-410 and H2-419 were obtained from the chemically mutated survivors of wild Haematococcus pluvialis 2 by using ethyl methanesulphonate (EMS). Strains H2-410 and H2-419 showed a fast cell growth with 13% and 20% increase in biomass compared to wild type, respectively. Then H2-419-4, a fast cell growth and high astaxanthin accumulation strain, was obtained by exposing the strain H2-419 to ultraviolet radiation (UV) further. The total biomass, the astaxanthin content per cell, astaxanthin production of H2-419-4 showed 68%, 28%, and 120% increase compared to wild H. pluvialis 2, respectively. HPLC (High Performance Liquid Chromatography) data showed also an obvious proportional variation of different carotenoid compositions in the extracts of H2-419-4 and the wild type, although no peak of carotenoids appeared or disappeared. Therefore, the main compositions in strain H2-419-4, like its wild one, were free of astaxanthin, monoester, and diester of astaxanthin. The asexual reproduction in survivors after exposed to UV was not synchronous, and different from the normal synchronous asexual reproduction as the mother cells were motile instead of non-motile. Interestingly, some survivors from UV irradiation produced many mini-spores (or gamete?), the spores moved away from the mother cell gradually 4 or 5 days later. This is quite similar to sexual reproduction described by Elliot in 1934. However, whether this was sexual reproduction remains questionable, as no mating process has been observed.

  18. On reversible H2 loss upon N2 binding to FeMo-cofactor of nitrogenase

    PubMed Central

    Yang, Zhi-Yong; Khadka, Nimesh; Lukoyanov, Dmitriy; Hoffman, Brian M.; Dean, Dennis R.; Seefeldt, Lance C.

    2013-01-01

    Nitrogenase is activated for N2 reduction by the accumulation of four electrons/protons on its active site FeMo-cofactor, yielding a state, designated as E4, which contains two iron-bridging hydrides [Fe–H–Fe]. A central puzzle of nitrogenase function is an apparently obligatory formation of one H2 per N2 reduced, which would “waste” two reducing equivalents and four ATP. We recently presented a draft mechanism for nitrogenase that provides an explanation for obligatory H2 production. In this model, H2 is produced by reductive elimination of the two bridging hydrides of E4 during N2 binding. This process releases H2, yielding N2 bound to FeMo-cofactor that is doubly reduced relative to the resting redox level, and thereby is activated to promptly generate bound diazene (HN=NH). This mechanism predicts that during turnover under D2/N2, the reverse reaction of D2 with the N2-bound product of reductive elimination would generate dideutero-E4 [E4(2D)], which can relax with loss of HD to the state designated E2, with a single deuteride bridge [E2(D)]. Neither of these deuterated intermediate states could otherwise form in H2O buffer. The predicted E2(D) and E4(2D) states are here established by intercepting them with the nonphysiological substrate acetylene (C2H2) to generate deuterated ethylenes (C2H3D and C2H2D2). The demonstration that gaseous H2/D2 can reduce a substrate other than H+ with N2 as a cocatalyst confirms the essential mechanistic role for H2 formation, and hence a limiting stoichiometry for biological nitrogen fixation of eight electrons/protons, and provides direct experimental support for the reductive elimination mechanism. PMID:24062454

  19. Working with "H2S": facts and apparent artifacts.

    PubMed

    Wedmann, Rudolf; Bertlein, Sarah; Macinkovic, Igor; Böltz, Sebastian; Miljkovic, Jan Lj; Muñoz, Luis E; Herrmann, Martin; Filipovic, Milos R

    2014-09-15

    Hydrogen sulfide (H2S) is an important signaling molecule with physiological endpoints similar to those of nitric oxide (NO). Growing interest in its physiological roles and pharmacological potential has led to large sets of contradictory data. The principle cause of these discrepancies can be the common neglect of some of the basic H2S chemistry. This study investigates how the experimental outcome when working with H2S depends on its source and dose and the methodology employed. We show that commercially available NaHS should be avoided and that traces of metal ions should be removed because these can reduce intramolecular disulfides and change protein structure. Furthermore, high H2S concentrations may lead to a complete inhibition of cell respiration, mitochondrial membrane potential depolarization and superoxide generation, which should be considered when discussing the biological effects observed upon treatment with high concentrations of H2S. In addition, we provide chemical evidence that H2S can directly react with superoxide. H2S is also capable of reducing cytochrome c(3+) with the concomitant formation of superoxide. H2S does not directly react with nitrite but with NO electrodes that detect H2S. In addition, H2S interferes with the Griess reaction and should therefore be removed from the solution by Cd(2+) or Zn(2+) precipitation prior to nitrite quantification. 2-Phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide (PTIO) is reduced by H2S, and its use should be avoided in combination with H2S. All these constraints must be taken into account when working with H2S to ensure valid data. PMID:24932545

  20. Modeling of H2S migration through landfill cover materials.

    PubMed

    Xu, Qiyong; Powell, Jon; Jain, Pradeep; Townsend, Timothy

    2014-01-15

    The emission of H2S from landfills in the United States is an emergent problem because measured concentrations within the waste mass and in ambient air have been observed at potentially unsafe levels for on-site workers and at levels that can cause a nuisance and potentially deleterious health impacts to surrounding communities. Though recent research has provided data on H2S concentrations that may be observed at landfills, facility operators and landfill engineers have limited predictive tools to anticipate and plan for potentially harmful H2S emissions. A one-dimensional gas migration model was developed to assist engineers and practitioners better evaluate and predict potential emission levels of H2S based on four factors: concentration of H2S below the landfill surface (C0), advection velocity (v), H2S effective diffusion coefficient (D), and H2S adsorption coefficient of landfill cover soil (μ). Model simulations indicated that H2S migration into the atmosphere can be mitigated by reducing H2S diffusion and advection or using alternative cover soils with a high H2S adsorption coefficient. Laboratory column experiments were conducted to investigate the effects of the four parameters on H2S migration in cover soils and to calculate the adsorption coefficient of different cover materials. The model was validated by comparing results with laboratory column experiments. Based on the results, the laboratory column provides an effective way to estimate the H2S adsorption coefficient, which can then be incorporated into the developed model to predict the depth of cover soil required to reduce emitted H2S concentrations below a desired level. PMID:24316799

  1. First spectrally-resolved H2 observations towards HH 54 . Low H2O abundance in shocks

    NASA Astrophysics Data System (ADS)

    Santangelo, G.; Antoniucci, S.; Nisini, B.; Codella, C.; Bjerkeli, P.; Giannini, T.; Lorenzani, A.; Lundin, L. K.; Cabrit, S.; Calzoletti, L.; Liseau, R.; Neufeld, D.; Tafalla, M.; van Dishoeck, E. F.

    2014-09-01

    Context. Herschel observations suggest that the H2O distribution in outflows from low-mass stars resembles the H2 emission. It is still unclear which of the different excitation components that characterise the mid- and near-IR H2 distribution is associated with H2O. Aims: The aim is to spectrally resolve the different excitation components observed in the H2 emission. This will allow us to identify the H2 counterpart associated with H2O and finally derive directly an H2O abundance estimate with respect to H2. Methods: We present new high spectral resolution observations of H2 0-0 S(4), 0-0 S(9), and 1-0 S(1) towards HH 54, a bright nearby shock region in the southern sky. In addition, new Herschel/HIFI H2O (212 - 101) observations at 1670 GHz are presented. Results: Our observations show for the first time a clear separation in velocity of the different H2 lines: the 0-0 S(4) line at the lowest excitation peaks at -7 km s-1, while the more excited 0-0 S(9) and 1-0 S(1) lines peak at -15 km s-1. H2O and high-J CO appear to be associated with the H2 0-0 S(4) emission, which traces a gas component with a temperature of 700-1000 K. The H2O abundance with respect to H2 0-0 S(4) is estimated to be X(H2O) < 1.4 × 10-5 in the shocked gas over an area of 13''. Conclusions: We resolve two distinct gas components associated with the HH 54 shock region at different velocities and excitations. This allows us to constrain the temperature of the H2O emitting gas (≤1000 K) and to derive correct estimates of H2O abundance in the shocked gas, which is lower than what is expected from shock model predictions. Based on observations made with ESO telescopes at the La Silla Paranal Observatory under programme IDs: 089.C-0772, 292.C-5025.

  2. H2O-H2SO4 system in Venus' clouds and OCS, CO, and H2SO4 profiles in Venus' troposphere.

    PubMed

    Krasnopolsky, V A; Pollack, J B

    1994-05-01

    A coupled problem of diffusion and condensation is solved for the H2SO4-H2O system in Venus' cloud layer. The position of the lower cloud boundary and profiles of the H2O and H2SO4 vapor mixing ratios and of the H2O/H2SO4 ratio of sulfuric acid aerosol and its flux are calculated as functions of the column photochemical production rate of sulfuric acid, phi H2SO4. Variations of the lower cloud boundary are considered. Our basic model, which is constrained to yield fH2O (30 km) = 30 ppm (Pollack et al. 1993), predicts the position of the lower cloud boundary at 48.4 km coinciding with the mean Pioneer Venus value, the peak H2SO4 mixing ratio of 5.4 ppm, and the H2SO4 production rate phi H2SO4 = 2.2 x 10(12) cm-2 sec-1. The sulfur to sulfuric acid mass flux ratio in the clouds is 1 : 27 in this model, and the mass loading ratio may be larger than this value if sulfur particles are smaller than those of sulfuric acid. The model suggests that the extinction coefficient of sulfuric acid particles with radius 3.7 micrometers (mode 3) is equal to 0.3 km-1 in the middle cloud layer. The downward flux of CO is equal to 1.7 x 10(12) cm-2 sec-1 in this model. Our second model, which is constrained to yield fH2SO4 = 10 ppm at the lower cloud boundary, close to the value measured by the Magellan radiooccultations, predicts the position of this boundary to be at 46.5 km, which agrees with the Magellan data; fH2O(30 km) = 90 ppm, close to the data of Moroz et al. (1983) at this altitude; phi H2SO4 = 6.4 x 10(12) cm-2 sec-1; and phi co = 4.2 x 10(12) cm-2 sec-1. The S/H2SO4 flux mass ratio is 1 : 18, and the extinction coefficient of the mode 3 sulfuric acid particles is equal to 0.9 km-1 in the middle cloud layer. A strong gradient of the H2SO4 vapor mixing ratio near the bottom of the cloud layer drives a large upward flux of H2SO4, which condenses and forms the excessive downward flux of liquid sulfuric acid, which is larger by a factor of 4-7 than the flux in the middle cloud

  3. Ni-H2 cell separator matrix engineering

    NASA Technical Reports Server (NTRS)

    Scott, W. E.

    1992-01-01

    This project was initiated to develop alternative separator materials to the previously used asbestos matrices which were removed from the market for health and environmental reasons. The objective of the research was to find a material or combination of materials that had the following characteristics: (1) resistant to the severe conditions encountered in Ni-H2 cells; (2) satisfactory electrical, electrolyte management, and thermal management properties to function properly; (3) environmentally benign; and (4) capable of being manufactured into a separator matrix. During the course of the research it was discovered that separators prepared from wettable polyethylene fibers along and in combination with potassium titanate pigment performed satisfactory in preliminary characterization tests. Further studies lead to the optimization of the separator composition and manufacturing process. Single ply separator sheets were manufactured with 100 percent polyethylene fibers and also with a combination of polyethylene fibers and potassium titanate pigment (PKT) in the ratio of 60 percent PKT and 40 percent fibers. A pilot paper machine was used to produce the experimental separator material by a continuous, wet laid process. Both types of matrices were produced at several different area densities (grams/sq m).

  4. Detection of a new interstellar molecule, H2CN.

    PubMed

    Ohishi, M; McGonagle, D; Irvine, W M; Yamamoto, S; Saito, S

    1994-05-20

    We have detected a new interstellar molecule, H2CN (methylene amidogen), in the cold, dark molecular cloud TMC-l. The column density of H2CN is estimated to be approximately 1.5 x 10(11) cm-2 by assuming an excitation temperature of 5 K. This column density corresponds to a fractional abundance relative to H2 of approximately 1.5 x 10(-11). This value is more than three orders of magnitude less than the abundance of the related molecule HCN in TMC-1. We also report a tentative detection of H2CN in Sgr B2(N). The formation mechanism of H2CN is discussed. Our detection of the H2CN molecule may suggest the existence of a new series of carbon-chain molecules, CH2CnN (n = 0, 1, 2,...). PMID:11539493

  5. H2 adsorption in Li-decorated porous graphene

    NASA Astrophysics Data System (ADS)

    Seenithurai, S.; Pandyan, R. Kodi; Kumar, S. Vinodh; Munieswaran, P.; Saranya, C.; Mahendran, M.

    2015-06-01

    Porous graphene (PG) has been decorated with Li atoms and subsequently studied the hydrogen (H2) adsorption characteristics, by using Density Functional Theory (DFT)-based calculations. A 2×2 PG has been decorated with eight Li atoms. Upto four H2 molecules get adsorbed on each Li atom. The maximum H2 storage capacity that could be achieved in 2×2PG-8Li is 8.95 wt% which is higher than the U.S. DOE's revised target for the on-board vehicles. The average H2 adsorption binding energy is 0.535 eV/H2, which lies between 0.2-0.6 eV/H2 that is required for achieving adsorption and desorption at near ambient conditions. Thus, Li-decorated PG could be a viable option for on-board automobile applications.

  6. Oxygen related chemoreceptor drive to breathe during H2S infusion

    PubMed Central

    Philippe, Haouzi; Sonobe, Takashi; Chenuel, Bruno

    2014-01-01

    This study addresses the following question: Could the acute depression in breathing produced by hyperoxia, a reflection of the tonic drive to breathe from the arterial chemoreceptors, be accounted for by the presence a background level of local endogenous H2S? To address this question, we produced a stable but moderate increase in breathing (24 ± 11%) via continuous infusion of low levels of H2S, in 10 spontaneously breathing urethane-sedated rats. We found that acute exposure to 100% O2 (20 tests) decreased minute ventilation (VI) from 301 ± 51 to 210 ± 43 ml/min within 15 seconds in control conditions, but no additional significant drop in VI was observed during H2S induced hyperpnea. In addition, no decrease in the estimated concentrations of gaseous H2S in the arterial blood was observed during the hyperoxic tests. It is concluded that the ventilatory depression induced by high O2 appears to be limited to the tonic background peripheral chemosensory drive to breathe, but has little or no impact on the CB stimulation produced by low levels of H2S. PMID:24973475

  7. Quantum chemical study of ternary mixtures of: HNO3:H2SO4:H2O

    NASA Astrophysics Data System (ADS)

    Verdes, M. A.; Gómez, P. C.; Gálvez, O.

    2009-04-01

    Water, nitric acid and sulfuric acid are important atmospheric species as individual species and as hydrogen-bonded aggregates involved in many physical-chemical processes both superficial and bulk. The importance of heterogeneous chemical reactions taking place on ice surfaces, either solid water or solid water plus nitric or sulfuric acid, is well established now in relation to the ozone-depleting mechanisms. Also the importance of liquid droplets formed by HNO3.H2SO4.H2O as components of PSC was soon recognized [1-3]. Finally the physical properties of finely divided aqueous systems is an interesting and active field of research in which theoretical information on the microphysical domain systems may help to understand and rationalize the wealth of experimental information. This can also be the initial step in the study of more complex mixtures with higher amounts of water or variable proportions of their constituents. This kind of calculations have been successfully performed in the past[4]. We present here our results on the structure and spectroscopic and thermodynamic properties of the energy-lowest lying structures among those thermodynamically stable formed by linking the acids plus water. The calculations have been carried out by means of DFT methods (in particular the successful B3LYP) using different basis sets that contain appropriate sets of polarization and diffuse functions up to quadruple-Z quality (Dunninǵs aug-cc-pVQZ). Careful assessment of the dependability of the methodology used has been carried out. This work has been supported by the Spanish Ministry of Education, Projects FIS2007-61686 and CTQ2008-02578/BQU References: [1] Carslaw, K. S. et al.: Geophys. Res. Lett. 21, 2479-2482, 1994 [2] Drdla, K. Et al. :Geophys. Res. Lett. 21, 2473-2478, 1994 [3] Tabazadeh, A. et al.: Geophys. Res. Lett 21, 1619-1622, 1994 [4] Escribano, R et al.: J. J. Chem. Phys A 2003, 107, 652.

  8. 26 CFR 31.3406(h)-2 - Special rules.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 26 Internal Revenue 15 2014-04-01 2014-04-01 false Special rules. 31.3406(h)-2 Section 31.3406(h... Collection of Income Tax at Source § 31.3406(h)-2 Special rules. (a) Joint accounts—(1) Relevant name and...)(1)(C). (3) Joint foreign payees—(i) For further guidance, see § 31.3406(h)-2T(a)(3)(i)....

  9. Microwave Spectra and Structures of H_2S-CuCl and H_2O-CuCl.

    NASA Astrophysics Data System (ADS)

    Walker, N. R.; Wheatley, D. E.; Stephens, S. L.; Roberts, F. J.; Mikhailov, V. A.; Legon, A. C.

    2010-06-01

    A Balle-Flygare FT-MW spectrometer coupled to a laser ablation source has been used to measure the pure rotational spectra of H2S-CuCl and H2O-CuCl. Both molecules are generated via laser ablation (532 nm) of a metal rod in the presence of CCl4, argon, a low partial pressure of H2S or H2O and are stabilized by supersonic expansion. Rotational constants and centrifugal distortion constants have been measured for eight isotopologues of H2S-CuCl with substitutions available at the copper, chlorine and hydrogen atoms. Transitions in the spectra of nine isotopologues of H2O-CuCl have been measured with isotopic substitutions achieved for every atom. The spectra of both H2S-CuCl and H2O-CuCl are consistent with a linear arrangement of sulphur or oxygen, metal and chlorine atoms. The structure of H2S-CuCl is pyramidal with CS symmetry. The structure of H2O-CuCl is either C2v planar at equilibrium or CS pyramidal but with a low potential-energy barrier to planarity such that the v=0 and 1 states associated with the motion that inverts the configuration at the O atom are well separated. Nuclear quadrupole coupling constants have been measured for the chlorine and copper atoms in each molecule. Nuclear spin-rotation constants have been determined for the copper atom.

  10. Particulate filtration for sorbent-based H2 storage

    NASA Astrophysics Data System (ADS)

    van Hassel, Bart A.; Karra, Jagadeswara R.

    2016-01-01

    A method was developed for sizing the particulate filter that can be used inside a sorption-based onboard hydrogen storage system for light-duty vehicles. The method is based on a trade-off between the pressure drop across the particulate filter (during the fill of the H2 storage tank or during its discharge while driving) and the effect of this pressure drop on the usable amount of H2 gas from the H2 storage system. The permeability and filtration efficiency of the particulate filters (in the absence and presence of MOF-5 particulates) was quantified in this study, with an emphasis on meeting DOE's H2 purity requirements.

  11. Carbonate control of H2 and CH4 production in serpentinization systems at elevated P-Ts

    USGS Publications Warehouse

    Jones, L. Camille; Rosenbauer, Robert; Goldsmith, Jonas I.; Oze, Christopher

    2010-01-01

    Serpentinization of forsteritic olivine results in the inorganic synthesis of molecular hydrogen (H2) in ultramafic hydrothermal systems (e.g., mid-ocean ridge and forearc environments). Inorganic carbon in those hydrothermal systems may react with H2 to produce methane (CH4) and other hydrocarbons or react with dissolved metal ions to form carbonate minerals. Here, we report serpentinization experiments at 200°C and 300 bar demonstrating Fe2+ being incorporated into carbonates more rapidly than Fe2+ oxidation (and concomitant H2 formation) leading to diminished yields of H2 and H2-dependent CH4. In addition, carbonate formation is temporally fast in carbonate oversaturated fluids. Our results demonstrate that carbonate chemistry ultimately modulates the abiotic synthesis of both H2 and CH4 in hydrothermal ultramafic systems and that ultramafic systems present great potential for CO2-mineral sequestration.

  12. Relative Importance of H2 and H2S as Energy Sources for Primary Production in Geothermal Springs▿ †

    PubMed Central

    D'Imperio, Seth; Lehr, Corinne R.; Oduro, Harry; Druschel, Greg; Kühl, Michael; McDermott, Timothy R.

    2008-01-01

    Geothermal waters contain numerous potential electron donors capable of supporting chemolithotrophy-based primary production. Thermodynamic predictions of energy yields for specific electron donor and acceptor pairs in such systems are available, although direct assessments of these predictions are rare. This study assessed the relative importance of dissolved H2 and H2S as energy sources for the support of chemolithotrophic metabolism in an acidic geothermal spring in Yellowstone National Park. H2S and H2 concentration gradients were observed in the outflow channel, and vertical H2S and O2 gradients were evident within the microbial mat. H2S levels and microbial consumption rates were approximately three orders of magnitude greater than those of H2. Hydrogenobaculum-like organisms dominated the bacterial component of the microbial community, and isolates representing three distinct 16S rRNA gene phylotypes (phylotype = 100% identity) were isolated and characterized. Within a phylotype, O2 requirements varied, as did energy source utilization: some isolates could grow only with H2S, some only with H2, while others could utilize either as an energy source. These metabolic phenotypes were consistent with in situ geochemical conditions measured using aqueous chemical analysis and in-field measurements made by using gas chromatography and microelectrodes. Pure-culture experiments with an isolate that could utilize H2S and H2 and that represented the dominant phylotype (70% of the PCR clones) showed that H2S and H2 were used simultaneously, without evidence of induction or catabolite repression, and at relative rate differences comparable to those measured in ex situ field assays. Under in situ-relevant concentrations, growth of this isolate with H2S was better than that with H2. The major conclusions drawn from this study are that phylogeny may not necessarily be reliable for predicting physiology and that H2S can dominate over H2 as an energy source in terms of

  13. Relative importance of H2 and H2S as energy sources for primary production in geothermal springs.

    PubMed

    D'Imperio, Seth; Lehr, Corinne R; Oduro, Harry; Druschel, Greg; Kühl, Michael; McDermott, Timothy R

    2008-09-01

    Geothermal waters contain numerous potential electron donors capable of supporting chemolithotrophy-based primary production. Thermodynamic predictions of energy yields for specific electron donor and acceptor pairs in such systems are available, although direct assessments of these predictions are rare. This study assessed the relative importance of dissolved H(2) and H(2)S as energy sources for the support of chemolithotrophic metabolism in an acidic geothermal spring in Yellowstone National Park. H(2)S and H(2) concentration gradients were observed in the outflow channel, and vertical H(2)S and O(2) gradients were evident within the microbial mat. H(2)S levels and microbial consumption rates were approximately three orders of magnitude greater than those of H(2). Hydrogenobaculum-like organisms dominated the bacterial component of the microbial community, and isolates representing three distinct 16S rRNA gene phylotypes (phylotype = 100% identity) were isolated and characterized. Within a phylotype, O(2) requirements varied, as did energy source utilization: some isolates could grow only with H(2)S, some only with H(2), while others could utilize either as an energy source. These metabolic phenotypes were consistent with in situ geochemical conditions measured using aqueous chemical analysis and in-field measurements made by using gas chromatography and microelectrodes. Pure-culture experiments with an isolate that could utilize H(2)S and H(2) and that represented the dominant phylotype (70% of the PCR clones) showed that H(2)S and H(2) were used simultaneously, without evidence of induction or catabolite repression, and at relative rate differences comparable to those measured in ex situ field assays. Under in situ-relevant concentrations, growth of this isolate with H(2)S was better than that with H(2). The major conclusions drawn from this study are that phylogeny may not necessarily be reliable for predicting physiology and that H(2)S can dominate over H(2

  14. Gasification Mechanism of Carbon with Supercritical Water at Very High Pressures: Effects on H2 Production.

    PubMed

    Martin-Sanchez, Nicolas; Salvador, Francisco; Sanchez-Montero, M Jesus; Izquierdo, Carmen

    2014-08-01

    The scarce data concerning the gasification of carbonaceous solids with supercritical water (SCW) suggest the great potential of this method to produce a valuable green fuel such as H2. However, the extraordinary properties of SCW have not been properly applied to H2 production because the mechanism that governs gasification under these conditions remains unclear. Here, we present a study in which this reaction is explored within the largest pressure range ever assayed in this field, from 1 to 1000 bar. The amplitude of the experimental conditions investigated highlights the various pathways that govern gasification with steam and SCW. Under supercritical conditions, the clusters formed around the superficial groups of the solid reduce the energetic requirements for gasification and generate CO2 as a primary product of the reaction. Consequently, gasification with SCW is significantly faster than that using steam, and the produced gases are richer and more appropriate to obtain pure H2. PMID:26277952

  15. Tuning the conductance of H2O@C60 by position of the encapsulated H2O.

    PubMed

    Zhu, Chengbo; Wang, Xiaolin

    2015-01-01

    The change of conductance of single-molecule junction in response to various external stimuli is the fundamental mechanism for the single-molecule electronic devices with multiple functionalities. We propose the concept that the conductance of molecular systems can be tuned from inside. The conductance is varied in C60 with encapsulated H2O, H2O@C60. The transport properties of the H2O@C60-based nanostructure sandwiched between electrodes are studied using first-principles calculations combined with the non-equilibrium Green's function formalism. Our results show that the conductance of the H2O@C60 is sensitive to the position of the H2O and its dipole direction inside the cage with changes in conductance up to 20%. Our study paves a way for the H2O@C60 molecule to be a new platform for novel molecule-based electronics and sensors. PMID:26643873

  16. Calculation of molecular mean excitation energies via the polarization propagator formalism: H2 and H2O

    NASA Astrophysics Data System (ADS)

    Geertsen, Jan; Oddershede, Jens; Sabin, John R.

    1986-08-01

    We present ab initio calculations of oscillator-strength sum rules S(μ) and mean exciton energies Iμ for -1<=μ<=1. We use the polarization propagator formalism at the random-phase approximation level. Calculations are performed for H2 and H2O using large basis sets: 90 uncontracted Gaussian-type orbitals (CGTO's) for H2 and 101 CGTO's for water. We find that I0=19.12 eV for H2 (including thermal averaging) and 72.46 eV for H2O. They agree very well with previous semiempirical estimates. The same holds for the other Iμ moments. The fulfillment of the Thomas-Reiche-Kuhn sum rule in both the dipole length and velocity formulations shows that the basis sets employed are satisfactory. We have also investigated the ``shell-wise'' contributions to S(0) and I0 for H2O.

  17. Tuning the conductance of H2O@C60 by position of the encapsulated H2O

    PubMed Central

    Zhu, Chengbo; Wang, Xiaolin

    2015-01-01

    The change of conductance of single-molecule junction in response to various external stimuli is the fundamental mechanism for the single-molecule electronic devices with multiple functionalities. We propose the concept that the conductance of molecular systems can be tuned from inside. The conductance is varied in C60 with encapsulated H2O, H2O@C60. The transport properties of the H2O@C60-based nanostructure sandwiched between electrodes are studied using first-principles calculations combined with the non-equilibrium Green’s function formalism. Our results show that the conductance of the H2O@C60 is sensitive to the position of the H2O and its dipole direction inside the cage with changes in conductance up to 20%. Our study paves a way for the H2O@C60 molecule to be a new platform for novel molecule-based electronics and sensors. PMID:26643873

  18. Tuning the conductance of H2O@C60 by position of the encapsulated H2O

    NASA Astrophysics Data System (ADS)

    Zhu, Chengbo; Wang, Xiaolin

    2015-12-01

    The change of conductance of single-molecule junction in response to various external stimuli is the fundamental mechanism for the single-molecule electronic devices with multiple functionalities. We propose the concept that the conductance of molecular systems can be tuned from inside. The conductance is varied in C60 with encapsulated H2O, H2O@C60. The transport properties of the H2O@C60-based nanostructure sandwiched between electrodes are studied using first-principles calculations combined with the non-equilibrium Green’s function formalism. Our results show that the conductance of the H2O@C60 is sensitive to the position of the H2O and its dipole direction inside the cage with changes in conductance up to 20%. Our study paves a way for the H2O@C60 molecule to be a new platform for novel molecule-based electronics and sensors.

  19. Infrared Response of H2 to X-Rays in Dense Clouds

    NASA Technical Reports Server (NTRS)

    Tine, S.; Lepp, S.; Gredel, R.; Dalgarno, A.

    1997-01-01

    The excitation by X-rays and cosmic rays of molecular hydrogen in interstellar clouds is analyzed. We carried out detailed calculations of entry efficiencies in rovibrational levels of H2 following impact with fast electrons produced by X-ray ionization of the gas. The competing effect of collisional excitation, and quenching by the ambient gas is examined in detail. Up to date values for H-H2 collisional rate coefficients are adopted, and some derivations of H2-H2 rovibrational rate coefficients from existing literature data are proposed. Several models as a function of temperature, density, and ionization rate are presented. We found that H2 infrared emission in X-ray dominated regions (XDR) is potentially observable for temperatures and ionization rates lower than certain critical values (typically T < 1000 K and zeta/n(sub H) < 10(exp -15) cc/s where zeta is the ionization rate). At higher temperatures, collisional excitation by the ambient gas dominates the population of low vibrational levels, and at higher values of zeta/n(sub H) the abundance of H2 is negligible. If such conditions are satisfied, the resulting infrared emission spectrum can be used as a diagnostic of nearby X-ray sources such as in cooling flows in galaxy clusters, quasars, Seyfert galaxies and supernova remnants. The intensity ratio of the 2-1S(1) and 1-0S(1) lines measured for the Seyfert galaxy NGC 1275 is consistent with X-ray pumping.

  20. Production and characterization of recombinant lignin peroxidase isozyme H2 from Phanerochaete chrysosporium using recombinant baculovirus.

    PubMed

    Johnson, T M; Pease, E A; Li, J K; Tien, M

    1992-08-01

    Recombinant Phanerochaete chrysosporium lignin peroxidase isozyme H2 (pI 4.4) was produced in insect cells infected with a genetically engineered baculovirus containing a copy of the cDNA clone lambda ML-6. The recombinant enzyme was purified to near homogeneity and is capable of oxidizing veratryl alcohol, iodide, and, to a lesser extent, guaiacol. The Km of the recombinant enzyme for veratryl alcohol and H2O2 is similar to that of the fungal enzyme. The guaiacol oxidation activity or any other activity is not dependent upon Mn2+. The purified recombinant peroxidase is glycosylated with N-linked carbohydrate(s). The recombinant lignin peroxidase eluted from an anion exchange resin similar to that of native isozyme H1 rather than H2. However, the pI of the recombinant enzymes is different from both H1 and H2 isozymes. Further characterization of native isozymes H1 and H2 from the fungal cultures revealed identical N-terminus residues. This indicates that isozymes H1 and H2 differ in post-translational modification. PMID:1632652

  1. Exotic SiO2H2 Isomers: Theory and Experiment Working in Harmony.

    PubMed

    McCarthy, Michael C; Gauss, Jürgen

    2016-05-19

    Replacing carbon with silicon can result in dramatic and unanticipated changes in isomeric stability, as the well-studied CO2H2 and the essentially unknown SiO2H2 systems illustrate. Guided by coupled-cluster calculations, three SiO2H2 isomers have been detected and spectroscopically characterized in a molecular beam discharge source using rotational spectroscopy. The cis,trans conformer of dihydroxysilylene HOSiOH, the ground-state isomer, and the high-energy, metastable dioxasilirane c-H2SiO2 are abundantly produced in a dilute SiH4/O2 electrical discharge, enabling precise structural determinations of both by a combination of isotopic measurements and calculated vibrational corrections. The isotopic studies also provide insight into their formation route, suggesting that c-H2SiO2 is formed promptly in the expansion but that cis,trans-HOSiOH is likely formed by secondary reactions following formation of the most stable dissociation pair, SiO + H2O. Although less abundant, the rotational spectrum of trans-silanoic acid, the silicon analogue of formic acid, HSi(O)OH, has also been observed. PMID:27139016

  2. Active sites and mechanisms for H2O2 decomposition over Pd catalysts.

    PubMed

    Plauck, Anthony; Stangland, Eric E; Dumesic, James A; Mavrikakis, Manos

    2016-04-01

    A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2 We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O-O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O-O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

  3. Cross Talk between H2O2 and Interacting Signal Molecules under Plant Stress Response.

    PubMed

    Saxena, Ina; Srikanth, Sandhya; Chen, Zhong

    2016-01-01

    It is well established that oxidative stress is an important cause of cellular damage. During stress conditions, plants have evolved regulatory mechanisms to adapt to various environmental stresses. One of the consequences of stress is an increase in the cellular concentration of reactive oxygen species, which is subsequently converted to H2O2. H2O2 is continuously produced as the byproduct of oxidative plant aerobic metabolism. Organelles with a high oxidizing metabolic activity or with an intense rate of electron flow, such as chloroplasts, mitochondria, or peroxisomes are major sources of H2O2 production. H2O2 acts as a versatile molecule because of its dual role in cells. Under normal conditions, H2O2 immerges as an important factor during many biological processes. It has been established that it acts as a secondary messenger in signal transduction networks. In this review, we discuss potential roles of H2O2 and other signaling molecules during various stress responses. PMID:27200043

  4. Quantification of the production of hydrogen peroxide H2O2 during accelerated wine oxidation.

    PubMed

    Héritier, Julien; Bach, Benoît; Schönenberger, Patrik; Gaillard, Vanessa; Ducruet, Julien; Segura, Jean-Manuel

    2016-11-15

    Understanding how wines react towards oxidation is of primary importance. Here, a novel approach was developed based on the quantitative determination of the key intermediate H2O2 produced during accelerated oxidation by ambient oxygen. The assay makes use of the conversion of the non-fluorescent Amplex Red substrate into a fluorescent product in presence of H2O2. The total production of H2O2 during 30min was quantified with low within-day and between-day variabilities. Polymerized pigments, but not total polyphenols, played a major role in the determination of H2O2 levels, which were lower in white wines than red wines. H2O2 amounts also increased with temperature and the addition of metal ions, but did not depend on the concentration of many other wine constituents such as SO2. H2O2 levels did not correlate with anti-oxidant properties. We believe that this novel methodology might be generically used to decipher the oxidation mechanisms in wines and food products. PMID:27283717

  5. Oxidative degradation of dimethyl phthalate (DMP) by UV/H(2)O(2) process.

    PubMed

    Xu, Bin; Gao, Nai-Yun; Cheng, Hefa; Xia, Sheng-Ji; Rui, Min; Zhao, Dan-Dan

    2009-03-15

    The photochemical degradation of dimethyl phthalate (DMP) in UV/H(2)O(2) advanced oxidation process was studied and a kinetic model based on the elementary reactions involved was developed in this paper. Relatively slow DMP degradation was observed during UV radiation, while DMP was not oxidized by H(2)O(2) alone. In contrast, the combined UV/H(2)O(2) process could effectively degraded DMP, which is attributed to the strong oxidation strength of hydroxyl radical produced. Results show that DMP degradation rate was affected by H(2)O(2) concentration, intensity of UV radiation, initial DMP concentration, and solution pH. A kinetic model without the pseudo-steady state assumption was established according to the generally accepted elementary reactions in UV/H(2)O(2) advanced oxidation process. The rate constant for the reaction between DMP and hydroxyl radical was found to be 4.0 x 10(9) M(-1)s(-1) through fitting the experimental data to this model. The kinetic model could adequately describe the influence of key factors on DMP degradation rate in UV/H(2)O(2) advanced oxidation process, and could serve as a guide in designing treatment systems for DMP removal. PMID:18639981

  6. Cross Talk between H2O2 and Interacting Signal Molecules under Plant Stress Response

    PubMed Central

    Saxena, Ina; Srikanth, Sandhya; Chen, Zhong

    2016-01-01

    It is well established that oxidative stress is an important cause of cellular damage. During stress conditions, plants have evolved regulatory mechanisms to adapt to various environmental stresses. One of the consequences of stress is an increase in the cellular concentration of reactive oxygen species, which is subsequently converted to H2O2. H2O2 is continuously produced as the byproduct of oxidative plant aerobic metabolism. Organelles with a high oxidizing metabolic activity or with an intense rate of electron flow, such as chloroplasts, mitochondria, or peroxisomes are major sources of H2O2 production. H2O2 acts as a versatile molecule because of its dual role in cells. Under normal conditions, H2O2 immerges as an important factor during many biological processes. It has been established that it acts as a secondary messenger in signal transduction networks. In this review, we discuss potential roles of H2O2 and other signaling molecules during various stress responses. PMID:27200043

  7. Ni/YSZ pattern anodes fabrication and their microstructure and electrochemical behavior changes in H2-H2O environments

    NASA Astrophysics Data System (ADS)

    Yao, W.; Croiset, E.

    2013-03-01

    An effective photolithographic process was investigated to fabricate Ni/YSZ pattern anodes using a bi-layer lift-off resist method. Suitable undercut size was found critical for successful pattern fabrication. Effects of Ni thickness, temperature and H2O content on Ni pattern microstructure were evaluated. Ni/YSZ pattern anodes with 0.5 μm thick Ni was tested in dry H2 at 550 °C without significantly changing the TPB line. Ni/YSZ pattern anodes with Ni thickness of 0.8 μm were tested at 550 °C under dry and humidified H2 (3-50% H2O) conditions without TPB line change. At 700 °C, and for 0.8 μm thick patterns, the TPB length showed pronounced change in H2 with 10-50% H2O. Significant increase in TPB length due to holes formation was observed at 800 °C with 3% and 10% H2O. Ni/YSZ pattern anodes with 1.0 μm thick Ni was stable in H2 with 3% H2O in the range 550-800 °C, with TPB line only slightly modified. However, distinct change of TPB line and Ni microstructure was observed with 10-70% H2O above 700 °C. Stabilization of the polarization resistance depends on temperature. To accelerate stabilization of the cell, pre-treatment of the cell in H2 with 3% H2O at 750 °C or 800 °C could be performed.

  8. Drosophila TRPA1 isoforms detect UV light via photochemical production of H2O2

    PubMed Central

    Guntur, Ananya R.; Gu, Pengyu; Takle, Kendra; Chen, Jingyi; Xiang, Yang; Yang, Chung-Hui

    2015-01-01

    The transient receptor potential A1 (TRPA1) channel is an evolutionarily conserved detector of temperature and irritant chemicals. Here, we show that two specific isoforms of TRPA1 in Drosophila are H2O2 sensitive and that they can detect strong UV light via sensing light-induced production of H2O2. We found that ectopic expression of these H2O2-sensitive Drosophila TRPA1 (dTRPA1) isoforms conferred UV sensitivity to light-insensitive HEK293 cells and Drosophila neurons, whereas expressing the H2O2-insensitive isoform did not. Curiously, when expressed in one specific group of motor neurons in adult flies, the H2O2-sensitive dTRPA1 isoforms were as competent as the blue light-gated channelrhodopsin-2 in triggering motor output in response to light. We found that the corpus cardiacum (CC) cells, a group of neuroendocrine cells that produce the adipokinetic hormone (AKH) in the larval ring gland endogenously express these H2O2-sensitive dTRPA1 isoforms and that they are UV sensitive. Sensitivity of CC cells required dTRPA1 and H2O2 production but not conventional phototransduction molecules. Our results suggest that specific isoforms of dTRPA1 can sense UV light via photochemical production of H2O2. We speculate that UV sensitivity conferred by these isoforms in CC cells may allow young larvae to activate stress response—a function of CC cells—when they encounter strong UV, an aversive stimulus for young larvae. PMID:26443856

  9. Radiolysis of H2O:CO2 ices by heavy energetic cosmic ray analogs

    NASA Astrophysics Data System (ADS)

    Pilling, S.; Seperuelo Duarte, E.; Domaracka, A.; Rothard, H.; Boduch, P.; da Silveira, E. F.

    2010-11-01

    An experimental study of the interaction of heavy, highly charged, and energetic ions (52 MeV 58Ni13+) with pure H2O, pure CO2 and mixed H2O:CO2 astrophysical ice analogs is presented. This analysis aims to simulate the chemical and the physicochemical interactions induced by heavy cosmic rays inside dense and cold astrophysical environments, such as molecular clouds or protostellar clouds. The measurements were performed at the heavy ion accelerator GANIL (Grand Accélérateur National d'Ions Lourds in Caen, France). The gas samples were deposited onto a CsI substrate at 13 K. In-situ analysis was performed by a Fourier transform infrared (FTIR) spectrometer at different fluences. Radiolysis yields of the produced species were quantified. The dissociation cross sections of pure H2O and CO2 ices are 1.1 and 1.9 × 10-13 cm2, respectively. For mixed H2O:CO2 (10:1), the dissociation cross sections of both species are about 1 × 10-13 cm2. The measured sputtering yield of pure CO2 ice is 2.2 × 104 molec ion-1. After a fluence of 2-3 × 1012 ions cm-2, the CO2/CO ratio becomes roughly constant (~0.1), independent of the initial CO2/H2O ratio. A similar behavior is observed for the H2O2/H2O ratio, which stabilizes at 0.01, independent of the initial H2O column density or relative abundance.

  10. Effect of H2O, and combined effects of H2O + F, H2O + CO2, and H2O + F + CO2 on the viscosity of a natural basalt from Fuego volcano, Guatemala

    NASA Astrophysics Data System (ADS)

    Robert, G.; Whittington, A. G.; Knipping, J.; Scherbarth, S.; Stechern, A.; Behrens, H.

    2012-12-01

    We measured the viscosity of 5 series of remelted natural basalt from Fuego volcano, Guatemala. These series include single and multiple volatile species: H2O, F, H2O-F, H2O-CO2, and H2O-CO2-F. The hydrous glasses were synthesized at 3 kbar and 1250°C in Internally Heated Pressure Vessels. The multiple volatile series were synthesized at 5 kbar and 1250°C. CO2 was added as Ag2C2O4, F as AlF3, and H2O as distilled water. The anhydrous, F-bearing series was synthesized at 1 atm by simply remelting the Fuego basalt and adding F as CaF2.The natural, dry, remelted Fuego basalt has an NBO/T of 0.64. The following comparisons are based on parallel-plate viscosity measurements in the range ~108 to 1012 Pa s. The temperature at which the viscosity is 1012 Pa s (T12) is taken to be the viscosimetric glass transition temperature (Tg). The addition of 2 wt.% H2O results in a decrease of T12 of ~150°C for basalt. Fluorine on its own has a measurable, but much smaller effect, than the equivalent amount of water. Indeed, ~2 wt.% F results in a T12 depression of only ~30°C. When H2O and F are both present, their effects are approximately additive. For example, the viscosity of a basalt with 1.44 wt.% H2O is very similar to the viscosity of a basalt with ~1 wt.% H2O and ~1.25 wt.% F, and the viscosities of a basalt with 2.29 wt.% H2O and a basalt with ~1.65 wt.% H2O and ~1.3 wt.% F are also very similar. The effect of CO2 is somewhat ambiguous. The viscosity of a basalt with ~1.7 wt.% H2O, ~1.3 wt.% F and ~0.2 wt.% CO2 is essentially the same as the viscosity of a basalt with 2.29 wt.% H2O, so CO2 seems to have a negligible or even viscosity-increasing effect when F and H2O are also present. However, a basalt with ~0.84 wt.% H2O and ~0.09 wt.% CO2 has about the same viscosity as a basalt with 1.34 wt.% H2O, which could suggest a strong (viscosity-decreasing) effect of very small amounts of CO2. These results suggest that the effects on viscosity of F in basaltic systems are

  11. Pressure-induced superconductivity in H2-containing hydride PbH4(H2)2

    PubMed Central

    Cheng, Ya; Zhang, Chao; Wang, Tingting; Zhong, Guohua; Yang, Chunlei; Chen, Xiao-Jia; Lin, Hai-Qing

    2015-01-01

    High pressure structure, stability, metallization, and superconductivity of PbH4(H2)2, a H2-containing compound combining one of the heaviest elements with the lightest element, are investigated by the first-principles calculations. The metallic character is found over the whole studied pressure range, although PbH4(H2)2 is metastable and easily decompose at low pressure. The decomposition pressure point of 133 GPa is predicted above which PbH4(H2)2 is stable both thermodynamically and dynamically with the C2/m symmetry. Interestedly, all hydrogen atoms pairwise couple into H2 quasi-molecules and remain this style up to 400 GPa in the C2/m structure. At high-pressure, PbH4(H2)2 tends to form the Pb-H2 alloy. The superconductivity of Tc firstly rising and then falling is observed in the C2/m PbH4(H2)2. The maximum of Tc is about 107 K at 230 GPa. The softening of intermediate-frequency phonon induced by more inserted H2 molecules is the main origin of the high Tc. The results obtained represent a significant step toward the understanding of the high pressure behavior of metallic hydrogen and hydrogen-rich materials, which is helpful for obtaining the higher Tc. PMID:26559369

  12. H2 oxidation versus organic substrate oxidation in non-heme iron mediated reactions with H2O2.

    PubMed

    Hassanpour, Azin; Acuña-Parés, Ferran; Luis, Josep M; Cusso, Olaf; Morales de la Rosa, Silvia; Campos-Martín, José Miguel; Fierro, Jose L G; Costas, Miquel; Lloret-Fillol, Julio; Mas-Ballesté, Rubén

    2015-10-18

    Herein we show that species generated upon reaction of α-[Fe(CF3SO3)2(BPMCN)] (BPMCN = N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane) with H2O2 (putatively [Fe(V)(O)(OH)(BPMCN)]) is able to efficiently oxidize H2 to H2O even in the presence of organic substrates, while species formed in the presence of acetic acid (putatively [Fe(V)(O)(OAc)(BPMCN)]) prefer organic substrate oxidation over H2 activation. Mechanistic implications have been analysed with the aid of computational methods. PMID:26311021

  13. Modeling the Interaction of H2 on Root Exudate Degradation and Methanogenesis in Wetland Sediments

    NASA Astrophysics Data System (ADS)

    Pal, D. S.; Jaffe, P. R.

    2014-12-01

    CH4 is produced in wetland sediments from the microbial degradation of organic carbon through multiple fermentation steps and methanogenesis pathways. There are many potential sources of carbon for methananogenesis; in vegetated wetland sediments, microbial communities consume root exudates as a major source of organic carbon. In many methane models propionate is used as a model carbon molecule. This simple sugar is fermented into acetate and H2, acetate is transformed to methane and CO2 while the H2 and CO2 is synthesized to form an additional CH4 molecule. The hydrogenotrophic pathway involves the equilibrium of two dissolved gases, CH4 and H2. In an effort to limit CH4 emissions from wetlands, there has been growing interest in finding ways to limit plant transport of soil gases through root systems. While this may decrease the direct emissions of methane, there is little understanding about how H2 dynamics may feedback into overall methane production. Since H2 is used in methane production and produced in propionate fermentation, increased subsurface H2 concentrations can simultaneously inhibit propionate fermentation and acetate production and enhance hydrogenotrophic methanogenesis. For this study, we incubated soil samples from vegetated wetland sediments with propionate or acetate and four different hydrogen concentrations. The headspaces from these incubations were simultaneously analyzed for H2 and CH4 at multiple time points over two months. The comparison of methane production between different hydrogen concentrations and different carbon sources can indicate which process is most affected by increased hydrogen concentrations. The results from this study were combined with a newly formulated steady-state model of propionate degradation and formation of methane, that also accounts for the venting off both gases via plants. The resulting model indicates how methane production and emissions would be affected by plant volatilization.

  14. H2 cycling and microbial bioenergetics in anoxic sediments

    NASA Technical Reports Server (NTRS)

    Hoehler, Tori M.; DeVincenzi, Donald (Technical Monitor)

    2001-01-01

    The simple biochemistry of H2 is central to a large number of microbial processes, affecting the interaction of organisms with each other and with the environment. In anoxic sediments, the great majority of microbial redox processes involve H2 as a reactant, product, or potential by-product, and the thermodynamics of these processes are thus highly sensitive to fluctuations in environmental H2 concentrations. In turn, H2 concentrations are controlled by the activity of H2-consuming microorganisms, which efficiently utilize this substrate down to levels which correspond to their bioenergetic limitations. Consequently, any environmental change which impacts the thermodynamics of H2-consuming organisms is mirrored by a corresponding change in H2 concentrations. This phenomenon is illustrated in anoxic sediments from Cape Lookout Bight, NC, USA: H2 concentrations are controlled by a suite of environmental parameters (e.g., temperature, sulfate concentrations) in a fashion which can be quantitatively described by a simple thermodynamic model. These findings allow us to calculate the apparent minimum quantity of biologically useful energy in situ. We find that sulfate reducing bacteria are not active at energy yields below -18 kJ per mole sulfate, while methanogenic archaea exhibit a minimum close to -10 kJ per mole methane.

  15. Endogenous mitigation of H2S inside of the landfills.

    PubMed

    Fang, Yuan; Zhong, Zhong; Shen, Dongsheng; Du, Yao; Xu, Jing; Long, Yuyang

    2016-02-01

    Vast quantities of hydrogen sulfide (H2S) emitted from landfill sites require urgent disposal. The current study focused on source control and examined the migration and conversion behavior of sulfur compounds in two lab-scale simulated landfills with different operation modes. It aimed to explore the possible strategies and mechanisms for H2S endogenous mitigation inside of landfills during decomposition. It was found that the strength of H2S emissions from the landfill sites was dependent on the municipal solid waste (MSW) degradation speed and vertical distribution of sulfide. Leachate recirculation can shorten both the H2S influence period and pollution risk to the surrounding environment. H2S endogenous mitigation may be achieved by chemical oxidation, biological oxidation, adsorption, and/or precipitation in different stages. Migration and conversion mainly affected H2S release behavior during the initial stabilization phase in the landfill. Microbial activities related to sulfur, nitrogen, and iron can further promote H2S endogenous mitigation during the high reducing phase. Thus, H2S endogenous mitigation can be effectively enhanced via control of the aforementioned processes. PMID:26423286

  16. The 50 Ah NiH2 CPV qualification tests

    NASA Technical Reports Server (NTRS)

    Garner, J. C.; Barnes, Wilbert L.; Hickman, Gary L.

    1995-01-01

    In 1992, the Naval Research Laboratory (NRL) started a program to qualify a large diameter common pressure vessel (CPV) nickel-hydrogen (NiH2) batteries for use on future Navy/NRL spacecraft electrical power subsystems. NRL's involvement with the qualification of CPV NiH2 batteries dates back to 1988 when COMSAT and Johnson Controls, Inc. initiated a joint effort to fly the first ever NiH2 CPV in space. A later NRL-JCI cooperative research and development agreement led to the launch of a space experiment in 1993 and to the use of a single NiH2 CPV battery on the BMDO Clementine spacecraft in 1994. NRL initiated procurement of two, 50 Ah CPV NiH2 batteries in the Fall of 1992. The two batteries were delivered to NRL in June 1994. NiH2 CPV batteries have almost 2x the specific energy (Wh/kg) of nickel cadium batteries and 2x the energy density (Wh/l) of individual pressure vessel NiH2 CPV's. This presentation discusses the results of electrical and mechanical qualification tests conducted at NRL. The tests included electrical characterization, standard capacity, random vibration, peak load, and thermal vacuum. The last slides of the presentation show initial results from the life cycle tests of the second NiH2 CPV battery at 40% depth of discharge and a temperature of 10 C.

  17. H2 production by Anabaena variabilis mutant in computer controlled two-stage air-lift tubular photobioreactor

    NASA Astrophysics Data System (ADS)

    Liu, Jian-Guo; Hall, D. O.; Rao, K. K.; Tsygankov, A. A.; Sveshnikov, D. A.

    2000-06-01

    A 4.34 liter two-stage air-lift photobioreactor incorporating Anabaena variabilis ATCC29413 mutant PK84 was used to study H2 production. Results showed that H2 production increased with increasing light intensity from 47 μE/(m2·s) up to 190 μE/(m2·s), but that further increase of light intensity decreased the H2 production because of the inhibition due to the high pO2. The data also indicated that longer argon gas charge resulted in more H2 produced due to the increase of nitrogenase activities and heterocyst frequency, and that more than 1.3 L net H2 was produced from this computer controlled photobioreactor.

  18. Use and abuse of exogenous H2O2 in studies of signal transduction

    PubMed Central

    Forman, Henry Jay

    2007-01-01

    The goal of this review is to present a rationale for use of exogenous H2O2, which has been demonstrated to have both toxicological and physiological signaling roles. Reasons for the use of exogenous application of non-toxic concentrations of H2O2 in model systems and caveats for interpretation of the data obtained will both be presented. Briefly, an argument for the cautious use of the addition of exogenous H2O2 is that, because of the permeability of cell membranes to this neutral small molecule, a concentration that is produced locally that is necessary for the physiological action can be mimicked. On the other hand, it must be recognized that the addition of an agent or its enzymatic generation in the media may produce reactions that may not normally occur because the total dose of H2O2 and the concentration of H2O2 in some cellular locations will exceed what is normally achieved even under a pathophysiological state. For this reason, this review will try to provide an unbiased balanced pros and cons analysis of this issue. PMID:17349920

  19. Gas-Phase Condensation Reactions of SixOyHz- Oxyanions with H2O

    SciTech Connect

    Groenewold, Gary Steven; Scott, Jill Rennee; Gianotto, Anita Kay; Hodges, Brittany DM; Kessinger, Glen Frank; Benson, Michael Timothy; Wright, J. B.

    2001-09-01

    Water was reacted with gas-phase oxyanions having the general composition SixOyHz- that were formed and isolated in an ion trap-secondary ion mass spectrometer (IT-SIMS). The radical SiO2- reacted slowly with H2O to abstract HO, forming SiO3H-, at a rate of 8 × 10-13 cm3 molecule-1 s-1, corresponding to an efficiency of about 0.03% compared with the theoretical collision rate constant (average dipole orientation). The product ion SiO3H- underwent a consecutive condensation reaction with H2O to form SiO4H3- at a rate that was approximately 0.4-0.7% efficient. SiO4H3- did not undergo further reaction with water. The multiple reaction pathways by which radical SiO3- reacted with H2O were kinetically modeled using a stochastic approach. SiO3- reacted with water by three parallel reaction pathways: (1) abstraction of a radical H to form SiO3H-, which then reacted with a second H2O to form SiO4H3-; (2) abstraction of a radical OH to form SiO4H-, which further reacted by consecutive H abstractions to form SiO4H2- and then SiO4H3-; and (3) condensation with H2O to form SiO4H2-, which subsequently abstracted a radical H from a second H2O to form SiO4H3-. In all of these reactions, the rate constants were determined to be very slow, as determined by both direct measurement and stochastic modeling. For comparison, the even electron ion Si2O5H- was also investigated: it underwent condensation with H2O to form Si2O6H3-, with a rate constant corresponding to 50% efficiency. The reactions were also modeled using ab initio calculations at the UB3LYP/6-311+G(2d,p) level. Addition of H2O to SiO3-, SiO3H-, and Si2O5H- was calculated to be approximately 42, 45, and 55 kcal mol-1 exothermic, respectively, and encountered low activation barriers. Modeling of SiO2- and SiO3- reactions with H2O failed to produce radical abstraction reaction pathways observed in the IT-SIMS, possibly indicating that alternative reaction mechanisms are operative.

  20. Chemiluminescent Probes for Imaging H2S in Living Animals†

    PubMed Central

    Cao, J.; Lopez, R.; Thacker, J.M.; Moon, J.Y.; Jiang, C.; Morris, S.N.S.; Bauer, J.H.; Tao, P.; Mason, R.P.

    2015-01-01

    Hydrogen sulphide (H2S) is an endogenous mediator of human health and disease, but precise measurement in living cells and animals remains a considerable challenge. We report the total chemical synthesis and characterization of three 1,2-dioxetane chemiluminescent reaction-based H2S probes, CHS-1, CHS-2, and CHS-3. Upon treatment with H2S at physiological pH, these probes display instantaneous light emission that is sustained for over an hour with high selectivity against other reactive sulphur, oxygen, and nitrogen species. Analysis of the phenol/phenolate equilibrium and atomic charges has provided a generally applicable predictive model to design improved chemiluminescent probes. The utility of these chemiluminescent reagents was demonstrated by applying CHS-3 to detect cellularly generated H2S using a multi-well plate reader and to image H2S in living mice using CCD camera technology. PMID:25709805

  1. Hormetic Effect of H2O2 in Saccharomyces cerevisiae

    PubMed Central

    Valishkevych, Bohdana V.

    2016-01-01

    In this study, we investigated the relationship between target of rapamycin (TOR) and H2O2-induced hormetic response in the budding yeast Saccharomyces cerevisiae grown on glucose or fructose. In general, our data suggest that: (1) hydrogen peroxide (H2O2) induces hormesis in a TOR-dependent manner; (2) the H2O2-induced hormetic dose–response in yeast depends on the type of carbohydrate in growth medium; (3) the concentration-dependent effect of H2O2 on yeast colony growth positively correlates with the activity of glutathione reductase that suggests the enzyme involvement in the H2O2-induced hormetic response; and (4) both TOR1 and TOR2 are involved in the reciprocal regulation of the activity of glucose-6-phosphate dehydrogenase and glyoxalase 1. PMID:27099601

  2. Altered Sulfide (H2S) Metabolism in Ethylmalonic Encephalopathy

    PubMed Central

    Tiranti, Valeria; Zeviani, Massimo

    2013-01-01

    Hydrogen sulfide (sulfide, H2S) is a colorless, water-soluble gas with a typical smell of rotten eggs. In the past, it has been investigated for its role as a potent toxic gas emanating from sewers and swamps or as a by-product of industrial processes. At high concentrations, H2S is a powerful inhibitor of cytochrome c oxidase; in trace amounts, it is an important signaling molecule, like nitric oxide (NO) and carbon monoxide (CO), together termed “gasotransmitters.” This review will cover the physiological role and the pathogenic effects of H2S, focusing on ethylmalonic encephalopathy, a human mitochondrial disorder caused by genetic abnormalities of sulfide metabolism. We will also discuss the options that are now conceivable for preventing genetically driven chronic H2S toxicity, taking into account that a complete understanding of the physiopathology of H2S has still to be achieved. PMID:23284046

  3. Detection of a new interstellar molecule, H2CN

    NASA Technical Reports Server (NTRS)

    Ohishi, Masatoshi; Mcgonagle, Douglas; Irvine, William M.; Yamamoto, Satoshi; Saito, Shuji

    1994-01-01

    We have detected a new interstellar molecule, H2CN (methylene amidogen), in the cold, dark molecular cloud TMC-1. The column density of H2CN is estimated to be approximately 1.5 x 10(exp 11) cm(exp -2) by assuming an excitation temperature of 5 K. This column density corresponds to a fractional abundance relative to H2 of approximately 1.5 x 10(exp -11). This value is more than three orders of magnitude less than the abundance of the related molecule HCN in TMC-1. We also report a tentative detection of H2CN in Sgr B2(N). The formation mechanism of H2CN is discussed. Our detection of the N2CN molecule may suggest the existence of a new series of carbon-chain molecules, CH2C(n)N (N = 0, 1, 2, ...).

  4. Polysulfides Link H2S to Protein Thiol Oxidation

    PubMed Central

    Greiner, Romy; Pálinkás, Zoltán; Bäsell, Katrin; Becher, Dörte; Antelmann, Haike; Nagy, Péter

    2013-01-01

    Abstract Aims: Hydrogen sulfide (H2S) is suggested to act as a gaseous signaling molecule in a variety of physiological processes. Its molecular mechanism of action was proposed to involve protein S-sulfhydration, that is, conversion of cysteinyl thiolates (Cys-S−) to persulfides (Cys-S-S−). A central and unresolved question is how H2S—that is, a molecule with sulfur in its lowest possible oxidation state (−2)—can lead to oxidative thiol modifications. Results: Using the lipid phosphatase PTEN as a model protein, we find that the “H2S donor” sodium hydrosulfide (NaHS) leads to very rapid reversible oxidation of the enzyme in vitro. We identify polysulfides formed in NaHS solutions as the oxidizing species, and present evidence that sulfane sulfur is added to the active site cysteine. Polysulfide-mediated oxidation of PTEN was induced by all “H2S donors” tested, including sodium sulfide (Na2S), gaseous H2S, and morpholin-4-ium 4-methoxyphenyl(morpholino) phosphinodithioate (GYY4137). Moreover, we show that polysulfides formed in H2S solutions readily modify PTEN inside intact cells. Innovation: Our results shed light on the previously unresolved question of how H2S leads to protein thiol oxidation, and suggest that polysulfides formed in solutions of H2S mediate this process. Conclusion: This study suggests that the effects that have been attributed to H2S in previous reports may in fact have been mediated by polysulfides. It also supports the notion that sulfane sulfur rather than sulfide is the actual in vivo agent of H2S signaling. Antioxid. Redox Signal. 19, 1749–1765. PMID:23646934

  5. Origin of methane in serpentinite-hosted hydrothermal systems: The CH4-H2-H2O hydrogen isotope systematics of the Hakuba Happo hot spring

    NASA Astrophysics Data System (ADS)

    Suda, Konomi; Ueno, Yuichiro; Yoshizaki, Motoko; Nakamura, Hitomi; Kurokawa, Ken; Nishiyama, Eri; Yoshino, Koji; Hongoh, Yuichi; Kawachi, Kenichi; Omori, Soichi; Yamada, Keita; Yoshida, Naohiro; Maruyama, Shigenori

    2014-01-01

    Serpentinite-hosted hydrothermal systems have attracted considerable attention as sites of abiotic organic synthesis and as habitats for the earliest microbial communities. Here, we report a systematic isotopic study of a new serpentinite-hosted system: the Hakuba Happo hot spring in the Shiroumadake area, Japan (36°42‧N, 137°48‧E). We collected water directly from the hot spring from two drilling wells more than 500 m deep; all water samples were strongly alkaline (pH>10) and rich in H2 (201-664 μmol/L) and CH4 (124-201 μmol/L). Despite the relatively low temperatures (50-60 °C), thermodynamic calculations suggest that the H2 was likely derived from serpentinization reactions. Hydrogen isotope compositions for Happo #1 (Happo #3) were found to be as follows: δD-H2=-700‰ (-710‰), δD-CH4=-210‰ (-300‰), and δD-H2O=-85‰ (-84‰). The carbon isotope compositions of methane from Happo #1 and #3 were found to be δC13=-34.5‰ and -33.9‰, respectively. The CH4-H2-H2O hydrogen isotope systematics indicate that at least two different mechanisms were responsible for methane formation. Happo #1 has a similar hydrogen isotope compositions to other serpentinite-hosted systems reported previously. The elevated δD-CH4 (with respect to the equilibrium relationship) suggests that the hydrogen of the Happo #1 methane was not sourced from molecular hydrogen but was derived directly from water. This implies that the methane may not have been produced via the Fischer-Tropsch-type (FTT) synthesis but possibly by the hydration of olivine. Conversely, the depleted δD-CH4 (with respect to the equilibrium relationship) in Happo #3 suggests the incorporation of biological methane. Based on a comparison of the hydrogen isotope systematics of our results with those of other serpentinite-hosted hydrothermal systems, we suggest that abiotic CH4 production directly from H2O (without mediation by H2) may be more common in serpentinite-hosted systems. Hydration of olivine

  6. Antimicrobial action of histone H2B in Escherichia coli: evidence for membrane translocation and DNA-binding of a histone H2B fragment after proteolytic cleavage by outer membrane proteinase T.

    PubMed

    Kawasaki, Hiroaki; Koyama, Takumi; Conlon, J Michael; Yamakura, Fumiyuki; Iwamuro, Shawichi

    2008-01-01

    Previous studies have led to the isolation of histone H2B with antibacterial properties from an extract of the skin of the Schlegel's green tree frog Rhacophorus schlegelii and it is now demonstrated that the intact peptide is released into norepinephrine-stimulated skin secretions. In order to investigate the mechanism of action of this peptide, a maltose-binding protein (MBP)-fused histone H2B (MBP-H2B) conjugate was prepared and subjected to antimicrobial assay. The fusion protein showed bacteriostatic activity against Escherichia coli strain JCM5491 with a minimum inhibitory concentration of 11 microM. The lysate prepared from JCM5491 cells was capable of fragmenting MBP-H2B within the histone H2B region, but the lysate from the outer membrane proteinase T (OmpT) gene-deleted BL21(DE3) cells was not. FITC-labeled MBP-H2B (FITC-MBP-H2B) penetrated into the bacterial cell membrane of JCM5491 and ompT-transformed BL21(DE3) cells, but not into ompT-deleted BL21(DE3) cells. Gel retardation assay using MBP-H2B-deletion mutants indicated that MBP-H2B bound to DNA at a site within the N-terminal region of histone H2B. Consequently, it is proposed that the antimicrobial action of histone H2B involves, at least in part, penetration of an OmpT-produced N-terminal histone H2B fragment into the bacterial cell membrane with subsequent inhibition of cell functions. PMID:18706965

  7. Production of high concentrations of H2O2 in a bioelectrochemical reactor fed with real municipal wastewater.

    PubMed

    Modin, Oskar; Fukushi, Kensuke

    2013-01-01

    Bioelectrochemical systems can be used to energy-efficiently produce hydrogen peroxide (H2O2) from wastewater. Organic compounds in the wastewater are oxidized by microorganisms using the anode as electron acceptor. H2O2 is produced by reduction of oxygen on the cathode. In this study, we demonstrate for the first time production of high concentrations of H2O2 production from real municipal wastewater. A concentration of 2.26 g/L H2O2 was produced in 9 h at 8.3 kWh/kgH2O2. This concentration could potentially be useful for membrane cleaning at membrane bioreactor wastewater treatment plants. With an acetate-containing nutrient medium as anode feed, a H2O2 concentration of 9.67 g/L was produced in 21 h at an energy cost of 3.0 kWh/kgH2O2. The bioelectrochemical reactor used in this study suffered from a high internal resistance, most likely caused by calcium carbonate deposits on the cathode-facing side of the cation exchange membrane separating the anode and cathode compartments. PMID:24527636

  8. H2O2 Production and Destruction in the Outer Solar System: Laboratory Studies

    NASA Astrophysics Data System (ADS)

    Loeffler, M. J.; Raut, U.; Vidal, R. A.; Baragiola, R. A.; Carlson, R. W.

    2004-11-01

    There has been a recent interest in the possible production mechanisms of H2O2 in water ice, since the Galileo NIMS instrument reported an absorption band (3.5 μm) on the surface of Europa (Carlson 1999). Here we present results from laboratory studies that show H2O2 creation and destruction by ion bombardment. We have found that 100 keV H+ irradiation can produce H2O2 from a water ice film at temperatures as high as 120 K and have measured the production rates at 20 K and 80 K. Furthermore, we have studied the temperature dependence and stability of the 3.5 μm band. To understand the nature of the peroxide produced by ion irradiation, we have grown solid hydrogen peroxide by distillation in an ultra high vacuum chamber and have used infrared spectroscopy to study the band shape and position as a function of temperature in various mixtures of water. Furthermore, we have measured the crystallization and sublimation of H2O2 at temperatures between 155 and 190 K. We have also irradiated a film of crystalline H2O2 with 20 keV H+ at 80 K and have observed what is most likely amorphization of the peroxide. Furthermore, infrared spectroscopy indicated that during irradiation, water and ozone are produced, while HO2 is not detected. The presence of ozone suggests that H2O2 is a likely precursor molecule for oxygen formation at 80 K. Work supported by NSF Astronomy, NASA Planetary Atmospheres and Origin programs.

  9. Microchannel Reactor System Design & Demonstration For On-Site H2O2 Production by Controlled H2/O2 Reaction

    SciTech Connect

    Adeniyi Lawal

    2008-12-09

    We successfully demonstrated an innovative hydrogen peroxide (H2O2) production concept which involved the development of flame- and explosion-resistant microchannel reactor system for energy efficient, cost-saving, on-site H2O2 production. We designed, fabricated, evaluated, and optimized a laboratory-scale microchannel reactor system for controlled direct combination of H2 and O2 in all proportions including explosive regime, at a low pressure and a low temperature to produce about 1.5 wt% H2O2 as proposed. In the second phase of the program, as a prelude to full-scale commercialization, we demonstrated our H2O2 production approach by ‘numbering up’ the channels in a multi-channel microreactor-based pilot plant to produce 1 kg/h of H2O2 at 1.5 wt% as demanded by end-users of the developed technology. To our knowledge, we are the first group to accomplish this significant milestone. We identified the reaction pathways that comprise the process, and implemented rigorous mechanistic kinetic studies to obtain the kinetics of the three main dominant reactions. We are not aware of any such comprehensive kinetic studies for the direct combination process, either in a microreactor or any other reactor system. We showed that the mass transfer parameter in our microreactor system is several orders of magnitude higher than what obtains in the macroreactor, attesting to the superior performance of microreactor. A one-dimensional reactor model incorporating the kinetics information enabled us to clarify certain important aspects of the chemistry of the direct combination process as detailed in section 5 of this report. Also, through mathematical modeling and simulation using sophisticated and robust commercial software packages, we were able to elucidate the hydrodynamics of the complex multiphase flows that take place in the microchannel. In conjunction with the kinetics information, we were able to validate the experimental data. If fully implemented across the whole

  10. TES/Aura L2 Water Vapor (H2O) Lite Nadir (TL2H2OLN)

    Atmospheric Science Data Center

    2015-06-16

    TES/Aura L2 Water Vapor (H2O) Lite Nadir (TL2H2OLN) News:  TES News ... Title:  TES Discipline:  Tropospheric Chemistry Version:  V6 Level:  L2 Instrument:  TES/Aura L2 Water Vapor Spatial Coverage:  5.3 km nadir ...

  11. The time dependent growth of H2O-H2SO4 aerosols by heteromolecular condensation

    NASA Technical Reports Server (NTRS)

    Hamill, P.

    1975-01-01

    A theory for the time-dependent growth of solution droplets by heteromolecular condensation is presented. The theory is applied to the growth of H2O-H2SO4 aerosols for relative humidities less than 100 per cent. Growth curves (droplet radius as a function of time) for different values of relative humidity are evaluated.

  12. Determination of the ortho to para ratio of H2Cl+ and H2O+ from submillimeter observations.

    PubMed

    Gerin, Maryvonne; de Luca, Massimo; Lis, Dariusz C; Kramer, Carsten; Navarro, Santiago; Neufeld, David; Indriolo, Nick; Godard, Benjamin; Le Petit, Franck; Peng, Ruisheng; Phillips, Thomas G; Roueff, Evelyne

    2013-10-01

    The opening of the submillimeter sky with the Herschel Space Observatory has led to the detection of new interstellar molecular ions, H2O(+), H2Cl(+), and HCl(+), which are important intermediates in the synthesis of water vapor and hydrogen chloride. In this paper, we report new observations of H2O(+) and H2Cl(+) performed with both Herschel and ground-based telescopes, to determine the abundances of their ortho and para forms separately and derive the ortho-to-para ratio. At the achieved signal-to-noise ratio, the observations are consistent with an ortho-to-para ratios of 3 for both H2O(+) and H2Cl(+), in all velocity components detected along the lines-of-sight to the massive star-forming regions W31C and W49N. We discuss the mechanisms that contribute to establishing the observed ortho-to-para ratio and point to the need for a better understanding of chemical reactions, which are important for establishing the H2O(+) and H2Cl(+) ortho-to-para ratios. PMID:23869910

  13. Cryo-chamber simulation of stratospheric H2SO4/H2O particles: Composition analysis and model comparison

    NASA Astrophysics Data System (ADS)

    Zink, Peter; Knopf, Daniel A.; Schreiner, Jochen; Mauersberger, Konrad; Möhler, Ottmar; Saathoff, Harald; Seifert, Marco; Tiede, Ralph; Schurath, Ulrich

    2002-06-01

    The combination of a large aerosol chamber and a recently developed Aerosol Composition Mass Spectrometer (ACMS) was used to investigate sulfuric acid aerosols at low temperatures. Concentrations of condensed phase H2SO4 and H2O were determined with an accuracy of better than 4 wt.%. Simultaneous measurements of temperature, partial pressure of water, total sulfate amount and particle size distribution permit to calculate the particle equilibrium composition. The model description of Carslaw et al. [1995a] for H2SO4/H2O solutions was confirmed in the composition range from 35 to 68 wt.% H2SO4 for temperatures between 188 and 236 K, extending the experimental verification to lower temperatures. Although the sub-micron particles were up to 25 K super-cooled with respect to solid sulfuric acid hydrates such as the tetrahydrate (SAT), they remained liquid for days.

  14. Magic numbers in Al n+(H 2O) 1 cluster cations

    NASA Astrophysics Data System (ADS)

    Lippa, T. P.; Lyapustina, S. A.; Xu, S.-J.; Thomas, O. C.; Bowen, K. H.

    1999-05-01

    We report the observation of magic numbers in the mass spectrum of Al n+(H 2O) 1. These cluster cations were produced in a laser vaporization source in the presence of trace amounts of water. The most prominent magic number species observed was Al 13+(H 2O) 1. We attribute its pronounced intensity to its enhanced stability resulting from the formation of a coordinate bond between the Al 13+ moiety and the oxygen atom of water. The sharing of an oxygen lone electron pair with Al 13+ lends to it some of the character of the 40-valence electron, closed shell Al 13- magic cluster.

  15. CO Diffusion into Amorphous H2O Ices

    NASA Astrophysics Data System (ADS)

    Lauck, Trish; Karssemeijer, Leendertjan; Shulenberger, Katherine; Rajappan, Mahesh; Öberg, Karin I.; Cuppen, Herma M.

    2015-03-01

    The mobility of atoms, molecules, and radicals in icy grain mantles regulates ice restructuring, desorption, and chemistry in astrophysical environments. Interstellar ices are dominated by H2O, and diffusion on external and internal (pore) surfaces of H2O-rich ices is therefore a key process to constrain. This study aims to quantify the diffusion kinetics and barrier of the abundant ice constituent CO into H2O-dominated ices at low temperatures (15-23 K), by measuring the mixing rate of initially layered H2O(:CO2)/CO ices. The mixed fraction of CO as a function of time is determined by monitoring the shape of the infrared CO stretching band. Mixing is observed at all investigated temperatures on minute timescales and can be ascribed to CO diffusion in H2O ice pores. The diffusion coefficient and final mixed fraction depend on ice temperature, porosity, thickness, and composition. The experiments are analyzed by applying Fick’s diffusion equation under the assumption that mixing is due to CO diffusion into an immobile H2O ice. The extracted energy barrier for CO diffusion into amorphous H2O ice is ˜160 K. This is effectively a surface diffusion barrier. The derived barrier is low compared to current surface diffusion barriers in use in astrochemical models. Its adoption may significantly change the expected timescales for different ice processes in interstellar environments.

  16. Analytic H i-to-H2 Photodissociation Transition Profiles

    NASA Astrophysics Data System (ADS)

    Bialy, Shmuel; Sternberg, Amiel

    2016-05-01

    We present a simple analytic procedure for generating atomic (H i) to molecular ({{{H}}}2) density profiles for optically thick hydrogen gas clouds illuminated by far-ultraviolet radiation fields. Our procedure is based on the analytic theory for the structure of one-dimensional H i/{{{H}}}2 photon-dominated regions, presented by Sternberg et al. Depth-dependent atomic and molecular density fractions may be computed for arbitrary gas density, far-ultraviolet field intensity, and the metallicity-dependent H2 formation rate coefficient, and dust absorption cross section in the Lyman–Werner photodissociation band. We use our procedure to generate a set of {{H}} {{I}}{-}{to}{-}{{{H}}}2 transition profiles for a wide range of conditions, from the weak- to strong-field limits, and from super-solar down to low metallicities. We show that if presented as functions of dust optical depth, the {{H}} {{I}} and {{{H}}}2 density profiles depend primarily on the Sternberg “α G parameter” (dimensionless) that determines the dust optical depth associated with the total photodissociated {{H}} {{I}} column. We derive a universal analytic formula for the {{H}} {{I}}{-}{to}{-}{{{H}}}2 transition points as a function of just α G. Our formula will be useful for interpreting emission-line observations of H i/{{{H}}}2 interfaces, for estimating star formation thresholds, and for sub-grid components in hydrodynamics simulations.

  17. TOPORS modulates H2AX discriminating genotoxic stresses.

    PubMed

    Seong, Ki Moon; Nam, Seon Young; Kim, Ji-Young; Yang, Kwang Hee; An, Sungkwan; Jin, Young-Woo; Kim, Cha Soon

    2012-11-01

    H2AX plays an important role in chromatin reorganization implicated in DNA repair and apoptosis under various DNA damaging conditions. In this study, the interaction between TOPORS (topoisomerase I-binding protein) and H2AX was verified using mammalian cell extracts exposed to diverse DNA damaging stresses such as ionizing radiation, doxorubicin, camptothecin, and hydrogen peroxide. In vitro assays for ubiquitination revealed that TOPORS functions as a novel E3 ligase for H2AX ubiquitination. TOPORS was found to be dissociated from H2AX proteins when cells were exposed to oxidative stress, but not replication-inducing DNA damaging stress. The protein stability of H2AX was decreased when TOPORS was ectopically expressed in cells, and oxidative stresses such as hydrogen peroxide and ionizing radiation induced recovery of the H2AX protein level. Therefore, these biochemical data suggest that TOPORS plays a key role in the turnover of H2AX protein, discriminating the type of DNA damaging stress. PMID:22972498

  18. Analytic H i-to-H2 Photodissociation Transition Profiles

    NASA Astrophysics Data System (ADS)

    Bialy, Shmuel; Sternberg, Amiel

    2016-05-01

    We present a simple analytic procedure for generating atomic (H i) to molecular ({{{H}}}2) density profiles for optically thick hydrogen gas clouds illuminated by far-ultraviolet radiation fields. Our procedure is based on the analytic theory for the structure of one-dimensional H i/{{{H}}}2 photon-dominated regions, presented by Sternberg et al. Depth-dependent atomic and molecular density fractions may be computed for arbitrary gas density, far-ultraviolet field intensity, and the metallicity-dependent H2 formation rate coefficient, and dust absorption cross section in the Lyman-Werner photodissociation band. We use our procedure to generate a set of {{H}} {{I}}{-}{to}{-}{{{H}}}2 transition profiles for a wide range of conditions, from the weak- to strong-field limits, and from super-solar down to low metallicities. We show that if presented as functions of dust optical depth, the {{H}} {{I}} and {{{H}}}2 density profiles depend primarily on the Sternberg “α G parameter” (dimensionless) that determines the dust optical depth associated with the total photodissociated {{H}} {{I}} column. We derive a universal analytic formula for the {{H}} {{I}}{-}{to}{-}{{{H}}}2 transition points as a function of just α G. Our formula will be useful for interpreting emission-line observations of H i/{{{H}}}2 interfaces, for estimating star formation thresholds, and for sub-grid components in hydrodynamics simulations.

  19. Arginine-Containing Ligands Enhance H-2 Oxidation Catalyst Performance

    SciTech Connect

    Dutta, Arnab; Roberts, John A.; Shaw, Wendy J.

    2014-06-16

    In H2 fuel cells, performance depends on factors controlling turnover frequency and energy efficiency in the electrocatalytic oxidation of H2. Nature uses the hydrogenase enzymes to oxidize H2 at high turnover frequencies (up to 20,000 s-1) and low overpotentials (<100 mV), while the fastest synthetic catalyst reported to date only oxidizes H2 at 50 s-1 under 1 atm H2. Here we report a water-soluble complex incorporating the amino acid arginine, [NiII(PCy2NArg2)2]6+, that operates at 210 s-1 (180 mV overpotential) under 1 atm H2 and 144,000 s-1 (460 mV overpotential) under 133 atm H2. The complex functions from pH 0-14 with rates increasing at lower pH values. The arginine groups impart water solubility and play a critical role in enhancing turnover frequency, most consistent with an intramolecular Arg-Arg interaction that controls the structure of the catalyst active site. This work was funded by the Office of Science Early Career Research Program through the US DOE, BES (AD, WJS), and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US DOE, BES (JASR). PNNL is operated by Battelle for the US DOE.

  20. Influence of O2 and H2O on carbothermal reduction of SO2 by oil-sand fluid coke.

    PubMed

    Feng, Wenguo; Jia, Charles Q

    2005-12-15

    To develop a new process for removing high-concentration SO2 from industrial flue gases, the carbothermal reduction of SO2 by oil-sand fluid coke at 700 degrees C was investigated by varying the inlet concentration of either O2 or H2O. Concentrations of O2 and H2O ranged from 0 to 20% and from 0 to 30%, respectively, in a stream of SO2 (18%) with the balance helium. Addition of O2 and H2O was found to enhance SO2 reduction. The enhancement was attributed to the reducing gases, CO and H2, produced by solid-gas reactions between carbon and O2 or H2O. The effects of O2 and H2O on sulfur yield, however, were bifacial: adding O2 and/or H2O increased the sulfur yield when SO2 conversion was incomplete, otherwise, it decreased the sulfur yield through the formation of sulfides such as H2S. The results of a thermodynamic analysis were in a good agreementwith the experimental results, suggesting that gas-solid reactions were slow enough to allow gas-phase equilibrium. This study indicates that carbon, such as oil-sand fluid coke, can be utilized to remove SO2 in flue gases containing O2/H2O and to convert it to elemental sulfur. PMID:16475356

  1. Photosynthetic H2 metabolism in Chlamydomonas reinhardtii (unicellular green algae).

    PubMed

    Melis, Anastasios

    2007-10-01

    Unicellular green algae have the ability to operate in two distinctly different environments (aerobic and anaerobic), and to photosynthetically generate molecular hydrogen (H2). A recently developed metabolic protocol in the green alga Chlamydomonas reinhardtii permitted separation of photosynthetic O2-evolution and carbon accumulation from anaerobic consumption of cellular metabolites and concomitant photosynthetic H2-evolution. The H2 evolution process was induced upon sulfate nutrient deprivation of the cells, which reversibly inhibits photosystem-II and O2-evolution in their chloroplast. In the absence of O2, and in order to generate ATP, green algae resorted to anaerobic photosynthetic metabolism, evolved H2 in the light and consumed endogenous substrate. This study summarizes recent advances on green algal hydrogen metabolism and discusses avenues of research for the further development of this method. Included is the mechanism of a substantial tenfold starch accumulation in the cells, observed promptly upon S-deprivation, and the regulated starch and protein catabolism during the subsequent H2-evolution. Also discussed is the function of a chloroplast envelope-localized sulfate permease, and the photosynthesis-respiration relationship in green algae as potential tools by which to stabilize and enhance H2 metabolism. In addition to potential practical applications of H2, approaches discussed in this work are beginning to address the biochemistry of anaerobic H2 photoproduction, its genes, proteins, regulation, and communication with other metabolic pathways in microalgae. Photosynthetic H2 production by green algae may hold the promise of generating a renewable fuel from nature's most plentiful resources, sunlight and water. The process potentially concerns global warming and the question of energy supply and demand. PMID:17721788

  2. Pyruvate Protects Pathogenic Spirochetes from H2O2 Killing

    PubMed Central

    Troxell, Bryan; Zhang, Jun-Jie; Bourret, Travis J.; Zeng, Melody Yue; Blum, Janice; Gherardini, Frank; Hassan, Hosni M.; Yang, X. Frank

    2014-01-01

    Pathogenic spirochetes cause clinically relevant diseases in humans and animals, such as Lyme disease and leptospirosis. The causative agent of Lyme disease, Borrelia burgdorferi, and the causative agent of leptospirosis, Leptospria interrogans, encounter reactive oxygen species (ROS) during their enzootic cycles. This report demonstrated that physiologically relevant concentrations of pyruvate, a potent H2O2 scavenger, and provided passive protection to B. burgdorferi and L. interrogans against H2O2. When extracellular pyruvate was absent, both spirochetes were sensitive to a low dose of H2O2 (≈0.6 µM per h) generated by glucose oxidase (GOX). Despite encoding a functional catalase, L. interrogans was more sensitive than B. burgdorferi to H2O2 generated by GOX, which may be due to the inherent resistance of B. burgdorferi because of the virtual absence of intracellular iron. In B. burgdorferi, the nucleotide excision repair (NER) and the DNA mismatch repair (MMR) pathways were important for survival during H2O2 challenge since deletion of the uvrB or the mutS genes enhanced its sensitivity to H2O2 killing; however, the presence of pyruvate fully protected ΔuvrB and ΔmutS from H2O2 killing further demonstrating the importance of pyruvate in protection. These findings demonstrated that pyruvate, in addition to its classical role in central carbon metabolism, serves as an important H2O2 scavenger for pathogenic spirochetes. Furthermore, pyruvate reduced ROS generated by human neutrophils in response to the Toll-like receptor 2 (TLR2) agonist zymosan. In addition, pyruvate reduced neutrophil-derived ROS in response to B. burgdorferi, which also activates host expression through TLR2 signaling. Thus, pathogenic spirochetes may exploit the metabolite pyruvate, present in blood and tissues, to survive H2O2 generated by the host antibacterial response generated during infection. PMID:24392147

  3. Implications of Hydrogen Sulfide in Glucose Regulation: How H2S Can Alter Glucose Homeostasis through Metabolic Hormones

    PubMed Central

    Pichette, Jennifer

    2016-01-01

    Diabetes and its comorbidities continue to be a major health problem worldwide. Understanding the precise mechanisms that control glucose homeostasis and their dysregulation during diabetes are a major research focus. Hydrogen sulfide (H2S) has emerged as an important regulator of glucose homeostasis. This is achieved through its production and action in several metabolic and hormone producing organs including the pancreas, liver, and adipose. Of importance, H2S production and signaling in these tissues are altered during both type 1 and type 2 diabetes mellitus. This review first examines how H2S is produced both endogenously and by gastrointestinal microbes, with a particular focus on the altered production that occurs during obesity and diabetes. Next, the action of H2S on the metabolic organs with key roles in glucose homeostasis, with a particular focus on insulin, is described. Recent work has also suggested that the effects of H2S on glucose homeostasis goes beyond its role in insulin secretion. Several studies have demonstrated important roles for H2S in hepatic glucose output and adipose glucose uptake. The mechanism of H2S action on these metabolic organs is described. In the final part of this review, future directions examining the roles of H2S in other metabolic and glucoregulatory hormone secreting tissues are proposed. PMID:27478532

  4. Implications of Hydrogen Sulfide in Glucose Regulation: How H2S Can Alter Glucose Homeostasis through Metabolic Hormones.

    PubMed

    Pichette, Jennifer; Gagnon, Jeffrey

    2016-01-01

    Diabetes and its comorbidities continue to be a major health problem worldwide. Understanding the precise mechanisms that control glucose homeostasis and their dysregulation during diabetes are a major research focus. Hydrogen sulfide (H2S) has emerged as an important regulator of glucose homeostasis. This is achieved through its production and action in several metabolic and hormone producing organs including the pancreas, liver, and adipose. Of importance, H2S production and signaling in these tissues are altered during both type 1 and type 2 diabetes mellitus. This review first examines how H2S is produced both endogenously and by gastrointestinal microbes, with a particular focus on the altered production that occurs during obesity and diabetes. Next, the action of H2S on the metabolic organs with key roles in glucose homeostasis, with a particular focus on insulin, is described. Recent work has also suggested that the effects of H2S on glucose homeostasis goes beyond its role in insulin secretion. Several studies have demonstrated important roles for H2S in hepatic glucose output and adipose glucose uptake. The mechanism of H2S action on these metabolic organs is described. In the final part of this review, future directions examining the roles of H2S in other metabolic and glucoregulatory hormone secreting tissues are proposed. PMID:27478532

  5. Quantification and kinetics of H2 generation during hydrothermal serpentinisation experiments

    NASA Astrophysics Data System (ADS)

    Castelain, Teddy; Fauguerolles, Colin; Villeneuve, Johan; Pichavant, Michel

    2013-04-01

    H2-rich hydrothermal fluids generated by serpentinisation of mantle rocks at slow-spreading ridges have been revealed by recent studies [1, 2]. Fluxes and the future of the H2 produced by this process are poorly constrained [1, 3]. In this study, we aim to quantitatively evaluate the H2 production fluxes associated with these hydrothermal systems and to document the kinetics of the hydrogen-producing reaction. For this matter, hydrothermal serpentinisation experiments are being undertaken on mixtures composed of a natural peridotite from the Pindus ophiolite and olivine crystals from San Carlos. The experiments are conducted at a temperature of ~ 300° C and a pressure of 450-500 bars in large-volume Dickson-Seyfried bombs for periods of × 1 month. Starting materials are powders between 1 - 100 μm for the peridotites and individual grains ranging from 1 - 2 mm for the San Carlos olivine. They are reacted with a homemade artificial seawater in such proportion that water-rock ratio = 1.8. The reactants are loaded in a modified Ti cell fitted with a semi-permeable Au-Pd membrane simultaneously allowing direct sampling of the hydrothermal fluid and in situ monitoring of the pH2 during the advancement of the reaction. The gas fraction of the fluid sampled is then analyzed by gas chromatography (GC). The pH2 readings show traces of H2 to be present from the second day of experiment. The increase of the pH2 reaches a maximum after ~ 6 days and the pH2 finally stabilizes after ~ 16 days at ~ 12.5 bars, which corresponds to a local fO2 of about NNO-4. The GC measurements, performed after 30, 43, 51 and 65 days, yield respectively, H2 concentrations of 82.4, 89.7, 90.3 and 101 mmol.kg-1 of water, in reasonable agreement with results from previous studies [4-6]. Further experiments are being undertaken in order to: duplicate observations, especially the pH2 readings, more closely link the GC measurements and the in situ pH2 readings, especially during the first 15 days of

  6. Lifetime studies in H2/Br2 fuel cells

    NASA Astrophysics Data System (ADS)

    Barna, G. G.; Frank, S. N.; Teherani, T. H.; Weedon, L. D.

    1984-09-01

    A fully computerized system has been set up for the life testing of H2 electrodes in 48 percent HBr, and of H2/Br2 fuel cells. Given a fuel cell design with dry H2 and no anolyte loop, the prime parameters influencing the operating lifetime are the hydrophobicity of the anode and the electrolyte transport property of the membrane. A systematic optimization of all the parameters has generated fuel cells that have operated for 10,000h at 2 A/sq in., with no significant degradation.

  7. The Anharmonic Force Field of BeH2 Revisited

    NASA Technical Reports Server (NTRS)

    Martin, Jan M. L.; Lee, Timothy J.

    2003-01-01

    The anharmonic force field of BeH2 has been calculated near the basis set and n-particle space limits. The computed antisymmetric stretch frequencies of BeH2 and BeD2 are in excellent agreement with recent high-resolution gas-phase measurements. The agreement between theory and experiment for the other spectroscopic constants is also excellent, except for omega(sub 3) and X(sub 33) for BeH2 and G(sub 22) for BeD2. It is concluded that further experimental work is needed in order to resolve these discrepancies.

  8. A global potential energy surface for ArH2

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.; Walch, Stephen P.; Taylor, Peter R.

    1992-01-01

    We describe a simple analytic representation of the ArH2 potential energy surface which well reproduces the results of extensive ab initio electronic structure calculations. The analytic representation smoothly interpolates between the dissociated H2 and strong bonding limits. In the fitting process, emphasis is made on accurately reproducing regions of the potential expected to be important for high temperature (ca. 3000 K) collision processes. Overall, the anisotropy and H2 bond length dependence of the analytic representation well reproduce the input data.

  9. Uncertainties in H2 and HD chemistry and cooling and their role in early structure formation

    NASA Astrophysics Data System (ADS)

    Glover, S. C. O.; Abel, T.

    2008-08-01

    At low temperatures, the main coolant in primordial gas is molecular hydrogen, H2. Recent work has shown that primordial gas that is not collapsing gravitationally but is cooling from an initially ionized state forms hydrogen deuteride, HD, in sufficient amounts to cool the gas to the temperature of the cosmic microwave background. This extra cooling can reduce the characteristic mass for gravitational fragmentation and may cause a shift in the characteristic masses of Population III stars. Motivated by the importance of the atomic and molecular data for the cosmological question, we assess several chemical and radiative processes that have hitherto been neglected: the sensitivity of the low-temperature H2 cooling rate to the ratio of ortho-H2 to para-H2, the uncertainty in the low-temperature cooling rate of H2 excited by collisions with atomic hydrogen, the effects of cooling from H2 excited by collisions with protons and electrons, and the large uncertainties in the rates of several of the reactions responsible for determining the H2 fraction in the gas. It is shown that the most important of neglected processes is the excitation of H2 by collisions with protons and electrons. Their effect is to cool the gas more rapidly at early times, and consequently to form less H2 and HD at late times. This fact, as well as several of the chemical uncertainties presented here, significantly affects the thermal evolution of the gas. We anticipate that this may lead to clear differences in future detailed three-dimensional studies of first structure formation. In such calculations it has previously been shown that the details of the timing between cooling and merger events decide between immediate runaway gravitational collapse and a slower collapse delayed by turbulent heating. Finally, we show that although the thermal evolution of the gas is in principle sensitive to the ortho-para ratio, in practice the standard assumption of a 3:1 ratio produces results that are almost

  10. Phosphorylated H2AX in parthenogenetically activated, in vitro fertilized and cloned bovine embryos.

    PubMed

    Pereira, A F; Melo, L M; Freitas, V J F; Salamone, D F

    2015-08-01

    In vitro embryo production methods induce DNA damage in the embryos. In response to these injuries, histone H2AX is phosphorylated (γH2AX) and forms foci at the sites of DNA breaks to recruit repair proteins. In this work, we quantified the DNA damage in bovine embryos undergoing parthenogenetic activation (PA), in vitro fertilization (IVF) or somatic cell nuclear transfer (SCNT) by measuring γH2AX accumulation at different developmental stages: 1-cell, 2-cell and blastocyst. At the 1-cell stage, IVF embryos exhibited a greater number of γH2AX foci (606.1 ± 103.2) and greater area of γH2AX staining (12923.6 ± 3214.1) than did PA and SCNT embryos. No differences at the 2-cell stage were observed among embryo types. Although PA, IVF and SCNT were associated with different blastocyst formation rates (31.1%, 19.7% and 8.3%, P < 0.05), no differences in the number of γH2AX foci or area were detected among the treatments. γH2AX is detected in bovine preimplantation embryos produced by PA, IVF and SCNT; the amount of DNA damage was comparable among those embryos developing to the blastocyst stage among different methods for in vitro embryo production. While IVF resulted in increased damage at the 1-cell embryo stage, no difference was observed between PA and SCNT embryos at any developmental stage. The decrease in the number of double-stranded breaks at the blastocyst stage seems to indicate that DNA repair mechanisms are functional during embryo development. PMID:24735637

  11. Magnesium Corrosion Triggered Spontaneous Generation of H2O2 on Oxidized Titanium for Promoting Angiogenesis.

    PubMed

    Park, Jimin; Du, Ping; Jeon, Jin-Kyung; Jang, Gun Hyuk; Hwang, Mintai Peter; Han, Hyung-Seop; Park, Kwideok; Lee, Kwan Hyi; Lee, Jee-Wook; Jeon, Hojeong; Kim, Yu-Chan; Park, Jong Woong; Seok, Hyun-Kwang; Ok, Myoung-Ryul

    2015-12-01

    Although the use of reactive oxygen species (ROS) has been extensively studied, current systems employ external stimuli such as light or electrical energy to produce ROS, which limits their practical usage. In this report, biocompatible metals were used to construct a novel electrochemical system that can spontaneously generate H2O2 without any external light or voltage. The corrosion of Mg transfers electrons to Au-decorated oxidized Ti in an energetically favorable process, and the spontaneous generation of H2O2 in an oxygen reduction reaction was revealed to occur at titanium by combined spectroscopic and electrochemical analyses. The controlled release of H2O2 noticeably enhanced in vitro angiogenesis even in the absence of growth factors. Finally, a new titanium implant prototype was developed by Mg incorporation, and its potential for promoting angiogenesis was demonstrated. PMID:26482466

  12. Metal-Organic Framework/PVDF Composite Membranes with High H2 Permselectivity Synthesized by Ammoniation.

    PubMed

    Li, Wanbin; Meng, Qin; Zhang, Congyang; Zhang, Guoliang

    2015-05-01

    Herein we report a new ammoniation-based chemical modification strategy for synthesis of continuous and uniform metal-organic framework (MOF)/polyvinylidene fluoride (PVDF) membranes with attractive performance. Ammoniation can promote the support PVDF membrane to produce amino groups, form a nanoparticle structure, and be well cross-linked; therefore, the high-density heterogeneous nucleation sites for MOFs growth were provided and the thermal stability and chemical resistance of composite membranes can be greatly improved. The high-quality layers of representative Cu-BTC and ZIF-8 were synthesized on the chemically modified PVDF membranes. By ammoniation, ZIF-7 can even be grown under harsh synthetic conditions such as in DMF precursor solutions at 403 K. The fabricated MOF/PVDF composite membranes with excellent hollow fiber structures and enhanced structural stability exhibited high H2 permselectivities for H2 /CO2 and H2 /N2 . PMID:25810142

  13. CO2 and H2O diluted oxy-fuel combustion for zero-emission power

    SciTech Connect

    G A Richards; K H Casleton; B T Chorpening

    2005-01-01

    Concerns about climate change have encouraged significant interest in concepts for zero-emission power generation systems. These systems are intended to produce power without releasing CO2 into the atmosphere. One method to achieve this goal is to produce hydrogen from the gasification of fossil or biomass fuels. Using various membrane and reforming technologies, the carbon in the parent fuel can be shifted to CO2 and removed from the fuel stream, followed by direct CO2 sequestration. The hydrogen fuel can be used directly in gas turbines fitted with low-NOx combustors. A second approach to producing zero-emission power is to replace the nitrogen diluent that accompanies conventional combustion in air with either CO2 or H2O. In this concept, CO2 or H2O is added to oxygen to control combustion temperatures in oxygen–fuel reactions. In the absence of nitrogen, the primary combustion products for any hydrocarbon under lean conditions are then simply CO2 and H2O. Thus, merely cooling the exhaust stream condenses the water and produces an exhaust of pure CO2, ready for sequestration. The dilute oxy-fuel combustion strategy can be incorporated in power cycles that are similar to Brayton or Rankine configurations, using CO2 or H2O as the primary diluent respectively. While the relativemerits of the various strategies to zero-emission power are the subject of various technical and economic studies, very little work has focused on defining the combustion issues associated with the dilute oxy-fuel option. In this paper, the expected combustion performance of CO2 and H2O diluted systems are compared. Experimental results from a high-pressure oxy-fuel combustor are also presented.

  14. Mapping Post-translational Modifications of Histones H2A, H2B and H4 in Schizosaccharomyces pombe.

    PubMed

    Xiong, Lei; Wang, Yinsheng

    2011-03-30

    Core histones are known to carry a variety of post-translational modifications (PTMs), including acetylation, phosphorylation, methylation and ubiquitination, which play important roles in the epigenetic control of gene expression. The nature and biological functions of these PTMs in histones from plants, animals and budding yeast have been extensively investigated. In contrast, the corresponding studies for fission yeast were mainly focused on histone H3. In the present study, we applied LC-nano-ESI-MS/MS, coupled with multiple protease digestion, to identify PTMs in histones H2A, H2B and H4 from Schizosaccharomyces pombe (S. pombe), the typical model organism of fission yeast. Various protease digestions provided high sequence coverage for PTM mapping, and accurate mass measurement of fragment ions allowed for unambiguous differentiation of acetylation from tri-methylation. Many modification sites conserved in other organisms were identified in S. pombe. In addition, some unique modification sites, including N-terminal acetylation in H2A and H2B as well as K123 acetylation in H2A.β, were observed. Our results provide a comprehensive picture of the PTMs of histones H2A, H2B and H4 in S. pombe, which serves as a foundation for future investigations on the regulation and functions of histone modifications in this important model organism. PMID:21516229

  15. Metal-graphene heterojunction modulation via H2 interaction

    NASA Astrophysics Data System (ADS)

    Cadore, A. R.; Mania, E.; de Morais, E. A.; Watanabe, K.; Taniguchi, T.; Lacerda, R. G.; Campos, L. C.

    2016-07-01

    Combining experiment and theory, we investigate how a naturally created heterojunction (pn junction) at a graphene and metallic contact interface is modulated via interaction with molecular hydrogen (H2). Due to an electrostatic interaction, metallic electrodes induce pn junctions in graphene, leading to an asymmetrical resistance in electronic transport for electrons and holes. We report that the asymmetry in the resistance can be tuned in a reversible manner by exposing graphene devices to H2. The interaction between the H2 and graphene occurs solely at the graphene-contact pn junction and induces a modification on the electrostatic interaction between graphene and metallic contacts. We explain the experimental data with theory providing information concerning the length of the heterojunction and how it changes as a function of H2 adsorption. Our results are valuable for understanding the nature of the metal-graphene interfaces and have potential application for selective sensors of molecular hydrogen.

  16. Evaluation of H2CHXdedpa, H2dedpa- and H2CHXdedpa-N,N'-propyl-2-NI ligands for (64)Cu(ii) radiopharmaceuticals.

    PubMed

    Ramogida, Caterina F; Boros, Eszter; Patrick, Brian O; Zeisler, Stefan K; Kumlin, Joel; Adam, Michael J; Schaffer, Paul; Orvig, Chris

    2016-08-16

    The chiral acyclic "pa" ligand (pa = picolinic acid) H2CHXdedpa (N4O2) and two NI-containing dedpa analogues (H2CHXdedpa-N,N'-propyl-2-NI, H2dedpa-N,N'-propyl-2-NI, NI = nitroimidazole) were studied as chelators for copper radiopharmaceuticals (CHX = cyclohexyl, H2dedpa = 1,2-[[carboxypyridin-2-yl]methylamino]ethane). The hexadentate ligand H2CHXdedpa was previously established as a superb system for (67/68)Ga radiochemistry. The solid state X-ray crystal structures of [Cu(CHXdedpa-N,N'-propyl-2-NI)] and [Cu(dedpa-N,N'-propyl-2-NI)] reveal the predicted hexadentate, distorted octahedral binding of the copper(ii) ion. Cyclic voltammetry of [Cu(dedpa-N,N'-propyl-2-NI)] shows that there is one reversible couple associated with the NI redox, and one irreversible but reproducible couple attributed to the Cu(ii)/Cu(i) redox cycle. Quantitative radiolabeling (>99%) of CHXdedpa(2-) and (dedpa-N,N'-propyl-2-NI)(2-) with (64)Cu was achieved under fast and efficient labeling conditions (10 min, RT, 0.5 M sodium acetate buffer, pH 5.5) at ligand concentrations as low as 10(-6) M. In vitro kinetic inertness studies of the (64)Cu labelled complexes were studied in human serum at 37 °C over 24 hours; [(64)Cu(CHXdedpa)] was found to be 98% stable compared to previously investigated [(64)Cu(dedpa)] which was only 72% intact after 24 hours. PMID:27161975

  17. Photogeneration of H2O2 in SPEEK/PVA aqueous polymer solutions.

    PubMed

    Little, Brian K; Lockhart, PaviElle; Slaten, B L; Mills, G

    2013-05-23

    Photolysis of air-saturated aqueous solutions containing sulphonated poly(ether etherketone) and poly(vinyl alcohol) results in the generation of hydrogen peroxide. Consumption of oxygen and H2O2 formation are initially concurrent processes with a quantum yield of peroxide generation of 0.02 in stirred or unstirred solutions within the range of 7 ≤ pH ≤ 9. The results are rationalized in terms of O2 reduction by photogenerated α-hydroxy radicals of the polymeric ketone in competition with radical-radical processes that consume the macromolecular reducing agents. Generation of H2O2 is controlled by the photochemical transformation that produces the polymer radicals, which is most efficient in neutral and slightly alkaline solutions. Quenching of the excited state of the polyketone by both H3O(+) and OH(-) affect the yields of the reducing macromolecular radicals and of H2O2. Deprotonation of the α-hydroxy polymeric radicals at pH > 9 accelerate their decay and contribute to suppressing the peroxide yields in basic solutions. Maxima in [H2O2] are observed when illuminations are performed with static systems, where O2 reduction is faster than diffusion of oxygen into the solutions. Under such conditions H2O2 can compete with O2 for the reducing radicals resulting in a consumption of the peroxide. PMID:23654204

  18. Effect of H2 and redox condition on biotic and abiotic MTBE transformation

    USGS Publications Warehouse

    Bradley, P.M.; Chapelle, F.H.; Landmeyer, J.E.

    2006-01-01

    Laboratory studies conducted with surface water sediment from a methyl tert-butyl ether (MTBE)-contaminated site in South Carolina demonstrated that, under methanogenic conditions, [U-14C] MTBE was transformed to 14C tert-butyl alcohol (TBA) with no measurable production of 14CO2. Production of TBA was not attributed to the activity of methanogenic microorganisms, however, because comparable transformation of [U-14C] MTBE to 14C-TBA also was observed in heat-sterilized controls with dissolved H2 concentrations > 5 nM. The results suggest that the transformation of MTBE to TBA may be an abiotic process that is driven by biologically produced H2 under in situ conditions. In contrast, mineralization of [U-14C] MTBE to 14CO2 was completely inhibited by heat sterilization and only observed in treatments characterized by dissolved H2 concentrations < 2 nM. These results suggest that the pathway of MTBE transformation is influenced by in situ H2 concentrations and that in situ H2 concentrations may be an useful indicator of MTBE transformation pathways in ground water systems.

  19. H2S and its role in redox signaling☆,☆☆

    PubMed Central

    Kabil, Omer; Motl, Nicole; Banerjee, Ruma

    2014-01-01

    Hydrogen sulfide (H2S) has emerged as an important gaseous signaling molecule that is produced endogenously by enzymes in the sulfur metabolic network. H2S exerts its effects on multiple physiological processes important under both normal and pathological conditions. These functions include neuromodulation, regulation of blood pressure and cardiac function, inflammation, cellular energetics and apoptosis. Despite the recognition of its biological importance and its beneficial effects, the mechanism of H2S action and the regulation of its tissue levels remain unclear in part owing to its chemical and physical properties that render handling and analysis challenging. Furthermore, the multitude of potential H2S effects has made it difficult to dissect its signaling mechanism and to identify specific targets. In this review, we focus on H2S metabolism and provide an overview of the recent literature that sheds some light on its mechanism of action in cellular redox signaling in health and disease. This article is part of a Special Issue entitled: Thiol-Based Redox Processes. PMID:24418393

  20. H2O2-responsive molecularly engineered polymer nanoparticles as ischemia/reperfusion-targeted nanotherapeutic agents

    NASA Astrophysics Data System (ADS)

    Lee, Dongwon; Bae, Soochan; Hong, Donghyun; Lim, Hyungsuk; Yoon, Joo Heung; Hwang, On; Park, Seunggyu; Ke, Qingen; Khang, Gilson; Kang, Peter M.

    2013-07-01

    The main culprit in the pathogenesis of ischemia/reperfusion (I/R) injury is the overproduction of reactive oxygen species (ROS). Hydrogen peroxide (H2O2), the most abundant form of ROS produced during I/R, causes inflammation, apoptosis and subsequent tissue damages. Here, we report H2O2-responsive antioxidant nanoparticles formulated from copolyoxalate containing vanillyl alcohol (VA) (PVAX) as a novel I/R-targeted nanotherapeutic agent. PVAX was designed to incorporate VA and H2O2-responsive peroxalate ester linkages covalently in its backbone. PVAX nanoparticles therefore degrade and release VA, which is able to reduce the generation of ROS, and exert anti-inflammatory and anti-apoptotic activity. In hind-limb I/R and liver I/R models in mice, PVAX nanoparticles specifically reacted with overproduced H2O2 and exerted highly potent anti-inflammatory and anti-apoptotic activities that reduced cellular damages. Therefore, PVAX nanoparticles have tremendous potential as nanotherapeutic agents for I/R injury and H2O2-associated diseases.

  1. Enhanced Synthesis of Alkyl Amino Acids in Miller's 1958 H2S Experiment

    NASA Technical Reports Server (NTRS)

    Parker, Eric T.; Cleaves, H. James; Callahan, Michael P.; Dworkin, James P.; Glavin, Daniel P.; Lazcano, Antonio; Bada, Jeffrey L.

    2011-01-01

    Stanley Miller's 1958 H2S-containing experiment, which included a simulated prebiotic atmosphere of methane (CH4), ammonia (NH3), carbon dioxide (CO2), and hydrogen sulfide (H2S) produced several alkyl amino acids, including the alpha-, beta-, and gamma-isomers of aminobutyric acid (ABA) in greater relative yields than had previously been reported from his spark discharge experiments. In the presence of H2S, aspariic and glutamic acids could yield alkyl amino acids via the formation of thioimide intermediates. Radical chemistry initiated by passing H2S through a spark discharge could have also enhanced alkyl amino acid synthesis by generating alkyl radicals that can help form the aldehyde and ketone precursors to these amino acids. We propose mechanisms that may have influenced the synthesis of certain amino acids in localized environments rich in H2S and lightning discharges, similar to conditions near volcanic systems on the early Earth, thus contributing to the prebiotic chemical inventory of the primordial Earth.

  2. Vacuum ultraviolet photolysis of hydrogenated amorphous carbons . I. Interstellar H2 and CH4 formation rates

    NASA Astrophysics Data System (ADS)

    Alata, I.; Cruz-Diaz, G. A.; Muñoz Caro, G. M.; Dartois, E.

    2014-09-01

    Context. The interstellar hydrogenated amorphous carbons (HAC or a-C:H) observed in the diffuse medium are expected to disappear in a few million years, according to the destruction time scale from laboratory measurements. The existence of a-C:H results from the equilibrium between photodesorption, radiolysis, hydrogenation and resilience of the carbonaceous network. During this processing, many species are therefore injected into the gas phase, in particular H2, but also small organic molecules, radicals or fragments. Aims: We perform experiments on interstellar a-C:H analogs to quantify the release of these species in the interstellar medium. Methods: The vacuum ultraviolet (VUV) photolysis of interstellar hydrogenated amorphous carbon analogs was performed at low (10 K) to ambient temperature, coupled to mass-spectrometry detection and temperature-programed desorption. Using deuterium isotopic substitution, the species produced were unambiguously separated from background contributions. Results: The VUV photolysis of hydrogenated amorphous carbons leads to the efficient production of H2 molecules, but also to small hydrocarbons. Conclusions: These species are formed predominantly in the bulk of the a-C:H analog carbonaceous network, in addition to the surface formation. Compared with species made by the recombination of H atoms and physisorbed on surfaces, they diffuse out at higher temperatures. In addition to the efficient production rate, it provides a significant formation route in environments where the short residence time scale for H atoms inhibits H2 formation on the surface, such as PDRs. The photolytic bulk production of H2 with carbonaceous hydrogenated amorphous carbon dust grains can provide a very large portion of the contribution to the H2 molecule formation. These dust grains also release small hydrocarbons (such as CH4) into the diffuse interstellar medium, which contribute to the formation of small carbonaceous radicals after being dissociated

  3. A comparison of ice VII formed in the H2O, NaCl-H2O, and CH3OH-H2O systems: Implications for H2O-rich planets

    NASA Astrophysics Data System (ADS)

    Frank, Mark R.; Aarestad, Elizabeth; Scott, Henry P.; Prakapenka, Vitali B.

    2013-02-01

    High-pressure H2O polymorphs, namely ice VI, ice VII, and ice X, are hypothesized to make up a considerable portion of the interiors of large icy satellites and select extra-solar planets. The incorporation of foreign ions or molecules into these high-pressure phases is possible through ocean-ice interaction, rock-ice interaction at depth, or processes that occurred during accretion. Recent research concerning the effects charged ions have on ice VII has shown that these ions notably affect the structure of ice VII (Frank et al., 2006; Klotz et al., 2009). This study was designed to determine the effects of a molecular impurity on ice VII and compare those effects to both pure H2O ice and ice with an ionic impurity. Ice samples were formed in this study via compression in a diamond anvil cell from either H2O, a 1.60 mol% NaCl aqueous solution, a 1.60 mol% CH3OH aqueous solution, or a 5.00 mol% CH3OH aqueous solution and were compressed up to 71 GPa at room temperature. Ice formed from pure H2O had no impurities whereas ices formed in the NaCl-H2O and CH3OH-H2O systems contained the impurities Na+ and Cl- and CH3OH, respectively. Pressure-volume relations were observed in situ by using synchrotron based X-ray diffraction and were used to determine the equations of state for ices formed in the H2O, NaCl-H2O and CH3OH-H2O systems. The data illustrate that ice VII formed from a NaCl-bearing aqueous solution exhibited a depressed volume when compared to that of H2O-only ice VII at any given pressure, whereas ice VII formed from CH3OH-bearing aqueous solutions showed an opposite trend, with an increase in volume relative to that of pure ice VII. The ices within planetary bodies will most likely have both ionic and molecular impurities and the trends outlined in this study can be used to improve density profiles of H2O-rich planetary bodies.

  4. Are CO Observations of Interstellar Clouds Tracing the H2?

    NASA Astrophysics Data System (ADS)

    Federrath, Christoph; Glover, S. C. O.; Klessen, R. S.; Mac Low, M.

    2010-01-01

    Interstellar clouds are commonly observed through the emission of rotational transitions from carbon monoxide (CO). However, the abundance ratio of CO to molecular hydrogen (H2), which is the most abundant molecule in molecular clouds is only about 10-4. This raises the important question of whether the observed CO emission is actually tracing the bulk of the gas in these clouds, and whether it can be used to derive quantities like the total mass of the cloud, the gas density distribution function, the fractal dimension, and the velocity dispersion--size relation. To evaluate the usability and accuracy of CO as a tracer for H2 gas, we generate synthetic observations of hydrodynamical models that include a detailed chemical network to follow the formation and photo-dissociation of H2 and CO. These three-dimensional models of turbulent interstellar cloud formation self-consistently follow the coupled thermal, dynamical and chemical evolution of 32 species, with a particular focus on H2 and CO (Glover et al. 2009). We find that CO primarily traces the dense gas in the clouds, however, with a significant scatter due to turbulent mixing and self-shielding of H2 and CO. The H2 probability distribution function (PDF) is well-described by a log-normal distribution. In contrast, the CO column density PDF has a strongly non-Gaussian low-density wing, not at all consistent with a log-normal distribution. Centroid velocity statistics show that CO is more intermittent than H2, leading to an overestimate of the velocity scaling exponent in the velocity dispersion--size relation. With our systematic comparison of H2 and CO data from the numerical models, we hope to provide a statistical formula to correct for the bias of CO observations. CF acknowledges financial support from a Kade Fellowship of the American Museum of Natural History.

  5. The interstellar chemistry of H2C3O isomers

    NASA Astrophysics Data System (ADS)

    Loison, Jean-Christophe; Agúndez, Marcelino; Marcelino, Núria; Wakelam, Valentine; Hickson, Kevin M.; Cernicharo, José; Gerin, Maryvonne; Roueff, Evelyne; Guélin, Michel

    2016-03-01

    We present the detection of two H2C3O isomers, propynal and cyclopropenone, toward various starless cores and molecular clouds, together with upper limits for the third isomer propadienone. We review the processes controlling the abundances of H2C3O isomers in interstellar media showing that the reactions involved are gas-phase ones. We show that the abundances of these species are controlled by kinetic rather than thermodynamic effects.

  6. 26 CFR 25.2523(h)-2 - Effective dates.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

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  7. 26 CFR 31.3406(h)-2 - Special rules.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

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  8. 26 CFR 25.2523(h)-2 - Effective dates.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 26 Internal Revenue 14 2013-04-01 2013-04-01 false Effective dates. 25.2523(h)-2 Section 25.2523(h... TAXES GIFT TAX; GIFTS MADE AFTER DECEMBER 31, 1954 Deductions § 25.2523(h)-2 Effective dates. Except as... §§ 25.2523(e)-1(c), 25.2523(f)-1, 25.2523(g)-1, and 25.2523(h)-1 are effective with respect to...

  9. 26 CFR 25.2523(h)-2 - Effective dates.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 26 Internal Revenue 14 2012-04-01 2012-04-01 false Effective dates. 25.2523(h)-2 Section 25.2523(h... TAXES GIFT TAX; GIFTS MADE AFTER DECEMBER 31, 1954 Deductions § 25.2523(h)-2 Effective dates. Except as... §§ 25.2523(e)-1(c), 25.2523(f)-1, 25.2523(g)-1, and 25.2523(h)-1 are effective with respect to...

  10. 26 CFR 31.3406(h)-2 - Special rules.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 26 Internal Revenue 15 2013-04-01 2013-04-01 false Special rules. 31.3406(h)-2 Section 31.3406(h... Collection of Income Tax at Source § 31.3406(h)-2 Special rules. (a) Joint accounts—(1) Relevant name and... subject to the penalty under section 6705 (failure of a broker to provide notice to a payor). (h) To...

  11. 26 CFR 25.2523(h)-2 - Effective dates.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

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  12. 26 CFR 25.2523(h)-2 - Effective dates.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 26 Internal Revenue 14 2011-04-01 2010-04-01 true Effective dates. 25.2523(h)-2 Section 25.2523(h... TAXES GIFT TAX; GIFTS MADE AFTER DECEMBER 31, 1954 Deductions § 25.2523(h)-2 Effective dates. Except as... §§ 25.2523(e)-1(c), 25.2523(f)-1, 25.2523(g)-1, and 25.2523(h)-1 are effective with respect to...

  13. 26 CFR 31.3406(h)-2 - Special rules.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 26 Internal Revenue 15 2010-04-01 2010-04-01 false Special rules. 31.3406(h)-2 Section 31.3406(h... Collection of Income Tax at Source § 31.3406(h)-2 Special rules. (a) Joint accounts—(1) Relevant name and... subject to the penalty under section 6705 (failure of a broker to provide notice to a payor). (h) To...

  14. 26 CFR 31.3406(h)-2 - Special rules.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 26 Internal Revenue 15 2011-04-01 2011-04-01 false Special rules. 31.3406(h)-2 Section 31.3406(h... Collection of Income Tax at Source § 31.3406(h)-2 Special rules. (a) Joint accounts—(1) Relevant name and... subject to the penalty under section 6705 (failure of a broker to provide notice to a payor). (h) To...

  15. Microalgae: a green source of renewable H(2).

    PubMed

    Ghirardi, M L; Zhang, L; Lee, J W; Flynn, T; Seibert, M; Greenbaum, E; Melis, A

    2000-12-01

    This article summarizes recent advances in the field of algal hydrogen production. Two fundamental approaches are being developed. One involves the temporal separation of the usually incompatible reactions of O(2) and H(2) production in green algae, and the second involves the use of classical genetics to increase the O(2) tolerance of the reversible hydrogenase enzyme. The economic and environmental impact of a renewable source of H(2) are also discussed. PMID:11102662

  16. Al-TiH2 Composite Foams Magnesium Alloy

    NASA Astrophysics Data System (ADS)

    Prasada Rao, A. K.; Oh, Y. S.; Ain, W. Q.; A, Azhari; Basri, S. N.; Kim, N. J.

    2016-02-01

    The work presented here in describes the synthesis of aluminum based titanium-hydride particulate composite by casting method and its foaming behavior of magnesium alloy. Results obtained indicate that the Al-10TiH2 composite can be synthesized successfully by casting method. Further, results also reveal that closed-cell magnesium alloy foam can be synthesized by using Al-10TiH2 composite as a foaming agent.

  17. The interstellar chemistry of H2C3O isomers

    PubMed Central

    Loison, Jean-Christophe; Agúndez, Marcelino; Marcelino, Núria; Wakelam, Valentine; Hickson, Kevin M.; Cernicharo, José; Gerin, Maryvonne; Roueff, Evelyne; Guélin, Michel

    2016-01-01

    We present the detection of two H2C3O isomers, propynal and cyclopropenone, toward various starless cores and molecular clouds, together with upper limits for the third isomer propadienone. We review the processes controlling the abundances of H2C3O isomers in interstellar media showing that the reactions involved are gas-phase ones. We show that the abundances of these species are controlled by kinetic rather than thermodynamic effects. PMID:27013768

  18. Cross sections for production of H(2p, 2s, 1s) by electron collisional dissociation of H2

    NASA Technical Reports Server (NTRS)

    Ajello, J. M.; James, G. K.; Shemansky, D. E.

    1991-01-01

    The excitation function of H Ly-alpha from the astrophysically important dissociation of electron-excited H2 over the range 10-700 eV has been measured. The analysis predicts the cross section to energies higher than the present experimental limit, and it is found that the predicted shape is in close agreement with measured results. At 6 eV the cross section is dominated by the electric dipole first Born component, while at 100 eV the electric dipole component constitutes 73 percent of the total H(2p) cross section. The cross sections of the H(2s) and H(1s) components are calculated.

  19. Enhanced photo-fermentative H2 production using Rhodobacter sphaeroides by ethanol addition and analysis of soluble microbial products

    PubMed Central

    2014-01-01

    Background Biological fermentation routes can provide an environmentally friendly way of producing H2 since they use renewable biomass as feedstock and proceed under ambient temperature and pressure. In particular, photo-fermentation has superior properties in terms of achieving high H2 yield through complete degradation of substrates. However, long-term H2 production data with stable performance is limited, and this data is essential for practical applications. In the present work, continuous photo-fermentative H2 production from lactate was attempted using the purple non-sulfur bacterium, Rhodobacter sphaeroides KD131. As a gradual drop in H2 production was observed, we attempted to add ethanol (0.2% v/v) to the medium. Results As continuous operation went on, H2 production was not sustained and showed a negligible H2 yield (< 0.5 mol H2/mol lactateadded) within two weeks. Electron balance analysis showed that the reason for the gradual drop in H2 production was ascribed to the increase in production of soluble microbial products (SMPs). To see the possible effect of ethanol addition, a batch test was first conducted. The presence of ethanol significantly increased the H2 yield from 1.15 to 2.20 mol H2/mol lactateadded, by suppressing the production of SMPs. The analysis of SMPs by size exclusion chromatography showed that, in the later period of fermentation, more than half of the low molecular weight SMPs (< 1 kDa) were consumed and used for H2 production when ethanol had been added, while the concentration of SMPs continuously increased in the absence of ethanol. It was found that the addition of ethanol facilitated the utilization of reducing power, resulting in an increase in the cellular levels of NAD+ and NADP+. In continuous operation, ethanol addition was effective, such that stable H2 production was attained with an H2 yield of 2.5 mol H2/mol lactateadded. Less than 15% of substrate electrons were used for SMP production, whereas 35% were used in

  20. H2S mediated thermal and photochemical methane activation

    PubMed Central

    Baltrusaitis, Jonas; de Graaf, Coen; Broer, Ria; Patterson, Eric

    2013-01-01

    Sustainable, low temperature methods of natural gas activation are critical in addressing current and foreseeable energy and hydrocarbon feedstock needs. Large portions of natural gas resources are still too expensive to process due to their high content of hydrogen sulfide gas (H2S) in mixture with methane, CH4, altogether deemed as sub-quality or “sour” gas. We propose a unique method for activating this “sour” gas to form a mixture of sulfur-containing hydrocarbon intermediates, CH3SH and CH3SCH3, and an energy carrier, such as H2. For this purpose, we computationally investigated H2S mediated methane activation to form a reactive CH3SH species via direct photolysis of sub-quality natural gas. Photoexcitation of hydrogen sulfide in the CH4+H2S complex results in a barrier-less relaxation via a conical intersection to form a ground state CH3SH+H2 complex. The resulting CH3SH can further be heterogeneously coupled over acidic catalysts to form higher hydrocarbons while the H2 can be used as a fuel. This process is very different from a conventional thermal or radical-based processes and can be driven photolytically at low temperatures, with enhanced controllability over the process conditions currently used in industrial oxidative natural gas activation. Finally, the proposed process is CO2 neutral, as opposed to the currently industrially used methane steam reforming (SMR). PMID:24150813

  1. Hydrogen Storage Properties of New Hydrogen-Rich BH3NH3-Metal Hydride (TiH2, ZrH2, MgH2, and/or CaH2) Composite Systems

    SciTech Connect

    Choi, Young Joon; Xu, Yimin; Shaw, Wendy J.; Ronnebro, Ewa

    2012-04-19

    Ammonia borane (AB = NH3BH3) is one of the most attractive materials for chemical hydrogen storage due to its high hydrogen contents of 19.6 wt.%, however, impurity levels of borazine, ammonia and diborane in conjunction with foaming and exothermic hydrogen release calls for finding ways to mitigate the decomposition reactions. In this paper we present a solution by mixing AB with metal hydrides (TiH2, ZrH2, MgH2 and CaH2) which have endothermic hydrogen release in order to control the heat release and impurity levels from AB upon decomposition. The composite materials were prepared by mechanical ball milling, and their H2 release properties were characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The formation of volatile products from decomposition side reactions, such as borazine (N3B3H6) was determined by mass spectrometry (MS). Sieverts type pressure-composition-temperature (PCT) gas-solid reaction instrument was adopted to observe the kinetics of the H2 release reactions of the combined systems and neat AB. In situ 11B MAS-NMR revealed a destabilized decomposition pathway. We found that by adding specific metal hydrides to AB we can eliminate the impurities and mitigate the heat release.

  2. High/variable mixture ratio O2/H2 engine

    NASA Technical Reports Server (NTRS)

    Adams, A.; Parsley, R. C.

    1988-01-01

    Vehicle/engine analysis studies have identified the High/Dual Mixture Ratio O2/H2 Engine cycle as a leading candidate for an advanced Single Stage to Orbit (SSTO) propulsion system. This cycle is designed to allow operation at a higher than normal O/F ratio of 12 during liftoff and then transition to a more optimum O/F ratio of 6 at altitude. While operation at high mixture ratios lowers specific impulse, the resultant high propellant bulk density and high power density combine to minimize the influence of atmospheric drag and low altitude gravitational forces. Transition to a lower mixture ratio at altitude then provides improved specific impulse relative to a single mixture ratio engine that must select a mixture ratio that is balanced for both low and high altitude operation. This combination of increased altitude specific impulse and high propellant bulk density more than offsets the compromised low altitude performance and results in an overall mission benefit. Two areas of technical concern relative to the execution of this dual mixture ratio cycle concept are addressed. First, actions required to transition from high to low mixture ratio are examined, including an assessment of the main chamber environment as the main chamber mixture ratio passes through stoichiometric. Secondly, two approaches to meet a requirement for high turbine power at high mixture ratio condition are examined. One approach uses high turbine temperature to produce the power and requires cooled turbines. The other approach incorporates an oxidizer-rich preburner to increase turbine work capability via increased turbine mass flow.

  3. Photochemical modeling of H2O in Titan's atmosphere constrained by Herschel Observations

    NASA Astrophysics Data System (ADS)

    Lara, L. M.; Lellouch, E.; Moreno, R.; Courtin, R.; Hartogh, P.; Rengel, M.

    2012-04-01

    As a species subject to photolytic, chemical and condensation losses, H2O present in Titan's stratosphere must be of external origin. The discovery of CO2 by Voyager (Samuelson et al. 1981) pointed to an external supply of oxygen to Titan's atmosphere. Indeed, CO2, which also condenses, was recognized to be formed via CO+OH, where OH was likely produced by H2O photolysis. This view was supported by the ground-based discovery of CO (Lutz et al. 1983) and subsequent measurements confirming an abundance of ~50 ppm. The source of CO itself remained elusive, but inspired by the Cassini/CAPS discovery of a O+ influx rate (Hartle et al. 2006), Hörst et al. (2008) showed that an external source of O or O+ leads to the formation of CO, also pointing to the likely external origin of this compound. The most up-to-date model of Titan's oxygen chemistry by Hörst et al. (2008) adjusted the OH/H2O deposition rate as a function of the eddy diffusion coefficient below 200 km to match the observed CO2 mixing ratio (15 ppb, uniform over 100-200 km), and producing a H2O profile that was deemed consistent with ISO/SWS measurement of the H2O abundance at a nominal altitude of 400 km (Coustenis et al. 1998). Therefore, the Hörst et al. (2008) study provided an apparently self-consistent picture of the origin of oxygen compounds in Titan's atmosphere, with the three main species (CO, CO2 and H2O) being produced from a permanent external supply of oxygen in two distinct forms. However, recent measurements of several H2O lines by the HIFI and PACS instruments (Herschel Space Observatory) have shown that none of the H2O profiles calculated in Hörst et al. (2008) reproduces the observed lines (Moreno et al., this workshop), and neither does the Lara et al. (1996) H2O profile. Here we revisit the Lara et al. (1996) photochemical model by including (i) an updated eddy diffusion coefficient profile (K(z)), constrained by the C2H6 vertical distribution (ii) an adjustable O+/OH/H2O influx. Our

  4. Melting of H_2SO_4\\cdot4H_2O Particles upon Cooling: Implications for Polar Stratospheric Clouds

    NASA Astrophysics Data System (ADS)

    Koop, Thomas; Carslaw, Kenneth S.

    1996-06-01

    Polar stratospheric clouds (PSCs) are important for the chemical activation of chlorine compounds and subsequent ozone depletion. Solid PSCs can form on sulfuric acid tetrahydrate (SAT) (H_2SO_4\\cdot4H_2O) nuclei, but recent laboratory experiments have shown that PSC nucleation on SAT is strongly hindered. A PSC formation mechanism is proposed in which SAT particles melt upon cooling in the presence of HNO_3 to form liquid HNO_3-H_2SO_4\\cdotH_2O droplets 2 to 3 kelvin above the ice frost point. This mechanism offers a PSC formation temperature that is defined by the ambient conditions and sets a temperature limit below which PSCs should form.

  5. H 2 inhibition of radiation induced dissolution of spent nuclear fuel

    NASA Astrophysics Data System (ADS)

    Trummer, Martin; Roth, Olivia; Jonsson, Mats

    2009-01-01

    In order to elucidate the effect of noble metal clusters in spent nuclear fuel on the kinetics of radiation induced spent fuel dissolution we have used Pd particle doped UO 2 pellets. The catalytic effect of Pd particles on the kinetics of radiation induced dissolution of UO 2 during γ-irradiation in HCO3- containing solutions purged with N 2 and H 2 was studied in this work. Four pellets with Pd concentrations of 0%, 0.1%, 1% and 3% were produced to mimic spent nuclear fuel. The pellets were placed in 10 mM HCO3- aqueous solutions and γ-irradiated, and the dissolution of UO22+ was measured spectrophotometrically as a function of time. Under N 2 atmosphere, 3% Pd prevent the dissolution of uranium by reduction with the radiolytically produced H 2, while the other pellets show a rate of dissolution of around 1.6 × 10 -9 mol m -2 s -1. Under H 2 atmosphere already 0.1% Pd effectively prevents the dissolution of uranium, while the rate of dissolution for the pellet without Pd is 1.4 × 10 -9 mol m -2 s -1. It is also shown in experiments without radiation in aqueous solutions containing H 2O 2 and O 2 that ɛ-particles catalyze the oxidation of the UO 2 matrix by these molecular oxidants, and that the kinetics of the catalyzed reactions is close to diffusion controlled.

  6. Destruction and Sequestration of H2O on Mars

    NASA Astrophysics Data System (ADS)

    Clark, Benton

    2016-07-01

    The availability of water in biologically useable form on any planet is a quintessential resource, even if the planet is in a zone habitable with temperature regimes required for growth of organisms (above -18 °C). Mars and most other planetary objects in the solar system do not have sufficient liquid water at their surfaces that photosynthesis or chemolithoautotrophic metabolism could occur. Given clear evidence of hydrous mineral alteration and geomorphological constructs requiring abundant supplies of liquid water in the past, the question arises whether this H2O only became trapped physically as ice, or whether there could be other, more or less accessible reservoirs that it has evolved into. Salts containing S or Cl appear to be ubiquitous on Mars, having been measured in soils by all six Mars landed missions, and detected in additional areas by orbital investigations. Volcanoes emit gaseous H2S, S, SO2, HCl and Cl2. A variety of evidence indicates the geochemical fate of these gases is to be transformed into sulfates, chlorides, chlorates and perchlorates. Depending on the gas, the net reaction causes the destruction of between one and up to eight molecules of H2O per atom of S or Cl (although hydrogen atoms are also released, they are lost relatively rapidly to atmospheric escape). Furthermore, the salt minerals formed often incorporate H2O into their crystalline structures, and can result in the sequestration of up to yet another six (sometimes, more) molecules of H2O. In addition, if the salts are microcrystalline or amorphous, they are potent adsorbents for H2O. In certain cases, they are even deliquescent under martian conditions. Finally, the high solubility of the vast majority of these salts (with notable exception of CaSO4) can result in dense brines with low water activity, aH, as well as cations which can be inimical to microbial metabolism, effectively "poisoning the well." The original geologic materials on Mars, igneous rocks, also provide some

  7. Interaction between sulphide and H 2O in silicate melts

    NASA Astrophysics Data System (ADS)

    Stelling, Jan; Behrens, Harald; Wilke, Max; Göttlicher, Jörg; Chalmin-Aljanabi, Emilie

    2011-06-01

    Reaction between dissolved water and sulphide was experimentally investigated in soda-lime-silicate (NCS) and sodium trisilicate (NS3) melts at temperatures from 1000 to 1200 °C and pressures of 100 or 200 MPa in internally heated gas pressure vessels. Diffusion couple experiments were conducted at water-undersaturated conditions with one half of the couple being doped with sulphide (added as FeS or Na 2S; 1500-2000 ppm S by weight) and the other with H 2O (˜3.0 wt.%). Additionally, two experiments were performed using a dry NCS glass cylinder and a free H 2O fluid. Here, the melt was water-saturated at least at the melt/fluid interface. Profiling by electron microprobe (sulphur) and infrared microscopy (H 2O) demonstrate that H 2O diffusion in the melts is faster by 1.5-2.3 orders of magnitude than sulphur diffusion and, hence, H 2O can be considered as a rapidly diffusing oxidant while sulphur is quasi immobile in these experiments. In Raman spectra a band at 2576 cm -1 appears in the sulphide - H 2O transition zone which is attributed to fundamental S-H stretching vibrations. Formation of new IR absorption bands at 5025 cm -1 (on expense of the combination band of molecular H 2O at 5225 cm -1) and at 3400 cm -1 was observed at the front of the in-diffusing water in the sulphide bearing melt. The appearance and intensity of these two IR bands is correlated with systematic changes in S K-edge XANES spectra. A pre-edge excitation at 2466.5 eV grows with increasing H 2O concentration while the sulphide peak at 2474.0 eV decreases in intensity relative to the peak at 2477.0 eV and the feature at 2472.3 eV becomes more pronounced (all energies are relative to the sulphate excitation, calibrated to 2482.5 eV). The observations by Raman, IR and XANES spectroscopy indicate a well coordinated S 2- - H 2O complex which was probably formed in the glasses during cooling at the glass transition. No oxidation of sulphide was observed in any of the diffusion couple

  8. Unusual Enterobacteriaceae: H2S+ Shigella sonnei, one authentic and one false positive due to contamination with the obligate anaerobe Eubacterium lentum.

    PubMed Central

    Farmer, J J; Riddle, C F; Stargel, M D; Iida, H; Aikawa, T; Achanzar, D; Taylor, W I

    1976-01-01

    A mixture of Shigella sonnei and Eubacterium lentum produced H2S in triple sugar iron agar; however, neither produced any in pure culture. A second culture of S. sonnei, isolated in Japan, is thought to be the first documented H2S+ Shigella. PMID:767362

  9. A coupled soil-atmosphere model of H2O2 on Mars.

    PubMed

    Bullock, M A; Stoker, C R; McKay, C P; Zent, A P

    1994-01-01

    The Viking Gas Chromatograph Mass Spectrometer failed to detect organic compounds on Mars, and both the Viking Labeled Release and the Viking Gas Exchange experiments indicated a reactive soil surface. These results have led to the widespread belief that there are oxidants in the martian soil. Since H2O2 is produced by photochemical processes in the atmosphere of Mars, and has been shown in the laboratory to reproduce closely the Viking LR results, it is a likely candidate for a martian soil oxidant. Here, we report on the results of a coupled soil/atmosphere transport model for H2O2 on Mars. Upon diffusing into the soil, its concentration is determined by the extent to which it is adsorbed and by the rate at which it is catalytically destroyed. An analytical model for calculating the distribution of H2O2 in the martian atmosphere and soil is developed. The concentration of H2O2 in the soil is shown to go to zero at a finite depth, a consequence of the nonlinear soil diffusion equation. The model is parameterized in terms of an unknown quantity, the lifetime of H2O2 against heterogeneous catalytic destruction in the soil. Calculated concentrations are compared with a H2O2 concentration of 30 nmoles/cm3, inferred from the Viking Labeled Release experiment. A significant result of this model is that for a wide range of H2O2 lifetimes (up to 10(5) years), the extinction depth was found to be less than 3 m. The maximum possible concentration in the top 4 cm is calculated to be approximately 240 nmoles/cm3, achieved with lifetimes of greater than 1000 years. Concentrations higher than 30 nmoles/cm3 require lifetimes of greater than 4.3 terrestrial years. For a wide range of H2O2 lifetimes, it was found that the atmospheric concentration is only weakly coupled with soil loss processes. Losses to the soil become significant only when lifetimes are less than a few hours. If there are depths below which H2O2 is not transported, it is plausible that organic compounds

  10. H2O2: A precursor for O2 on icy satellites? Laboratory studies

    NASA Astrophysics Data System (ADS)

    Loeffler, M. J.; Baragiola, R. A.

    2005-08-01

    Radiation processes affect the surface chemistry in planetary systems and in the ISM, and thus they need to be studied extensively. Recently, we have studied H2O2 production in water ice by 100 keV H+ irradiation at temperatures relevant to Europa and the ISM. Although hydrogen peroxide has only been detected so far in the infrared reflectance of Europa, this molecule is believed to be an important factor for the radiation-induced chemistry that occurs in water ice in other outer solar system objects. In particular, it has been proposed that this molecule may be a precursor for the production of O2 exospheres around icy satellites and Saturn's rings. Previously, we have irradiated crystalline H2O2 and identified the synthesis of H2O and O3. The saturation water concentration appeared to be high, but quantification of initial radiation yields (G values) was not possible because of the large change in the shape of the infrared absorption bands due to the concurrent amorphization. Further measurements could not be made, because we could only grow H2O2 at high temperatures by distillation, and thus growing amorphous H2O2 was not possible. Recently, we developed a method to grow amorphous H2O2 in the solid phase that allowed us to measure H2O2 destruction quantitatively. We have performed radiolysis with 50 keV H+ at 17 K to ensure that most radiolytic products stay in the ice and have detected H2O, O2 and O3 but not HO2; we have measured initial radiation yields for H2O and O2. Annealing the irradiated samples at 0.2 K/min to 200 K we found that most of the O2 produced stays trapped in the ice until 154 K, where it leaves immediately. Infrared absorption shows the production of dangling H bonds, which grow in importance during annealing and can even be observed at 150 K.

  11. Olivine alteration and H2 production in carbonate-rich, low temperature aqueous environments

    NASA Astrophysics Data System (ADS)

    Neubeck, Anna; Duc, Nguyen Thanh; Hellevang, Helge; Oze, Christopher; Bastviken, David; Bacsik, Zoltán; Holm, Nils G.

    2014-06-01

    Hydrous alteration of olivine is capable of producing molecular hydrogen (H2) under a wide variety of hydrothermal conditions. Although olivine hydrolysis (i.e., serpentinization) has commonly been assessed at elevated temperatures (>100 °C), the nature of these reactions in relation to H2 production at lower temperatures has not been systematically evaluated, especially with regard to carbonate-rich fluids. Specifically, carbonate formation may kinetically infringe on geochemical routes related to serpentinization and H2 production at lower temperatures. Here time-dependent interactions of solid, liquid, and gaseous phases with respect to olivine hydrolysis in a carbonate-rich solution (20 mM HCO3-) at 30, 50 and 70 °C for 315 days is investigated experimentally. Within the first two months, amorphous Si-rich (i.e., talc-like) and carbonate phases precipitated; however, no inhibition of olivine dissolution is observed at any temperature based on surface chemistry analyses. High-resolution surface analyses confirm that precipitates grew as spheroids or vertically to form topographic highs allowing further dissolution of the free olivine surfaces and exposing potential catalysts. Despite no magnetite (Fe3O4) being detected, H2 increased with time in experiments carried out at 70 °C, indicating an alternative coupled route for Fe oxidation and H2 production. Spectrophotometry analyses show that aqueous Fe(II) is largely converted to Fe(III) potentially integrating into other phases such as serpentine and talc, thus providing a viable pathway for H2 production. No increase in H2 production was observed in experiments carried out at 30 and 50 °C supporting observations that incorporation of Fe(II) into carbonates occurred faster than the intertwined processes of olivine hydrolysis and Fe(III) oxidation. Overall, carbonate formation is confirmed to be a major influence related to H2 production in low-temperature serpentinization systems. We studied low temperature

  12. Photoionization Models of the H_2 Emission of the Narrow Line Region of AGNs

    NASA Astrophysics Data System (ADS)

    Aleman, I.; Gruenwald, R.

    2011-05-01

    The excitation mechanism of the narrow line region (NLR) of AGNs is still an open question. Excitation by UV radiation from O and B stars, x-rays from the central black hole, shock from supernovae or jets, or a combination of these mechanisms have been suggested. In the present work, we use photoionization models to study the excitation mechanisms of the H_2 infrared emission lines in the NLR. In the literature, analyzes of the H_2 emission have been done assuming that the molecules is present only in neutral regions (photodissociation regions, x-ray-dominated regions, or shocks; Veilleux et al. 1997, Krabbe et al. 2000, Rigopoulou et al. 2002, Rodriguez-Ardila et al. 2004, 2005, and Davies et al. 2005). However, they are not conclusive. In previous work (Aleman & Gruenwald 2004, 2011), we show that the H_2 emission from the ionized region of PNe can be significant for planetary nebulae (PNe) with hot central stars (T⋆ > 150000 K). Such stars produce copious amounts of high energy photons, which create an extended partially ionized region that favors the H_2 survival. The conditions in the NLR are similar to those in PNe with hot central stars, so we can expect that the H_2 emission might also be important. We obtain and analyze a grid of photoionization models for different NRL parameters. We study the resulting H_2 density and emission, as well as, the formation, destruction, excitation, and de-excitation mechanisms. The higher values observed for the H_2 1-0 S(1)/Brγ ratio cannot be reproduced by our models. The calculated ratios are between 10^-8 and 10^-1, while the observational ration can be as high as 10. The calculated ratio is strongly anti-correlated with the ionization parameter (U) and only models with U<10-3 result in ratios inside the observational range. We show that the NLR is an environment more hostile to the H_2 molecule than the ionized region of PNe. Another interesting result of our calculations is that the H_2 formation on grain surfaces

  13. Metagenomic evidence for h(2) oxidation and h(2) production by serpentinite-hosted subsurface microbial communities.

    PubMed

    Brazelton, William J; Nelson, Bridget; Schrenk, Matthew O

    2012-01-01

    Ultramafic rocks in the Earth's mantle represent a tremendous reservoir of carbon and reducing power. Upon tectonic uplift and exposure to fluid flow, serpentinization of these materials generates copious energy, sustains abiogenic synthesis of organic molecules, and releases hydrogen gas (H(2)). In order to assess the potential for microbial H(2) utilization fueled by serpentinization, we conducted metagenomic surveys of a marine serpentinite-hosted hydrothermal chimney (at the Lost City hydrothermal field) and two continental serpentinite-hosted alkaline seeps (at the Tablelands Ophiolite, Newfoundland). Novel [NiFe]-hydrogenase sequences were identified at both the marine and continental sites, and in both cases, phylogenetic analyses indicated aerobic, potentially autotrophic Betaproteobacteria belonging to order Burkholderiales as the most likely H(2)-oxidizers. Both sites also yielded metagenomic evidence for microbial H(2) production catalyzed by [FeFe]-hydrogenases in anaerobic Gram-positive bacteria belonging to order Clostridiales. In addition, we present metagenomic evidence at both sites for aerobic carbon monoxide utilization and anaerobic carbon fixation via the Wood-Ljungdahl pathway. In general, our results point to H(2)-oxidizing Betaproteobacteria thriving in shallow, oxic-anoxic transition zones and the anaerobic Clostridia thriving in anoxic, deep subsurface habitats. These data demonstrate the feasibility of metagenomic investigations into novel subsurface habitats via surface-exposed seeps and indicate the potential for H(2)-powered primary production in serpentinite-hosted subsurface habitats. PMID:22232619

  14. Metagenomic Evidence for H2 Oxidation and H2 Production by Serpentinite-Hosted Subsurface Microbial Communities

    PubMed Central

    Brazelton, William J.; Nelson, Bridget; Schrenk, Matthew O.

    2012-01-01

    Ultramafic rocks in the Earth’s mantle represent a tremendous reservoir of carbon and reducing power. Upon tectonic uplift and exposure to fluid flow, serpentinization of these materials generates copious energy, sustains abiogenic synthesis of organic molecules, and releases hydrogen gas (H2). In order to assess the potential for microbial H2 utilization fueled by serpentinization, we conducted metagenomic surveys of a marine serpentinite-hosted hydrothermal chimney (at the Lost City hydrothermal field) and two continental serpentinite-hosted alkaline seeps (at the Tablelands Ophiolite, Newfoundland). Novel [NiFe]-hydrogenase sequences were identified at both the marine and continental sites, and in both cases, phylogenetic analyses indicated aerobic, potentially autotrophic Betaproteobacteria belonging to order Burkholderiales as the most likely H2-oxidizers. Both sites also yielded metagenomic evidence for microbial H2 production catalyzed by [FeFe]-hydrogenases in anaerobic Gram-positive bacteria belonging to order Clostridiales. In addition, we present metagenomic evidence at both sites for aerobic carbon monoxide utilization and anaerobic carbon fixation via the Wood–Ljungdahl pathway. In general, our results point to H2-oxidizing Betaproteobacteria thriving in shallow, oxic–anoxic transition zones and the anaerobic Clostridia thriving in anoxic, deep subsurface habitats. These data demonstrate the feasibility of metagenomic investigations into novel subsurface habitats via surface-exposed seeps and indicate the potential for H2-powered primary production in serpentinite-hosted subsurface habitats. PMID:22232619

  15. Quantum dynamics of rovibrational transitions in H2-H2 collisions: internal energy and rotational angular momentum conservation effects.

    PubMed

    Fonseca dos Santos, S; Balakrishnan, N; Lepp, S; Quéméner, G; Forrey, R C; Hinde, R J; Stancil, P C

    2011-06-01

    We present a full dimensional quantum mechanical treatment of collisions between two H(2) molecules over a wide range of energies. Elastic and state-to-state inelastic cross sections for ortho-H(2) + para-H(2) and ortho-H(2) + ortho-H(2) collisions have been computed for different initial rovibrational levels of the molecules. For rovibrationally excited molecules, it has been found that state-to-state transitions are highly specific. Inelastic collisions that conserve the total rotational angular momentum of the diatoms and that involve small changes in the internal energy are found to be highly efficient. The effectiveness of these quasiresonant processes increases with decreasing collision energy and they become highly state-selective at ultracold temperatures. They are found to be more dominant for rotational energy exchange than for vibrational transitions. For non-reactive collisions between ortho- and para-H(2) molecules for which rotational energy exchange is forbidden, the quasiresonant mechanism involves a purely vibrational energy transfer albeit with less efficiency. When inelastic collisions are dominated by a quasiresonant transition calculations using a reduced basis set involving only the quasiresonant channels yield nearly identical results as the full basis set calculation leading to dramatic savings in computational cost. PMID:21663358

  16. Kinetics and Efficiency of H2O2 Activation by Iron-Containing Minerals and Aquifer Materials

    PubMed Central

    Pham, Anh Le-Tuan; Doyle, Fiona M.; Sedlak, David L.

    2014-01-01

    To gain insight into factors that control H2O2 persistence and ˙OH yield in H2O2-based in situ chemical oxidation systems, the decomposition of H2O2 and transformation of phenol were investigated in the presence of iron-containing minerals and aquifer materials. Under conditions expected during remediation of soil and groundwater, the stoichiometric efficiency, defined as the amount of phenol transformed per mole of H2O2 decomposed, varied from 0.005 to 0.28%. Among the iron-containing minerals, iron oxides were 2 to 10 times less efficient in transforming phenol than iron-containing clays and synthetic iron-containing catalysts. In both iron-containing mineral and aquifer materials systems, the stoichiometric efficiency was inversely correlated with the rate of H2O2 decomposition. In aquifer materials systems, the stoichiometric efficiency was also inversely correlated with the Mn content, consistent with the fact that the decomposition of H2O2 on manganese oxides does not produce ˙OH. Removal of iron and manganese oxide coatings from the surface of aquifer materials by extraction with citrate-bicarbonate-dithionite slowed the rate of H2O2 decomposition on aquifer materials and increased the stoichiometric efficiency. In addition, the presence of 2 mM of dissolved SiO2 slowed the rate of H2O2 decomposition on aquifer materials by over 80% without affecting the stoichiometric efficiency. PMID:23047055

  17. Corrosion of 310 stainless steel in H2-H2O-H2S gas mixtures: Studies at constant temperature and fixed oxygen potential

    NASA Technical Reports Server (NTRS)

    Rao, D. B.; Jacob, K. T.; Nelson, H. G.

    1981-01-01

    Corrosion of SAE 310 stainless steel in H2-H2O-H2S gas mixtures was studied at a constant temperature of 1150 K. Reactive gas mixtures were chosen to yield a constant oxygen potential of approximately 6 x 10 to the minus 13th power/cu Nm and sulfur potentials ranging from 0.19 x 10 to the minus 2nd power/cu Nm to 33 x 10 to the minus 2nd power/cu Nm. The kinetics of corrosion were determined using a thermobalance, and the scales were analyzed using metallography, scanning electron microscopy, and energy dispersive X-ray analysis. Two corrosion regimes, which were dependent on sulfur potential, were identified. At high sulfur potentials (p sub S sub 2 less than or equal to 2.7 x 10 to the minus 2nd power/cu Nm) the corrosion rates were high, the kinetics obeyed a linear rate equation, and the scales consisted mainly of sulfide phases similar to those observed from pure sulfication. At low sulfur potentials (P sub S sub 2 less than or equal to 0.19 x 10 to the minus 2nd power/cu Nm) the corrosion rates were low, the kinetics obeyed a parabolic rate equation, and scales consisted mainly of oxide phases.

  18. The role and synergistic effect of the light irradiation and H2O2 in photocatalytic inactivation of Escherichia coli.

    PubMed

    Ng, Tsz Wai; An, Taicheng; Li, Guiying; Ho, Wing Kei; Yip, Ho Yin; Zhao, Huijun; Wong, Po Keung

    2015-08-01

    Inactivation of Escherichia coli K-12 was conducted by applying a continuous supplying of commercial H2O2 to mimic the H2O2 production in a photocatalytic system, and the contribution of H2O2 in photocatalytic inactivation was investigated using a modified "partition system" and five E. coli mutants. The concentration of exogenous H2O2 required for complete inactivation of bacterial cells was much higher than that produced in-situ in common photocatalytic system, indicating that H2O2 alone plays a minor role in photocatalytic inactivation. However, the concentration of exogenously produced H2O2 required for effective inactivation of E. coli K-12 was much lower when the light irradiation was applied. To further investigate the possible physiological changes, inactivation of E. coli BW25113 (the parental strain), and its corresponding isogenic single-gene deletion mutants with light pretreatment was compared. The results indicate that light irradiation increases the bacterial intracellular Fe(2+) level and favors hydroxyl radical (OH) production via the catalytic reaction of Fe(2+), leading to increase in DNA damage. Moreover, the results indicate that the properties of light source, such as intensity and major emission wavelength, may alter the physiology of bacterial cells and affect the susceptibility to in-situ resultant H2O2 in the photocatalytic inactivation processes, leading to significant influence on the photocatalytic inactivation efficiencies of E. coli K-12. PMID:26083904

  19. Multichannel processes of H2O in the 18 eV region

    NASA Technical Reports Server (NTRS)

    Wu, C. Y. Robert; Judge, D. L.

    1988-01-01

    Measurements were made of: (1) the fluorescence cross sections of OH(A 2Sigma+) fragments; (2) the absolute cross sections producing H atoms in the n = 2, 3, and 4 states; (3) the cross section for producing excited O atoms which has an upper limit of 5 x 10 to the -21 sq cm; and (4) the fluorescence cross section for producing H2(a 3Sigma g +) fragments. It is shown that, in the 16-20 eV region, there are excellent correspondences in the peak positions and spacings among the photoabsorption, photoionization spectra, and fluorescence functions of OH(A) and H(n).

  20. Experimental investigation on thermochemical sulfate reduction by H2S initiation

    USGS Publications Warehouse

    Zhang, T.; Amrani, A.; Ellis, G.S.; Ma, Q.; Tang, Y.

    2008-01-01

    and sulfides, was performed on the products of the reaction of H2S and HC from a series of gold-tube non-isothermal hydrous pyrolysis experiments conducted at about pH 3 from 300 to 370 ??C and a 0.1-??C/h heating rate. Incorporation of sulfur into HC resulted in an appreciable amount of thiol and sulfide formation. The rate of LSC formation positively correlated with the initial H2S pressure. Thus, we propose that the LSC produced from H2S reaction with HC are most likely the reactive intermediates for H2S initiation of sulfate reduction. We further propose a three-step reaction scheme of sulfate reduction by HC under reservoir conditions, and discuss the geological implications of our experimental findings with regard to the effect of formation water and oil chemistry, in particular LSC content. ?? 2008 Elsevier Ltd. All rights reserved.

  1. Theoretical characterization of the reaction CH3 +OH yields CH3OH yeilds products: The (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO channels

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.

    1993-01-01

    The potential energy surface (PES) for the CH3OH system has been characterized for the (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO product channels using complete-active-space self-consistent-field (CASSCF) gradient calculations to determine the stationary point geometries and frequencies followed by CASSCF/internally contracted configuration-interaction (CCI) calculations to refine the energetics. The (1)CH2 + H2O channel is found to have no barrier. The long range interaction is dominated by the dipole-dipole term, which orients the respective dipole moments parallel to each other but pointing in opposite directions. At shorter separations there is a dative bond structure in which a water lone pair donates into the empty a" orbital of CH2. Subsequent insertion of CH2 into an OH bond of water have barriers located at -5.2 kcal/mol and 1.7 kcal/mol, respectively, with respect to CH3 + OH. From comparison of the computed energetics of the reactants and products to known thermochemical data it is estimated that the computed PES is accurate to plus or minus 2 kcal/mol.

  2. Staphylococcal enterotoxins bind H-2Db molecules on macrophages

    NASA Technical Reports Server (NTRS)

    Beharka, A. A.; Iandolo, J. J.; Chapes, S. K.; Spooner, B. S. (Principal Investigator)

    1995-01-01

    We screened a panel of monoclonal antibodies against selected macrophage cell surface molecules for their ability to inhibit enterotoxin binding to major histocompatibility complex class II-negative C2D (H-2b) macrophages. Two monoclonal antibodies, HB36 and TIB126, that are specific for the alpha 2 domain of major histocompatibility complex class I, blocked staphylococcal enterotoxins A and B (SEA and SEB, respectively) binding to C2D macrophages in a specific and concentration-dependent manner. Inhibitory activities were haplotype-specific in that SEA and SEB binding to H-2k or H-2d macrophages was not inhibited by either monoclonal antibody. HB36, but not TIB126, inhibited enterotoxin-induced secretion of cytokines by H-2b macrophages. Lastly, passive protection of D-galactosamine-sensitized C2D mice by injection with HB36 antibody prevented SEB-induced death. Therefore, SEA and SEB binding to the alpha 2 domain of the H-2Db molecule induces biological activity and has physiological consequences.

  3. Impurity-stimulated heterogeneous nucleation of supercooled H2 clusters.

    PubMed

    Knuth, Eldon; Schaper, Sven; Toennies, J Peter

    2004-01-01

    The sizes and mass spectra of large (N=1900-13,700 molecules) cold (approximately 3.1 K) H2 clusters have been measured after scattering from CO molecules. Cluster-size measurements after between 2 and 8 collisions indicate that 7% of the H2 molecules are evaporated. This loss agrees with calculations for the number of H2 molecules evaporated by the heat released in the transition from an initial liquid state to a final solid state. Even though heterogeneous nucleation is initiated after only a few collisions with CO molecules, the mass spectra show that additional captured CO molecules coagulate to form large CO clusters with up to n=11 molecules, suggesting that the outer layer is sufficiently liquidlike to facilitate mobility of the CO molecules. Since the calculated H2 cluster temperature (approximately 3.1 K) is below the superfluid transition temperature predicted for pH2 with density between 40% and 80% of the triple-point density, a shell-like region of low density near the cluster surface can be expected to be superfluid. PMID:15267283

  4. High resolution, low temperature photoabsorption cross-section of C2H2 with application to Saturn's atmosphere

    NASA Technical Reports Server (NTRS)

    Caldwell, John; Wu, C. Y. R.; Xia, T. J.; Judge, D. L.; Wagener, R.

    1990-01-01

    New laboratory observations of the VUV absorption cross-section of C2H2, obtained under physical conditions approximating stratospheres of the giant planets, were combined with IUE observations of the albedo of Saturn, for which improved data reduction techniques have been used, to produce new models for that atmosphere. When the effects of C2H2 absorption are accounted for, additional absorption by other molecules is required. The best-fitting model also includes absorption by PH3, H2O, C2H6 and CH4. A small residual disagreement near 1600 A suggests that an additional trace species may be required to complete the model.

  5. Elementary Electrochemical reactions of H2-CO mixtures over an SOFC anode

    NASA Astrophysics Data System (ADS)

    Valle Marchante, Nicolas

    SOFC is a mature technology suitable for producing potentially clean energy. Understanding the reaction mechanism of a complex H2 - CO fuel is presented in this work. By using existent fundamental reaction mechanisms and kinetic parameters, elementary reactions involved in an SOFC anode have been detailed, modeled and analyzed. This involves both homogeneous and heterogeneous chemistry, electrochemistry and surface diffusion. Modeling has been implemented in a patterned anode geometry with a C++ code using the open-source code CANTERA for chemical kinetics. The use of the patterned anode approach removes the mass transport complications and allows comparison with pre-existent experimental data. The model provides both the polarization curves and the surface coverage distribution and allows a high level of detail on the physical phenomena involved. In particular, understanding of how the competitive reactions behave is achieved. Results show a good agreement with the experimental conclusions provided previously by Sukesini et al., where concentrations on the fuel stream up to 75% CO behave similarly to those with pure H2 . Further analysis has been performed as well to understand both temperature and composition effects on the cell performance. CO has shown to stabilize the OCV response to temperature, improving the H2 response to such effect. At the same time, high temperatures have proven to improve the CO tolerance in the stream, providing good performance. Surface analysis shows that CO occupies most of the active sites present in the electrode, although it does not penalize the cell performance as far as there is some H2 in the stream. On the other hand, the presence of oxidized species (i.e., H2 O and CO2 ) in the anode compartment when the corresponding reductant species (i.e., H2 and CO) provokes a reversible reaction at the TPB vicinity, penalizing the performance of the cell.

  6. Use of Enzymatic Biosensors to Quantify Endogenous ATP or H2O2 in the Kidney.

    PubMed

    Palygin, Oleg; Levchenko, Vladislav; Evans, Louise C; Blass, Gregory; Cowley, Allen W; Staruschenko, Alexander

    2015-01-01

    Enzymatic microelectrode biosensors have been widely used to measure extracellular signaling in real-time. Most of their use has been limited to brain slices and neuronal cell cultures. Recently, this technology has been applied to the whole organs. Advances in sensor design have made possible the measuring of cell signaling in blood-perfused in vivo kidneys. The present protocols list the steps needed to measure ATP and H2O2 signaling in the rat kidney interstitium. Two separate sensor designs are used for the ex vivo and in vivo protocols. Both types of sensor are coated with a thin enzymatic biolayer on top of a permselectivity layer to give fast responding, sensitive and selective biosensors. The permselectivity layer protects the signal from the interferents in biological tissue, and the enzymatic layer utilizes the sequential catalytic reaction of glycerol kinase and glycerol-3-phosphate oxidase in the presence of ATP to produce H2O2. The set of sensors used for the ex vivo studies further detected analyte by oxidation of H2O2 on a platinum/iridium (Pt-Ir) wire electrode. The sensors for the in vivo studies are instead based on the reduction of H2O2 on a mediator coated gold electrode designed for blood-perfused tissue. Final concentration changes are detected by real-time amperometry followed by calibration to known concentrations of analyte. Additionally, the specificity of the amperometric signal can be confirmed by the addition of enzymes such as catalase and apyrase that break down H2O2 and ATP correspondingly. These sensors also rely heavily on accurate calibrations before and after each experiment. The following two protocols establish the study of real-time detection of ATP and H2O2 in kidney tissues, and can be further modified to extend the described method for use in other biological preparations or whole organs. PMID:26485400

  7. H2, N2, and O2 metabolism by isolated heterocysts from Anabaena sp. strain CA.

    PubMed Central

    Smith, R L; Kumar, D; Zhang, X K; Tabita, F R; Van Baalen, C

    1985-01-01

    Metabolically active heterocysts isolated from wild-type Anabaena sp. strain CA showed high rates of light-dependent acetylene reduction and hydrogen evolution. These rates were similar to those previously reported in heterocysts isolated from the mutant Anabaena sp. strain CA-V possessing fragile vegetative cell walls. Hydrogen production was observed with isolated heterocysts. The ratio of C2H4 to H2 produced ranged from 0.9 to 1.2, and H2 production exhibited unique biphasic kinetics consisting of a 1 to 2-min burst of hydrogen evolution followed by a lower, steady-state rate of hydrogen production. This burst was found to be dependent upon the length of the dark period immediately preceding illumination and may be related to dark-to-light ATP transients. The presence of 100 nM NiCl2 in the growth medium exerted an effect on both acetylene reduction and hydrogen evolution in the isolated heterocysts from strain CA. H2-stimulated acetylene reduction was increased from 2.0 to 3.2 mumol of C2H4 per mg (dry weight) per h, and net hydrogen production was abolished. A phenotypic Hup- mutant (N9AR) of Anabaena sp. strain CA was isolated which did not respond to nickel. In isolated heterocysts from N9AR, ethylene production rates were the same under both 10% C2H2-90% Ar and 10% C2H2-90% H2 with or without added nickel, and net hydrogen evolution was not affected by the presence of 100 nM Ni2+. Isolated heterocysts from strain CA were shown to have a persistent oxygen uptake of 0.7 mumol of O2 per mg (dry weight) per h, 35% of the rate of whole filaments, at air saturating O2 levels, indicating that O2 impermeability is not a requirement for active heterocysts. PMID:3921524

  8. Inhibitory Effect of Dissolved Silica on the H2O2 Decomposition by Iron(III) and Manganese(IV) Oxides: Implications for H2O2-based In Situ Chemical Oxidation

    PubMed Central

    Pham, Anh Le-Tuan; Doyle, Fiona M.; Sedlak, David L.

    2011-01-01

    The decomposition of H2O2 on iron minerals can generate •OH, a strong oxidant that can transform a wide range of contaminants. This reaction is critical to In Situ Chemical Oxidation (ISCO) processes used for soil and groundwater remediation, as well as advanced oxidation processes employed in waste treatment systems. The presence of dissolved silica at concentrations comparable to those encountered in natural waters decreases the reactivity of iron minerals toward H2O2, because silica adsorbs onto the surface of iron minerals and alters catalytic sites. At circumneutral pH values, goethite, amorphous iron oxide, hematite, iron-coated sand and montmorillonite that were pre-equilibrated with 0.05 – 1.5 mM SiO2 were significantly less reactive toward H2O2 decomposition than their original counterparts, with the H2O2 loss rates inversely proportional to the SiO2 concentration. In the goethite/H2O2 system, the overall •OH yield, defined as the percentage of decomposed H2O2 producing •OH, was almost halved in the presence of 1.5 mM SiO2. Dissolved SiO2 also slows the H2O2 decomposition on manganese(IV) oxide. The presence of dissolved SiO2 results in greater persistence of H2O2 in groundwater, lower H2O2 utilization efficiency and should be considered in the design of H2O2-based treatment systems. PMID:22129132

  9. Substrate Recognition of Histone H2B by DUBm

    NASA Astrophysics Data System (ADS)

    Henderson, Elizabeth; Berndsen, Christopher; Wolberger, Cynthia

    2011-03-01

    The SAGA complex is a transcriptional coactivator that regulates gene expression in eukaryotes via histone acetylation and deubiquitination, which are crucial for transcription. Our lab is investigating the SAGA-dependent deubiquitination of histone H2B. The deubiquitinating module (DUBm) of SAGA is comprised of a ubiquitin-specific protease, Ubp8, and three other proteins. It is known that Ubp8 cleaves ubiquitin from histone H2B, however, the specific way in which the enzyme binds to the substrate remains elusive. In order to unravel this mechanism, we attempted to determine the crystal structure of the substrate binding complex. We obtained this substrate by exploiting the techniques of intein chemistry to artificially ubiquitinate a histone H2B peptide, which we then co-crystallized with DUBm. Additionally, we synthesized Ub-K63R-linked chains and Ub-K48-linked chains and co-crystallized them with DUBm.

  10. H2 -norm of fractional transfer functions of implicit type

    NASA Astrophysics Data System (ADS)

    Malti, Rachid; Chevrié, Mathieu; Farges, Christophe; Sabatier, Jocelyn

    2015-09-01

    This paper studies the H2 -norm (or impulse response energy) of fractional transfer functions of implicit type. Stability conditions are first shown to be identical as in rational systems with all poles located in the open left half complex plane. Then, analytical expressions of the H2 -norm are derived for elementary fractional transfer functions of the first and the second kind cascaded with a pure fractional integrator. Next, general boundedness conditions are established in terms of transfer function relative degree. Three illustrative examples are finally proposed. The first one evaluates the quality of a rational approximation of a fractional model of implicit type on the basis of the H2 -norm of the error signal. The second one evaluates the Integral Squared Error of a CRONE control loop and compares it to a classical proportional-derivative controller in a vehicle suspension. Finally, the third one allows to set up an implicit fractional preshaping filter for closed-loop control.

  11. Amorphous and Crystalline H2O-Ice

    NASA Astrophysics Data System (ADS)

    Mastrapa, Rachel M. E.; Grundy, William M.; Gudipati, Murthy S.

    On the surfaces of Solar System objects, H2O-ice can form in several different phases, including amorphous and crystalline. The stability of these phases as a function of thermal and radiation history is an active area of laboratory research. Meanwhile, remote detection of H2O-ice depends on the interpretation of infrared absorptions that are also dependent on phase and temperature. Surface processes, such as surface chemistry, micrometeorite gardening, and cryovolcanic resurfacing, on the surfaces of objects are linked to H2O-ice phase. We review the current state of laboratory measurements in the context of observations of Solar System objects and list the areas where new measurements are needed.

  12. Permeance of H2 through porous graphene from molecular dynamics

    NASA Astrophysics Data System (ADS)

    Liu, Hongjun; Dai, Sheng; Jiang, De-en

    2013-12-01

    A recent experiment (Koenig et al., 2012 [15]) demonstrated the capability of porous graphene as one-atom-thin membrane to separate gases by molecular sieving. A quantitative connection between the measured leak rate and the simulated gas permeance has yet to be established. Using H2 as a model gas, here we determine its permeance through porous graphene from molecular dynamics (MD) simulations. Trajectories are used to directly obtain H2 flux, pressure drop across the graphene membrane, and subsequently, H2 permeance. The permeance is determined to be on the order of 105 GPU (gas permeance unit) for pressure driving forces ranging from 2 to 163 atm. By relating to the experimental leak rate, we then use the permeation data to estimate the pore density in the experimentally created porous graphene.

  13. Reconstructing Final H2O Contents of Hydrated Rhyolitic Glasses: Insights into H2O Degassing and Eruptive Style of Silicic Submarine Volcanoes

    NASA Astrophysics Data System (ADS)

    McIntosh, I. M.; Nichols, A. R.; Tani, K.; Llewellin, E. W.

    2015-12-01

    H2O degassing influences the evolution of magma viscosity and vesicularity during ascent through the crust, and ultimately the eruptive style. Investigating H2O degassing requires data on both initial and final H2O contents. Initial H2O contents are revealed by melt inclusion data, while final H2O contents are found from dissolved H2O contents of volcanic glass. However volcanic glasses, particularly of silicic composition, are susceptible to secondary hydration i.e. the addition of H2O from the surrounding environment at ambient temperature during the time following pyroclast deposition. Obtaining meaningful final H2O data therefore requires distinguishing between the original final dissolved H2O content and the H2O added subsequently during hydration. Since H2O added during hydration is added as molecular H2O (H2Om), and the species interconversion between H2Om and hydroxyl (OH) species is negligible at ambient temperature, the final OH content of the glass remains unaltered during hydration. By using H2O speciation models to find the original H2Om content that would correspond to the measured OH content of the glass, the original total H2O (H2Ot) content of the glass prior to hydration can be reconstructed. These H2O speciation data are obtained using FTIR spectroscopy. In many cases, particularly where vesicular glasses necessitate thin wafers, OH cannot be measured directly and instead is calculated indirectly as OH = H2Ot - H2Om. Here we demonstrate the importance of using a speciation-dependent H2Ot molar absorptivity coefficient to obtain accurate H2Ot and H2O speciation data and outline a methodology for calculating such a coefficient for rhyolite glasses, with application to hydrated silicic pumice from submarine volcanoes in the Japanese Izu-Bonin Arc. Although hydrated pumice from Kurose Nishi and Oomurodashi now contain ~1.0 - 2.5 wt% H2Ot, their pre-hydration final H2O contents were typically ~0.3 - 0.4 wt% H2Ot. Furthermore, we show that pre

  14. V2O2F4(H2O)2·H2O: a new V(4+) layer structure related to VOF3.

    PubMed

    Black, Cameron; Lightfoot, Philip

    2016-01-01

    V(IV) oxyfluorides are of interest as frustrated magnets. The successful synthesis of two-dimensionally connected vanadium(IV) oxyfluoride structures generally requires the use of ionic liquids as solvents. During solvothermal synthesis experiments aimed at producing two- and three-dimensional vanadium(IV) selenites with triangular lattices, the title compound, diaquatetra-μ-fluorido-dioxidodivanadium(IV) monohydrate, V2O2F4(H2O)2·H2O, was discovered and features a new infinite V(4+)-containing two-dimensional layer comprised of fluorine-bridged corner- and edge-sharing VOF4(H2O) octahedral building units. The synthesis was carried out under solvothermal conditions. The V(4+) centre exhibits a typical off-centring, with a short V=O bond and an elongated trans-V-F bond. Hydrogen-bonded water molecules occur between the layers. The structure is related to previously reported vanadium oxyfluoride structures, in particular, the same layer topology is seen in VOF3. PMID:26742832

  15. A novel Gaussian Binning (1GB) analysis of vibrational state distributions in highly excited H2O from reactive quenching of OH* by H2

    NASA Astrophysics Data System (ADS)

    Conte, Riccardo; Fu, Bina; Kamarchik, Eugene; Bowman, Joel M.

    2013-07-01

    As shown in experiments by Lester and co-workers [J. Chem. Phys. 110, 11117 (1999)], 10.1063/1.479053, the reactive quenching of OH* by H_2 produces highly excited H_2O. Previous limited analysis of quasiclassical trajectory calculations using standard Histogram Binning (HB) was reported [B. Fu, E. Kamarchik, and J. M. Bowman, J. Chem. Phys. 133, 164306 (2010)], 10.1063/1.3488167. Here, we examine the quantized internal state distributions of H_2O in more detail, using two versions of Gaussian Binning (denoted 1GB). In addition to the standard version of 1GB, which relies on the harmonic energies of the states (1GB-H), we propose a new and more accurate technique based on exact quantum vibrational energies (1GB-EQ). Data from about 42 000 trajectories from previous calculations that give excited water molecules are used in the two versions of 1GB as well as HB. For the vibrationally hot molecules considered in this study, the classical internal energy distribution serves as a benchmark to estimate the accuracy of the different binning methods analyzed. The 1GB discretization methods, especially the one using exact quantum energies, reconstruct the classical distribution much more accurately than HB and also the original, more elaborate Gaussian Binning method. Detailed quantum state distributions are presented for pure overtone excitations as well as several antisymmetric stretch distributions. The latter are focused on because the antisymmetric stretch has the largest emission oscillator strength of the three water modes.

  16. Synthesis of acetic acid via methanol hydrocarboxylation with CO2 and H2

    PubMed Central

    Qian, Qingli; Zhang, Jingjing; Cui, Meng; Han, Buxing

    2016-01-01

    Acetic acid is an important bulk chemical that is currently produced via methanol carbonylation using fossil based CO. Synthesis of acetic acid from the renewable and cheap CO2 is of great importance, but state of the art routes encounter difficulties, especially in reaction selectivity and activity. Here we report a route to produce acetic acid from CO2, methanol and H2. The reaction can be efficiently catalysed by Ru–Rh bimetallic catalyst using imidazole as the ligand and LiI as the promoter in 1,3-dimethyl-2-imidazolidinone (DMI) solvent. It is confirmed that methanol is hydrocarboxylated into acetic acid by CO2 and H2, which accounts for the outstanding reaction results. The reaction mechanism is proposed based on the control experiments. The strategy opens a new way for acetic acid production and CO2 transformation, and represents a significant progress in synthetic chemistry. PMID:27165850

  17. Synthesis of acetic acid via methanol hydrocarboxylation with CO2 and H2.

    PubMed

    Qian, Qingli; Zhang, Jingjing; Cui, Meng; Han, Buxing

    2016-01-01

    Acetic acid is an important bulk chemical that is currently produced via methanol carbonylation using fossil based CO. Synthesis of acetic acid from the renewable and cheap CO2 is of great importance, but state of the art routes encounter difficulties, especially in reaction selectivity and activity. Here we report a route to produce acetic acid from CO2, methanol and H2. The reaction can be efficiently catalysed by Ru-Rh bimetallic catalyst using imidazole as the ligand and LiI as the promoter in 1,3-dimethyl-2-imidazolidinone (DMI) solvent. It is confirmed that methanol is hydrocarboxylated into acetic acid by CO2 and H2, which accounts for the outstanding reaction results. The reaction mechanism is proposed based on the control experiments. The strategy opens a new way for acetic acid production and CO2 transformation, and represents a significant progress in synthetic chemistry. PMID:27165850

  18. Multiple Stokes wavelength generation in H2, D2, and CH4 for lidar aerosol measurements

    NASA Technical Reports Server (NTRS)

    Chu, Zhiping; Wilkerson, Thomas D.; Singh, Upendra N.

    1991-01-01

    Experimental results are reported of multiple Stokes generation of a frequency-doubled Nd:YAG laser in H2, D2, and CH4 in a focusing geometry. The energies at four Stokes orders were measured as functions of pump energy and gas pressure. The characteristics of the Stokes radiation generated in these gases are compared for optical production of multiple wavelengths. The competition between Raman components is analyzed in terms of cascade Raman scattering and four-wave mixing. The results indicate the possibility of using these generation processes for atmospheric aerosol measurements by means of multiwavelength lidar systems. Also, this study distinguishes between the gases, as regards the tendency to produce several wavelengths (H2,D2) versus the preference to produce mainly first Stokes radiation (CH4).

  19. Hydrogen Financial Analysis Scenario Tool (H2FAST); NREL (National Renewable Energy Laboratory)

    SciTech Connect

    Melaina, Marc

    2015-04-21

    This presentation describes the Hydrogen Financial Analysis Scenario Tool, H2FAST, and provides an overview of each of the three H2FAST formats: the H2FAST web tool, the H2FAST Excel spreadsheet, and the H2FAST Business Case Scenario (BCS) tool. Examples are presented to illustrate the types of questions that H2FAST can help answer.

  20. Thermodynamics of the formation of sulfuric acid dimers in the binary (H2SO4-H2O) and ternary (H2SO4-H2O-NH3) system

    NASA Astrophysics Data System (ADS)

    Kürten, A.; Münch, S.; Rondo, L.; Bianchi, F.; Duplissy, J.; Jokinen, T.; Junninen, H.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Almeida, J.; Amorim, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Franchin, A.; Kirkby, J.; Kupc, A.; Makhmutov, V.; Petäjä, T.; Praplan, A. P.; Riccobono, F.; Steiner, G.; Tomé, A.; Tsagkogeorgas, G.; Wagner, P. E.; Wimmer, D.; Baltensperger, U.; Kulmala, M.; Worsnop, D. R.; Curtius, J.

    2015-09-01

    Sulfuric acid is an important gas influencing atmospheric new particle formation (NPF). Both the binary (H2SO4-H2O) system and the ternary system involving ammonia (H2SO4-H2O-NH3) may be important in the free troposphere. An essential step in the nucleation of aerosol particles from gas-phase precursors is the formation of a dimer, so an understanding of the thermodynamics of dimer formation over a wide range of atmospheric conditions is essential to describe NPF. We have used the CLOUD chamber to conduct nucleation experiments for these systems at temperatures from 208 to 248 K. Neutral monomer and dimer concentrations of sulfuric acid were measured using a chemical ionization mass spectrometer (CIMS). From these measurements, dimer evaporation rates in the binary system were derived for temperatures of 208 and 223 K. We compare these results to literature data from a previous study that was conducted at higher temperatures but is in good agreement with the present study. For the ternary system the formation of H2SO4·NH3 is very likely an essential step in the formation of sulfuric acid dimers, which were measured at 210, 223, and 248 K. We estimate the thermodynamic properties (dH and dS) of the H2SO4·NH3 cluster using a simple heuristic model and the measured data. Furthermore, we report the first measurements of large neutral sulfuric acid clusters containing as many as 10 sulfuric acid molecules for the binary system using chemical ionization-atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometry.

  1. NASA Lewis H2-O2 MHD program

    NASA Technical Reports Server (NTRS)

    Smith, M.; Nichols, L. D.; Seikel, G. R.

    1974-01-01

    Performance and power costs of H2-O2 combustion powered steam-MHD central power systems are estimated. Hydrogen gas is assumed to be transmitted by pipe from a remote coal gasifier into the city and converted to electricity in a steam MHD plant having an integral gaseous oxygen plant. These steam MHD systems appear to offer an attractive alternative to both in-city clean fueled conventional steam power plants and to remote coal fired power plants with underground electric transmission into the city. Status and plans are outlined for an experimental evaluation of H2-O2 combustion-driven MHD power generators at NASA Lewis Research Center.

  2. Maps of [HDO]/[H2O] near Mars’ Aphelion

    NASA Astrophysics Data System (ADS)

    Novak, Robert E.; Mumma, M. J.; Villanueva, G. L.

    2013-10-01

    We report maps of HDO and H2O taken at three seasonal points before and near Mars’ aphelion (Ls = 71°). These observations were taken at Ls = 357° (15 January 2006), Ls = 50° (26 March 2008) and Ls = 72° (2/3 April 2010) using CSHELL at the NASA Infrared Telescope Facility. For these three seasonal dates, the entrance slit of the spectrometer was positioned N-S on Mars centered at the sub-Earth point; on 3 April 2010, the slit was positioned E-W. Data were extracted at 0.6 arc-second intervals from the spectral-spatial images. Individual spectral lines were measured near 3.67 μm (HDO) and 3.29 μm (H2O). The column densities were obtained by comparing the observed lines to those of a multi-layered, radiative transfer model. The model includes solar Fraunhofer lines, two-way transmission through Mars’ atmosphere, thermal emission from Mars’ surface and atmosphere, and a one-way transmission through the Earth’s atmosphere. Latitudinal maps of HDO, H2O, and their ratios were then constructed. The [HDO]/[H2O] ratios have been found to be larger than those on Earth and they vary with both latitude and season. For the Ls = 357° and 50° observations, the ratio peaks near the sub-solar latitude ([HDO]/[H2O] ~ 6.9 VSMOW) and decreases towards both the North and South polar-regions. At Ls = 72°, column densities of both HDO and H2O and their ratios increase from the Southern hemisphere to the North polar-region. Observations from 3 April 2013 show diurnal variations of both the column densities and their ratio. Specific points on Mars’ surface were tracked for four hours. It is believed that this variation is caused by the vaporization of ground frost and water ice clouds that are formed during the night and disappear during daytime. Our results for H2O column densities will be compared to TES results. The results for HDO and the [HDO]/[H2O] ratios will be compared to model results.This work was partially funded by grants from NASA's Planetary Astronomy

  3. Ferromagnetic resonance spectra of H2-reduced minerals and glasses

    NASA Technical Reports Server (NTRS)

    Morris, Richard V.; Allen, Carlton C.

    1994-01-01

    In an earlier paper, we reported that H2 reduction of basaltic glass, olivine, pyroxene, and plagioclase resulted in the formation of metallic iron, in the darkening and reddening of the reflectance spectra, and the masking of individual spectral features in the visible and near-IR. In this work, we report FMR spectra for H2-reduced minerals and glasses that include the samples studied in the earlier paper. The FMR spectra were reduced at room temperature at a nominal frequency of 9.5 GHz. Sample saturation magnetization reported as F3(0) was measured with a vibrating sample magnetometer.

  4. Physisorbed H2@Cu(100) surface: potential and spectroscopy.

    PubMed

    Bernard, Eddy; Houriez, Céline; Mitrushchenkov, Alexander O; Guitou, Marie; Chambaud, Gilberte

    2015-02-01

    Using an embedding approach, a 2-D potential energy function has been calculated to describe the physisorption interaction of H2 with a Cu(100) surface. For this purpose, a cluster model of the system calculated with highly correlated wavefunctions is combined with a periodic Density-Functional-Theory method using van der Waals-DF2 functional. Rotational and vibrational energy levels of physisorbed H2, as well as D2 and HD, are calculated using the 2D embedding corrected potential energy function. The calculated transitions are in a very good agreement with Electron-Energy-Loss-Spectroscopy observations. PMID:25662656

  5. Reduction of nitrobenzene with H2 using a microbial consortium.

    PubMed

    Cao, Hong-Bin; Li, Yu-Ping; Zhang, Gui-Feng; Zhang, Yi

    2004-02-01

    Proof of concept was obtained that nitrobenzene can be reduced to aniline by a mixed reductive microbial culture using H2 as the sole electron donor source. In a continuous-flow anaerobic bioreactor, both pH and temperature affected nitrobenzene reduction with optima of pH 6.5-6.8 and 30 degrees C. The efficiency of nitrobenzene degradation increased with H2 up to 10% (v/v). An increase in sulfate concentration decreased the removal rate of nitrobenzene. PMID:15055766

  6. Effect of H2 and CO contents in syngas during combustion using Micro Gas Turbine

    NASA Astrophysics Data System (ADS)

    Othman, N. F.; Boosroh, M. H.

    2016-03-01

    Synthetic gas or syngas is produced from the gasification process. Its main compositions are hydrogen, H2; carbon monoxide, CO; methane, CH4; carbon dioxide, CO2 and nitrogen, N2. Syngas is a substitute for the depleting natural gas (80-90%.vol. CH4). Natural gas is combusted in gas turbine in gas-fired power plant to produce electricity. However, combustion of syngas using gas turbine is expected to show different behavior compared to natural gas combustion. This is because of H2 and CO contents in syngas have higher adiabatic flame temperature than CH4. In this study, different quality of syngas with different contents of H2 (0.6-0.8 %.vol.) and CO (1-3 %.vol.) were combusted using 30kW Micro Gas Turbine (MGT). Performances of different syngas quality were studied using NOx, CO, CO2 emissions and combustion efficiency parameters. NOx and CO are the main pollutants from the combustion process. NOx emissions were the highest for syngas with H2 contents of 0.8 %.vol. and CO contents of 3 %.vol. CO emissions were in the range of 220-310 ppm for all the tested syngas. While, CO2 emissions were in the range of 0.96-1.06 % for all the tested syngas. Combustion efficiencies were reduced for syngas with CO contents of 1 %.vol. and H2 contents of 0.6-0.8 %.vol. This is most probably due to the dilution effect of N2 in syngas.

  7. Helicity in Supercritical O2/H2 and C7H16/N2 Mixing Layers

    NASA Technical Reports Server (NTRS)

    Okongo, Nora; Bellan, Josette

    2004-01-01

    This report describes a study of databases produced by direct numerical simulation of mixing layers developing between opposing flows of two fluids under supercritical conditions, the purpose of the study being to elucidate chemical-species-specific aspects of turbulence, with emphasis on helicity. The simulations were performed for two different fluid pairs -- O2/H2 and C7H16/N2 -- at similar values of reduced pressure.

  8. Preliminary results in the NASA Lewis H2-O2 combustion MHD experiment

    NASA Technical Reports Server (NTRS)

    Smith, J. M.

    1979-01-01

    MHD (magnetohydrodynamic) power generation experiments were carried out in the NASA Lewis Research Center cesium-seeded H2-O2 combustion facility. This facility uses a neon-cooled cryomagnet capable of producing magnetic fields in excess of 5 tesla. The effects of power takeoff location, generator loading, B-field strength, and electrode breakdown on generator performance are discussed. The experimental data is compared to a theory based on one-dimensional flow with heat transfer, friction, and voltage drops.

  9. The H 2O 2-NO 2- and H 2NO 4- isomers of the nitrate anion-water complex

    NASA Astrophysics Data System (ADS)

    Shen, Mingzuo; Xie, Yaoming; Schaefer, Henry F.; Deakyne, Carol A.

    1991-03-01

    Ab initio quantum mechanical methods have been applied to two isomers of the complex of the conventional nitrate anion (D 3hNO 3-) with the water molecule, namely, H 2NO 4- (two conformers) and H 2O 2-NO 2-. The nitrogen atom in H 2NO 4- is tetrahedrally coordinated to the four oxygen atoms, while H 2O 2-NO 2- is a doubly hydrogen-bonded system. Equilibrium geometries and vibrational frequencies for these three energy minima on the ground state (singlet) potential energy surface have been determined using analytic energy first and second derivative techniques. The standard level of theory employed is the self-consistent-field (SCF) method with a double-zeta plus polarization (DZP) basis set. However, the effects of diffuse basis set and electron correlation effects were also carefully considered. At this level of theory, all three structures studied lie energetically well above the complex between the conventional nitrate anion and the water molecule. The system H 2O 2-NO 2-, with two strong, equivalent, and nearly linear hydrogen bonds, lies energetically closest (˜46 kcal/mol) to the nitrate anion-water molecule complex.

  10. Rototranslational collision-induced absorption by H2-H2 pairs at temperatures from 600 to 7000 K

    NASA Technical Reports Server (NTRS)

    Zheng, Chunguang; Borysow, Aleksandra

    1995-01-01

    The computation of the far-infrared, rototranslational (RT) collision-induced absorption (CIA) spectra of H2-H2 pairs is presented at temperatures from 600 to 7000 K for the first time. Theoretical results are based on the quantum mechanical and semiclassical, three lowest translational spectral moments obtained for H2 pairs. The effective, isotropic H2-H2 interaction potential, suitable for the high-temperature computations, and the ab initio induced dipoles, have been used as input. Special effort has been made to account for the rotational and vibrational states dependence of the dipoles, since it was found to be relevant at the high temperatures employed. The computations of the entire RT band account for all populated vibrational states of hydrogen molecule and include vibrational transitions v tends towards v-prime = v, with v = 0, 1, 2 and 3. The described method makes use of the adequately selected model line shapes with the temperature-dependent parameters. The presented model is useful for the 'model atmospheres' of zero- and low-metallicity, cool and dense stellar atmospheres, where CIA is known to be imporatnt.

  11. Physical Chemistry of the H2SO4/HNO3/H2O System: Implications for Polar Stratospheric Clouds.

    PubMed

    Molina, M J; Zhang, R; Wooldridge, P J; McMahon, J R; Kim, J E; Chang, H Y; Beyer, K D

    1993-09-10

    Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO(3) hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H(2)SO(4)/H(2)O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO(3) vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO(3) and H(2)O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H(2)SO(4) solutions and on solid H(2)SO(4) hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles. PMID:17745351

  12. Physical chemistry of the H2SO4/HNO3/H2O system - Implications for polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Molina, M. J.; Zhang, R.; Wooldridge, P. J.; Mcmahon, J. R.; Kim, J. E.; Chang, H. Y.; Beyer, K. D.

    1993-01-01

    Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO3 hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H2SO4/H2O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO3 vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO3 and H2O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H2SO4 solutions and on solid H2SO4 hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

  13. Photo-induced H2 production from a CH3OH-H2O solution at insulator surface

    PubMed Central

    Li, Rengui; Wang, Xiuli; Jin, Shaoqing; Zhou, Xin; Feng, Zhaochi; Li, Zheng; Shi, Jingying; Zhang, Qiao; Li, Can

    2015-01-01

    In a conventional photocatalytic or photochemical process, either a photocatalyst or a molecule is excited by irradiation light that has energy greater than the forbidden band (i.e., the band gap) of the semiconductor or the transition energy of an excited state of the molecule, respectively, for a reaction to occur. However, in this work, we found that a considerable amount of H2 can be generated from a CH3OH-H2O solution at a quartz surface using light with energy far outside the electronic absorbance range of the CH3OH-H2O solution; this process should not occur in principle via either conventional photocatalysis or a photochemical process. The H2 production was further confirmed using 266 nm and 355 nm lasers as light sources. Our work demonstrates that photo-induced H2 production can occur on insulator surfaces (e.g., quartz), which were commonly believed to be inert, and will shed light on the surface nature of insulators. PMID:26315657

  14. Photo-induced H2 production from a CH3OH-H2O solution at insulator surface.

    PubMed

    Li, Rengui; Wang, Xiuli; Jin, Shaoqing; Zhou, Xin; Feng, Zhaochi; Li, Zheng; Shi, Jingying; Zhang, Qiao; Li, Can

    2015-01-01

    In a conventional photocatalytic or photochemical process, either a photocatalyst or a molecule is excited by irradiation light that has energy greater than the forbidden band (i.e., the band gap) of the semiconductor or the transition energy of an excited state of the molecule, respectively, for a reaction to occur. However, in this work, we found that a considerable amount of H2 can be generated from a CH3OH-H2O solution at a quartz surface using light with energy far outside the electronic absorbance range of the CH3OH-H2O solution; this process should not occur in principle via either conventional photocatalysis or a photochemical process. The H2 production was further confirmed using 266 nm and 355 nm lasers as light sources. Our work demonstrates that photo-induced H2 production can occur on insulator surfaces (e.g., quartz), which were commonly believed to be inert, and will shed light on the surface nature of insulators. PMID:26315657

  15. The H2 + CO ↔ H2CO Reaction: Rate Constants and Relevance to Hot and Dense Astrophysical Media

    NASA Astrophysics Data System (ADS)

    Vichietti, R. M.; Spada, R. F. K.; da Silva, A. B. F.; Machado, F. B. C.; Haiduke, R. L. A.

    2016-07-01

    A theoretical thermochemical and kinetic investigation of the thermal H2 + CO ↔ H2CO reaction was performed for a temperature range from 200 to 4000 K. Geometries and vibrational frequencies of reactants, product, and transition state (TS) were obtained at CCSD/cc-pVxZ (x = T and Q) levels and scaling factors were employed to consider anharmonicity effects on vibrational frequencies, zero-point energies, and thermal corrections provided by these methodologies. Enthalpies Gibbs energies, and rate constants for this reaction were determined by including a complete basis set extrapolation correction for the electronic properties calculated at CCSD(T)/cc-pVyZ (y = Q and 5) levels. Our study indicates that enthalpy changes for this reaction are highly dependent on temperature. Moreover, forward and reverse (high-pressure limit) rate constants were obtained from variational TS theory with quantum tunneling corrections. Thus, modified Arrhenius’ equations were fitted by means of the best forward and reverse rate constant values, which provide very reliable estimates for these quantities within the temperature range between 700 and 4000 K. To our knowledge, this is the first kinetic study done for the forward H2 + CO \\to H2CO process in a wide temperature range. Finally, these results can be used to explain the formaldehyde abundance in hot and dense interstellar media, possibly providing data about the physical conditions associated with H2CO masers close to massive star-forming regions.

  16. Reinvestigation of the annite = sanidine + magnetite + H2 reaction using the fH2-sensor technique

    USGS Publications Warehouse

    Cygan, G.L.; Chou, I.-Ming; Sherman, David M.

    1996-01-01

    The decomposition of the iron mica, annite, to sanidine plus magnetite and vapor, KFe3AlSi3O10(OH)2 = KAlSi3O8 + Fe3O4 + H2, has been reexamined experimentally with the use of a variety of buffers coupled with fH2 sensors at 2 kbar and between 400 and 840 ??C. Various capsule configurations were used in this study to delineate the equilibrium constant for this reaction in conjunction with 57Fe Mo??ssbauer spectroscopy measurements to monitor the oxy-annite component in mica in selected experiments. Results at the most reducing and highest temperature conditions of this study extend the annite stability field to higher temperature and fo2 values than those defined in previous work. Lower temperature results indicate that the annite-sanidine-magnetite stability boundary does not intersect the hematite + magnetite + H2O buffer at 400??C as previously reported but rather is subparallel to the buffer curve at lower fo2 values. The equilibrium fH2 (in bars) for the assemblage annite + sanidine + magnetite + vapor at 2 kbar and between 400 and 840 ??C can be described by the relation log fH2 (??0.08) = 13.644 - (17368/T) + (5.168 ?? 106)/T2, where T is temperature in kelvins.

  17. Pressure-induced metallization of dense (H2S)2H2 with high-Tc superconductivity

    PubMed Central

    Duan, Defang; Liu, Yunxian; Tian, Fubo; Li, Da; Huang, Xiaoli; Zhao, Zhonglong; Yu, Hongyu; Liu, Bingbing; Tian, Wenjing; Cui, Tian

    2014-01-01

    The high pressure structures, metallization, and superconductivity of recently synthesized H2-containing compounds (H2S)2H2 are elucidated by ab initio calculations. The ordered crystal structure with P1 symmetry is determined, supported by the good agreement between theoretical and experimental X-ray diffraction data, equation of states, and Raman spectra. The Cccm structure is favorable with partial hydrogen bond symmetrization above 37 GPa. Upon further compression, H2 molecules disappear and two intriguing metallic structures with R3m and Im-3m symmetries are reconstructive above 111 and 180 GPa, respectively. The predicted metallization pressure is 111 GPa, which is approximately one-third of the currently suggested metallization pressure of bulk molecular hydrogen. Application of the Allen-Dynes-modified McMillan equation for the Im-3m structure yields high Tc values of 191 K to 204 K at 200 GPa, which is among the highest values reported for H2-rich van der Waals compounds and MH3 type hydride thus far. PMID:25382349

  18. Low-Lying Energy Isomers and Global Minima of Aqueous Nanoclusters: Structures and Spectroscopic Features of the Pentagonal Dodecahedron (H2O)20 and (H3O)+(H2O)20

    SciTech Connect

    Xantheas, Sotiris S.

    2012-08-01

    We rely on a hierarchy of methods to identify the low-lying isomers for the pentagonal dodecahedron (H2O)20 and the H3O+(H2O)20 clusters. Initial screening of isomers was performed with classical potentials [TIP4P, TTM2-F, TTM2.1-F for (H2O)20 and ASP for H3O+(H2O)20] and the networks obtained with those potentials were subsequently reoptimized at the DFT (B3LYP) and MP2 levels of theory. For the pentagonal dodecahedron (H2O)20 it was found that DFT (B3LYP) and MP2 produced the same global minimum. However, this was not the case for the H3O+(H2O)20 cluster, for which MP2 produced a different network for the global minimum when compared to DFT (B3LYP). All low-lying minima of H3O+(H2O)20 correspond to hydrogen bonding networks having 9 ''free'' OH bonds and the hydronium ion on the surface of the cluster. The fact that DFT (B3LYP) and MP2 produce different results and issues related to the use of a smaller basis set, explains the discrepancy between the current results and the structure previously suggested [Science 304, 1137 (2004)] for the global minimum of the H3O+(H2O)20 cluster. Additionally, the IR spectra of the MP2 global minimum are closer to the experimentally measured ones than the spectra of the previously suggested DFT global minimum. The latter exhibit additional bands in the most red-shifted region of the OH stretching vibrations (corresponding to the ''fingerprint'' of the underlying hydrogen bonding network), which are absent from both the experimental as well as the spectra of the new structure suggested for the global minimum of this cluster.

  19. Methylene blue counteracts H2S toxicity-induced cardiac depression by restoring L-type Ca channel activity.

    PubMed

    Judenherc-Haouzi, Annick; Zhang, Xue-Qian; Sonobe, Takashi; Song, Jianliang; Rannals, Matthew D; Wang, JuFang; Tubbs, Nicole; Cheung, Joseph Y; Haouzi, Philippe

    2016-06-01

    We have previously reported that methylene blue (MB) can counteract hydrogen sulfide (H2S) intoxication-induced circulatory failure. Because of the multifarious effects of high concentrations of H2S on cardiac function, as well as the numerous properties of MB, the nature of this interaction, if any, remains uncertain. The aim of this study was to clarify 1) the effects of MB on H2S-induced cardiac toxicity and 2) whether L-type Ca(2+) channels, one of the targets of H2S, could transduce some of the counteracting effects of MB. In sedated rats, H2S infused at a rate that would be lethal within 5 min (24 μM·kg(-1)·min(-1)), produced a rapid fall in left ventricle ejection fraction, determined by echocardiography, leading to a pulseless electrical activity. Blood concentrations of gaseous H2S reached 7.09 ± 3.53 μM when cardiac contractility started to decrease. Two to three injections of MB (4 mg/kg) transiently restored cardiac contractility, blood pressure, and V̇o2, allowing the animals to stay alive until the end of H2S infusion. MB also delayed PEA by several minutes following H2S-induced coma and shock in unsedated rats. Applying a solution containing lethal levels of H2S (100 μM) on isolated mouse cardiomyocytes significantly reduced cell contractility, intracellular calcium concentration ([Ca(2+)]i) transient amplitudes, and L-type Ca(2+) currents (ICa) within 3 min of exposure. MB (20 mg/l) restored the cardiomyocyte function, ([Ca(2+)]i) transient, and ICa The present results offer a new approach for counteracting H2S toxicity and potentially other conditions associated with acute inhibition of L-type Ca(2+) channels. PMID:26962024

  20. N 2O accumulation in estuarine and coastal sediments: The influence of H 2S on dissimilatory nitrate reduction

    NASA Astrophysics Data System (ADS)

    Senga, Yukiko; Mochida, Kazuo; Fukumori, Ryouko; Okamoto, Norihisa; Seike, Yasushi

    2006-03-01

    The effects of H 2S on the production and accumulation of N 2O in surface sediments of the coastal lagoons of Lakes Shinji and Nakaumi were studied using sediment suspensions and isolated strains of halophilic N 2O producers. Denitrification and N 2O accumulation were determined by anaerobic incubations with and without C 2H 2, respectively. Denitrifying activities in the sediment suspensions of both lakes decreased markedly at an H 2S concentration of 3 mg S l -1, whereas N 2O accumulations in the sediment suspensions of Lakes Shinji and Nakaumi were highest at 75-100 mg S l -1 and 15-50 mg S l -1 H 2S, respectively. In addition, H 2S had marked inhibiting (about 30 h) and retarding effects on N 2O reduction in the suspensions of both lakes. Two strains of halophilic N 2O producers were isolated from the sediment of Lake Shinji ( Aeromonas sp. and Vibrio sp.). N 2O accumulation rates by Aeromonas sp. and Vibrio sp. were accelerated at 1-5 mg S l -1 and 1-10 mg S l -1 H 2S, respectively. Patterns of inorganic nitrogen compounds after the incubations revealed the accumulation of NH 4+ and NO 2-, with concomitant N 2O, were accelerated by H 2S. These results indicate that H 2S plays a key role in regulation of N 2O accumulation in the eutrophic estuarine or coastal sediments. Furthermore, the accumulation of N 2O in the sediments of Lakes Shinji and Nakaumi is predicted to derive through dissimilatory nitrate reduction to ammonium (DNRA) not only denitrification in the presence of H 2S.

  1. Corrosion of 310 stainless steel in H2- H2O- H2S gas mixtures: Studies at constant temperature and fixed oxygen potential

    NASA Astrophysics Data System (ADS)

    Rao, D. Bhogeswara; Jacob, K. T.; Nelson, Howard G.

    1983-02-01

    Corrosion of SAE 310 stainless steel in H2-H2O-H2S gas mixtures was studied at a constant temperature of 1150 K. Reactive gas mixtures were chosen to yield a constant oxygen potential of approximately 6 × 10-13 Nm-2 and sulfur potentials ranging from 0.19 × 10-2 Nm-2 to 33 × 10-2 Nm-2. The kinetics of corrosion were determined using a thermobalance, and the scales were analyzed using metallography, scanning electron microscopy, and energy dispersive X-ray analysis. Two corrosion regimes, which were dependent on sulfur potential, were identified. At high sulfur potentials ( P S 2 ± 2.7 × 10-2 Nm-2) the corrosion rates were high, the kinetics obeyed a linear rate equation, and the scales consisted mainly of sulfide phases similar to those observed from pure sulfidation. At low sulfur potentials ( P S 2 ± 0.19 × 10-2 Nm-2) the corrosion rates were low, the kinetics obeyed a parabolic rate equation, and scales consisted mainly of oxide phases. Thermochemical diagrams for the Fe-Cr-S-O, Fe-Ni-S-O, Cr-Ni-S-O, and Si-Cr-S-O systems were constructed, and the experimental results are discussed in relation to these diagrams. Based on this comparison, reasonable corrosion mechanisms were developed. At high sulfur potentials, oxide and sulfide phases initially nucleate as separate islands. Overgrowth of the oxide by the sulfide occurs and an exchange reaction governs the corrosion process. Preoxidation at low oxygen potentials and 1150 K is beneficial in suppressing sulfidation at high sulfur potentials.

  2. A comparative study of the Au + H2, Au+ + H2, and Au- + H2 systems: Potential energy surfaces and dynamics of reactive collisions

    NASA Astrophysics Data System (ADS)

    Dorta-Urra, Anaís; Zanchet, Alexandre; Roncero, Octavio; Aguado, Alfredo

    2015-04-01

    In order to study the Au- + H2 collision, a new global potential energy surface (PES) describing the ground electronic state of AuH 2- system is developed and compared with the PESs of the neutral [Zanchet et al., J. Chem. Phys. 132, 034301 (2010)] and cationic systems [Anaís et al., J. Chem. Phys. 135, 091102 (2011)]. We found that Au- - H2 presents a H-Au-H insertion minimum attributed to the stabilization of the LUMO 3b2 orbital, which can be considered as the preamble of the chemisorption well appearing in larger gold clusters. While the LUMO orbital is stabilized, the HOMO 6a1 is destabilized, creating a barrier at the geometry where the energy orbitals' curves are crossing. In the anion, this HOMO is doubly occupied, while in the neutral system is half-filled and completely empty in the cation, explaining the gradual disappearance of the well and the barrier as the number of electrons decreases. The cation presents a well in the entrance channel partially explained by electrostatic interactions. The three systems' reactions are highly endothermic, by 1.66, 2.79, and 3.23 eV for AuH, AuH+, and AuH- products, respectively. The reaction dynamics is studied using quasi-classical trajectory method for the three systems. The one corresponding to the anionic system is new in this work. Collision energies between 1.00 and 8.00 eV, measured for the cation, are in good agreement with the simulated cross section for the AuH+. It was also found that the total fragmentation, in three atoms, competes becoming dominant at sufficiently high energy. Here, we study the competition between the two different reaction pathways for the anionic, cationic, and neutral species, explaining the differences using a simple model based on the topology of the potential energy surfaces.

  3. Effects of H2 and electrochemical reducing power on metabolite production by Clostridium acetobutylicum KCTC1037.

    PubMed

    Jeon, Boyoung; Yi, Junyeong; Park, Doohyun

    2014-01-01

    A conventional fermenter (CF), a single-cathode fermenter (SCF), and a double-cathode fermenter (DCF) were employed to evaluate and compare the effects of H2 and electrochemical reducing power on metabolite production by Clostridium acetobutylicum KCTC1037. The source of the external reducing power for CF was H2, for the SCF was electrochemically reduced neutral red-modified graphite felt electrode (NR-GF), and for the DCF was electrochemically reduced combination of NR-GF and platinum plate electrodes (NR-GF/PtP). The metabolites produced from glucose or CO2 by strain KCTC1037 cultivated in the DCF were butyrate, ethanol, and butanol, but ethanol and butanol were not produced from glucose or CO2 by strain KCTC1037 cultivated in the CF and SCF. It is possible that electrochemically reduced NR-GF/PtP is a more effective source of internal and external reducing power than H2 or NR-GF for strain KCTC1037 to produce metabolites from glucose and CO2. This research might prove useful in developing fermentation technology to actualize direct bioalcohol production of fermentation bacteria from CO2. PMID:25036842

  4. Calculations of rate constants for the three-body recombination of H2 in the presence of H2

    NASA Technical Reports Server (NTRS)

    Schwenke, David W.

    1988-01-01

    A new global potential energy hypersurface for H2 + H2 is constructed and quasiclassical trajectory calculations performed using the resonance complex theory and energy transfer mechanism to estimate the rate of three body recombination over the temperature range 100 to 5000 K. The new potential is a faithful representation of ab initio electron structure calculations, is unchanged under the operation of exchanging H atoms, and reproduces the accurate H3 potential as one H atom is pulled away. Included in the fitting procedure are geometries expected to be important when one H2 is near or above the dissociation limit. The dynamics calculations explicitly include the motion of all four atoms and are performed efficiently using a vectorized variable-stepsize integrator. The predicted rate constants are approximately a factor of two smaller than experimental estimates over a broad temperature range.

  5. Global Flux Balance in the Terrestrial H2O Cycle: Reconsidering the Post-Arc Subducted H2O Flux

    NASA Astrophysics Data System (ADS)

    Parai, R.; Mukhopadhyay, S.

    2010-12-01

    Quantitative estimates of H2O fluxes between the mantle and the exosphere (i.e., the atmosphere, oceans and crust) are critical to our understanding of the chemistry and dynamics of the solid Earth: the abundance and distribution of water in the mantle has dramatic impacts upon mantle melting, degassing history, structure and style of convection. Water is outgassed from the mantle is association with volcanism at mid-ocean ridges, ocean islands and convergent margins. H2O is removed from the exosphere at subduction zones, and some fraction of the subducted flux may be recycled past the arc into the Earth’s deep interior. Estimates of the post-arc subducted H2O flux are primarily based on the stability of hydrous phases at subduction zone pressures and temperatures (e.g. Schmidt and Poli, 1998; Rüpke et al., 2004; Hacker, 2008). However, the post-arc H2O flux remains poorly quantified, in part due to large uncertainties in the water content of the subducting slab. Here we evaluate estimated post-arc subducted fluxes in the context of mantle-exosphere water cycling, using a Monte Carlo simulation of the global H2O cycle. Literature estimates of primary magmatic H2O abundances and magmatic production rates at different tectonic settings are used with estimates of the total subducted H2O flux to establish the parameter space under consideration. Random sampling of the allowed parameter space affords insight into which input and output fluxes satisfy basic constraints on global flux balance, such as a limit on sea-level change over time. The net flux of H2O between mantle and exosphere is determined by the total mantle output flux (via ridges and ocean islands, with a small contribution from mantle-derived arc output) and the input flux subducted beyond the arc. Arc and back-arc output is derived mainly from the slab, and therefore cancels out a fraction of the trench intake in an H2O subcycle. Limits on sea-level change since the end of the Archaean place

  6. Surface Adsorbed Species: IR Studies of SO2 and H2S Adsorbed on Oxides

    NASA Astrophysics Data System (ADS)

    Lavalley, J. C.; Lamotte, J.; Saur, O.; Mohammed Saad, A. B.; Tripp, C.; Morrow, B. A.

    1985-12-01

    The adsorption of SO, on alumina leads to the formation of several species such as SO3=, HSO3- and coordinated SO2. In addition sulfates are produced under oxidizing conditions. However, definitive vibra- tional assignments are hampered by the paucity of data below 1000 cm-1 where alumina is strongly absorbing. On the other hand, silica is partially transparent at low frequencies and subtractive IR spectroscopy has permitted us to observe bands which are tentatively assigned to the SO bending modes of bisulfite (HSO3-, 635 cm-I) and disulfite (S2O5-, 660 cm-I) surface species on sodium promoted silica catalysts when SO and H2O are coadsorbed. H2S addition to a surface pretreated with SO2 gives rise to a new band at 680 cm-1 which is pos- sibly due to S2O3 orS2O on the surface. The results are discussed in terms of intermediates in the Claus process (2 H2S + SO2 + 3/n Sn + 2 H2O).

  7. Hollow Fibers Networked with Perovskite Nanoparticles for H2 Production from Heavy Oil

    PubMed Central

    Jeon, Yukwon; Park, Dae-Hwan; Park, Joo-Il; Yoon, Seong-Ho; Mochida, Isao; Choy, Jin-Ho; Shul, Yong-Gun

    2013-01-01

    Design of catalytic materials has been highlighted to build ultraclean use of heavy oil including liquid-to-gas technology to directly convert heavy hydrocarbons into H2–rich gas fuels. If the H2 is produced from such heavy oil through high-active and durable catalysts in reforming process that is being constructed in hydrogen infrastructure, it will be addressed into renewable energy systems. Herein, the three different hollow fiber catalysts networked with perovskite nanoparticles, LaCr0.8Ru0.2O3, LaCr0.8Ru0.1Ni0.1O3, and LaCr0.8Ni0.2O3 were prepared by using activated carbon fiber as a sacrificial template for H2 production from heavy gas oil reforming. The most important findings were arrived at: (i) catalysts had hollow fibrous architectures with well-crystallized structures, (ii) hollow fibers had a high specific surface area with a particle size of ≈50 nm, and (iii) the Ru substituted ones showed high efficiency for H2 production with substantial durability under high concentrations of S, N, and aromatic compounds. PMID:24104596

  8. The Electronic Spectrum of H_2PO, the Prototypical Phosphoryl Free Radical

    NASA Astrophysics Data System (ADS)

    Gharaibeh, Mohammed A.; Clouthier, Dennis J.

    2011-06-01

    The electronic spectrum of the H_2PO radical has been identified by laser-induced fluorescence (LIF) and single vibronic level (SVL) emission techniques. The radical was produced in a pulsed electric discharge jet using a precursor mixture of phosphine (PH_3) and carbon dioxide in high-pressure argon and the tilde{B}^2A' - tilde{X}^2A' electronic transition was detected in the 410-338 nm region. Low resolution LIF and SVL emission spectra of H_2PO and D_2PO have been recorded and the A' vibrational frequencies have been determined in both states. High-resolution spectra of the 0_0^0 bands of H_2PO and D_2PO, which consist of strong a-type and weaker c-type components, were recorded. The spectra have been rotationally analyzed and the excited state molecular structure determined. The spectrum of H_2PO will be discussed in comparison with the spectra of other phosphoryl and arsenyl radicals that have been recently studied in our laboratory.

  9. High Concentrations of H2O2 Make Aerobic Glycolysis Energetically More Favorable for Cellular Respiration.

    PubMed

    Molavian, Hamid R; Kohandel, Mohammad; Sivaloganathan, Sivabal

    2016-01-01

    Since the original observation of the Warburg Effect in cancer cells, over 8 decades ago, the major question of why aerobic glycolysis is favored over oxidative phosphorylation has remained unresolved. An understanding of this phenomenon may well be the key to the development of more effective cancer therapies. In this paper, we use a semi-empirical method to throw light on this puzzle. We show that aerobic glycolysis is in fact energetically more favorable than oxidative phosphorylation for concentrations of peroxide (H2O2) above some critical threshold value. The fundamental reason for this is the activation and high engagement of the pentose phosphate pathway (PPP) in response to the production of reactive oxygen species (ROS) H2O2 by mitochondria and the high concentration of H2O2 (produced by mitochondria and other sources). This makes oxidative phosphorylation an inefficient source of energy since it leads (despite high levels of ATP production) to a concomitant high energy consumption in order to respond to the hazardous waste products resulting from cellular processes associated with this metabolic pathway. We also demonstrate that the high concentration of H2O2 results in an increased glucose consumption, and also increases the lactate production in the case of glycolysis. PMID:27601999

  10. High Concentrations of H2O2 Make Aerobic Glycolysis Energetically More Favorable for Cellular Respiration

    PubMed Central

    Molavian, Hamid R.; Kohandel, Mohammad; Sivaloganathan, Sivabal

    2016-01-01

    Since the original observation of the Warburg Effect in cancer cells, over 8 decades ago, the major question of why aerobic glycolysis is favored over oxidative phosphorylation has remained unresolved. An understanding of this phenomenon may well be the key to the development of more effective cancer therapies. In this paper, we use a semi-empirical method to throw light on this puzzle. We show that aerobic glycolysis is in fact energetically more favorable than oxidative phosphorylation for concentrations of peroxide (H2O2) above some critical threshold value. The fundamental reason for this is the activation and high engagement of the pentose phosphate pathway (PPP) in response to the production of reactive oxygen species (ROS) H2O2 by mitochondria and the high concentration of H2O2 (produced by mitochondria and other sources). This makes oxidative phosphorylation an inefficient source of energy since it leads (despite high levels of ATP production) to a concomitant high energy consumption in order to respond to the hazardous waste products resulting from cellular processes associated with this metabolic pathway. We also demonstrate that the high concentration of H2O2 results in an increased glucose consumption, and also increases the lactate production in the case of glycolysis. PMID:27601999

  11. The Spatial Distribution of Fluorescent H2 Emission Near T Tauri

    NASA Technical Reports Server (NTRS)

    Saucedo, Jose; Calvet, Nuria; Hartmann, Lee; Raymond, John

    2003-01-01

    New subarcsecond far-UV observations of T Tau with Hubble Space Telescope STIS show spatially resolved structure in the 2in. x 2in. area around the star. The structures are apparent in multiline emission of fluorescent H2 pumped by Ly(alpha). One emission structure follows the cavity walls observed around T Tau N in scattered light in the optical. A temperature of greater than or = l000 K is required to have a high enough population in the H2 to produce the observed fluorescent lines; in the cool environment of the T Tau system, shock heating is required to achieve this temperature at distances of a few tens of AU. Fluorescent H2 along the cavity wall represent the best evidence to date for the action of low-density, wide opening angle outflows driving cavities into the molecular medium at scales less than or = 100 AU. A southern region of emission consists of two arcs, with shape and orientation similar to the arcs of H2 2.12 microns and forbidden-line emission crossing the outflow associated with the embedded system T Tau S. This region is located near the centroid of forbidden-line emission at the blueshifted lobe of the north-south outflow.

  12. Responses of the rabbit tracheal epithelium in vitro to H(2)O(2)-induced oxidative stress.

    PubMed

    Baeza-Squiban, A; Delcher, L; Kukreti, R; Joly, A C; Guennou, C; Houcine, O; Marano, F

    2000-04-01

    A model of rabbit tracheal epithelial (RTE) cells in primary culture was used to characterize specific and repair responses of airway epithelial cells to oxidative stress. Two well-known reactive oxygen species (ROS) generating systems were used: H(2)O(2) alone or in combination with Fe(2+) to produce the hydroxyl radical. RTE cells exhibited lipid peroxidation when exposed to H(2)O(2) + Fe(2+). Moreover, catalase (CAT) activity decreased after a 1-hour treatment in 3-day-old cultures but increased in 7-day-old cultures which have higher antioxidant enzyme activities. Superoxide dismutase (SOD) activity was never affected. In addition, RTE cells displayed a repair response leading to squamous metaplasia. H(2)O(2) + Fe(2+) treatment resulted in a time-dependent increase in the steady-state level of c-myc mRNA while c-jun and c-fos were not activated. Moreover, a chronic exposure induced the expression of the squamous phenotype characterized by the expression of the cytokeratin 13 confirmed both at the message and protein levels. RTE cells in primary culture react early to H(2)O(2) + Fe(2+) exposure by an increase in c-myc expression and by modifications in CAT activity. Further, a lipid peroxidation occurs and the tracheal epithelium evolves to squamous metaplasia. PMID:10793294

  13. Possibility of vibrationally resolved cross section measurements for low energy charge transfer in H + H2+

    NASA Astrophysics Data System (ADS)

    Guillen, C. I.; Strom, R. A.; Tobar, J. A.; Panchenko, D. I.; Andrianarijaona, V. M.

    2015-04-01

    Charge transfer (CT) in H + H2+--> H+ + H2 has fundamental implications because it involves the smallest atomic ion, atom, molecular ion, and molecule possible. The current merged-beam apparatus at Oak Ridge National Laboratory (ORNL) in Oak Ridge, Tennessee, can reliably create and access low collision energies; the existing ion-atom merged beams apparatus there is currently able to benchmark the CT of these fundamental systems at energies below 0.1eV/u (Phys. Rev. A 84, 062716, 2011). A strong contribution from vi = 2 is observed, however, the data analysis still suffers from the lack of information on the vibrational state distribution of H2+.We are exploring the possibility of inserting a three-dimensional imaging technique at the end station of the ORNL apparatus in order to measure the vibrational state distribution of H2+that are produced by the electron cyclotron resonance (ECR) ion source. Discussion of our initial design for the insertion of this technique in the aforementioned system will be presented here. Work supported by the National Science Foundation under Grant No. PHY-1068877.

  14. H2S induced coma and cardiogenic shock in the rat: Effects of phenothiazinium chromophores

    PubMed Central

    SONOBE, TAKASHI; HAOUZI, PHILIPPE

    2015-01-01

    Context Hydrogen sulfide (H2S) intoxication produces an acute depression in cardiac contractility-induced circulatory failure, which has been shown to be one of the major contributors to the lethality of H2S intoxication or to the neurological sequelae in surviving animals. Methylene blue (MB), a phenothiazinium dye, can antagonize the effects of the inhibition of mitochondrial electron transport chain, a major effect of H2S toxicity. Objectives We investigated whether MB could affect the immediate outcome of H2S-induced coma in unanesthetized animals. Second, we sought to characterize the acute cardiovascular effects of MB and two of its demethylated metabolites—azure B and thionine—in anesthetized rats during lethal infusion of H2S. Materials and methods First, MB (4 mg/kg, intravenous [IV]) was administered in non-sedated rats during the phase of agonal breathing, following NaHS (20 mg/kg, IP)-induced coma. Second, in 4 groups of urethane-anesthetized rats, NaHS was infused at a rate lethal within 10 min (0.8 mg/min, IV). Whenever cardiac output (CO) reached 40% of its baseline volume, MB, azure B, thionine, or saline were injected, while sulfide infusion was maintained until cardiac arrest occurred. Results Seventy-five percent of the comatose rats that received saline (n = 8) died within 7 min, while all the 7 rats that were given MB survived (p = 0.007). In the anesthetized rats, arterial, left ventricular pressures and CO decreased during NaHS infusion, leading to a pulseless electrical activity within 530 s. MB produced a significant increase in CO and dP/dtmax for about 2 min. A similar effect was produced when MB was also injected in the pre-mortem phase of sulfide exposure, significantly increasing survival time. Azure B produced an even larger increase in blood pressure than MB, while thionine had no effect. Conclusion MB can counteract NaHS-induced acute cardiogenic shock; this effect is also produced by azure B, but not by thionine, suggesting

  15. New Optical Constants for Amorphous and Crystalline H2O-ice and H2O-mixtures.

    NASA Technical Reports Server (NTRS)

    Mastrapa, Rachel; Bernstein, Max; Sandford, Scott

    2006-01-01

    We will present the products of new laboratory measurements of ices relevant to Trans-Neptunian Objects. We have calculated the real and imaginary indices of refraction for amorphous and crystalline H2O-ice and also H2O-rich ices containing other molecular species. We create ice samples by condensing gases onto a cold substrate. We measure the thickness of the sample by reflecting a He-Ne laser off of the sample and counting interference fringes as it grows. We then collect transmission spectra of the samples in the wavelength range from 0.7-22 micrometers. Using the thickness and the transmission spectra of the ice we calculate the imaginary part of the index of refraction. We then use a Kramers-Kronig calculation to calculate the real part of the index of refraction (Berland et al. 1994; Hudgins et al. 1993). These optical constants can then be used to create model spectra for comparison to spectra from Solar System objects, including TNOs. We will summarize the difference between the amorphous and crystalline H2O-ice spectra. These changes include weakening of features and shifting of features to shorter wavelength. One important result is that the 2 pm feature is stronger in amorphous H2O ice than it is in crystalline H2O-ice. We will also discuss the changes seen when H2O is mixed with other components, including CO2, CH4, HCN, and NH3 (Bernstein et al. 2005; Bernstein et al. 2006).

  16. Preformance Analysis of NH3-H2O Absorption Cycle

    NASA Astrophysics Data System (ADS)

    Tsujimori, Atsushi; Ozaki, Eiichi

    Different from H2O-LiBr absorption cycle, it is necessary to have rectifier between generator and condenser in NH3-H2O absorption cycle, because there mixes some steam in refrigerant vapor in the process of regenerating refrigerant from the ammonia strong aqueous solution. And in some case ex. partial load or heating, the efficiency of rectifier might decrease, if the flow rate of refrigerant vapor and ammonia aqueous solution decrease. As a result, steam flow into condenser with ammonia refrigerant vapor, which reduces cycle COPs of cooling and heating. Accordingly in order to evaluate the effect of ammonia concentration in refrigerant for the performance of NH3-H2O absorption heat pump, the simple design approach of modeling condenser and evaporator is introduced in this paper. In the model, the calculation of heat rate in condenser and evaporator was simplified considering the characteristic of NH3-H2O liquid-vapor equilibrium. Then the simulation for cycle perforance based on GAX absorption cycle was made using the efficiency of rectifier that established the ammonia concentration in refrigerant and it was derived that 3 [%] decrease of ammonia concentration in refrigerant induced 15 [%] decrcase of cooling COP and 7 [%] decrease of heating COP and that there existed the most suitable circulation ratio for each ammonia concentration in refrigerant.

  17. REACTION OF H2S AND SULFUR WITH LIMESTONE PARTICLES

    EPA Science Inventory

    The paper gives results of a study of the direct-displacement reaction of limestone with hydrogen sulfide (H2S) over the temperature range 570-850 C in a differential reactor. It is one of several possible mechanisms of sulfur capture in limestone-injection multistage burners whi...

  18. Coaxial rings and H2 knots in Hubble 12

    NASA Astrophysics Data System (ADS)

    Hsia, Chih-Hao; Kwok, Sun; Chau, Wayne; Zhang, Yong

    2016-07-01

    Hubble 12 (Hb 12) is a young planetary nebula (PN) exhibiting nested shells. We present new near-infrared narrow-band imaging observations of Hb 12 using the Canada-France- Hawaii Telescope (CFHT). A number of co-axial rings aligned with the bipolar lobes and two pairs of separate H2 knots with different orientations are detected.

  19. Structure A, architectural sections & details. Drawing no. H2, revised ...

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

    Structure A, architectural sections & details. Drawing no. H2, revised as-built dated October 11, 1951. Original drawing by Black & Veatch, consulting engineers, Kansas City, Missouri, prepared for the U.S. Department of the Army, Office of Engineers, Military Construction Division, Washington, D.C. dated October 1. - Travis Air Force Base, Building No. 925, W Street, Fairfield, Solano County, CA

  20. Extended H2 emission line sources from UWISH2

    NASA Astrophysics Data System (ADS)

    Froebrich, D.; Makin, S. V.; Davis, C. J.; Gledhill, T. M.; Kim, Y.; Koo, B.-C.; Rowles, J.; Eislöffel, J.; Nicholas, J.; Lee, J. J.; Williamson, J.; Buckner, A. S. M.

    2015-12-01

    We present the extended source catalogue for the UKIRT Wide Field Infrared Survey for H2 (UWISH2). The survey is unbiased along the inner Galactic Plane from l ≈ 357° to l ≈ 65° and |b| ≤ 1.5° and covers 209 deg2. A further 42.0 and 35.5 deg2 of high dust column density regions have been targeted in Cygnus and Auriga. We have identified 33 200 individual extended H2 features. They have been classified to be associated with about 700 groups of jets and outflows, 284 individual (candidate) planetary nebulae, 30 supernova remnants and about 1300 photodissociation regions. We find a clear decline of star formation activity (traced by H2 emission from jets and photodissociation regions) with increasing distance from the Galactic Centre. About 60 per cent of the detected candidate planetary nebulae have no known counterpart and 25 per cent of all supernova remnants have detectable H2 emission associated with them.

  1. Multidimentional Normal Mode Calculations for the OH Vibrational Spectra of (H_2O)_3^+, (H_2O)_3^+Ar, H^+(H_2O)_3, and H^+(H_2O)_3Ar

    NASA Astrophysics Data System (ADS)

    Li, Ying-Cheng; Chuang, Hsiao-Han; Tan, Jake Acedera; Takahashi, Kaito; Kuo, Jer-Lai

    2014-06-01

    Recent experimental observations of (H_2O)_3^+, (H_2O)_3^+Ar, H^+(H_2O)_3, and H^+(H_2O)_3Ar clusters in the region 1400-3800 wn show that the OH stretching vibration has distinct characteristics. Multidimensional normal mode calculations were carried out for OH stretching vibrations in the 1200-4000 wn photon energy range. The potential energy and dipole surfaces were evaluated by using first-principles methods. By comparing the calculated frequencies and intensities of OH stretching vibration with experimental spectra, we found that the assignment of OH strecthing of H_3O^+ moiety and free OH strectching vibration have resonable agreement with experimental data. Jeffrey M. Headrick, Eric G. Diken, Richard S. Walters, Nathan I. Hammer, Richard A. Christie, Jun Cui, Evgeniy M. Myshakin, Michael A. Duncan, Mark A. Johnson, Kenneth D. Jordan, Science, 2005, 17, 1765. Kenta Mizuse, Jer-Lai Kuo and Asuka Fujii, Chem. Sci., 2011, 2, 868 Kenta Mizuse and Asuka Fujii, J. Phys. Chem. A, 2013, 117, 929.

  2. PEM Electrolysis H2A Production Case Study Documentation

    SciTech Connect

    James, Brian; Colella, Whitney; Moton, Jennie; Saur, G.; Ramsden, T.

    2013-12-31

    This report documents the development of four DOE Hydrogen Analysis (H2A) case studies for polymer electrolyte membrane (PEM) electrolysis. The four cases characterize PEM electrolyzer technology for two hydrogen production plant sizes (Forecourt and Central) and for two technology development time horizons (Current and Future).

  3. Evaluation of an electrochemical N2/H2 gas separator

    NASA Technical Reports Server (NTRS)

    Marshall, R. D.; Wynveen, R. A.; Carlson, J. N.

    1973-01-01

    A program was successfully completed to evaluate an electrochemical nitrogen/hydrogen (N2/H2) separator for use in a spacecraft nitrogen (N2) generator. Based on the technical data obtained a N2/H2 separator subsystem consisting of an organic polymer gas permeator first stage and an electrochemical second and third stage was estimated to have the lowest total spared equivalent weight, 257 kg (566 lb), for a 15 lb/day N2 generation rate. A pre-design analysis of the electrochemical N2/H2 separator revealed that its use as a first stage resulted in too high a power requirement to be competitive with the organic polymer membrane and the palladium-silver membrane separation methods. As a result, program emphasis was placed on evaluating the electrochemical. A parametric test program characterized cell performance and established second- and third-stage electrochemical N2/H2 separator operating conditions. A design verification test was completed on the second and third stages. The second stage was then successfully endurance tested for 200 hours.

  4. Ni-H2 cell characterization for INTELSAT programs

    NASA Technical Reports Server (NTRS)

    Dunnet, Andrew F.; Earl, Martin W.

    1994-01-01

    Various Ni/H2 cell designs manufactured for INTELSAT Programs during the past decade have been characterized electrically as a function of temperature. The resulting data for these INTELSAT V, VI, VII and VIIA cells are assembled in a manner which allows ready comparison of performance. Also included is a detailed description of each design.

  5. H2A Production Model, Version 2 User Guide

    SciTech Connect

    Steward, D.; Ramsden, T.; Zuboy, J.

    2008-09-01

    The H2A Production Model analyzes the technical and economic aspects of central and forecourt hydrogen production technologies. Using a standard discounted cash flow rate of return methodology, it determines the minimum hydrogen selling price, including a specified after-tax internal rate of return from the production technology. Users have the option of accepting default technology input values--such as capital costs, operating costs, and capacity factor--from established H2A production technology cases or entering custom values. Users can also modify the model's financial inputs. This new version of the H2A Production Model features enhanced usability and functionality. Input fields are consolidated and simplified. New capabilities include performing sensitivity analyses and scaling analyses to various plant sizes. This User Guide helps users already familiar with the basic tenets of H2A hydrogen production cost analysis get started using the new version of the model. It introduces the basic elements of the model then describes the function and use of each of its worksheets.

  6. H2 excitation in HD 34078 from FUSE observations

    NASA Astrophysics Data System (ADS)

    Petit, F. Le; Boissé, P.; Roueff, E.; Gry, C.; Le Brun, V.

    We present preliminary results from FUSE on the HD 34078 line of sight from 980 to 1080 Angströms. Many atomic and molecular lines are detected, especially from H2 observed up to the first vibrational excited levels. HD and CO are also clearly present. The column densities found for CO and atomic hydrogen are close to those given by Mc Lachlan and Nandy (1984). We deduce an excitation temperature of 70K from the column densities of the two first rotational levels of H2. The molecular fraction (2 \\cdot N(H2))/ (2 \\cdot N(H2)+N(H)) is about 0.5 toward HD34078 corresponding to a color excess, E(B-V) of 0.52. The results will be discussed with the help of a model of photodominated regions. References: A. Mc Lachlan and K. Nandy, MNRAS, 207, 355 S.R. Federman, C.J. Strom, D.L. Lambert, Jason A. Cardelli, V.V. Smith and C.L. Joseph, ApJ, 424, 772

  7. Ion-Molecule Reaction of Gas-Phase Chromium Oxyanions: CrxOyHz- + H2O

    SciTech Connect

    Gianotto, Anita Kay; Hodges, Brittany DM; Benson, Michael Timothy; Harrington, Peter Boves; Appelhans, Anthony David; Olson, John Eric; Groenewold, Gary Steven

    2003-08-01

    Chromium oxyanions having the general formula CrxOyHz- play a key role in many industrial, environmental, and analytical processes, which motivated investigations of their intrinsic reactivity. Reactions with water are perhaps the most significant, and were studied by generating CrxOyHz- in the gas phase using a quadrupole ion trap secondary ion mass spectrometer. Of the ions in the Cr1OyHz envelope (y = 2, 3, 4; z = 0, 1), only CrO2- was observed to react with H2O, producing the hydrated CrO3H2- at a slow rate (~0.07% of the ion-molecule collision constant at 310 K). CrO3-, CrO4-, and CrO4H- were unreactive. In contrast, Cr2O4-, Cr2O5-, and Cr2O5H2- displayed a considerable tendency to react with H2O. Cr2O4- underwent sequential reactions with H2O, initially producing Cr2O5H2- at a rate that was ~7% efficient. Cr2O5H2- then reacted with a second H2O by addition to form Cr2O6H4- (1.8% efficient) and by OH abstraction to form Cr2O6H3- (0.6% efficient). The reactions of Cr2O5- were similar to those of Cr2O5H2-: Cr2O5- underwent addition to form Cr2O6H2- (3% efficient) and OH abstraction to form Cr2O6H- (<1% efficient). By comparison, Cr2O6- was unreactive with H2O, and in fact, no further H2O addition could be observed for any of the Cr2O6Hz- anions. Hartree-Fock ab initio calculations showed that reactive CrxOyHz- species underwent nucleophilic attack by the incoming H2O molecules, which produced an initially formed adduct in which the water O was bound to a Cr center. The experimental and computational studies suggested that Cr2OyHz- species that have bi- or tricoordinated Cr centers are susceptible to attack by H2O; however, when the metal becomes tetracoordinate, reactivity stops. For the Cr2OyHz- anions the lowest energy structures all contained rhombic Cr2O2 rings with pendant O atoms and/or OH groups. The initially formed [Cr2Oy- + H2O] adducts underwent H rearrangement to a gem O atom to produce stable dihydroxy structures. The calculations indicated that

  8. Infrared band extinctions and complex refractive indices of crystalline C2H2 and C4H2

    NASA Astrophysics Data System (ADS)

    Khanna, R. K.; Ospina, Mario J.; Zhao, Guizhi

    1988-03-01

    Thermal IR absorption intensities are obtained for thin films of crystalline C2H2 and C4H2 at 70 K, and their n and k complex refractive indices are ascertained by separating true film absorption from interface reflection on the basis of an analysis of the transmission spectrum ratio for two sample thicknesses. This method significantly simplifies the n and k iteration process. The n and k values determined in the laboratory will in most cases reproduce a given sample thickness' observed transmission to within + or - 5 percent.

  9. Infrared band extinctions and complex refractive indices of crystalline C2H2 and C4H2

    NASA Technical Reports Server (NTRS)

    Khanna, R. K.; Ospina, Mario J.; Zhao, Guizhi

    1988-01-01

    Thermal IR absorption intensities are obtained for thin films of crystalline C2H2 and C4H2 at 70 K, and their n and k complex refractive indices are ascertained by separating true film absorption from interface reflection on the basis of an analysis of the transmission spectrum ratio for two sample thicknesses. This method significantly simplifies the n and k iteration process. The n and k values determined in the laboratory will in most cases reproduce a given sample thickness' observed transmission to within + or - 5 percent.

  10. The barley Frost resistance-H2 locus.

    PubMed

    Pasquariello, Marianna; Barabaschi, Delfina; Himmelbach, Axel; Steuernagel, Burkhard; Ariyadasa, Ruvini; Stein, Nils; Gandolfi, Francesco; Tenedini, Elena; Bernardis, Isabella; Tagliafico, Enrico; Pecchioni, Nicola; Francia, Enrico

    2014-03-01

    Frost resistance-H2 (Fr-H2) is a major QTL affecting freezing tolerance in barley, yet its molecular basis is still not clearly understood. To gain a better insight into the structural characterization of the locus, a high-resolution linkage map developed from the Nure × Tremois cross was initially implemented to map 13 loci which divided the 0.602 cM total genetic distance into ten recombination segments. A PCR-based screening was then applied to identify positive bacterial artificial chromosome (BAC) clones from two genomic libraries of the reference genotype Morex. Twenty-six overlapping BACs from the integrated physical-genetic map were 454 sequenced. Reads assembled in contigs were subsequently ordered, aligned and manually curated in 42 scaffolds. In a total of 1.47 Mbp, 58 protein-coding sequences were identified, 33 of which classified according to similarity with sequences in public databases. As three complete barley C-repeat Binding Factors (HvCBF) genes were newly identified, the locus contained13 full-length HvCBFs, four Related to AP2 Triticeae (RAPT) genes, and at least five CBF pseudogenes. The final overall assembly of Fr-H2 includes more than 90 % of target region: all genes were identified along the locus, and a general survey of Repetitive Elements obtained. We believe that this gold-standard sequence for the Morex Fr-H2 will be a useful genomic tool for structural and evolutionary comparisons with Fr-H2 in winter-hardy cultivars along with Fr-2 of other Triticeae crops. PMID:24442711

  11. Far-Ultraviolet Studies of H2 in Photodissociation Regions

    NASA Astrophysics Data System (ADS)

    France, Kevin; McCandliss, Stephan R.; Burgh, Eric B.

    2009-05-01

    We present a brief review of molecules studied with far-ultraviolet spectroscopy, discussing absorption line measurements of the dominant interstellar molecules (H2 and CO) and H2 emission from molecular clouds near hot stars. We give two examples where the CO/H2 ratio, which can only be derived uniquely in the far-ultraviolet, can be used to study the structure of the interstellar medium. Prospects are discussed for future work with deeper observations that would allow one to probe farther into molecular clouds in the galaxy. We describe a mini-survey of five local photodissociation regions (PDRs) carried out with FUSE. We use these data to characterize the far-UV spectra of PDRs for the first time and to refine models of the H2 fluorescent emission process. We find that our models can adequately reproduce the observed emission spectra of three of these regions (IC 63, M42, and IC 405). The remaining two (NGC 2023 and NGC 7023) do not show clear emission from H2 in the FUSE band, despite the well defined and characteristic double-peaked emission features at 1575 and 1608 Å observed in archival observations, as well as the clear fluorescent signatures in the well studied near-IR rovibrational emission lines, thus suggesting a more complex radiative transfer scenario in these environments. We conclude with simple simulations showing the potential gains that could be made in the studies of PDRs with future far-ultraviolet spectrographs with increased effective area and resolving power over current instruments.

  12. Vibrational investigations of CO2-H2O, CO2-(H2O)2, and (CO2)2-H2O complexes isolated in solid neon.

    PubMed

    Soulard, P; Tremblay, B

    2015-12-14

    The van der Waals complex of H2O with CO2 has attracted considerable theoretical interest as a typical example of a weak binding complex with a dissociation energy less than 3 kcal/mol. Up to now, experimental vibrational data are sparse. We have studied by FTIR the complexes involving CO2 and water molecules in solid neon. Many new absorption bands close to the well known monomers fundamentals give evidence for at least three (CO2)n-(H2O)m complexes, noted n:m. Concentration effects combined with a detailed vibrational analysis allow for the identification of sixteen, twelve, and five transitions for the 1:1, 1:2, and 2:1 complexes, respectively. Careful examination of the far infrared spectral region allows the assignment of several 1:1 and 1:2 intermolecular modes, confirmed by the observation of combinations of intra + intermolecular transitions, and anharmonic coupling constants have been derived. Our results demonstrate the high sensibility of the solid neon isolation to investigate the hydrogen-bonded complexes in contrast with the gas phase experiments for which two quanta transitions cannot be easily observed. PMID:26671379

  13. X-ray investigation of molten crystal hydrates H2SO4(nH2O) and HNO3(nH2O)

    NASA Technical Reports Server (NTRS)

    Romanova, A. V.; Skryshevskiy, A. F.

    1979-01-01

    Integral analysis of the intensity of the electron density distribution curve in molten crystal hydrates provided by X-ray analysis, permits the following conclusions on the structure of the complex SO and NO ions, and the short-range order in the structure of the solution. The SO4 ion in the solution has a tetrahedral structure with an S to O distance equal to 1.5 A. For the NO3 in the solution, a planar triangular shape is probable, with an N to O distance equal to 1.2 A. Preferential distances between each of the oxygens of the SO ion and the nearest molecules of water proved near to the corresponding distances in solid crystal hydrates. For an (H2SO4)(H2O) solution, the average number of water molecules surrounding each oxygen atom of the SO4 (--) ion was on the order of 1.3 molecules. Hence the preferential distances between the water molecules and the oxygen atoms of the SO ion, and the preference of their mutual position, correspond to the fixed position of these same elements of the structure in the solid crystal hydrate.

  14. Vibrational investigations of CO2-H2O, CO2-(H2O)2, and (CO2)2-H2O complexes isolated in solid neon

    NASA Astrophysics Data System (ADS)

    Soulard, P.; Tremblay, B.

    2015-12-01

    The van der Waals complex of H2O with CO2 has attracted considerable theoretical interest as a typical example of a weak binding complex with a dissociation energy less than 3 kcal/mol. Up to now, experimental vibrational data are sparse. We have studied by FTIR the complexes involving CO2 and water molecules in solid neon. Many new absorption bands close to the well known monomers fundamentals give evidence for at least three (CO2)n-(H2O)m complexes, noted n:m. Concentration effects combined with a detailed vibrational analysis allow for the identification of sixteen, twelve, and five transitions for the 1:1, 1:2, and 2:1 complexes, respectively. Careful examination of the far infrared spectral region allows the assignment of several 1:1 and 1:2 intermolecular modes, confirmed by the observation of combinations of intra + intermolecular transitions, and anharmonic coupling constants have been derived. Our results demonstrate the high sensibility of the solid neon isolation to investigate the hydrogen-bonded complexes in contrast with the gas phase experiments for which two quanta transitions cannot be easily observed.

  15. Silicate-H2O Systems at High Pressure Conditions

    NASA Astrophysics Data System (ADS)

    Tailby, N.; Mavrogenes, J. A.; Hermann, J.; O'Neill, H. S.

    2008-12-01

    Since the discovery of the second critical endpoint (CP2) in the albite-water system, numerous attempts have been made to determine the pressure and temperature of this CP2 and the mutual solubilities within more complex systems. The P-T position of the CP2 has been estimated for many systems: SiO2 (<10 kb/900 °C, Newton and Manning, 2008); NaAlSi3O8 (15 kb/800 °C, Burnham and Davis, 1974; Shen and Keppler, 1997); Pelite (50 kb/1,000 °C, Schmidt et al., 2004), basalt (50 kb/ 1000 °C, Kessel et al., 2004), Peridotite (38 kb/1000 °C, Mibe et al., 2007). A number of experimental techniques have been used to determine phase relations and H2O solubility in experiments. These include in-situ experimental techniques (e.g., HYDAC; Shen and Keppler, 1997), fluid trap techniques (e.g., diamond traps; Stalder et al., 2000), and single crystal weight-loss techniques (e.g., SiO2-H2O techniques employed by Newton and Manning, 2008). None of these techniques is without difficulties, as H2O rich experiments need to overcome huge retrograde fluid solubilities upon quench in order to determine mutual solubilities at experimental conditions. We have developed a new technique to determine "rock"-H2O relationships at high-P conditions, with particular focus on the shape and locus of solvi in pressure temperature space. In this series of experiments, an oxygen fugacity buffer (Re-ReO2) and a sliding H-fugacity sensor (NiO-Ni-Pd mixture) are combined to monitor H2O activity over the entire range of pressure and temperature. Unlike other techniques, the use of sensor capsules does not require textural interpretation of experiments. H2O activity is related to oxygen and hydrogen fugacity by the reaction: H2O = H2 + ½O2 NiO-Ni-Pd mixtures were placed within a ZrO2 jacket and sealed within a welded 2.3 mm Pt capsule. This 2.3 mm Pt sensor capsule was then encased within a larger, thick walled 6 mm diameter Ag capsule. Pelite-H2O mixtures and oxygen buffers were held within this larger

  16. ERO1-independent production of H2O2 within the endoplasmic reticulum fuels Prdx4-mediated oxidative protein folding

    PubMed Central

    Konno, Tasuku; Pinho Melo, Eduardo; Lopes, Carlos; Mehmeti, Ilir; Lenzen, Sigurd

    2015-01-01

    The endoplasmic reticulum (ER)–localized peroxiredoxin 4 (PRDX4) supports disulfide bond formation in eukaryotic cells lacking endoplasmic reticulum oxidase 1 (ERO1). The source of peroxide that fuels PRDX4-mediated disulfide bond formation has remained a mystery, because ERO1 is believed to be a major producer of hydrogen peroxide (H2O2) in the ER lumen. We report on a simple kinetic technique to track H2O2 equilibration between cellular compartments, suggesting that the ER is relatively isolated from cytosolic or mitochondrial H2O2 pools. Furthermore, expression of an ER-adapted catalase to degrade lumenal H2O2 attenuated PRDX4-mediated disulfide bond formation in cells lacking ERO1, whereas depletion of H2O2 in the cytosol or mitochondria had no similar effect. ER catalase did not effect the slow residual disulfide bond formation in cells lacking both ERO1 and PRDX4. These observations point to exploitation of a hitherto unrecognized lumenal source of H2O2 by PRDX4 and a parallel slow H2O2-independent pathway for disulfide formation. PMID:26504166

  17. γH2AX expression in cytological specimens as a biomarker of response to radiotherapy in solid malignancies

    PubMed Central

    Shah, Ketan; Boghozian, Ramon A.; Kartsonaki, Christiana; Shah, Ketan A.

    2015-01-01

    Many anticancer treatments, including radiotherapy, act by damaging DNA and hindering cell function and proliferation. H2AX is a histone protein directly associated with DNA that is phosphorylated to produce γH2AX that accumulates in foci in an early response to DNA double‐strand breaks, the most deleterious lesion caused by anticancer therapy. This study reports a γH2AX detection assay that has the potential to be used as a biomarker of response to guide cancer treatment. γH2AX immunostaining was applied to tumour cell specimens obtained using fine needle aspiration (FNA). Liquid‐based cytology and direct smear cytology methods were evaluated and immunostaining protocols established using FNA samples from five cancer patients. The assay was then applied to three patients before and after radiotherapy. Results demonstrate induction of γH2AX foci following treatment, persisting for as long as one week after therapy. Immunostaining for γH2AX has been successfully applied to FNA samples, providing an opportunity to evaluate γH2AX as a treatment response marker in cancer. Diagn. Cytopathol. 2016;44:141–146. © 2015 The Authors Diagnostic Cytopathology Published by Wiley Periodicals, Inc. PMID:26667983

  18. Treatment with NaHSO3 greatly enhances photobiological H2 production in the green alga Chlamydomonas reinhardtii.

    PubMed

    Ma, Weimin; Chen, Ming; Wang, Lianjun; Wei, Lanzhen; Wang, Quanxi

    2011-09-01

    Treatment with NaHSO3 induces a 10-fold increase in H2 photoproduction in the filamentous N2-fixing cyanobacterium Anabaena sp. strain PCC 7120. However, it is unclear whether this treatment also increases H2 photoproduction in green alga. In this study, treatment with 13 mM NaHSO3 resulted in about a 200-fold increase in H2 production in Chlamydomonas reinhardtii, and this increase was most probably the result of reduced O2 content and enhanced hydrogenase activity. Compared to the conventional strategy of sulfur deprivation, NaHSO3 treatment results in a higher maximum rate of H2 photoproduction, greater efficiency of conversion of light energy into H2, shorter half-time to produce the maximum accumulated H2 levels, and reduced costs because no centrifugation is involved. We therefore conclude that NaHSO3 treatment is an efficient, rapid, and economic strategy for improving photobiological H2 production in the green alga C. reinhardtii. PMID:21489780

  19. Noteworthy performance of La(1-x)Ca(x)MnO3 perovskites in generating H2 and CO by the thermochemical splitting of H2O and CO2.

    PubMed

    Dey, Sunita; Naidu, B S; Govindaraj, A; Rao, C N R

    2015-01-01

    Perovskite oxides of the composition La1-xCaxMnO3 (LCM) have been investigated for the thermochemical splitting of H2O and CO2 to produce H2 and CO, respectively. The study was carried out in comparison with La1-xSrxMnO3, CeO2 and other oxides. The LCM system exhibits superior characteristics in high-temperature evolution of oxygen, and in reducing CO2 to CO and H2O to H2. The best results were obtained with La0.5Ca0.5MnO3 whose performance is noteworthy compared to that of other oxides including ceria. The orthorhombic structure of LCM seems to be a crucial factor. PMID:25406376

  20. Lyman-alpha fluorescence from hydrogen photofragments of CH4 and H2O

    NASA Technical Reports Server (NTRS)

    Wu, C. Y. R.; Judge, D. L.

    1981-01-01

    The process of H-Lyman-alpha fluorescence produced through photodissociation of CH4 and H2O provides an example for the usefulness of the detection of fluorescence of dissociation fragments as an aid in identifying some high lying Rydberg states. In the first experiment reported, an electron storage ring synchrotron radiation source was used. The fluorescence produced was detected with a solar blind photomultiplier and a Cs photocathode with a spectral sensitivity in the wavelength range from 1050 to 1950 A. In the second experiment considered, an intense atomic line source was employed.

  1. Mapping of [HDO]/[H2O] in the Martian Atmosphere

    NASA Astrophysics Data System (ADS)

    Novak, R. E.; Mumma, M. J.; Villanueva, G.; Bonev, B.; Disanti, M.

    Observations of the Martian atmosphere were taken for several seasonal dates at NASA's IRTF using CSHELL. Column densities of HDO and H2O were extracted from individual spectral lines near 3.67 ìm and 3.29 ìm. The slit was positioned N-S on Mars centered at the sub-earth point producing spectral/spatial images. Spectra were extracted at 0.6 arc-sec. intervals and analyzed with models created from GENLN2 atmospheric software; the models include solar Fraunhofer lines, a two-way transmission through Mars' atmosphere, thermal emission from Mars' surface and atmosphere, and a one way transmission through the Earth's atmosphere. From these, latitudinal maps of HDO/H2O were constructed across the observable planet. The HDO/H2O ratios have been found to be larger than those on Earth and they vary with both latitude and season. The higher global HDO/H2O value on Mars compared to that of the Earth is attributed to differential Jeans escape of D and H over geologic time. The ratio in the southern Martian hemisphere is found to be larger than that in the north. This difference could be the signature of Rayleigh distillation, a process in which the different mean temperatures of the polar caps causes a different degree of HDO sequestration resulting in different degrees of enrichment in the polar caps. Detailed results for Ls= 357o in 2006 will be presented when both the HDO and the H2O column densities were obtain from CSHELL data. These will be compared to results from other seasons.Observations of the Martian atmosphere were taken for several seasonal dates at NASA's IRTF using CSHELL. Column densities of HDO and H2O were extracted from individual spectral lines near 3.67 ìm and 3.29 ìm. The slit was positioned N-S on Mars centered at the sub-earth point producing spectral/spatial images. Spectra were extracted at 0.6 arc-sec. intervals and analyzed with models created from GENLN2 atmospheric software; the models include solar Fraunhofer lines, a two-way transmission

  2. Oxidative degradation of endotoxin by advanced oxidation process (O3/H2O2 & UV/H2O2).

    PubMed

    Oh, Byung-Taek; Seo, Young-Suk; Sudhakar, Dega; Choe, Ji-Hyun; Lee, Sang-Myeong; Park, Youn-Jong; Cho, Min

    2014-08-30

    The presence of endotoxin in water environments may pose a serious public health hazard. We investigated the effectiveness of advanced oxidative processes (AOP: O3/H2O2 and UV/H2O2) in the oxidative degradation of endotoxin. In addition, we measured the release of endotoxin from Escherichia coli following typical disinfection methods, such as chlorine, ozone alone and UV, and compared it with the use of AOPs. Finally, we tested the AOP-treated samples in their ability to induce tumor necrosis factor alpha (TNF-α) in mouse peritoneal macrophages. The production of hydroxyl radical in AOPs showed superior ability to degrade endotoxin in buffered solution, as well as water samples from Korean water treatment facilities, with the ozone/H2O2 being more efficient compared to UV/H2O2. In addition, the AOPs proved effective not only in eliminating E. coli in the samples, but also in endotoxin degradation, while the standard disinfection methods lead to the release of endotoxin following the bacteria destruction. Furthermore, in the experiments with macrophages, the AOPs-deactivated endotoxin lead to the smallest induction of TNF-α, which shows the loss of inflammation activity, compared to ozone treatment alone. In conclusion, these results suggest that AOPs offer an effective and mild method for endotoxin degradation in the water systems. PMID:25038578

  3. Full-dimensional quantum wave packet study of rotationally inelastic transitions in H2+H2 collision

    NASA Astrophysics Data System (ADS)

    Ying Lin, Shi; Guo, Hua

    2002-09-01

    We report full-dimensional accurate quantum dynamical calculations of the rotationally inelastic collision: para-H2(ν1=0,j1)=0+para- H2(ν2=0,j2)=0→para- H2(ν1=0,j1)'+para- H2(ν2=0,j2)', using a wave packet approach based on the Chebyshev polynomial expansion of Green's operator. The six-dimensional Hamiltonian within the coupled-states approximation is discretized in a mixed grid/basis representation and its action is computed in appropriate representations facilitated by a series of one-dimensional pseudo-spectral transformations. Both the parity and diatomic exchange symmetry are adapted. The S-matrix elements for the rotational transitions are obtained at all energies by the Fourier transform of Chebyshev correlation functions and used to compute transition probabilities, differential and integral cross sections, and state-resolved thermal rate constants. Results are compared for two recently proposed ab initio based potential energy surfaces and with previous quantum results.

  4. Crystalline and amorphous H2O on Charon

    NASA Astrophysics Data System (ADS)

    Dalle Ore, Cristina M.; Cruikshank, Dale P.; Grundy, Will M.; Ennico, Kimberly; Olkin, Catherine B.; Stern, S. Alan; Young, Leslie A.; Weaver, Harold A.

    2015-11-01

    Charon, the largest satellite of Pluto, is a gray-colored icy world covered mostly in H2O ice, with spectral evidence for NH3, as previously reported (Cook et al. 2007, Astrophys. J. 663, 1406-1419 Merlin, et al. 2010, Icarus, 210, 930; Cook, et al. 2014, AAS/Division for Planetary Sciences Meeting Abstracts, 46, #401.04). Images from the New Horizons spacecraft reveal a surface with terrains of widely different ages and a moderate degree of localized coloration. The presence of H2O ice in its crystalline form (Brown & Calvin 2000 Science 287, 107-109; Buie & Grundy 2000 Icarus 148, 324-339; Merlin et al, 2010) along with NH3 is consistent with a fresh surface.The phase of H2O ice is a key tracer of variations in temperature and physical conditions on the surface of outer Solar System objects. At Charon’s surface temperature H2O is expected to be amorphous, but ground-based observations (e.g., Merlin et al. 2010) show a clearly crystalline signature. From laboratory experiments it is known that amorphous H2O ice becomes crystalline at temperatures of ~130 K. Other mechanisms that can change the phase of the ice from amorphous to crystalline include micro-meteoritic bombardment (Porter et al. 2010, Icarus, 208, 492) or resurfacing processes such as cryovolcanism.New Horizons observed Charon with the LEISA imaging spectrometer, part of the Ralph instrument (Reuter, D.C., Stern, S.A., Scherrer, J., et al. 2008, Space Science Reviews, 140, 129). Making use of high spatial resolution (better than 10 km/px) and spectral resolving power of 240 in the wavelength range 1.25-2.5 µm, and 560 in the range 2.1-2.25 µm, we report on an analysis of the phase of H2O ice on parts of Charon’s surface with a view to investigate the recent history and evolution of this small but intriguing object.This work was supported by NASA’s New Horizons project.

  5. [Functional characteristics of yeast cells in nutrient aqueous solution enriched with ortho-H2O isomers].

    PubMed

    Pershin, S M; Ismailov, E Sh; Suleimanova, Z G; Abdulmagomedova, Z N; Zagirova, D Z

    2014-01-01

    It has been experimentally established that cultivation of yeast cells in depleted, dietary or normal nutrient aqueous solutions enriched with ortho-H2O spin isomers is accompanied by an increase in the amount of carbon dioxide produced by the cells and an increase in their biomass. It has been revealed that the rate of metabolic processes and biological activity depends on the quality of nutrition and enhances in time in both nutrient solutions. In contrast, the reproductive function and the rate of cell division are insusceptible to the components of nutrition, but intensified in a solution enriched with ortho-H2O similar to retardation of aging. The observed effects are discussed in assumption that an increase of a portion of ortho-H2O molecules occurs in the neighborhood of water channels in the cell membrane that let through only monomers of H2O and determine the rate of metabolic processes. PMID:25702495

  6. Quantitative C2H2 measurements in sooty flames using mid-infrared polarization spectroscopy

    NASA Astrophysics Data System (ADS)

    Sun, Z. W.; Li, Z. S.; Li, B.; Alwahabi, Z. T.; Aldén, M.

    2010-10-01

    Quantitative measurements of acetylene (C2H2) molecules as a combustion intermediate species in a series of rich premixed C2H4/air flames were non-intrusively performed, spatially resolved, using mid-infrared polarization spectroscopy (IRPS), by probing its fundamental ro-vibrational transitions. The flat sooty C2H4/air premixed flames with different equivalence ratios varying from 1.25 to 2.50 were produced on a 6 cm diameter porous-plug McKenna type burner at atmospheric pressure, and all measurements were performed at a height of 8.5 mm above the burner surface. IRPS excitation scans in different flame conditions were performed and rotational line-resolved spectra were recorded. Spectral features of acetylene molecules were readily recognized in the spectral ranges selected, with special attention to avoid the spectral interference from the large amount of coexisting hot water and other hydrocarbon molecules. On-line calibration of the optical system was performed in a laminar C2H2/N2 gas flow at ambient conditions. Using the flame temperatures measured by coherent anti-Stokes Raman spectroscopy in a previous work, C2H2 mole fractions in different flames were evaluated with collision effects and spectral overlap between molecular line and laser source being analyzed and taken into account. C2H2 IRPS signals in two different buffering gases, N2 and CO2, had been investigated in a tube furnace in order to estimate the spectral overlap coefficients and collision effects at different temperatures. The soot-volume fractions (SVF) in the studied flames were measured using a He-Ne laser-extinction method, and no obvious degrading of the IRPS technique due to the sooty environment has been observed in the flame with SVF up to ˜2×10-7. With the increase of flame equivalence ratios not only the SVF but also the C2H2 mole fractions increased.

  7. Shocking H2O Ice: The Role of Phase Changes during Impact Crater Formation

    NASA Astrophysics Data System (ADS)

    Stewart, S. T.; Senft, L. E.; Seifter, A.; Obst, A. W.

    2008-12-01

    New experimental data and cratering calculations illustrate the complex response of H2O ice to shock compression. We present peak and post-shock temperature measurements from shocked H2O ice. In experiments with shock pressures between 8 and 14 GPa, initially ~150 K ice is compressed to a supercritical state. In the time frame of the experiment, the supercritical H2O releases to the saturation vapor curve and does not achieve full decompression. Further decompression requires a significant volume expansion. In general, the time scale of expansion will depend on the internal energy and the surrounding conditions (e.g., confined or unconfined). The temperature data validate a new 5-Phase hydrocode equation of state model for H2O, which includes ice Ih, VI, VII, liquid, and vapor. Using the 5-Phase EOS, we model impact cratering onto icy satellites. After passage of the impact-generated shock wave, material beneath the growing transient crater has a layered composition: vapor, liquid, high- pressure phases (ices VII and VI), and ice Ih. The high pressure phases cannot fully decompress without a large volume increase. Thus, these phases initially unload to the pressure along the phase boundary; this pressurized region affects the excavation flow field. The changes in crater excavation lead to differences in crater size and amount of ejecta compared to excavation in a homogeneous target. The differences are significant for large craters (e.g., complex craters on Ganymede and Callisto). The modified excavation flow field also concentrates highly shocked material in the crater floor. In cases where a large, hot plug is buried during crater collapse, explosions occur as the material cools by transforming to vapor, producing features similar to central pits observed on Ganymede, Callisto, and Mars. The behavior of shocked H2O ice during decompression should lead to a variety of features that depend on the ambient conditions specific to each icy planetary body.

  8. Distillation of H2O from hard-frozen Martian permafrost

    NASA Technical Reports Server (NTRS)

    Zent, A. P.; Gwynne, O.

    1991-01-01

    The authors present a method for distillation of hard-frozen Martian permafrost. A cable-tool is drilled into hard frozem permafrost to a depth of 10 to 20 m. They calculate that a 10 m hole could be drilled in a few days. A 10 m shaft with a diameter equal to the bore is inserted into the hole, and a air tight tent-like structure is erected over the borehole. Photovoltaic cells mounted on the tent supply electrical energy that is dissipated in the shaft. Drilling power can be supplied by other sources. With 1000 watts, the shaft can be heated to near 350 K, producing relatively high temperatures in the vicinity of the borehole. Surrounding H2O is vaporized and diffuses up through the regolith. The authors calculate that a tent of a radius of no more than a few meters would intercept most of the H2O as it diffused to the surface. Calculations suggest that it would require perhaps 30 days to extract H2O from most of the volume drained by this technique. Assuming that the hard frozen regolith is no more than 10 percent ice, the author's calculate that that about 2890 kg of H2O could be extracted in 30 days. Since the nominal requirement for each crew member is about 5 kg/day, one such borehole might be expected to supply enough H2O to maintain a crew of 5 for perhaps 100 days. Additional engineering studies will be done to attempt to improve the capacity or efficiency of this method.

  9. Distillation of H2O from hard-frozen Martian permafrost

    NASA Astrophysics Data System (ADS)

    Zent, A. P.; Gwynne, O.

    The authors present a method for distillation of hard-frozen Martian permafrost. A cable-tool is drilled into hard frozem permafrost to a depth of 10 to 20 m. They calculate that a 10 m hole could be drilled in a few days. A 10 m shaft with a diameter equal to the bore is inserted into the hole, and a air tight tent-like structure is erected over the borehole. Photovoltaic cells mounted on the tent supply electrical energy that is dissipated in the shaft. Drilling power can be supplied by other sources. With 1000 watts, the shaft can be heated to near 350 K, producing relatively high temperatures in the vicinity of the borehole. Surrounding H2O is vaporized and diffuses up through the regolith. The authors calculate that a tent of a radius of no more than a few meters would intercept most of the H2O as it diffused to the surface. Calculations suggest that it would require perhaps 30 days to extract H2O from most of the volume drained by this technique. Assuming that the hard frozen regolith is no more than 10 percent ice, the author's calculate that that about 2890 kg of H2O could be extracted in 30 days. Since the nominal requirement for each crew member is about 5 kg/day, one such borehole might be expected to supply enough H2O to maintain a crew of 5 for perhaps 100 days. Additional engineering studies will be done to attempt to improve the capacity or efficiency of this method.

  10. Promotion of CO oxidation on PdO(101) by adsorbed H2O

    NASA Astrophysics Data System (ADS)

    Choi, Juhee; Pan, Li; Mehar, Vikram; Zhang, Feng; Asthagiri, Aravind; Weaver, Jason F.

    2016-08-01

    We investigated the influence of adsorbed H2O on the oxidation of CO on PdO(101) using temperature programmed reaction spectroscopy (TPRS), reflection absorption infrared spectroscopy (RAIRS) and density functional theory (DFT) calculations. We find that water inhibits CO adsorption on PdO(101) by site blocking, but also provides a more facile pathway for CO oxidation compared with the bare oxide surface. In the presence of adsorbed H2O, the oxidation of CO on PdO(101) produces a CO2 TPRS peak that is centered at a temperature ~ 50 K lower than the main CO2 TPRS peak arising from CO oxidation on clean PdO(101) (~ 330 vs. 380 K). RAIRS shows that CO continues to adsorb on atop-Pd sites of PdO(101) when H2O is co-adsorbed, and provides no evidence of other reactive intermediates. DFT calculations predict that the CO oxidation mechanism follows the same steps for CO adsorbed on PdO(101) with and without co-adsorbed H2O, wherein an atop-CO species recombines with an oxygen atom from the oxide surface lattice. According to DFT, hydrogen bonding interactions with adsorbed H2O species stabilize the carboxyl-like transition structure and intermediate that result from the initial recombination of CO and O on the PdO(101) surface. This stabilization lowers the energy barrier for CO oxidation on PdO(101) by ~ 10 kJ/mol, in good agreement with our experimental estimate.

  11. Hydrogen sulfide-based therapies: focus on H2S releasing NSAIDs.

    PubMed

    Fiorucci, Stefano; Santucci, Luca

    2011-04-01

    Nonsteroidal anti-inflammatory pain medications, commonly referred to as NSAIDs, are effective treatment for pain, fever and inflammation. However their use associates with a 4-6 fold increase in the risk of gastrointestinal bleeding. The basic mode of action of NSAIDs lies in the inhibition of cyclooxygenases (COXs), a family of enzymes involved in the generation of prostaglandins (PGs). The COX exists at least in two isoforms, COX-1 and COX-2, with PGs mediating inflammation at site of injury generated by the COX-2, while COX-1 produces PGs that are essential in maintaining integrity in the gastrointestinal tract. Selective inhibitors of COX-2, the coxibs, spare the gastrointestinal tract while exerting anti-inflammatory and analgesic effects. However, their use has been linked to an increased risk of thrombo-embolic events. Nitric oxide (NO) and hydrogen sulfide (H(2)S), are potent vasodilatory agents that maintain mucosal integrity in the gastrointestinal tract. In the last decade hybrid molecules that release NO or H(2)S have been coupled with non-selective NSAIDs to generate new classes of anti-inflammatory and analgesic agents with the potential to spare the gastrointestinal and cardiovascular system. These agents, the NO-releasing NSAIDs, or CINOD, and the H(2)S-releasing NSAIDs are currently investigated as a potential alternative to NSAIDs and coxibs. Naproxcinod has been the first, and so far the only, CINOD extensively investigated in clinical trials. Despite its promising profile, the approval of this drug was recently rejected by the Food and Drug Administration because the lack of long-term controlled studies. NSAIDs that release H(2)S as a mechanism to support an enhanced gastrointestinal and cardiovascular safety are being investigated in preclinical studies. Either naproxen or diclofenac coupled to an H(2)S releasing moiety has been reported to cause less gastrointestinal and cardiovascular injury than parent NSAIDs in preclinical models. PMID

  12. High Resolution Infrared Spectroscopy of CH_3F-({ortho}-H_2){n} Cluster in Solid {para}-H_2

    NASA Astrophysics Data System (ADS)

    Kawasaki, Hiroyuki; Mizoguchi, Asao; Kanamori, Hideto

    2015-06-01

    The absorption spectrum of the ν3 (C-F stretching) mode of CH_3F in solid {para}-H_2 by FTIR showed a series of equal interval peaks. Their interpretation was that the {}-th peak of this series was due to CH_3F-({ortho}-H_2){n} clusters which were formed CH_3F and {n}'s {ortho}-H_2 in first nearest neighbor sites of the {para}-H_2 crystal with {hcp} structure. In order to understand this system in more detail, we have studied these peaks, especially {n} = 0 - 3 corresponding to 1037 - 1041 wn, by using high-resolution and high-sensitive infrared quantum cascade (QC) laser spectroscopy. Before now, we found many peaks around each {n}-th peak of the cluster, which we didn't know their origins. We observed photochromic phenomenon of these peaks by taking an advantage of the high brightness of the laser. In this study, we focus on satellite series consisting of six peaks which locate at the lower energy side of each main peak. All the peaks showed a common red shouldered line profile, which corresponds to partly resolved transitions of {ortho}- and {para}- CH_3F. The spectral pattern and time behavior of the peaks may suggest that these satellite series originate from a family of CH_3F clusters involving {ortho}-H_2 in second nearest neighbor sites. A model function assuming this idea is used to resolve the observed spectrum into each Lorentzian component, and then some common features of the satellite peaks are extracted and the physical meanings of them will be discussed. K. Yoshioka and D. T. Anderson, J. Chem. Phys. 119 (2003) 4731-4742 A. R. W. McKellar, A. Mizoguchi, and H. Kanamori, J. Chem. Phys. 135 (2011) 124511 A. R. W. McKellar, A. Mizoguchi, and H. Kanamori, Phys. Chem. Chem. Phys. 13 (2011) 11587-11589.

  13. Biofilter for generation of concentrated sulphuric acid from H2S.

    PubMed

    Rabbani, K A; Charles, W; Kayaalp, A; Cord-Ruwisch, R; Ho, G

    2016-08-01

    Biofilters are used for the conversion of odorous hydrogen sulphide to odourless sulphate in wastewater treatment plants under the right conditions of moisture and pH. One of the consequences of maintaining the suitable pH and moisture content is the production of large volumes of weakly acidic leachate. This paper presents a biofilter with a maximum H2S elimination capacity of 16.3 g m(-3) h(-1) and removal efficiency greater than 95 % which produces small volumes (1 mL of solution L(-1) of reactor day(-1)) of sulphuric acid with a concentration greater than 5.5 M after 150 days of continuous operation. The concentrated sulphuric acid was produced by intermittently trickling a minimum amount of nutrient solution down the upflow biofilter which created a moisture and pH gradient within the biofilter resulting in an environment at the top for the bacterial conversion of H2S, while sulphuric acid was accumulated at the base. Genetic diversity profiling of samples taken from different sections of the biofilter confirms that the upper sections of the biofilter had the best environment for the bacteria to convert H2S to sulphate. The formation of concentrated sulphuric acid presents an opportunity for the recovery of sulphur from the waste stream as a usable product. PMID:27189453

  14. [Effect of Residual Hydrogen Peroxide on Hydrolysis Acidification of Sludge Pretreated by Microwave -