WorldWideScience

Sample records for carbonyl sulfide

  1. Stratospheric carbonyl sulfide (OCS) burden

    Science.gov (United States)

    Kloss, Corinna; Walker, Kaley A.; Deshler, Terry; von Hobe, Marc

    2015-04-01

    An estimation of the global stratospheric burden of carbonyl sulfide (OCS) calculated using satellite based measurements from the Atmospheric Chemistry Experiment - Fourier Transform Spectrometer (ACE-FTS) will be presented. OCS is the most abundant sulfur containing gas in the atmosphere in the absence of volcanic eruptions. With a long lifetime of 2-6 years it reaches the stratosphere where it is photolyzed and the sulfur oxidized and condensed to aerosols, contributing to the stratospheric aerosol layer. The aerosol layer is the one factor of the middle-atmosphere with a direct impact on the Earth's climate by scattering incoming solar radiation back to space. Therefore it is crucial to understand and estimate the different processes and abundances of the species contributing to the aerosol layer. However, the exact amount of OCS in the stratosphere has not been quantified yet. A study on the OCS mixing ratio distribution based on ACE-FTS data has already been made by Barkley et al. (2008), also giving an estimation for the total atmospheric OCS mass. ACE-FTS is an infrared solar occultation spectrometer providing high- resolution profile observations since 2004. In the scope of this work the focus lies on the stratospheric OCS burden, calculated by integrating the ACE profiles. A global overview on the stratospheric OCS amount in the past and present based on the ACE data as well as a look at regional and seasonal variability will be given. Furthermore, the results of this work will be useful for further studies on OCS fluxes and lifetimes, and in quantifying the contribution of OCS to the global stratospheric sulfur burden. Barkley et al., 2008, Geophys. Res. Lett., 35, L14810.

  2. Acute inhalation toxicity of carbonyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Benson, J.M.; Hahn, F.F.; Barr, E.B. [and others

    1995-12-01

    Carbonyl sulfide (COS), a colorless gas, is a side product of industrial procedures sure as coal hydrogenation and gasification. It is structurally related to and is a metabolite of carbon disulfide. COS is metabolized in the body by carbonic anhydrase to hydrogen sulfide (H{sub 2}S), which is thought to be responsible for COS toxicity. No threshold limit value for COS has been established. Results of these studies indicate COS (with an LC{sub 50} of 590 ppm) is slightly less acutely toxic than H{sub 2}S (LC{sub 50} of 440 ppm).

  3. Oxidation of Reduced Sulfur Species: Carbonyl Sulfide

    DEFF Research Database (Denmark)

    Glarborg, Peter; Marshall, Paul

    2013-01-01

    A detailed chemical kinetic model for oxidation of carbonyl sulfide (OCS) has been developed, based on a critical evaluation of data from the literature. The mechanism has been validated against experimental results from batch reactors, flow reactors, and shock tubes. The model predicts satisfact......A detailed chemical kinetic model for oxidation of carbonyl sulfide (OCS) has been developed, based on a critical evaluation of data from the literature. The mechanism has been validated against experimental results from batch reactors, flow reactors, and shock tubes. The model predicts...... satisfactorily oxidation of OCS over a wide range of stoichiometric air–fuel ratios (0.5 ≤λ≤7.3), temperatures (450–1700 K), and pressures (0.02–3.0 atm) under dry conditions. The governing reaction mechanisms are outlined based on calculations with the kinetic model. The oxidation rate of OCS is controlled...

  4. The Hydrolysis of Carbonyl Sulfide at Low Temperature: A Review

    Science.gov (United States)

    Zhao, Shunzheng; Yi, Honghong; Tang, Xiaolong; Jiang, Shanxue; Gao, Fengyu; Zhang, Bowen; Zuo, Yanran; Wang, Zhixiang

    2013-01-01

    Catalytic hydrolysis technology of carbonyl sulfide (COS) at low temperature was reviewed, including the development of catalysts, reaction kinetics, and reaction mechanism of COS hydrolysis. It was indicated that the catalysts are mainly involved metal oxide and activated carbon. The active ingredients which can load on COS hydrolysis catalyst include alkali metal, alkaline earth metal, transition metal oxides, rare earth metal oxides, mixed metal oxides, and nanometal oxides. The catalytic hydrolysis of COS is a first-order reaction with respect to carbonyl sulfide, while the reaction order of water changes as the reaction conditions change. The controlling steps are also different because the reaction conditions such as concentration of carbonyl sulfide, reaction temperature, water-air ratio, and reaction atmosphere are different. The hydrolysis of carbonyl sulfide is base-catalyzed reaction, and the force of the base site has an important effect on the hydrolysis of carbonyl sulfide. PMID:23956697

  5. Carbonyl Sulfide for Tracing Carbon Fluxes Field Campaign Report

    Energy Technology Data Exchange (ETDEWEB)

    Campbell, J. Elliott [Univ. of California, Merced, CA (United States); Berry, Joseph A. [Carnegie Inst. of Science, Stanford, CA (United States); Billesbach, Dave [Univ. of Nebraska, Lincoln, NE (United States); Torn, Margaret S [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Zahniser, Mark [Aerodyne Research, Inc., Billerica, MA (United States); Seibt, Ulrike [Univ. of California, Los Angeles, CA (United States); Maseyk, Kadmiel [Pierre and Marie Curie Univ., Paris (France)

    2016-04-01

    The April-June 2012 campaign was located at the U.S. Department of Energy (DOE)’s Atmospheric Radiation Measurement (ARM) Climate Research Facility Southern Great Plains (SGP) site Central Facility and had three purposes. One goal was to demonstrate the ability of current instrumentation to correctly measure fluxes of atmospheric carbonyl sulfide (COS). The approach has been describe previously as a critical approach to advancing carbon cycle science1,2, but requires further investigation at the canopy scale to resolve ecosystem processes. Previous canopy-scale efforts were limited to data rates of 1Hz. While 1 Hz measurements may work in a few ecosystems, it is widely accepted that data rates of 10 to 20 Hz are needed to fully capture the exchange of traces gases between the atmosphere and vegetative canopy. A second goal of this campaign was to determine if canopy observations could provide information to help interpret the seasonal double peak in airborne observations at SGP of CO2 and COS mixing ratios. A third goal was to detect potential sources and sinks of COS that must be resolved before using COS as a tracer of gross primary productivity (GPP).

  6. Characterization of aura tropospheric emissions spectrometer carbonyl sulfide retrievals

    Directory of Open Access Journals (Sweden)

    L. Kuai

    2013-07-01

    Full Text Available We present a description of the Tropospheric Emission Spectrometer (TES carbonyl sulfide (OCS retrieval algorithm, along with evaluation of the biases and uncertainties against aircraft profiles from the HIPPO campaign and data from the NOAA Mauna Loa site. In general, the OCS retrievals (1 have less than 1.0 degree of freedom for signals (DOFs, (2 are sensitive in the mid-troposphere with a peak sensitivity typically between 300 to 500 hPa, (3 but have much smaller systematic errors from temperature, CO2 and H2O calibrations relative to random errors from measurement noise. Here we estimate the monthly means from TES measurements averaged over multiple years so that random errors are reduced and useful information about OCS seasonal and latitudinal variability can be derived. With this averaging, TES OCS data are found to be consistent (within the calculated uncertainties with NOAA ground observations and HIPPO aircraft measurements. TES OCS data also captures the seasonal and latitudinal variations observed by these in situ data.

  7. Heterogeneous oxidation of carbonyl sulfide on mineral oxides

    Institute of Scientific and Technical Information of China (English)

    LIU YongChun; LIU JunFeng; HE Hong; YU YunBo; XUE Li

    2007-01-01

    Heterogeneous oxidation of carbonyl sulfide (OCS) on mineral oxides including SiO2, Fe2O3, CaO, MgO, ZnO and TiO2, which are the main components of atmospheric particles, were investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS), ion chromatography (IC), temperature-programmed desorption (TPD), X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) methods. The main products and intermediates of the heterogeneous oxidation of OCS on these oxides were identified with in situ DRIFTS and IC. The reaction mechanism and kinetics were also discussed. It is found that the reaction mechanism on these mineral oxides is the same as that on Al2O3 for the same final products and the intermediates at room temperature. Namely, OCS can be catalytically oxidized to produce surface SO42- species and gaseous CO2 through the surface hydrogen thiocarbonate (HSCO2-) and HSO3- species. The activity series for heterogeneous oxidation of OCS follows: Al2O3 ≈ CaO>MgO>TiO2 ≈ ZnO>Fe2O3>SiO2. The specific area, basic hydroxyl and surface basicity of these oxides have effect on the reactivity. This study suggests that heterogeneous reactions of OCS on mineral dust may be an unneglectable sink of OCS.

  8. The oceanic cycle and global atmospheric budget of carbonyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, P.S.

    1994-12-31

    A significant portion of stratospheric air chemistry is influenced by the existence of carbonyl sulfide (COS). This ubiquitous sulfur gas represents a major source of sulfur to the stratosphere where it is converted to sulfuric acid aerosol particles. Stratospheric aerosols are climatically important because they scatter incoming solar radiation back to space and are able to increase the catalytic destruction of ozone through gas phase reactions on particle surfaces. COS is primarily formed at the surface of the earth, in both marine and terrestrial environments, and is strongly linked to natural biological processes. However, many gaps in the understanding of the global COS cycle still exist, which has led to a global atmospheric budget that is out of balance by a factor of two or more, and a lack of understanding of how human activity has affected the cycling of this gas. The goal of this study was to focus on COS in the marine environment by investigating production/destruction mechanisms and recalculating the ocean-atmosphere flux.

  9. Tropical sources and sinks of carbonyl sulfide observed from space

    Science.gov (United States)

    Glatthor, N.; Höpfner, M.; Baker, I. T.; Berry, J.; Campbell, J. E.; Kawa, S. R.; Krysztofiak, G.; Leyser, A.; Sinnhuber, B.-M.; Stiller, G. P.; Stinecipher, J.; Clarmann, T.

    2015-11-01

    According to current budget estimations the seasonal variation of carbonyl sulfide (COS) is governed by oceanic release and vegetation uptake. Its assimilation by plants is assumed to be similar to the photosynthetic uptake of CO2 but, contrary to the latter process, to be irreversible. Therefore, COS has been suggested as cotracer of the carbon cycle. Observations of COS, however, are sparse, especially in tropical regions. We use the comprehensive data set of spaceborne measurements of the Michelson Interferometer for Passive Atmospheric Sounding to analyze its global distribution. Two major features are observed in the tropical upper troposphere around 250 hPa: enhanced amounts over the western Pacific and the Maritime Continent, peaking around 550 parts per trillion by volume (pptv) in boreal summer, and a seasonally varying depletion of COS extending from tropical South America to Africa. The large-scale COS depletion, which in austral summer amounts up to -40 pptv as compared to the rest of the respective latitude band, has not been observed before and reveals the seasonality of COS uptake through tropical vegetation. The observations can only be reproduced by global models, when a large vegetation uptake and a corresponding increase in oceanic emissions as proposed in several recent publications are assumed.

  10. Seasonal fluxes of carbonyl sulfide in a midlatitude forest

    Science.gov (United States)

    Commane, Róisín; Meredith, Laura K.; Baker, Ian T.; Berry, Joseph A.; Munger, J. William; Montzka, Stephen A.; Templer, Pamela H.; Juice, Stephanie M.; Zahniser, Mark S.; Wofsy, Steven C.

    2015-11-01

    Carbonyl sulfide (OCS), the most abundant sulfur gas in the atmosphere, has a summer minimum associated with uptake by vegetation and soils, closely correlated with CO2. We report the first direct measurements to our knowledge of the ecosystem flux of OCS throughout an annual cycle, at a mixed temperate forest. The forest took up OCS during most of the growing season with an overall uptake of 1.36 ± 0.01 mol OCS per ha (43.5 ± 0.5 g S per ha, 95% confidence intervals) for the year. Daytime fluxes accounted for 72% of total uptake. Both soils and incompletely closed stomata in the canopy contributed to nighttime fluxes. Unexpected net OCS emission occurred during the warmest weeks in summer. Many requirements necessary to use fluxes of OCS as a simple estimate of photosynthesis were not met because OCS fluxes did not have a constant relationship with photosynthesis throughout an entire day or over the entire year. However, OCS fluxes provide a direct measure of ecosystem-scale stomatal conductance and mesophyll function, without relying on measures of soil evaporation or leaf temperature, and reveal previously unseen heterogeneity of forest canopy processes. Observations of OCS flux provide powerful, independent means to test and refine land surface and carbon cycle models at the ecosystem scale.

  11. Atmospheric measurements of carbonyl sulfide, dimethyl sulfide, and carbon disulfide using the electron capture sulfur detector

    Science.gov (United States)

    Johnson, James E.; Bates, Timothy S.

    1993-01-01

    Measurements of atmospheric dimethyl sulfide (DMS), carbonyl sulfide (COS), and carbon disulfide (CS2) were conducted over the Atlantic Ocean on board the NASA Electra aircraft during the Chemical Instrumentation Test and Evaluation (CITE 3) project using the electron capture sulfur detector (ECD-S). The system employed cryogenic preconcentration of air samples, gas chromatographic separation, catalytic fluorination, and electron capture detection. Samples collected for DMS analysis were scrubbed of oxidants with NaOH impregnated glass fiber filters to preconcentration. The detection limits (DL) of the system for COS, DMS, and CS2 were 5, 5, and 2 ppt, respectively. COS concentrations ranged from 404 to 603 ppt with a mean of 489 ppt for measurements over the North Atlantic Ocean (31 deg N to 41 deg N), and from 395 to 437 ppt with a mean of 419 ppt for measurements over the Tropical Atlantic Ocean (11 deg S to 2 deg N). DMS concentrations in the lower marine boundary layer, below 600-m altitude, ranged from below DL to 150 ppt from flights over the North Atlantic, and from 9 to 104 ppt over the Tropical Atlantic. CS2 concentrations ranged from below DL to 29 ppt over the North Atlantic. Almost all CS2 measurements over the Tropical Atlantic were below DL.

  12. Hydrolysis of Carbonyl Sulfide in Binary Mixture of Diethylene Glycol Diethyl Ether and Water

    Institute of Scientific and Technical Information of China (English)

    李新学; 刘迎新; 魏雄辉

    2005-01-01

    The solubility and hydrolysis of carbonyl sulfide in binary mixture of diethylene glycol diethyl ether and water are studied as a function of composition. The use of an aqueous solution of diethylene glycol diethyl ether enhances the solubility and hydrolysis rate of carbonyl sulfide compared with that in pure water. The composition of the mixture with maximum hydrolysis rate varies with temperature. The thermophysical properties including density, viscosity, and surface tension as a function of composition at 20℃ under atmospheric pressure as well as liquid-liquid equilibrium (LLE) data over the temperature range from 28℃ to 90℃ are also measured for the binary mixture.

  13. Carbonyl sulfide exchange in soils for better estimates of ecosystem carbon uptake

    OpenAIRE

    Whelan, Mary E.; Hilton, Timothy W.; Berry, Joseph A; Berkelhammer, Max; Desai, Ankur R; Campbell, J. Elliott

    2016-01-01

    Carbonyl sulfide (COS) measurements are one of the emerging tools to better quantify gross primary production (GPP), the largest flux in the global carbon cycle. COS is a gas with a similar structure to CO2; COS uptake is thought to be a proxy for GPP. However, soils are a potential source or sink of COS. This study presents a framework for understanding soil–COS interactions. Excluding wetlands, most of the few observations of isolated soils that have been made show smal...

  14. Exchange of carbonyl sulfide (COS) between the atmosphere and various soils in China

    OpenAIRE

    Liu, J; C. Geng; Mu, Y; Zhang, Y.; Z. Xu; Wu, H

    2010-01-01

    Using a dynamic enclosure, the exchange rates of carbonyl sulfide (COS) between the atmosphere and 18 soils from 12 provinces in China were investigated. The emission or uptake of COS from the soils was highly dependent on the soil type, soil temperature, soil moisture, and atmospheric COS mixing ratio. In general, with the only exception being paddy soils, the soils in this investigation acted as sinks for atmospheric COS under wide ranges of soil temperature and soil moisture. Two intensive...

  15. Carbonyl sulfide exchange in soils for better estimates of ecosystem carbon uptake

    OpenAIRE

    M. E. Whelan; T. W. Hilton; J. A. Berry; M. Berkelhammer; A. R. Desai; Campbell, J. E.

    2015-01-01

    Carbonyl sulfide (COS) measurements are one of the emerging tools to better quantify gross primary production (GPP), the largest flux in the global carbon cycle. COS is a gas with a similar structure to CO2; COS uptake is thought to be a proxy for GPP. However, soils are a potential source or sink of COS. This study presents a framework for understanding soil-COS interactions. Excluding wetlands, most of the few observations of isolated soils that have been ...

  16. Exchange of carbonyl sulfide (COS) between the atmosphere and various soils in China

    OpenAIRE

    Liu, J; C. Geng; Mu, Y; Zhang, Y.; Wu, H

    2009-01-01

    Using a dynamic enclosure, the exchange fluxes of carbonyl sulfide (COS) between the atmosphere and 18 soils from 10 provinces in China were investigated. The emission or uptake of COS from the soils was highly dependent on the soil type, soil temperature, soil moisture, and atmospheric COS mixing ratio. In general, with the only exception being paddy soils, the soils in this investigation acted as sinks for atmospheric COS under wide ranges of soil temperature and soil moisture. Two i...

  17. Influence of Gas Components on the Formation of Carbonyl Sulfide over Water-Gas Shift Catalyst B303Q

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Water-gas shift reaction catalyst at lower temperature (200-400 ℃) may improve the conversion of carbon monoxide. But carbonyl sulfide was found to be present over the sulfided cobaltmolybdenum/alumina catalyst for water-gas shift reaction. The influences of temperature, space velocity,and gas components on the formation of carbonyl sulfide over sulfided cobalt-molybdenum/alumina catalyst B303Q at 200-400 ℃ were studied in a tubular fixed-bed quartz-glass reactor under simulated water-gas shift conditions. The experimental results showed that the yield of carbonyl sulfide over B303Q catalyst reached a maximum at 220 ℃ with the increase in temperature, sharply decreased with the increase in space velocity and the content of water vapor, increased with the increase in the content of carbon monoxide and carbon dioxide, and its yield increased and then reached a stable value with the increase in the content of hydrogen and hydrogen sulfide. The formation mechanism of carbonyl sulfide over B303Q catalyst at 200-400 ℃ was discussed on the basis of how these factors influence the formation of COS. The yield of carbonyl sulfide over B303Q catalyst at 200-400 ℃ was the combined result of two reactions, that is, COS was first produced by the reaction of carbon monoxide with hydrogen sulfide,and then the as-produced COS was converted to hydrogen sulfide and carbon dioxide by hydrolysis. The mechanism of COS formation is assumed as follows: sulfur atoms in the Co9Ss-MoS2/Al2O3 crystal lattice were easily removed and formed carbonyl sulfide with CO, and then hydrogen sulfide in the water-gas shift gas reacted with the crystal lattice oxygen atoms in CoO-MoO3/Al2O3 to form Co9Ss-MoS2/Al2O3.This mechanism for the formation of COS over water-gas shift catalyst B303Q is in accordance with the Mars-Van Krevelen's redox mechanism over metal sulfide.

  18. Carbonyl sulfide hydrolysis in Antarctic ice cores and an atmospheric history for the last 8000 years

    OpenAIRE

    Aydin, M.; Fudge, TJ; Verhulst, KR; Nicewonger, MR; Waddington, ED; Saltzman, Es

    2014-01-01

    ©2014. American Geophysical Union. All Rights Reserved. Carbonyl sulfide (COS) was measured in Antarctic ice core samples from the Byrd, Siple Dome, Taylor Dome, and West Antarctic Ice Sheet Divide sites covering the last 8000 years of the Holocene. COS levels decrease downcore in most of these ice cores. The magnitude of the downcore trends varies among the different ice cores and is related to the thermal histories of the ice sheet at each site. We hypothesize that this is due to the temper...

  19. Carbonyl sulfide detection with a thermoelectrically cooled midinfrared quantum cascade laser

    Science.gov (United States)

    Roller, Chad; Kosterev, Anatoliy A.; Tittel, Frank K.; Uehara, Kiyoji; Gmachl, Claire; Sivco, Deborah L.

    2003-11-01

    A compact absorption spectrometer with a midinfrared tunable quantum cascade laser operating at 4.86 μm (2054 cm-1) is used to measure lower concentrations of carbonyl sulfide (COS) in air. A detection sensitivity of ~30 parts in 109 of COS and the selectivity of two stable isotopes, 12C16O32S and 12C16O34S, are demonstrated. Specifically, the feasibility of detecting COS in expired human breath as a potential noninvasive medical diagnostic tool is investigated.

  20. Adiabatic mixed-field orientation of ground-state-selected carbonyl sulfide molecules

    CERN Document Server

    Kienitz, Jens S; Mullins, Terry; Długołęcki, Karol; González-Férez, Rosario; Küpper, Jochen

    2016-01-01

    We experimentally demonstrated strong adiabatic mixed-field orientation of carbonyl sulfide molecules (OCS) in their absolute ground state of $\\text{N}_{\\text{up}}/\\text{N}_{\\text{tot}}=0.882$. OCS was oriented in combined non-resonant laser and static electric fields inside a two-plate velocity map imaging spectrometer. The transition from non-adiabatic to adiabatic orientation for the rotational ground state was studied by varying the applied laser and static electric field. Above static electric field strengths of 10~kV/cm and laser intensities of $10^{11} \\text{W/cm}^2$ the observed degree of orientation reached a plateau. These results are in good agreement with computational solutions of the time-dependent Schr\\"odinger equation.

  1. Ionization of oriented carbonyl sulfide molecules by intense circularly polarized laser pulses

    DEFF Research Database (Denmark)

    Dimitrovski, Darko; Abu-Samha, Mahmoud; Madsen, Lars Bojer;

    2011-01-01

    We present combined experimental and theoretical results on strong-field ionization of oriented carbonyl sulfide molecules by circularly polarized laser pulses. The obtained molecular frame photoelectron angular distributions show pronounced asymmetries perpendicular to the direction of the......-dimensionally-oriented polar molecules, in particular asymmetries in the emission direction of the photoelectrons. In the following article [Phys. Rev. A 83, 023406 (2011)] the focus is to understand strong-field ionization from three-dimensionally-oriented asymmetric top molecules, in particular the suppression of electron...... molecular electric dipole moment. These findings are explained by a tunneling model invoking the laser-induced Stark shifts associated with the dipoles and polarizabilities of the molecule and its unrelaxed cation. The focus of the present article is to understand the strong-field ionization of one...

  2. Isotope effect in the carbonyl sulfide reaction with O(3P)

    DEFF Research Database (Denmark)

    Hattori, Shohei; Schmidt, Johan Albrecht; Mahler, Denise W.;

    2012-01-01

    The sulfur kinetic isotope effect (KIE) in the reaction of carbonyl sulfide (OCS) with O((3)P) was studied in relative rate experiments at 298 ± 2 K and 955 ± 10 mbar. The reaction was carried out in a photochemical reactor using long path FTIR detection, and data were analyzed using a nonlinear...... basis of isotopic analysis, OCS is an acceptable source of background stratospheric sulfate aerosol....

  3. Quantification of A Tropical Missing Source From Ocean For The Carbonyl Sulfide Global Budget

    Science.gov (United States)

    Kuai, Le; Worden, John; Campbell, Elliott; Kulawik, Susan; Lee, Meemong; Montzka, Stephen; Berry, Joe; Baker, Ian; Denning, Scott; Kawa, Randy; Bian, Huisheng; Yung, Yuk

    2015-04-01

    Quantifying the carbonyl sulfide (OCS) surface fluxes contributes to the understanding of both sulfur cycle and carbon cycle. Although the major sources and sinks of OCS are well recognized, the uncertainties of individual types of the fluxes remain large. With the understanding of a large underestimate of ecosystem uptake, it suggests a large missing ocean source over tropical region to compensate the increased sink. However before AURA Tropospheric Emissions Spectrometer (TES) OCS data is released, no direct measurements have been taken to test this hypothesis. In this study, we performed a flux inversion to update the fluxes from TES OCS. Then we compared three experimental GEOS-Chem forward model runs driven by different fluxes based on TES inversion to HIPPO aircraft estimates in free troposphere and also to NOAA near surface observations. The TES data supports the hypothesis that a large source from tropical ocean is missing in the current OCS global budget and suggests that the source is even larger than that proposed in Berry et al., (2013). Consequently, it leads to a larger land uptake and increase the estimates of GPP. TES data also suggests the missing oceanic source is not symmetric about equator. It is strong and distributed further north of the equator (to 40°N) but weak and narrow south of the equator (to 20°S).

  4. Estimate of carbonyl sulfide tropical oceanic surface fluxes using Aura Tropospheric Emission Spectrometer observations

    Science.gov (United States)

    Kuai, Le; Worden, John R.; Campbell, J. Elliott; Kulawik, Susan S.; Li, King-Fai; Lee, Meemong; Weidner, Richard J.; Montzka, Stephen A.; Moore, Fred L.; Berry, Joe A.; Baker, Ian; Denning, A. Scott; Bian, Huisheng; Bowman, Kevin W.; Liu, Junjie; Yung, Yuk L.

    2015-10-01

    Quantifying the carbonyl sulfide (OCS) land/ocean fluxes contributes to the understanding of both the sulfur and carbon cycles. The primary sources and sinks of OCS are very likely in a steady state because there is no significant observed trend or interannual variability in atmospheric OCS measurements. However, the magnitude and spatial distribution of the dominant ocean source are highly uncertain due to the lack of observations. In particular, estimates of the oceanic fluxes range from approximately 280 Gg S yr-1 to greater than 800 Gg S yr-1, with the larger flux needed to balance a similarly sized terrestrial sink that is inferred from NOAA continental sites. Here we estimate summer tropical oceanic fluxes of OCS in 2006 using a linear flux inversion algorithm and new OCS data acquired by the Aura Tropospheric Emissions Spectrometer (TES). Modeled OCS concentrations based on these updated fluxes are consistent with HIAPER Pole-to-Pole Observations during 4th airborne campaign and improve significantly over the a priori model concentrations. The TES tropical ocean estimate of 70 ± 16 Gg S in June, when extrapolated over the whole year (about 840 ± 192 Gg S yr-1 ), supports the hypothesis proposed by Berry et al. (2013) that the ocean flux is in the higher range of approximately 800 Gg S yr-1.

  5. Observations of the uptake of carbonyl sulfide (COS by trees under elevated atmospheric carbon dioxide concentrations

    Directory of Open Access Journals (Sweden)

    L. Sandoval-Soto

    2012-02-01

    Full Text Available Global change affects ecosystems to adapt to elevated atmospheric concentrations of carbon dioxide (CO2. We understand that carbonyl sulfide (COS, a trace gas which is involved in building up the stratospheric sulfate aerosol layer, is taken up by vegetation with the same triad of the enzmyes which are metabolizing the CO2, i.e. Ribulose-1,5-bisphosphate Carboxylase-Oxygenase (Rubisco, Phosphoenolpyruvate Carboxylase (PEP-Co and carbonic anhydrase (CA. Therefore, we discuss a physiological/biochemical adaptation of these enzymes to affect the sink strength of vegetation for COS. We investigated the adaption of two European tree species, Fagus sylvatica and Quercus ilex, grown inside chambers under elevated CO2 and determined the exchange characteristics and the content of CA after a 1–2 yr period of adaption from 350 ppm to 800 ppm CO2. We could demonstrate that the COS compensation point, the CA activity and the deposition velocities may change and cause a decrease of the COS uptake by plant ecosystems. As a consequence, the atmospheric COS level may rise leading to higher input of this trace gas into the stratosphere and causing a higher energy reflection by the stratospheric sulfur aerosol into space, thus counteracting the direct radiative forcing by the tropospheric COS.

  6. Controlling variables for the uptake of atmospheric carbonyl sulfide by soil

    Science.gov (United States)

    Kesselmeier, J.; Teusch, N.; Kuhn, U.

    1999-05-01

    Soil samples from arable land were investigated for their exchange of carbonyl sulfide (COS) with the atmosphere under controlled conditions using dynamic cuvettes in a climate chamber. The investigated soil type acted as a significant sink for the trace gas COS. Atmospheric COS mixing ratios, temperature, and soil water content were found to be the physicochemical parameters controlling the uptake. Emission was never observed under conditions representative of a natural environment. The observed compensation point (i.e., an ambient concentration where the consumption and production balance each other and the net flux is zero) for the uptake was about 53 parts per trillion. Uptake rates ranged between 1.5 and 10.3 pmol m-2 s-1. The consumption of COS by the soil sample depended on the physiological activity of the microorganisms in the soil, as indicated by a clear optimum temperature and by a drastic inhibition in the presence of the enzyme inhibitor 6-ethoxy-2-benzothiazole-2-sulfonamide (EZ), a specific inhibitor for carbonic anhydrase.

  7. Exchange of carbonyl sulfide (COS between the atmosphere and various soils in China

    Directory of Open Access Journals (Sweden)

    J. Liu

    2009-11-01

    Full Text Available Using a dynamic enclosure, the exchange fluxes of carbonyl sulfide (COS between the atmosphere and 18 soils from 10 provinces in China were investigated. The emission or uptake of COS from the soils was highly dependent on the soil type, soil temperature, soil moisture, and atmospheric COS mixing ratio. In general, with the only exception being paddy soils, the soils in this investigation acted as sinks for atmospheric COS under wide ranges of soil temperature and soil moisture. Two intensively investigated wheat soils and one forest soil, had optimal soil temperatures for COS uptake of around 15°C, and the optimal soil water content varied from 13 to 58%. The two paddy soils, exponentially COS emission fluxes increased with increasing soil temperature, and decreased COS emission fluxes with increased soil water content. However, negligible emission was found when the paddy soils were under waterlogging status. The observed compensation points for various soils were different and increased significantly with soil temperature. The laboratory simulation agreed with the preliminary field measurements for the paddy soil in Jiaxing, Zhejiang province.

  8. The flux of carbonyl sulfide and carbon disulfide between the atmosphere and a spruce forest

    Directory of Open Access Journals (Sweden)

    X. Xu

    2002-01-01

    Full Text Available Turbulent fluxes of carbonyl sulfide (COS and carbon disulfide (CS2 were measured over a spruce forest in Central Germany using the relaxed eddy accumulation (REA technique. A REA sampler was developed and validated using simultaneous measurements of CO2 fluxes by REA and by eddy correlation. REA measurements were conducted during six campaigns covering spring, summer, and fall between 1997 and 1999. Both uptake and emission of COS and CS2 by the forest were observed, with deposition occurring mainly during the sunlit period and emission mainly during the dark period. On the average, however, the forest acts as a sink for both gases. The average fluxes for COS and CS2 are  -93 ± 11.7 pmol m-2 s-1 and  -18 ± 7.6 pmol m-2 s-1, respectively. The fluxes of both gases appear to be correlated to photosynthetically active radiation and to the CO2 and chem{H_2O} fluxes, supporting the idea that the air-vegetation exchange of both gases is controlled by stomata. An uptake ratio COS/CO2 of 10 ± 1.7 pmol m mol-1 has been derived from the regression line for the correlation between the COS and CO2 fluxes. This uptake ratio, if representative for the global terrestrial net primary production, would correspond to a sink of 2.3 ± 0.5 Tg COS yr-1.

  9. Role of the oceans in the atmospheric cycle of carbonyl sulfide

    International Nuclear Information System (INIS)

    Carbonyl sulfide (OCS) is both the dominant sulfur gas in the remote troposphere and, along with volcanoes, a major source of sulfur for the stratospheric sulfate layer. Prior to this work the ocean was regarded as a major sink for atmospheric OCS. The purpose of this study has been to assess the magnitude of the global air-sea flux of OCS. The author designed an analytical system which was centered around a Varian-3700 gas chromatograph with a flame-photometric detector. To increase the sensitivity of the detector, the hydrogen gas for the flame was doped with sulfur hexafluoride. Air samples were concentrated in a liquid nitrogen cooled freeze-out loop, then injected into the gas chromatograph. Water samples purged with sulfur-free zero-air which was analyzed similarly. He also built a permeation tube system for chemical standardization. This equipment was taken on two oceanographic cruises on the Pacific Ocean, one in the spring of 1983 and a second in the spring of 1983. Both of these cruises included measurements of air and seawater concentrations of OCS from the equator to the Aleutian Islands. The Henry's law constant of solubility for OCS was measured in the laboratory for filtered and boiled seawater at three temperatures

  10. Eddy covariance carbonyl sulfide flux measurements with a quantum cascade laser absorption spectrometer

    Science.gov (United States)

    Gerdel, Katharina; Spielmann, Felix M.; Hammerle, Albin; Wohlfahrt, Georg

    2016-04-01

    Carbonyl sulfide (COS) is the most abundant sulfur containing trace gas present in the troposphere at concentrations of around 500 ppt. Recent interest in COS by the ecosystem-physiological community has been sparked by the fact that COS co-diffuses into plant leaves pretty much the same way as carbon dioxide (CO2) does, but in contrast to CO2, COS is not known to be emitted by plants. Thus uptake of COS by vegetation has the potential to be used as a tracer for canopy gross photosynthesis, which cannot be measured directly, however represents a key term in the global carbon cycle. Since a few years, quantum cascade laser absorption spectrometers (QCLAS) are commercially available with the precision, sensitivity and time response suitable for eddy covariance (EC) flux measurements. While there exist a handful of published reports on EC flux measurements in the recent literature, no rigorous investigation of the applicability of QCLAS for EC COS flux measurements has been carried out so far, nor have been EC processing and QA/QC steps developed for carbon dioxide and water vapor flux measurements within FLUXNET been assessed for COS. The aim of this study is to close this knowledge gap, to discuss critical steps in the post-processing chain of COS EC flux measurements and to devise best-practice guidelines for COS EC flux data processing. To this end we collected EC COS (and CO2, H2O and CO) flux measurements above a temperate mountain grassland in Austria over the vegetation period 2015 with a commercially available QCLAS. We discuss various aspects of EC data post-processing, in particular issues with the time-lag estimation between sonic anemometer and QCLAS signals and QCLAS time series detrending, as well as QA/QC, in particular flux detection limits, random flux uncertainty, the interaction of various processing steps with common EC QA/QC filters (e.g. detrending and stationarity tests), u*-filtering, etc.

  11. Variability of atmospheric carbonyl sulfide at a semi-arid urban site in western India.

    Science.gov (United States)

    Mallik, Chinmay; Chandra, Naveen; Venkataramani, S; Lal, Shyam

    2016-05-01

    Atmospheric carbonyl sulfide (COS) is a major precursor for sulfate aerosols that play a critical role in climate regulation. Recent studies have highlighted the importance of COS measurements as a reliable means to constrain biospheric carbon assimilation. In a scenario of limited availability of COS data around the globe, we present gas-chromatographic measurements of atmospheric COS mixing ratios over Ahmedabad, a semi-arid, urban region in western India. These measurements, being reported for the first time over an Indian site, enable us to understand the diurnal and seasonal variation in atmospheric COS with respect to its natural, anthropogenic and photochemical sources and sinks. The annual mean COS mixing ratio over Ahmedabad is found to be 0.83±0.43ppbv, which is substantially higher than free tropospheric values for the northern hemisphere. Inverse correlation of COS with soil and skin temperature, suggests that the dry soil of the semi-arid study region is a potential sink for atmospheric COS. Positive correlations of COS with NO2 and CO during post-monsoon and the COS/CO slope of 0.78pptv/ppbv reveals influence of diesel combustion and tire wear. The highest concentrations of COS are observed during pre-monsoon; COS/CO2 slope of 44.75pptv/ppmv combined with information from air mass back-trajectories reveal marshy wetlands spanning over 7500km(2) as an important source of COS in Ahmedabad. COS/CO2 slopes decrease drastically (8.28pptv/ppmv) during post-monsoon due to combined impact of biospheric uptake and anthropogenic emissions. PMID:26907740

  12. Carbonyl sulfide exchange in soils for better estimates of ecosystem carbon uptake

    Directory of Open Access Journals (Sweden)

    M. E. Whelan

    2015-08-01

    Full Text Available Carbonyl sulfide (COS measurements are one of the emerging tools to better quantify gross primary production (GPP, the largest flux in the global carbon cycle. COS is a gas with a similar structure to CO2; COS uptake is thought to be a proxy for GPP. However, soils are a potential source or sink of COS. This study presents a framework for understanding soil-COS interactions. Excluding wetlands, most of the few observations of isolated soils that have been made show small uptake of atmospheric COS. Recently, a series of studies at an agricultural site in the central United States found soil COS production under hot conditions an order of magnitude greater than fluxes at other sites. To investigate the extent of this phenomenon, soils were collected from 5 new sites and incubated in a variety of soil moisture and temperature states. We found that soils from a desert, an oak savannah, a deciduous forest, and a rainforest exhibited small COS fluxes, behavior resembling previous studies. However, soil from an agricultural site in Illinois, > 800 km away from the initial central US study site, demonstrated comparably large soil fluxes under similar conditions. These new data suggest that, for the most part, soil COS interaction is negligible compared to plant uptake of COS. We present a model that anticipates the large agricultural soil fluxes so that they may be taken into account. While COS air-monitoring data are consistent with the dominance of plant uptake, improved interpretation of these data should incorporate the soil flux parameterizations suggested here.

  13. Carbonyl sulfide exchange in a temperate loblolly pine forest grown under ambient and elevated CO2

    Directory of Open Access Journals (Sweden)

    B. C. Sive

    2009-08-01

    Full Text Available Vegetation, soil and ecosystem level carbonyl sulfide (COS exchange was observed at Duke Forest, a temperate loblolly pine forest, grown under ambient (Ring 1, R1 and elevated (Ring 2, R2 carbon dioxide (CO2. During calm meteorological conditions, ambient COS mixing ratios at the top of the forest canopy followed a distinct diurnal pattern in both CO2 growth regimes, with maximum COS mixing ratios during the day (R1=380±4 pptv and R2=373±3 pptv, daytime mean ±standard error and minimums at night (R1=340±6 pptv and R2=346±5 pptv, nighttime mean ±standard error reflecting a significant nighttime sink. Nocturnal vegetative uptake (−11 to −21 pmol m−2 s−1, negative values indicate uptake from the atmosphere dominated nighttime net ecosystem COS flux estimates (−10 to −30 pmol m−2 s−1 in both CO2 regimes. In comparison, soil uptake (−0.8 to −1.7 pmol m−2 s−1 was a minor component of net ecosystem COS flux. In both CO2 regimes, loblolly pine trees exhibited substantial COS consumption overnight (50% of daytime rates that was independent of CO2 assimilation. This suggests current estimates of the global vegetative COS sink, which assume that COS and CO2 are consumed simultaneously, may need to be reevaluated. Ambient COS mixing ratios, species specific diurnal patterns of stomatal conductance, temperature and canopy position were the major factors influencing the vegetative COS flux at the branch level. While variability in branch level vegetative COS consumption measurements in ambient and enhanced CO2 environments could not be attributed to CO2 enrichment effects, estimates of net ecosystem COS flux based on ambient canopy mixing ratio measurements suggest less nighttime uptake of COS in R2, the CO2 enriched environment.

  14. Carbonyl sulfide exchange in a temperate loblolly pine forest grown under ambient and elevated CO2

    Directory of Open Access Journals (Sweden)

    B. C. Sive

    2010-01-01

    Full Text Available Vegetation, soil and ecosystem level carbonyl sulfide (COS exchange was observed at Duke Forest, a temperate loblolly pine forest, grown under ambient (Ring 1, R1 and elevated (Ring 2, R2 CO2. During calm meteorological conditions, ambient COS mixing ratios at the top of the forest canopy followed a distinct diurnal pattern in both CO2 growth regimes, with maximum COS mixing ratios during the day (R1=380±4 pptv and R2=373±3 pptv, daytime mean ± standard error and minimums at night (R1=340±6 pptv and R2=346±5 pptv, nighttime mean ± standard error reflecting a significant nighttime sink. Nocturnal vegetative uptake (−11 to −21 pmol m−2s−1, negative values indicate uptake from the atmosphere dominated nighttime net ecosystem COS flux estimates (−10 to −30 pmol m−2s−1 in both CO2 regimes. In comparison, soil uptake (−0.8 to −1.7 pmol m−2 s−1 was a minor component of net ecosystem COS flux. In both CO2 regimes, loblolly pine trees exhibited substantial COS consumption overnight (50% of daytime rates that was independent of CO2 assimilation. This suggests current estimates of the global vegetative COS sink, which assume that COS and CO2 are consumed simultaneously, may need to be reevaluated. Ambient COS mixing ratios, species specific diurnal patterns of stomatal conductance, temperature and canopy position were the major factors influencing the vegetative COS flux at the branch level. While variability in branch level vegetative COS consumption measurements in ambient and enhanced CO2 environments could not be attributed to CO2 enrichment effects, estimates of net ecosystem COS flux based on ambient canopy mixing ratio measurements suggest less nighttime uptake of COS in R2, the CO2 enriched environment.

  15. Carbonyl sulfide exchange in soils for better estimates of ecosystem carbon uptake

    Science.gov (United States)

    Whelan, Mary E.; Hilton, Timothy W.; Berry, Joseph A.; Berkelhammer, Max; Desai, Ankur R.; Campbell, J. Elliott

    2016-03-01

    Carbonyl sulfide (COS) measurements are one of the emerging tools to better quantify gross primary production (GPP), the largest flux in the global carbon cycle. COS is a gas with a similar structure to CO2; COS uptake is thought to be a proxy for GPP. However, soils are a potential source or sink of COS. This study presents a framework for understanding soil-COS interactions. Excluding wetlands, most of the few observations of isolated soils that have been made show small uptake of atmospheric COS. Recently, a series of studies at an agricultural site in the central United States found soil COS production under hot conditions an order of magnitude greater than fluxes at other sites. To investigate the extent of this phenomenon, soils were collected from five new sites and incubated in a variety of soil moisture and temperature states. We found that soils from a desert, an oak savannah, a deciduous forest, and a rainforest exhibited small COS fluxes, behavior resembling previous studies. However, soil from an agricultural site in Illinois, > 800 km away from the initial central US study site, demonstrated comparably large soil fluxes under similar conditions. These new data suggest that, for the most part, soil COS interaction is negligible compared to plant uptake of COS. We present a model that anticipates the large agricultural soil fluxes so that they may be taken into account. While COS air-monitoring data are consistent with the dominance of plant uptake, improved interpretation of these data should incorporate the soil flux parameterizations suggested here.

  16. Sulfur Isotopic Fractionation of Carbonyl Sulfide during Degradation by Soil Bacteria.

    Science.gov (United States)

    Kamezaki, Kazuki; Hattori, Shohei; Ogawa, Takahiro; Toyoda, Sakae; Kato, Hiromi; Katayama, Yoko; Yoshida, Naohiro

    2016-04-01

    We performed laboratory incubation experiments on the degradation of gaseous phase carbonyl sulfide (OCS) by soil bacteria to determine its sulfur isotopic fractionation constants ((34)ε). Incubation experiments were conducted using strains belonging to the genera Mycobacterium, Williamsia, and Cupriavidus isolated from natural soil environments. The (34)ε values determined were -3.67 ± 0.33‰, -3.99 ± 0.19‰, -3.57 ± 0.22‰, and -3.56 ± 0.23‰ for Mycobacterium spp. strains THI401, THI402, THI404, and THI405; -3.74 ± 0.29‰ for Williamsia sp. strain THI410; and -2.09 ± 0.07‰ and -2.38 ± 0.35‰ for Cupriavidus spp. strains THI414 and THI415. Although OCS degradation rates divided by cell numbers (cell-specific activity) were different among strains of the same genus, the (34)ε values for same genus showed no significant differences. Even though the numbers of bacterial species examined were limited, our results suggest that (34)ε values for OCS bacterial degradation depend not on cell-specific activities, but on genus-level biological differences, suggesting that (34)ε values are dependent on enzymatic and/or membrane properties. Taking our (34)ε values as representative for bacterial OCS degradation, the expected atmospheric changes in δ(34)S values of OCS range from 0.5‰ to 0.9‰, based on previously reported decreases in OCS concentrations at Mt. Fuji, Japan. Consequently, tropospheric observation of δ(34)S values for OCS coupled with (34)ε values for OCS bacterial degradation can potentially be used to investigate soil as an OCS sink. PMID:26967120

  17. Observations of the uptake of carbonyl sulfide (COS by trees under elevated atmospheric carbon dioxide concentrations

    Directory of Open Access Journals (Sweden)

    L. Sandoval-Soto

    2012-08-01

    Full Text Available Global change forces ecosystems to adapt to elevated atmospheric concentrations of carbon dioxide (CO2. We understand that carbonyl sulfide (COS, a trace gas which is involved in building up the stratospheric sulfate aerosol layer, is taken up by vegetation with the same triad of the enzymes which are metabolizing CO2, i.e. ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco, phosphoenolpyruvate carboxylase (PEP-Co and carbonic anhydrase (CA. Therefore, we discuss a physiological/biochemical acclimation of these enzymes affecting the sink strength of vegetation for COS. We investigated the acclimation of two European tree species, Fagus sylvatica and Quercus ilex, grown inside chambers under elevated CO2, and determined the exchange characteristics and the content of CA after a 1–2 yr period of acclimation from 350 ppm to 800 ppm CO2. We demonstrate that a compensation point, by definition, does not exist. Instead, we propose to discuss a point of uptake affinity (PUA. The results indicate that such a PUA, the CA activity and the deposition velocities may change and may cause a decrease of the COS uptake by plant ecosystems, at least as long as the enzyme acclimation to CO2 is not surpassed by an increase of atmospheric COS. As a consequence, the atmospheric COS level may rise causing an increase of the radiative forcing in the troposphere. However, this increase is counterbalanced by the stronger input of this trace gas into the stratosphere causing a stronger energy reflection by the stratospheric sulfur aerosol into space (Brühl et al., 2012. These data are very preliminary but may trigger a discussion on COS uptake acclimation to foster measurements with modern analytical instruments.

  18. Litter dominates surface fluxes of carbonyl sulfide in a Californian oak woodland

    Science.gov (United States)

    Sun, Wu; Maseyk, Kadmiel; Lett, Céline; Seibt, Ulli

    2016-02-01

    Carbonyl sulfide (COS) is a promising tracer for partitioning terrestrial photosynthesis and respiration from net carbon fluxes, based on its daytime co-uptake alongside CO2 through leaf stomata. Because ecosystem COS fluxes are the sum of plant and soil fluxes, using COS as a photosynthesis tracer requires accurate knowledge of soil COS fluxes. At an oak woodland in Southern California, we monitored below-canopy surface (soil + litter) COS and CO2 fluxes for 40 days using chambers and laser spectroscopy. We also measured litter fluxes separately and used a depth-resolved diffusion-reaction model to quantify the role of litter uptake in surface COS fluxes. Soil and litter were primarily COS sinks, and mean surface COS uptake was small (˜1 pmol m-2 s-1). After rainfall, uptake rates were higher (6-8 pmol m-2 s-1), and litter contributed a significant fraction (up to 90%) to surface fluxes. We observed rapid concurrent increases in COS uptake and CO2 efflux following the onset of rain. The patterns were similar to the Birch effect widely documented for soils; however, both COS and CO2 flux increases originated mainly in the litter. The synchronous COS-CO2 litter Birch effect indicates that it results from a rapid increase in litter microbial activity after rainfall. We expect that the drying-rewetting cycles typical for mediterranean and other semiarid ecosystems create a pronounced seasonality in surface COS fluxes. Our results highlight that litter uptake is an important component of surface COS exchange that needs to be taken into account in ecosystem COS budgets and model simulations.

  19. Soil atmosphere exchange of Carbonyl Sulfide (COS regulated by diffusivity depending on water-filled pore space

    Directory of Open Access Journals (Sweden)

    H. Van Diest

    2007-10-01

    Full Text Available The exchange of carbonyl sulfide (COS between soil and the atmosphere was investigated for three arable soils from Germany, China and Finland and one forest soil from Siberia for parameterization in the relation to ambient carbonyl sulfide (COS concentration, soil water content (WC and air temperature. All investigated soils acted as significant sinks for COS. A clear and distinct uptake optimum was found for the German, Chinese, Finnish and Siberian soils at 11.5%, 9%, 11.5%, and 9% soil WC, respectively, indicating that the soil WC acts as an important biological and physical parameter for characterizing the exchange of COS between soils and the atmosphere. Different optima of deposition velocities (Vd as observed for the Chinese, Finnish and Siberian boreal soil types in relation to their soil WC, aligned at 19% in relation to the water-filled pore space (WFPS, indicating the dominating role of gas diffusion. This interpretation was supported by the linear correlation between Vd and bulk density. We suggest that the uptake of COS depends on the diffusivity dominated by WFPS, a parameter depending on soil WC, soil structure and porosity of the soil.

  20. Thioozonide decomposition: sulfur and oxygen atom transfer. Evidence for the formation of a carbonyl O-sulfide intermediate

    Energy Technology Data Exchange (ETDEWEB)

    Matturro, M.G.; Reynolds, R.P.; Kastrup, R.V.; Pictroski, C.F.

    1986-05-14

    The chemistry of ozonides is of considerable interest from a practical and theoretical viewpoint. Thioozonide 1, formally the monosulfur-substituted ozonide of dimethylcyclobutadiene, has been proposed as an intermediate in the room temperature photooxidation of 2,5-dimethylthiophene. Subsequent low-temperature studies confirmed this structural assignment. When 1 is allowed to warm to room temperature, it rearranges to a mixture of sulfine 2 and cis- and trans-3-hexene-2,5-diones (3c and 3t). Recent examination of the thermal decomposition of 1 has led to a proposed mechanism involving a carbonyl sulfide 4 as an intermediate along the sulfur expulsion pathway to 3c; however, no experimental support for this hypothesis was given. Carbonyl O-sulfides have also been implicated as intermediates from the photolysis of oxathiiranes. The authors report evidence for the formation of 4 during the decomposition of 1 and that elemental sulfur (S/sub 8/) is formed during the reaction by concatenation of sulfur atoms or fragments (S/sub 2/, S/sub 3/, etc.).

  1. Soil atmosphere exchange of carbonyl sulfide (COS regulated by diffusivity depending on water-filled pore space

    Directory of Open Access Journals (Sweden)

    H. Van Diest

    2008-04-01

    Full Text Available The exchange of carbonyl sulfide (COS between soil and the atmosphere was investigated for three arable soils from Germany, China and Finland and one forest soil from Siberia for parameterization in the relation to ambient carbonyl sulfide (COS concentration, soil water content (WC and air temperature. All investigated soils acted as sinks for COS. A clear and distinct uptake optimum was found for the German, Chinese, Finnish and Siberian soils at 11.5%, 9%, 11.5%, and 9% soil WC, respectively, indicating that the soil WC acts as an important biological and physical parameter for characterizing the exchange of COS between soils and the atmosphere. Different optima of deposition velocities (Vd as observed for the Chinese, Finnish and Siberian boreal soil types in relation to their soil WC, aligned at 19% in relation to the water-filled pore space (WFPS, indicating the dominating role of gas diffusion. This interpretation was supported by the linear correlation between Vd and bulk density. We suggest that the uptake of COS depends on the diffusivity dominated by WFPS, a parameter depending on soil WC, soil structure and porosity of the soil.

  2. Overcoming uncertainty with carbonyl sulfide-based GPP estimates: observing and modeling soil COS fluxes in terrestrial ecosystems

    Science.gov (United States)

    Whelan, M.; Hilton, T. W.; Berry, J. A.; Berkelhammer, M. B.; Desai, A. R.; Rastogi, B.; Campbell, J. E.

    2015-12-01

    Significant carbonyl sulfide (COS) exchange by soils limits the applicability of net ecosystem COS flux observations as a proxy for stomatal trace gas exchange. High frequency measurements of COS over urban and natural ecosystems offer a potential window into processes regulating the carbon and water cycle: photosynthetic carbon uptake and stomatal conductance. COS diffuses through plant stomata and is irreversibly consumed by enzymes involved in photosynthesis. In certain environments, the magnitude of soil COS fluxes may constitute one-quarter of COS uptake by plants. Here we present a way of anticipating conditions when anomalously large soil COS fluxes are likely to occur and be taken into account. Previous studies have pointed to either a tendency for soil uptake of COS from the atmosphere with a soil moisture optimum, or exponential COS production coincident with temperature. Data from field and laboratory studies were used to deconvolve the two processes. CO2 and COS fluxes were observed from forest, desert, grassland, and agricultural soils under a range of temperature and soil moisture conditions. We demonstrate how to estimate temperature and soil moisture impacts on COS soil production based on our cross-site incubations. By building a model of soil COS exchange that combines production and consumption terms, we offer a framework for interpreting the two disparate conclusions about soil COS exchange in previous studies. Such a construction should be used in ecosystem and continental scale modeling of COS fluxes to anticipate where the influence of soil COS exchange needs to be accounted for, resulting in greater utility of carbonyl sulfide as a tracer of plant physiological processes.

  3. Carbonyl sulfide hydrolase from Thiobacillus thioparus strain THI115 is one of the β-carbonic anhydrase family enzymes.

    Science.gov (United States)

    Ogawa, Takahiro; Noguchi, Keiichi; Saito, Masahiko; Nagahata, Yoshiko; Kato, Hiromi; Ohtaki, Akashi; Nakayama, Hiroshi; Dohmae, Naoshi; Matsushita, Yasuhiko; Odaka, Masafumi; Yohda, Masafumi; Nyunoya, Hiroshi; Katayama, Yoko

    2013-03-13

    Carbonyl sulfide (COS) is an atmospheric trace gas leading to sulfate aerosol formation, thereby participating in the global radiation balance and ozone chemistry, but its biological sinks are not well understood. Thiobacillus thioparus strain THI115 can grow on thiocyanate (SCN(-)) as its sole energy source. Previously, we showed that SCN(-) is first converted to COS by thiocyanate hydrolase in T. thioparus strain THI115. In the present work, we purified, characterized, and determined the crystal structure of carbonyl sulfide hydrolase (COSase), which is responsible for the degradation of COS to H2S and CO2, the second step of SCN(-) assimilation. COSase is a homotetramer composed of a 23.4 kDa subunit containing a zinc ion in its catalytic site. The amino acid sequence of COSase is homologous to the β-class carbonic anhydrases (β-CAs). Although the crystal structure including the catalytic site resembles those of the β-CAs, CO2 hydration activity of COSase is negligible compared to those of the β-CAs. The α5 helix and the extra loop (Gly150-Pro158) near the N-terminus of the α6 helix narrow the substrate pathway, which could be responsible for the substrate specificity. The k(cat)/K(m) value, 9.6 × 10(5) s(-1) M(-1), is comparable to those of the β-CAs. COSase hydrolyzes COS over a wide concentration range, including the ambient level, in vitro and in vivo. COSase and its structurally related enzymes are distributed in the clade D in the phylogenetic tree of β-CAs, suggesting that COSase and its related enzymes are one of the catalysts responsible for the global sink of COS. PMID:23406161

  4. Application of static and dynamic enclosures for determining dimethyl sulfide and carbonyl sulfide exchange in Sphagnum peatlands: Implications for the magnitude and direction of flux

    Science.gov (United States)

    De Mello, William Z.; Hines, Mark E.

    1994-01-01

    A static enclosure method was applied to determine the exchange of dimethyl sulfide (DMS) and carbonyl sulfide (OCS) between the surface of Sphagnum peatlands and the atmosphere. Measurements were performed concurrently with dynamic (flow through) enclosure measurements with sulfur-free air used as sweep gas. This latter technique has been used to acquire the majority of available data on the exchange of S gases between the atmosphere and the continental surfaces and has been criticized because it is thought to overestimate the true flux of gases by disrupting natural S gas gradients. DMS emission rates determined by both methods were not statistically different between 4 and greater than 400 nmol/sq m/h, indicating that previous data on emissions of at least DMS are probably valid. However, the increase in DMS in static enclosures was not linear, indicating the potential for a negative feedback of enlosure DMS concentrations on efflux. The dynamic enclosure method measured positive OCS flux rates (emission) at all sites, while data using static enclosures indicated that OCS was consumed from the atmosphere at these same sites at rates of 3.7 to 55 nmol/sq m/h. Measurements using both enclosure techniques at a site devoid of vegetation showed that peat was a source of both DMS and OCS. However, the rate of OCS efflux from decomposing peat was more than counterbalanced by OCS consumption by vegetation, including Sphagnum mosses, and net OCS uptake occurred at all sites. We propose that all wetlands are net sinks for OCS.

  5. Enhancement effects of ultrasound assisted in the synthesis of NiAl hydrotalcite for carbonyl sulfide removal.

    Science.gov (United States)

    Zhao, Shunzheng; Yi, Honghong; Tang, Xiaolong; Gao, Fengyu; Yu, Qingjun; Zhou, Yuansong; Wang, Jiangen; Huang, Yonghai; Yang, Zhongyu

    2016-09-01

    Ultrasonic effect in the synthesis of catalysts of NiAl oxides prepared starting from the coprecipitation method of a hydrotalcite structure was evaluated in this work. Removal of carbonyl sulfide (COS) at low temperature over the hydrotalcite-derived oxides was studied. The samples were characterized by X-ray Diffraction (XRD), scanning electron microscope (SEM), N2 adsorption/desorption techniques, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and CO2 temperature-programmed desorption (TPD). It is found that hydrotalcite treated with ultrasonic has smaller average crystallite size and higher particle dispersion compared to hydrotalcite without ultrasonic treatment. As a result, mixed oxides derived from hydrotalcite treated with ultrasonic show more developed pore structure which is good for the physical adsorption of gaseous pollutant. The result of desulfuration test showed that removal efficiency of COS on the NiAl mixed oxides prepared by ultrasonic method (30min) is greater than that on the catalyst prepared without the ultrasonic irradiation assistance with the same aging time. One important reason for the high activity is that when the ultrasonic is used the number of weak basic sites (OH(-) groups) and moderate basic sites (M-O) was increased, whereas the number of strong basic sites (O(2-)) was decreased. Therefore, ultrasonic treatment promoted the COS hydrolysis and suppress the poisoning of the catalyst. PMID:27150779

  6. Changes in atmospheric carbonyl sulfide over the last 54,000 years inferred from measurements in Antarctic ice cores

    Science.gov (United States)

    Aydin, M.; Campbell, J. E.; Fudge, T. J.; Cuffey, K. M.; Nicewonger, M. R.; Verhulst, K. R.; Saltzman, E. S.

    2016-02-01

    We measured carbonyl sulfide (COS) in air extracted from ice core samples from the West Antarctic Ice Sheet (WAIS) Divide, Antarctica, with the deepest sample dated to 54,300 years before present. These are the first ice core COS measurements spanning the Last Glacial Maximum (LGM), the last glacial/interglacial transition, and the early Holocene. The WAIS Divide measurements from the LGM and the last transition are the first COS measurements in air extracted from full clathrate (bubble-free) ice. This study also includes new COS measurements from Taylor Dome, Antarctica, including some in bubbly glacial ice that are concurrent with the WAIS Divide data from clathrate glacial ice. COS hydrolyzes in ice core air bubbles, and the recovery of an atmospheric record requires correcting for this loss. The data presented here suggest that the in situ hydrolysis of COS is significantly slower in clathrate ice than in bubbly ice. The clathrate ice measurements are corrected for the hydrolysis loss during the time spent as bubbly ice only. The corrected WAIS Divide record indicates that atmospheric COS was 250-300 parts per trillion (ppt) during the LGM and declined by 80-100 ppt during the last glacial/interglacial transition to a minimum of 160-210 ppt at the beginning of the Holocene. This decline was likely caused by an increase in the gross primary productivity of terrestrial plants, with a possible contribution from a reduction in ocean sources. COS levels were above 300 ppt in the late Holocene, indicating that large changes in the COS biogeochemical cycle occurred during the Holocene.

  7. Concentrations of carbonyl sulfide and hydrogen cyanide in the free upper troposphere and lower stratosphere deduced from ATMOS/Spacelab 3 infrared solar occultation spectra

    Science.gov (United States)

    Zander, R.; Rinsland, C. P.; Russell, J. M., III; Farmer, C. B.; Norton, R. H.

    1988-01-01

    This paper presents the results on the volume mixing ratio profiles of carbonyl sulfide and hydrogen cyanide, deduced from the spectroscopic analysis of IR solar absorption spectra obtained in the occultation mode with the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument during its mission aboard Spacelab 3. A comparison of the ATMOS measurements for both northern and southern latitudes with previous field investigations at low midlatitudes shows a relatively good agreement. Southern Hemisphere volume mixing ratio profiles for both molecules were obtained for the first time, as were the profiles for the Northern Hemisphere covering the upper troposphere and the lower stratosphere simultaneously.

  8. A Synthesized Model-Observation Approach to Constraining Gross Urban CO2 Fluxes Using 14CO2 and carbonyl sulfide

    Science.gov (United States)

    LaFranchi, B. W.; Campbell, J. E.; Cameron-Smith, P. J.; Bambha, R.; Michelsen, H. A.

    2013-12-01

    Urbanized regions are responsible for a disproportionately large percentage (30-40%) of global anthropogenic greenhouse gas (GHG) emissions, despite covering only 2% of the Earth's surface area [Satterthwaite, 2008]. As a result, policies enacted at the local level in these urban areas can, in aggregate, have a large global impact, both positive and negative. In order to address the scientific questions that are required to drive these policy decisions, methods are needed that resolve gross CO2 flux components from the net flux. Recent work suggests that the critical knowledge gaps in CO2 surface fluxes could be addressed through the combined analysis of atmospheric carbonyl sulfide (COS) and radiocarbon in atmospheric CO2 (14CO2) [e.g. Campbell et al., 2008; Graven et al., 2009]. The 14CO2 approach relies on mass balance assumptions about atmospheric CO2 and the large differences in 14CO2 abundance between fossil and natural sources of CO2 [Levin et al., 2003]. COS, meanwhile, is a potentially transformative tracer of photosynthesis because its variability in the atmosphere has been found to be influenced primarily by vegetative uptake, scaling linearly will gross primary production (GPP) [Kettle et al., 20027]. Taken together, these two observations provide constraints on two of the three main components of the CO2 budget at the urban scale: photosynthesis and fossil fuel emissions. The third component, respiration, can then be determined by difference if the net flux is known. Here we present a general overview of our synthesized model-observation approach for improving surface flux estimates of CO2 for the upwind fetch of a ~30m tower located in Livermore, CA, USA, a suburb (pop. ~80,000) at the eastern edge of the San Francisco Bay Area. Additionally, we will present initial results from a one week observational intensive, which includes continuous CO2, CH4, CO, SO2, NOx, and O3 observations in addition to measurements of 14CO2 and COS from air samples

  9. Hydrolysis of Carbonyl Sulfide in Binary Mixture of Diethylene Glycol Diethyl Ether and Water%羰基硫在二乙二醇二乙醚/水二元混合体系中的水解

    Institute of Scientific and Technical Information of China (English)

    李新学; 刘迎新; 魏雄辉

    2005-01-01

    The solubility and hydrolysis of carbonyl sulfide in binary mixture of diethylene glycol diethyl ether and water are studied as a function of composition. The use of an aqueous solution of diethylene glycol diethyl ether enhances the solubility and hydrolysis rate of carbonyl sulfide compared with that in pure water. The composition of the mixture with maximum hydrolysis rate varies with temperature. The thermophysical properties including density, viscosity, and surface tension as a function of composition at 20℃ under atmospheric pressure as well as liquid-liquid equilibrium (LLE) data over the temperature range from 28℃ to 90℃ are also measured for the binary mixture.

  10. Sources and sinks of carbonyl sulfide in a mountain grassland and relationships to the carbon dioxide exchange

    Science.gov (United States)

    Spielmann, Felix M.; Kitz, Florian; Hammerle, Albin; Gerdel, Katharina; Wohlfahrt, Georg

    2016-04-01

    The trace gas carbonyl sulfide (COS) has been proposed as a tracer for canopy gross primary production (GPP), canopy transpiration and stomatal conductance of plant canopies in the last few years. COS enters the plant leaf through the stomata and diffuses through the intercellular space, the cell wall, the plasma membrane and the cytosol like CO2. It is then catalyzed by the enzyme carbonic anhydrase (CA) in a one-way reaction to H2S and CO2. This one-way flux into the leaf makes COS a promising tracer for the GPP. However there is growing evidence, that plant leaves aren't the only contributors to the ecosystem flux of COS. Therefor the COS uptake of soil microorganisms also containing CA and abiotic COS production might have to be accounted for when using COS as a tracer at the ecosystem scale. The overarching objective of this study was to quantify the relationship between the ecosystem-scale exchange of COS, CO2 and H2O and thus to test for the potential of COS to be used as a tracer for the plant canopy CO2 and H2O exchange. More specifically we aimed at quantifying the contribution of the soil to the ecosystem-scale COS exchange in order to understand complications that may arise due to a non-negligible soil COS exchange. In May 2015 we set up our quantum cascade laser (QCL) (Aerodyne Research Inc., MA, USA) at a temperate mountain grassland in Stubai Valley close to the village of Neustift, Austria. Our site lies at the valley bottom and is an intensively managed mountain grassland, which is cut 3-4 times a year. With the QCL we were able to measure concurrently the concentrations of COS, CO2, H2O (and CO) at a frequency of 10 Hz with minimal noise. This allowed us to conduct ecosystem-scale eddy covariance measurements. The eddy covariance flux measurements revealed that the COS uptake continues at night, which we confirmed was not caused by soil microorganisms, as the soil exchange was close to neutral during nighttime. Instead, the nocturnal COS uptake

  11. What Controls the Net Forest-Atmosphere Exchange of Carbonyl Sulfide? Results from 2 Years of Eddy Flux Measurements and SiB Model Simulations

    Science.gov (United States)

    Wehr, R. A.; Commane, R.; Baker, I. T.; Munger, J. W.; Saleska, S. R.; Wofsy, S. C.

    2015-12-01

    Carbonyl sulfide (OCS) is currently a focus of ground-, aircraft-, and satellite-based measurements as well as of model development, owing mainly to its potential use as a large-scale proxy for gross primary production (GPP). OCS is taken up by leaves and either taken up or emitted by soils, depending on the circumstances. Because OCS is destroyed by the enzyme carbonic anhydrase within the leaf rather than by any light-dependent reaction, the leaf uptake is expected to be related to the conductance of the diffusive pathway into the leaf (stomata + mesophyll + leaf boundary air layer) rather than to GPP directly, though GPP and the diffusive conductance are often strongly correlated. Here we use 2 years of eddy covariance measurements of the net ecosystem-atmosphere exchange of OCS, along with measurements of the vertical profile of OCS within the forest, to investigate the controls on ecosystem-scale OCS uptake and emission. We compare the OCS measurements, and simultaneous CO2 isotope flux and profile measurements, to predictions from the Simple Biosphere (SiB) model, which has been used to simulate OCS and 13CO2 fluxes for both vegetation and soils but has not yet been systematically tested against these relatively novel tracers. We thereby address the key question: How can measurements of the net ecosystem-atmosphere OCS exchange contribute to empirical quantification of stomatal conductance and GPP and to improving process-based ecosystem models?

  12. Methanol absorption characteristics for the removal of H2S (hydrogen sulfide), COS (carbonyl sulfide) and CO2 (carbon dioxide) in a pilot-scale biomass-to-liquid process

    International Nuclear Information System (INIS)

    The BTL (biomass-to-liquid) process is an attractive process that produces liquid biofuels from biomass. The FT (Fisher–Tropsch) process is used to produce synfuels such as diesel and gasoline from gasified biomass. However, the H2S (hydrogen sulfide), COS (carbonyl sulfide) and CO2 (carbon dioxide) in the syngas that are produced from the biomass gasifiers cause a decrease of the conversion efficiency and deactivates the catalyst that is used in the FT process. To remove the acid gases, a pilot-scale methanol absorption tower producing diesel at a rate of 1 BPD (barrel per day) was developed, and the removal characteristics of the acid gases were determined. A total operation time of 500 h was achieved after several campaigns. The average syngas flow rate at the inlet of methanol absorption tower ranged from 300 to 800 L/min. The methanol absorption tower efficiently removed H2S from 30 ppmV to less than 1 ppmV and COS from 2 ppmV to less than 1 ppmV with a removal of CO2 from 20% to 5%. The outlet gas composition adhered to the guidelines for FT reactors. No remaining sulfurous components were found, and the tar component was analyzed in the spent methanol after long-term operations. - Highlights: • The gas cleaning system in a pilot-scale BTL (biomass-to-liquid) process is reported. • Although methanol absorption tower is conventional process, its application to BTL process is attempted. • The methanol absorption tower efficiently removed H2S, COS and CO2 in the syngas. • The sulfurous and tar components in the methanol are analyzed

  13. Determination of the sulfur isotope ratio in carbonyl sulfide using gas chromatography/isotope ratio mass spectrometry on fragment ions 32S+, 33S+, and 34S+.

    Science.gov (United States)

    Hattori, Shohei; Toyoda, Akari; Toyoda, Sakae; Ishino, Sakiko; Ueno, Yuichiro; Yoshida, Naohiro

    2015-01-01

    Little is known about the sulfur isotopic composition of carbonyl sulfide (OCS), the most abundant atmospheric sulfur species. We present a promising new analytical method for measuring the stable sulfur isotopic compositions (δ(33)S, δ(34)S, and Δ(33)S) of OCS using nanomole level samples. The direct isotopic analytical technique consists of two parts: a concentration line and online gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions (32)S(+), (33)S(+), and (34)S(+). The current levels of measurement precision for OCS samples greater than 8 nmol are 0.42‰, 0.62‰, and 0.23‰ for δ(33)S, δ(34)S, and Δ(33)S, respectively. These δ and Δ values show a slight dependence on the amount of injected OCS for volumes smaller than 8 nmol. The isotope values obtained from the GC-IRMS method were calibrated against those measured by a conventional SF6 method. We report the first measurement of the sulfur isotopic composition of OCS in air collected at Kawasaki, Kanagawa, Japan. The δ(34)S value obtained for OCS (4.9 ± 0.3‰) was lower than the previous estimate of 11‰. When the δ(34)S value for OCS from the atmospheric sample is postulated as the global signal, this finding, coupled with isotopic fractionation for OCS sink reactions in the stratosphere, explains the reported δ(34)S for background stratospheric sulfate. This suggests that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols. PMID:25439590

  14. Unveiling stomata 24/7: can we use carbonyl sulfide (COS) and oxygen isotopes (18O) to constrain estimates of nocturnal transpiration across different evolutionary plant forms?

    Science.gov (United States)

    Gimeno, Teresa E.; Ogee, Jerome; Bosc, Alexander; Genty, Bernard; Wohl, Steven; Wingate, Lisa

    2015-04-01

    Numerous studies have reported a continued flux of water through plants at night, suggesting that stomata are not fully closed. Growing evidence indicates that this nocturnal flux of transpiration might constitute an important fraction of total ecosystem water use in certain environments. However, because evaporative demand is usually low at night, nocturnal transpiration fluxes are generally an order of magnitude lower than rates measured during the day and perilously close to the measurement error of traditional gas-exchange porometers. Thus estimating rates of stomatal conductance in the dark (gnight) precisely poses a significant methodological challenge. As a result, we lack accurate field estimates of gnight and how it responds to different atmospheric drivers, indicating the need for a different measurement approach. In this presentation we propose a novel method to obtain detectable and robust estimates of gnight. We will demonstrate using mechanistic theory how independent tracers including the oxygen isotope composition of CO2 (δ18O) and carbonyl sulfide (COS) can be combined to obtain robust estimates of gnight. This is because COS and CO18O exchange within leaves are controlled by the light insensitive enzyme carbonic anhydrase. Thus, if plant stomata are open in the dark we will continue to observe COS and CO18O exchange. Using our theoretical model we will demonstrate that the exchange of these tracers can now be measured using advances in laser spectrometry techniques at a precision high enough to determine robust estimates of gnight. We will also present our novel experimental approach designed to measure simultaneously the exchange of CO18O and COS alongside the conventional technique that relies on measuring the total water flux from leaves in the dark. Using our theoretical approach we will additionally explore the feasibility of our proposed experimental design to detect variations in gnight during drought stress and across a variety of plant

  15. Carbonyl sulfide (OCS) as a proxy for GPP: Complications derived from studies on the impact of CO2, soil humidity and sterilization on the OCS exchange between soils and atmosphere

    Science.gov (United States)

    Bunk, Rüdiger; Behrendt, Thomas; Yi, Zhigang; Kesselmeier, Jürgen

    2016-04-01

    Carbonyl sulfide is discussed to be used as a proxy for gross primary productivity (GPP) of forest ecosystems. However, soils may interfere. Soils play an important role in budgeting global and local carbonyl sulfide (OCS) fluxes, yet the available data on the uptake and emission behavior of soils in conjunction with environmental factors is limited. The work of many authors has shown that the OCS exchange of soils depends on various factors, such as soil type, atmospheric OCS concentrations, temperature or soil water content (Kesselmeier et al., J. Geophys. Res., 104, No. D9, 11577-11584, 1999; Van Diest & Kesselmeier, Biogeosciences, 5, 475-483, 2008; Masyek et al., PNAS, 111, No 25, 9064-9069, doi: 10.1073/pnas.1319132111, 2014; Whelan and Rhew, J. Geophys. Res. Biogeosciences., 120, 54-62, doi: 10.1002/2014JG002661, 2015) and the light dependent and obviously abiotic OCS production as reported by Whelan and Rhew (2015). To get a better constraint on the impact of some environmental factors on the OCS exchange of soils we used a new laser based integrated cavity output spectroscopy instrument (LGR COS/CO Analyzer Model 907-0028, Los Gatos, Mountain View, California, USA) in conjunction with an automated soil chamber system (as described in Behrendt et al, Biogeosciences, 11, 5463-5492, doi: 10.5194/bg-11-5463-2014, 2014). The OCS exchange of various soils under the full range of possible soil humidity and various CO2 mixing ratios was examined. Additionally OCS exchange of chloroform sterilized subsamples was compared to their live counterparts to illuminate the influence of microorganisms. Results were quite heterogeneous between different soils. With few exceptions, all examined soils show dependence between OCS exchange and soil humidity, usually with strongest uptake at a certain humidity range and less uptake or even emission at higher and lower humidity. Differences in CO2 mixing ratio also clearly impacts on OCS exchange, but trends for different soils

  16. Towards understanding the variability in biospheric CO2 fluxes: using FTIR spectrometry and a chemical transport model to investigate the sources and sinks of carbonyl sulfide and its link to CO2

    Science.gov (United States)

    Wang, Yuting; Deutscher, Nicholas M.; Palm, Mathias; Warneke, Thorsten; Notholt, Justus; Baker, Ian; Berry, Joe; Suntharalingam, Parvadha; Jones, Nicholas; Mahieu, Emmanuel; Lejeune, Bernard; Hannigan, James; Conway, Stephanie; Mendonca, Joseph; Strong, Kimberly; Campbell, J. Elliott; Wolf, Adam; Kremser, Stefanie

    2016-02-01

    Understanding carbon dioxide (CO2) biospheric processes is of great importance because the terrestrial exchange drives the seasonal and interannual variability of CO2 in the atmosphere. Atmospheric inversions based on CO2 concentration measurements alone can only determine net biosphere fluxes, but not differentiate between photosynthesis (uptake) and respiration (production). Carbonyl sulfide (OCS) could provide an important additional constraint: it is also taken up by plants during photosynthesis but not emitted during respiration, and therefore is a potential means to differentiate between these processes. Solar absorption Fourier Transform InfraRed (FTIR) spectrometry allows for the retrievals of the atmospheric concentrations of both CO2 and OCS from measured solar absorption spectra. Here, we investigate co-located and quasi-simultaneous FTIR measurements of OCS and CO2 performed at five selected sites located in the Northern Hemisphere. These measurements are compared to simulations of OCS and CO2 using a chemical transport model (GEOS-Chem). The coupled biospheric fluxes of OCS and CO2 from the simple biosphere model (SiB) are used in the study. The CO2 simulation with SiB fluxes agrees with the measurements well, while the OCS simulation reproduced a weaker drawdown than FTIR measurements at selected sites, and a smaller latitudinal gradient in the Northern Hemisphere during growing season when comparing with HIPPO (HIAPER Pole-to-Pole Observations) data spanning both hemispheres. An offset in the timing of the seasonal cycle minimum between SiB simulation and measurements is also seen. Using OCS as a photosynthesis proxy can help to understand how the biospheric processes are reproduced in models and to further understand the carbon cycle in the real world.

  17. Carbonyl sulfide (OCS) in the Archean atmosphere

    DEFF Research Database (Denmark)

    Ueno, Yuichiro; Danielache, Sebastian Oscar; Johnson, Matthew Stanley;

    2009-01-01

    absorbs >200 nm region of solar UV flux. Further, we performed numerical simulation of atmospheric reactions including OCS chemistry and found that ppm-level OCS could be accumulated in a O2- free reducing atmosphere when CO/CO2 ratio is greater than 1. Therefore, appreciable amount of OCS is likely...

  18. Validation of protein carbonyl measurement

    DEFF Research Database (Denmark)

    Augustyniak, Edyta; Adam, Aisha; Wojdyla, Katarzyna; Rogowska-Wrzesinska, Adelina; Willetts, Rachel; Korkmaz, Ayhan; Atalay, Mustafa; Weber, Daniela; Grune, Tilman; Borsa, Claudia; Gradinaru, Daniela; Chand Bollineni, Ravi; Fedorova, Maria; Griffiths, Helen R

    Protein carbonyls are widely analysed as a measure of protein oxidation. Several different methods exist for their determination. A previous study had described orders of magnitude variance that existed when protein carbonyls were analysed in a single laboratory by ELISA using different commercial...... protein carbonyl analysis across Europe. ELISA and Western blotting techniques detected an increase in protein carbonyl formation between 0 and 5min of UV irradiation irrespective of method used. After irradiation for 15min, less oxidation was detected by half of the laboratories than after 5min...

  19. Radical carbonylations using a continuous microflow system

    Directory of Open Access Journals (Sweden)

    Takahide Fukuyama

    2009-07-01

    Full Text Available Radical-based carbonylation reactions of alkyl halides were conducted in a microflow reactor under pressurized carbon monoxide gas. Good to excellent yields of carbonylated products were obtained via radical formylation, carbonylative cyclization and three-component coupling reactions, using tributyltin hydride or TTMSS as a radical mediator.

  20. Kinetics of the Double Carbonylation of Benzylchloride

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    It is a multi-phase-catalyzed reaction to produce calcium phenylpyruvate by double carbonylation of benzylchloride. Based on the analysis of the reaction mechanism, a kinetic model of the carbonylation reaction was obtained. The model was verified through experiments in which the diffusion effect was neglected with the appropriate operation manner. But it is inevitable that the carbonylation process is controlled by diffusion as the autoclave scaling up.

  1. Surface decorated platinum carbonyl clusters

    Science.gov (United States)

    Ciabatti, Iacopo; Femoni, Cristina; Iapalucci, Maria Carmela; Longoni, Giuliano; Zacchini, Stefano; Zarra, Salvatore

    2012-06-01

    Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt13(CO)12{Cd5(μ-Br)5Br2(dmf)3}2]2- (1), [Pt19(CO)17{Cd5(μ-Br)5Br3(Me2CO)2}{Cd5(μ-Br)5Br(Me2CO)4}]2- (2), [H2Pt26(CO)20(CdBr)12]8- (3) and [H4Pt26(CO)20(CdBr)12(PtBr)x]6- (4) (x = 0-2), have been obtained from the reactions between [Pt3n(CO)6n]2- (n = 2-6) and CdBr2.H2O in dmf at 120 °C. The structures of these molecular clusters with diameters of 1.5-2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt-CO cores decorated on the surface by Cd-Br motifs, whereas 3 and 4 display a cubic close packed Pt26Cd12 metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au-thiolate nanoclusters.Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt13(CO)12{Cd5(μ-Br)5Br2(dmf)3}2]2- (1), [Pt19(CO)17{Cd5(μ-Br)5Br3(Me2CO)2}{Cd5(μ-Br)5Br(Me2CO)4}]2- (2), [H2Pt26(CO)20(CdBr)12]8- (3) and [H4Pt26(CO)20(CdBr)12(PtBr)x]6- (4) (x = 0-2), have been obtained from the reactions between [Pt3n(CO)6n]2- (n = 2-6) and CdBr2.H2O in dmf at 120 °C. The structures of these molecular clusters with diameters of 1.5-2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt-CO cores decorated on the surface by Cd-Br motifs, whereas 3 and 4 display a cubic close packed Pt26Cd12 metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au-thiolate nanoclusters. CCDC 867747 and 867748. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c2nr30400g

  2. Trifluoromethylation of Carbonyl Compounds with Sodium Trifluoroacetate

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    In the presence of copper (Ⅰ) halide as catalyst, a variety of carbonyl compounds could be trifluoromethylated with sodium trifluoroacetate to give the corresponding alcohols in moderate to high yields.

  3. Acrolein induces selective protein carbonylation in synaptosomes

    OpenAIRE

    C.F. Mello; R. Sultana; Piroddi, M.; J. Cai; PIERCE, W. M; Klein, J.B.; D. A. Butterfield

    2007-01-01

    Acrolein, the most reactive of the α,β-unsaturated aldehydes, is endogenously produced by lipid peroxidation, and has been found increased in the brain of patients with Alzheimer's disease. Although it is known that acrolein increases total protein carbonylation and impairs the function of selected proteins, no study has addressed which proteins are selectively carbonylated by this aldehyde. In this study we investigated the effect of increasing concentrations of acrolein (0, 0.005, 0.05, 0.5...

  4. Mesostructured metal germanium sulfides

    Energy Technology Data Exchange (ETDEWEB)

    MacLachlan, M.J.; Coombs, N.; Bedard, R.L.; White, S.; Thompson, L.K.; Ozin, G.A.

    1999-12-29

    A new class of mesostructured metal germanium sulfide materials has been prepared and characterized. The synthesis, via supramolecular assembly of well-defined germanium sulfide anionic cluster precursors and transition-metal cations in formamide, represents a new strategy for the formation of this class of solids. A variety of techniques were employed to examine the structure and composition of the materials. Structurally, the material is best described as a periodic mesostructured metal sulfide-based coordination framework akin to periodic hexagonal mesoporous silica, MCM-41. At the molecular scale, the materials strongly resemble microstructured metal germanium sulfides, in which the structure of the [Ge{sub 4}S{sub 10}]{sup 4{minus}} cluster building-blocks are intact and linked via {mu}-S-M-S bonds. Evidence for a metal-metal bond in mesostructured Cu/Ge{sub 4}S{sub 10} is also provided.

  5. Palladium-catalyzed oxidative carbonylation reactions.

    Science.gov (United States)

    Wu, Xiao-Feng; Neumann, Helfried; Beller, Matthias

    2013-02-01

    Palladium-catalyzed coupling reactions have become a powerful tool for advanced organic synthesis. This type of reaction is of significant value for the preparation of pharmaceuticals, agrochemicals, as well as advanced materials. Both, academic as well as industrial laboratories continuously investigate new applications of the different methodologies. Clearly, this area constitutes one of the major topics in homogeneous catalysis and organic synthesis. Among the different palladium-catalyzed coupling reactions, several carbonylations have been developed and widely used in organic syntheses and are even applied in the pharmaceutical industry on ton-scale. Furthermore, methodologies such as the carbonylative Suzuki and Sonogashira reactions allow for the preparation of interesting building blocks, which can be easily refined further on. Although carbonylative coupling reactions of aryl halides have been well established, palladium-catalyzed oxidative carbonylation reactions are also interesting. Compared with the reactions of aryl halides, oxidative carbonylation reactions offer an interesting pathway. The oxidative addition step could be potentially avoided in oxidative reactions, but only few reviews exist in this area. In this Minireview, we summarize the recent development in the oxidative carbonylation reactions. PMID:23307763

  6. Fast photolysis of carbonyl nitrates from isoprene

    Science.gov (United States)

    Müller, Jean-Francois; Peeters, Jozef; Stavrakou, Trisevgeni

    2014-05-01

    We show that photolysis is, by far, the major atmospheric sink of isoprene-derived carbonyl nitrates. Empirical evidence from published laboratory studies on the absorption cross sections and photolysis rates of α-nitrooxy ketones suggests that the presence of the nitrate group (i) greatly enhances the absorption cross sections, and (ii) facilitates dissociation to a point that the photolysis quantum yield is close to unity, with O-NO2 dissociation as the likely major channel. On this basis, we provide new recommendations for estimating the cross sections and photolysis rates of carbonyl nitrates. The newly estimated photorates are validated using a chemical box model against measured temporal profiles of carbonyl nitrates in an isoprene oxidation experiment by Paulot et al. (2009). The comparisons for ethanal nitrate and for the sum of methacrolein- and methylvinylketone nitrates strongly supports our assumptions of large cross section enhancements and a near-unit quantum yield for these compounds. These findings have significant atmospheric implications, as carbonyl nitrates constitute an important component of the total organic nitrate pool over vegetated areas: the photorates of key carbonyl nitrates from isoprene are estimated to be typically between ~3 and 20 times higher than their sink due to reaction with OH in relevant atmospheric conditions. Moreover, since the reaction is expected to release NO2, photolysis is especially effective in depleting the total organic nitrate pool.

  7. SULFIDE METHOD PLUTONIUM SEPARATION

    Science.gov (United States)

    Duffield, R.B.

    1958-08-12

    A process is described for the recovery of plutonium from neutron irradiated uranium solutions. Such a solution is first treated with a soluble sullide, causing precipitation of the plutoniunn and uraniunn values present, along with those impurities which form insoluble sulfides. The precipitate is then treated with a solution of carbonate ions, which will dissolve the uranium and plutonium present while the fission product sulfides remain unaffected. After separation from the residue, this solution may then be treated by any of the usual methods, such as formation of a lanthanum fluoride precipitate, to effect separation of plutoniunn from uranium.

  8. Synthesis of carbonyl-14C labelled 'acetochlor'

    International Nuclear Information System (INIS)

    Carbonyl-14C labelled 'acetochlor' (2-chloro-N-ethoxymethyl-N-(2-ethyl-6-methylphenyl)acetamide) was prepared by chlorination of acetic-1-14C acid obtained from barium radiocarbonate to monochloroacetic-1-14C acid which was further chlorinated to monochloroacetyl-1-14C chloride. The addition reaction of this latter with 2-ethyl-6-methylene aniline gave a chloromethyl derivative the ethanolysis of which resulted in 'acetochlor' labelled in its carbonyl carbon. The overall radiochemical yield is 51%. (author)

  9. Titanocene sulfide chemistry

    Czech Academy of Sciences Publication Activity Database

    Horáček, Michal

    2016-01-01

    Roč. 314, MAY 2016 (2016), s. 83-102. ISSN 0010-8545 R&D Projects: GA ČR(CZ) GAP207/12/2368 Institutional support: RVO:61388955 Keywords : titanocene sulfide chemistry * photolysis * titanocene hydrosulfides Ti-(SH)n Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 12.239, year: 2014

  10. Polyimides Containing Carbonyl and Ether Connecting Groups

    Science.gov (United States)

    Hergenrother, Paul M.; Havens, Stephen J.

    1987-01-01

    Semicrystallinity gives rise to tough, solvent-resistant polymers. New polyimides prepared from reaction of aromatic dianhydrides with new diamines containing carbonyl and ether connecting groups between aromatic rings. Damines prepared from reaction of 4-aminophenol with activated aromatic difluoro compounds in presence of potassium carbonate. These types of polymers have potential applications in molded products, films, adhesives, and composites.

  11. Pattern of occurrence and occupancy of carbonylation sites in proteins

    DEFF Research Database (Denmark)

    Rao, R Shyama Prasad; Møller, Ian Max

    2011-01-01

    Proteins are targets for modification by reactive oxygen species, and carbonylation is an important irreversible modification that increases during oxidative stress. While information on protein carbonylation is accumulating, its pattern is not yet understood. We have made a meta-analysis of the...... available literature data (456 carbonylation sites on 208 proteins) to appreciate the nature of carbonylation sites in proteins. Of the carbonylated (Arg, Lys, Pro, and Thr – RKPT) amino acids, Lys is the most abundant, whereas Pro is the most susceptible and Thr is the least susceptible. The incidence of...

  12. Effect of Sodium Sulfide on Ni-Containing Carbon Monoxide Dehydrogenases

    Energy Technology Data Exchange (ETDEWEB)

    Jian Feng; Paul A. Lindahl

    2004-07-28

    OAK-B135 The structure of the active-site C-cluster in CO dehydrogenase from Carboxythermus hydrogenoformans includes a {mu}{sup 2}-sulfide ion bridged to the Ni and unique Fe, while the same cluster in enzymes from Rhodospirillum rubrum (CODH{sub Rr}) and Moorella thermoacetica (CODH{sub Mt}) lack this ion. This difference was investigated by exploring the effects of sodium sulfide on activity and spectral properties. Sulfide partially inhibited the CO oxidation activity of CODH{sub Rr} and generated a lag prior to steady-state. CODH{sub Mt} was inhibited similarly but without a lag. Adding sulfide to CODH{sub Mt} in the C{sub red1} state caused the g{sub av} = 1.82 EPR signal to decline and new features to appear, including one with g = 1.95, 1.85 and (1.70 or 1.62). Removing sulfide caused the g{sub av} = 1.82 signal to reappear and activity to recover. Sulfide did not affect the g{sub av} = 1.86 signal from the C{sub red2} state. A model was developed in which sulfide binds reversibly to C{sub red1}, inhibiting catalysis. Reducing this adduct causes sulfide to dissociate, C{sub red2} to develop, and activity to recover. Using this model, apparent K{sub I} values are 40 {+-} 10 nM for CODH{sub Rr} and 60 {+-} 30 {micro}M for CODH{sub Mt}. Effects of sulfide are analogous to those of other anions, including the substrate hydroxyl group, suggesting that these ions also bridge the Ni and unique Fe. This proposed arrangement raises the possibility that CO binding labilizes the bridging hydroxyl and increases its nucleophilic tendency towards attacking Ni-bound carbonyl.

  13. Carbonyl Compounds Generated from Electronic Cigarettes

    Directory of Open Access Journals (Sweden)

    Kanae Bekki

    2014-10-01

    Full Text Available Electronic cigarettes (e-cigarettes are advertised as being safer than tobacco cigarettes products as the chemical compounds inhaled from e-cigarettes are believed to be fewer and less toxic than those from tobacco cigarettes. Therefore, continuous careful monitoring and risk management of e-cigarettes should be implemented, with the aim of protecting and promoting public health worldwide. Moreover, basic scientific data are required for the regulation of e-cigarette. To date, there have been reports of many hazardous chemical compounds generated from e-cigarettes, particularly carbonyl compounds such as formaldehyde, acetaldehyde, acrolein, and glyoxal, which are often found in e-cigarette aerosols. These carbonyl compounds are incidentally generated by the oxidation of e-liquid (liquid in e-cigarette; glycerol and glycols when the liquid comes in contact with the heated nichrome wire. The compositions and concentrations of these compounds vary depending on the type of e-liquid and the battery voltage. In some cases, extremely high concentrations of these carbonyl compounds are generated, and may contribute to various health effects. Suppliers, risk management organizations, and users of e-cigarettes should be aware of this phenomenon.

  14. Magnetorheological characterisation of carbonyl iron based suspension

    Directory of Open Access Journals (Sweden)

    M. Kciuk

    2009-04-01

    Full Text Available Purpose: The main aim of this article was to present the investigation results of magnetorheological fluids (MR composed of carbonyl iron (CI particles and analyse their flow behaviour in terms of the internal structure formation by a control of applied external magnetic field. The morphology, magnetic properties, sedimentation stability, and magnetorheological properties of the examined MR fluids were studied.Design/methodology/approach: Model MR fluid was prepared using silicone oil OKS 1050 mixed with carbonyl iron powder CI. Furthermore, to reduce sedimentation Aerosil 200 was added as stabilizers. In the purpose to determine the properties of the analyzed fluids the sedimentation and dynamic viscosity were investigated.Findings: Dynamic viscosity of investigated magnetorheological fluids rapidly and reversibly change in response to the applied external magnetic field. Moreover added particles of fumed silica inhibited sedimentation of carbonyl iron particles.Research limitations/implications: MR fluids with excellent properties can be applied in various fields of civil engineering, safety engineering, transportation and life science. They offer an outstanding capability of active control of mechanical properties. But there are no systematic published studies of factors affecting the durability of MR fluids and devices. There is very little information on the effects of exposing different MR fluids to temperature, for this reasons further efforts are needed in order to obtain even better results.Originality/value: The investigation results are reliable and could be very useful both for designers and the practitioners of many branches of industry.

  15. Sulfide oxidation in a biofilter

    DEFF Research Database (Denmark)

    Pedersen, Claus Lunde; Dezhao, Liu; Hansen, Michael Jørgen;

    oxidizing bacteria but several fungal families including Trichocomaceae. A positive correlation was found between the presence of mold and sulfide uptake. However there have been no reports on fungi metabolizing hydrogen sulfide. We hypothesize that the mold increases the air exposed surface, enabling...... higher hydrogen sulfide uptake followed by oxidation catalyzed by iron-containing enzymes such as cytochrome c oxidase in a process uncoupled from energy conservation....

  16. Sulfide oxidation in a biofilter

    DEFF Research Database (Denmark)

    Pedersen, Claus Lunde; Liu, Dezhao; Hansen, Michael Jørgen;

    2012-01-01

    oxidizing bacteria but several fungal families including Trichocomaceae. A positive correlation was found between the presence of mold and sulfide uptake. However there have been no reports on fungi metabolizing hydrogen sulfide. We hypothesize that the mold increases the air exposed surface, enabling...... higher hydrogen sulfide uptake followed by oxidation catalyzed by iron-containing enzymes such as cytochrome c oxidase in a process uncoupled from energy conservation....

  17. Polynuclear nitrosyl carbonyl Re1 complexes with thiolate and sulfide bridges

    International Nuclear Information System (INIS)

    The reactions between Re2(CO)4(NO)2Cl2(μ-Cl)2 and NaSCMe3 with different reagent ratios (from 1:2 to 1:6) were studied. In the case of a 1:2 reagent ratio the binuclear complex Re2(CO)4(NO)2Cl2(μ-SCMe3)2 was obtained as a mixture of syn- and anti-isomers having different Re2S2 cores. When the reagent ratio was 1:4, two compounds were formed: binuclear complex Re2(CO)4(NO)2(μ-SCMe3)2(μ-S) (a mixture of syn- and anti-isomers) and trinuclear cluster Re3(CO)3(NO)3(μ-SCMe3)3(μ3-S)(μ3-Cl). The structures of complexes were established by X-ray analysis of the single crystals

  18. On the isotopic fingerprint exerted on carbonyl sulfide by the stratosphere

    Directory of Open Access Journals (Sweden)

    J. A. Schmidt

    2012-09-01

    Full Text Available The isotopic fractionation in OCS photolysis is studied theoretically from first principles. UV absorption cross sections for OCS, OC33S, OC34S, OC36S and O13CS are calculated using the time-depedent quantum mechanical formalism and recent potential energy surfaces for the lowest four singlet and lowest four triplet electronic states. The calculated isotopic fractionations as a function of wavelength are in good agreement with recent measurements by Hattori et al. (2011 and indicate that photolysis leads to only a small enrichment of 34S in the remaining pool of OCS. A simple stratospheric model is constructed taking into account the main stratospheric sink reactions of OCS and it is found that stratospheric removal overall slightly favors light OCS in constrast to the findings of Leung et al. (2002. These results show, based on isotopic considerations, that OCS is an acceptable source of background stratosperic sulfate aerosol in agreement with a recent model study of Brühl et al. (2012. The 13C isotopic fractionation due to photolysis of OCS is significant and will leave a strong signal in the pool of remaining OCS making it a candidate for tracing using the ACE-FTS and MIPAS data sets.

  19. Essential Factors in Removing Carbonyl Sulfide from Coal Gas with Lime and Limestone

    Czech Academy of Sciences Publication Activity Database

    Hartman, Miloslav; Svoboda, Karel; Trnka, Otakar

    2000-01-01

    Roč. 54, č. 5 (2000), s. 302-306. ISSN 0366-6352 R&D Projects: GA AV ČR IAA4072711; GA ČR GA203/98/0101 Institutional research plan: CEZ:AV0Z4072921 Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 0.154, year: 2000

  20. Effects of carbonyl sulfide (COS) and carbonic anhydrase on stomatal conductance

    Science.gov (United States)

    Yakir, D.; Stimler, K.; Berry, J. A.

    2011-12-01

    The potential use of COS as tracer of the gross, one-way, CO2 flux into plants is based on its co-diffusion with CO2 into leaves without outflux stimulated research on COS-CO2 interactions during leaf gas exchange. We carried out gas exchange measurements of COS and CO2 in 22 plant species representing deciduous and evergreen trees, grasses, and shrubs, under a range of light intensities and ambient COS concentrations, using mid IR laser spectroscopy. A narrow range in the normalized ratio of the net uptake rates of COS (As) and CO2 (Ac; As/Ac*[CO2]/[COS]) was observed, with a mean value of 1.61±0.26. These results reflect the dominance of stomatal conductance over both COS and CO2 uptake, imposing a relatively constant ratio between the two fluxes (except under low light conditions when CO2, but not COS, metabolism is light limited). A relatively constant ratio under common ambient conditions will facilitate the application of COS as a tracer of gross photosynthesis from leaf to global scales. However, its effect on stomatal conductance may require a special attention. Increasing COS concentrations between 250 and 2800 pmol mol-1 (enveloping atmospheric levels) seems to stimulate stomatal conductance. We examined the stimulation of conductance by COS in a range of species and show that there is a large variation with some species showing almost no response while others are highly responsive (up to doubling stomatal conductance). Using C3 and C4 plants with antisense lines abolishing carbonic anhydrase activity, we show that the activity of this enzyme is essential for both the uptake of COS and the enhancement of stomatal conductance by COS. Since carbonic anhydrase catalyzes the conversion of COS to CO2 and H2S it seems likely that the stomata are responding to H2S produced in the mesophyll. In all natural species examined the uptake of COS and CO2 were highly correlated, and there was no relationship between the sensitivity of stomata and the rate of COS uptake (or by inference H2S production). The basis for this variation in sensitivity is still to be determined. The studies reported here clearly implicate CA as a plausible source of H2S within the leaf, and probably provide the first demonstration of a possible alternative mechanism, independent of the production of HCO3-, whereby CA could function as a biosensor ("sensoenzyme") influencing stomatal conductance and, in turn, ecosystem-atmosphere fluxes of carbon, water and energy.

  1. Pressure-induced Transformations of Dense Carbonyl Sulfide to Singly Bonded Amorphous Metallic Solid.

    Science.gov (United States)

    Kim, Minseob; Dias, Ranga; Ohishi, Yasuo; Matsuoka, Takehiro; Chen, Jing-Yin; Yoo, Choong-Shik

    2016-01-01

    The application of pressure, internal or external, transforms molecular solids into non-molecular extended network solids with diverse crystal structures and electronic properties. These transformations can be understood in terms of pressure-induced electron delocalization; however, the governing mechanisms are complex because of strong lattice strains, phase metastability and path dependent phase behaviors. Here, we present the pressure-induced transformations of linear OCS (R3m, Phase I) to bent OCS (Cm, Phase II) at 9 GPa; an amorphous, one-dimensional (1D) polymer at 20 GPa (Phase III); and an extended 3D network above ~35 GPa (Phase IV) that metallizes at ~105 GPa. These results underscore the significance of long-range dipole interactions in dense OCS, leading to an extended molecular alloy that can be considered a chemical intermediate of its two end members, CO2 and CS2. PMID:27527241

  2. Millimeter wave spectra of carbonyl cyanide

    Science.gov (United States)

    Bteich, S. B.; Tercero, B.; Cernicharo, J.; Motiyenko, R. A.; Margulès, L.; Guillemin, J.-C.

    2016-07-01

    Context. More than 30 cyanide derivatives of simple organic molecules have been detected in the interstellar medium, but only one dicarbonitrile has been found and that very recently. There is still a lack of high-resolution spectroscopic data particularly for dinitriles derivatives. The carbonyl cyanide molecule is a new and interesting candidate for astrophysical detection. It could be formed by the reaction of CO and CN radicals, or by substitution of the hydrogen atom by a cyano group in cyanoformaldehyde, HC(=O)CN, that has already been detected in the interstellar medium. Aims: The available data on the rotational spectrum of carbonyl cyanide is limited in terms of quantum number values and frequency range, and does not allow accurate extrapolation of the spectrum into the millimeter-wave range. To provide a firm basis for astrophysical detection of carbonyl cyanide we studied its millimeter-wave spectrum. Methods: The rotational spectrum of carbonyl cyanide was measured in the frequency range 152-308 GHz and analyzed using Watson's A- and S-reduction Hamiltonians. Results: The ground and first excited state of v5 vibrational mode were assigned and analyzed. More than 1100 distinct frequency lines of the ground state were fitted to produce an accurate set of rotational and centrifugal distortion constants up to the eighth order. The frequency predictions based on these constants should be accurate enough for astrophysical searches in the frequency range up to 500 GHz and for transition involving energy levels with J ≤ 100 and Ka ≤ 42. Based on the results we searched for interstellar carbonyl cyanide in available observational data without success. Thus, we derived upper limits to its column density in different sources. This paper makes use of the following ALMA data: ADS/JAO.ALMA#2011.0.00009.SV. ALMA is a partnership of ESO (representing its member states), NSF (USA), and NINS (Japan) with NRC (Canada), NSC, and ASIAA (Taiwan), and KASI (Republic of

  3. Infrared spectroscopy of mass-selected metal carbonyl cations

    Science.gov (United States)

    Ricks, A. M.; Reed, Z. E.; Duncan, M. A.

    2011-04-01

    Metal carbonyl cations of the form M(CO)n+ are produced in a molecular beam by laser vaporization in a pulsed nozzle source. These ions, and their corresponding rare gas atom "tagged" analogs, M(CO)n(RG)m+, are studied with mass-selected infrared photodissociation spectroscopy in the carbonyl stretching region and with density functional theory computations. The number of infrared-active bands, their frequency positions, and their relative intensities provide distinctive patterns allowing determination of the geometries and electronic structures of these complexes. Cobalt penta carbonyl and manganese hexacarbonyl cations are compared to isoelectronic iron pentacarbonyl and chromium hexacarbonyl neutrals. Gold and copper provide examples of "non-classical" carbonyls. Seven-coordinate carbonyls are explored for the vanadium group metal cations (V +, Nb + and Ta +), while uranium cations provide an example of an eight-coordinate carbonyl.

  4. Field method for sulfide determination

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, B L; Schwarser, R R; Chukwuenye, C O

    1982-01-01

    A simple and rapid method was developed for determining the total sulfide concentration in water in the field. Direct measurements were made using a silver/sulfide ion selective electrode in conjunction with a double junction reference electrode connected to an Orion Model 407A/F Specific Ion Meter. The method also made use of a sulfide anti-oxidant buffer (SAOB II) which consists of ascorbic acid, sodium hydroxide, and disodium EDTA. Preweighed sodium sulfide crystals were sealed in air tight plastic volumetric flasks which were used in standardization process in the field. Field standards were prepared by adding SAOB II to the flask containing the sulfide crystals and diluting it to the mark with deionized deaerated water. Serial dilutions of the standards were used to prepare standards of lower concentrations. Concentrations as low as 6 ppB were obtained on lake samples with a reproducibility better than +- 10%.

  5. Clinical Features of Schizophrenia With Enhanced Carbonyl Stress

    OpenAIRE

    Miyashita, Mitsuhiro; Arai, Makoto; Kobori, Akiko; Ichikawa, Tomoe; Toriumi, Kazuya; Niizato, Kazuhiro; Oshima, Kenichi; Okazaki, Yuji; Yoshikawa, Takeo; Amano, Naoji; Miyata, Toshio; Itokawa, Masanari

    2013-01-01

    Accumulating evidence suggests that advanced glycation end products, generated as a consequence of facilitated carbonyl stress, are implicated in the development of a variety of diseases. These diseases include neurodegenerative illnesses, such as Alzheimer disease. Pyridoxamine is one of the 3 forms of vitamin B6, and it acts by combating carbonyl stress and inhibiting the formation of AGEs. Depletion of pyridoxamine due to enhanced carbonyl stress eventually leads to a decrease in the other...

  6. Electrochemical Dissolution Behavior and the Residue Formation Mechanism of Laboratory Made Carbonyl Nickel

    International Nuclear Information System (INIS)

    Highlights: • Why residue is formed during anodic dissolution of carbonyl nickel was explained. • Spatiotemporal pattern of pitting in anodic Ni dissolution was described. • The role of sulfur impurities on anodic Ni dissolution was explained. - Abstract: The anodic dissolution of two laboratory-made Ni samples obtained using the carbonyl method was investigated to understand the origin of residue formation in the anode basket in an electroplating tank. The first sample was obtained with 3 ppm addition of carbonyl sulfide to introduce a small amount of sulfur (CN-S sample). The second was obtained without sulfur impurities (CN sample). Linear sweep voltammetry and chronopotentiometry were applied to characterize the dissolution of these samples. The dissolution of the CN-S sample took place in the active region at low overpotentials. This behavior is determined by the presence of sulfur impurities that break down the passive layer and facilitate Ni dissolution. The CN sample without sulfur was dissolved at high overpotentials. The overpotential-time plots displayed regular large amplitude oscillations in which the overvoltage periodically moved between the transpassive and passive regimes. The anodic dissolution of this sample was controlled by two competing processes: breakdown and formation of the passive layer. Scanning electron microscopy and white light interference microscopy were applied to monitor the morphological changes of the two samples as a function of the dissolution time. The results of these studies showed that the CN-S sample dissolved uniformly across the surface. However, the roughness and the aspect ratio of the protruding features on the surface increased with time. This sample produced a fine residue due to detachment of small protruding crystallites. In contrast, the dissolution of the CN sample involved pit formation and took place predominantly from the bulk of the pits. The dissolution of this sample left a porous skeleton of more

  7. Carbonyl emissions from gasoline and diesel motor vehicles.

    Science.gov (United States)

    Jakober, Chris A; Robert, Michael A; Riddle, Sarah G; Destaillats, Hugo; Charles, M Judith; Green, Peter G; Kleeman, Michael J

    2008-07-01

    Carbonyls from gasoline-powered light-duty vehicles (LDVs) and heavy-duty diesel-powered vehicles (HDDVs) operated on chassis dynamometers were measured by use of an annular denuder-quartz filter-polyurethane foam sampler with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine derivatization and chromatography-mass spectrometry analyses. Two internal standards were utilized based on carbonyl recovery: 4-fluorobenzaldehyde for or = C8 compounds. Gas- and particle-phase emissions for 39 aliphatic and 20 aromatic carbonyls ranged from 0.1 to 2000 microg/L of fuel for LDVs and from 1.8 to 27 000 microg/L of fuel for HDDVs. Gas-phase species accounted for 81-95% of the total carbonyls from LDVs and 86-88% from HDDVs. Particulate carbonyls emitted from a HDDV under realistic driving conditions were similar to concentrations measured in a diesel particulate matter (PM) standard reference material. Carbonyls accounted for 19% of particulate organic carbon (POC) emissions from low-emission LDVs and 37% of POC emissions from three-way catalyst-equipped LDVs. This identifies carbonyls as one of the largest classes of compounds in LDV PM emissions. The carbonyl fraction of HDDV POC was lower, 3.3-3.9% depending upon operational conditions. Partitioning analysis indicates the carbonyls had not achieved equilibrium between the gas and particle phases under the dilution factors of 126-584 used in the present study. PMID:18677993

  8. A novel method for improving cerussite sulfidization

    Science.gov (United States)

    Feng, Qi-cheng; Wen, Shu-ming; Zhao, Wen-juan; Cao, Qin-bo; Lü, Chao

    2016-06-01

    Evaluation of flotation behavior, solution measurements, and surface analyses were performed to investigate the effects of chloride ion addition on the sulfidization of cerussite in this study. Micro-flotation tests indicate that the addition of chloride ions prior to sulfidization can significantly increase the flotation recovery of cerussite, which is attributed to the formation of more lead sulfide species on the mineral surface. Solution measurement results suggest that the addition of chloride ions prior to sulfidization induces the transformation of more sulfide ions from pulp solution onto the mineral surface by the formation of more lead sulfide species. X-ray diffraction and energy-dispersive spectroscopy indicate that more lead sulfide species form on the mineral surface when chloride ions are added prior to sulfidization. These results demonstrate that the addition of chloride ions prior to sulfidization can significantly improve the sulfidization of cerussite, thereby enhancing the flotation performance.

  9. Pyrophoric nature of iron sulfides

    Energy Technology Data Exchange (ETDEWEB)

    Walker, R. [Univ. of Surrey, Guildford (United Kingdom). Dept. of Materials Science and Engineering; Steele, A.D.; Morgan, D.T.B. [Shell Research Centre Ltd., Chester (United Kingdom). Thornton Research Centre

    1996-05-01

    Hydrogen sulfide, often present in crude oil tankers, can react with rust to form various sulfides including mackinawite (FeS), greigite (Fe{sub 3}S{sub 4}), and pyrite (FeS{sub 2}). The tendency for these compounds to react with oxygen in air to form potentially explosive mixtures depends upon their morphology and the environmental conditions. The experimentally determined heat of oxidation of finely divided mackinawite was {minus}7.45 kJ/g. For samples with a larger particle size and smaller surface area the values measured were lower due to incomplete oxidation of the sulfide. All the sulfides produced, whether from magnetite or acicular, prismatic or spherical geothite, were approximately spherical in form. The heat of oxidation of greigite was found to be approximately {minus}2100 kJ/mol, and the heat of formation of greigite is approximately {minus}320 kJ/mol.

  10. Mechanochemical reduction of copper sulfide

    DEFF Research Database (Denmark)

    Balaz, P.; Takacs, L.; Jiang, Jianzhong; Soika, V.; Luxova, M.

    The mechanochemical reduction of copper sulfide with iron was induced in a Fritsch P-6 planetary mill, using WC vial filled with argon and WC balls. Samples milled for specific intervals were analyzed by XRD and Mossbauer spectroscopy. Most of the reaction takes place during the first 10 min of...... milling and only FeS and Cu are found after 60 min. The main chemical process is accompanied by phase transformations of the sulfide phases as a result of milling. Djurleite partially transformed to chalcocite and a tetragonal copper sulfide phase before reduction. The cubic modification of FeS was formed...... first, transforming to hexagonal during the later stages of the process. The formation of off-stoichiometric phases and the release of some elemental sulfur by copper sulfide are also probable....

  11. Carbonyl Emissions From Oil and Gas Production Facilities

    Science.gov (United States)

    Lyman, S. N.; O'Neil, T.; Tran, T.

    2015-12-01

    A number of recent studies have targeted emissions of methane and other hydrocarbons from oil and gas exploration and production activity. These measurements are greatly increasing understanding of the atmospheric impacts of oil and gas development. Very few measurements exist, however, of emissions of formaldehyde and other carbonyls from oil and gas equipment. Carbonyls are toxic and serve as important ozone precursors, especially during winter ozone episodes in places like Utah's Uintah Basin. Current air quality models are only able to reproduce observed high wintertime ozone if they incorporate emissions inventories with very high carbonyl emissions. We measured carbonyl emissions from oil and gas equipment and facilities—including glycol dehydrators, liquid storage tanks, raw gas leaks, raw gas-burning engines, and produced water surface impoundments—in Rocky Mountain oil and gas fields. Carbonyl emissions from raw gas were below detection, but emissions of formaldehyde, acetaldehyde, and other carbonyls were detected from liquid storage tanks, glycol dehydrators, and other oil and gas equipment. In some cases, carbonyls may be formed from the degradation of methanol and other chemicals used in oil and gas production, but the collected data provide evidence for other non-combustion formation pathways. Raw gas-burning engines also emitted carbonyls. Emissions from all measured sources were a small fraction of total volatile organic compound emissions. We incorporated our measurements into an emissions inventory, used that inventory in an air quality model (WRF-SMOKE-CAMx), and were unable to reproduce observed high wintertime ozone. This could be because (1) emission sources we have not yet measured, including compressors, gas processing plants, and others, are large; (2) non-carbonyl emissions, especially those that quickly degrade into carbonyls during photochemical processing, are underestimated in the inventory; or (3) the air quality model is unable

  12. A New HPLC Method to Determine Carbonyl Compounds in Air

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    In this paper, a new HPLC method was established to determine the carbonyl compounds in air. As the absorbent, 2, 4-dinitrophenylhydrazine (2, 4-DNPH) reacted with carbonyls specifically, which form the corresponding 2,4-dinitrophenylhydrazones, then analyzed by HPLC. The chromatographic conditions, the recovery rate, stability of samples, reagent blank, sampling efficiency were all studied systematically. The results showed that this established method had high sensitivity and good selectivity compared with other analytical methods, and it can determine ten carbonyl compounds in air in 26 min simultaneously.

  13. 16th Carbonyl Metabolism Meeting: from enzymology to genomics

    Directory of Open Access Journals (Sweden)

    Maser Edmund

    2012-12-01

    Full Text Available Abstract The 16th International Meeting on the Enzymology and Molecular Biology of Carbonyl Metabolism, Castle of Ploen (Schleswig-Holstein, Germany, July 10–15, 2012, covered all aspects of NAD(P-dependent oxido-reductases that are involved in the general metabolism of xenobiotic and physiological carbonyl compounds. Starting 30 years ago with enzyme purification, structure elucidation and enzyme kinetics, the Carbonyl Society members have meanwhile established internationally recognized enzyme nomenclature systems and now consider aspects of enzyme genomics and enzyme evolution along with their roles in diseases. The 16th international meeting included lectures from international speakers from all over the world.

  14. Targeting Reactive Carbonyl Species with Natural Sequestering Agents

    Directory of Open Access Journals (Sweden)

    Sung Won Hwang

    2016-02-01

    Full Text Available Reactive carbonyl species generated by the oxidation of polyunsaturated fatty acids and sugars are highly reactive due to their electrophilic nature, and are able to easily react with the nucleophilic sites of proteins as well as DNA causing cellular dysfunction. Levels of reactive carbonyl species and their reaction products have been reported to be elevated in various chronic diseases, including metabolic disorders and neurodegenerative diseases. In an effort to identify sequestering agents for reactive carbonyl species, various analytical techniques such as spectrophotometry, high performance liquid chromatography, western blot, and mass spectrometry have been utilized. In particular, recent advances using a novel high resolution mass spectrometry approach allows screening of complex mixtures such as natural products for their sequestering ability of reactive carbonyl species. To overcome the limited bioavailability and bioefficacy of natural products, new techniques using nanoparticles and nanocarriers may offer a new attractive strategy for increased in vivo utilization and targeted delivery of bioactives.

  15. Targeting Reactive Carbonyl Species with Natural Sequestering Agents.

    Science.gov (United States)

    Hwang, Sung Won; Lee, Yoon-Mi; Aldini, Giancarlo; Yeum, Kyung-Jin

    2016-01-01

    Reactive carbonyl species generated by the oxidation of polyunsaturated fatty acids and sugars are highly reactive due to their electrophilic nature, and are able to easily react with the nucleophilic sites of proteins as well as DNA causing cellular dysfunction. Levels of reactive carbonyl species and their reaction products have been reported to be elevated in various chronic diseases, including metabolic disorders and neurodegenerative diseases. In an effort to identify sequestering agents for reactive carbonyl species, various analytical techniques such as spectrophotometry, high performance liquid chromatography, western blot, and mass spectrometry have been utilized. In particular, recent advances using a novel high resolution mass spectrometry approach allows screening of complex mixtures such as natural products for their sequestering ability of reactive carbonyl species. To overcome the limited bioavailability and bioefficacy of natural products, new techniques using nanoparticles and nanocarriers may offer a new attractive strategy for increased in vivo utilization and targeted delivery of bioactives. PMID:26927058

  16. Theoretical Estimate of Hydride Affinities of Aromatic Carbonyl Compounds

    Institute of Scientific and Technical Information of China (English)

    AI Teng; ZHU Xiao-Qing; CHENG Jin-Pei

    2003-01-01

    @@ Aromatic carbonyl compounds are one type of the most important organic compounds, and the reductions ofthem by hydride agents such as LiAlH4 or NaBH4 are widely used in organic synthesis. The reactivity of carbonyl compounds generally increases in the following order: ketone < aldehyde, and amide < acid < ester < acid halide, which could be related to their hydride affinities (HA). In the previous paper, Robert[1] calculated the absolute HAof a series of small non-aromatic carbonyl compounds. In this paper, we use DFT method at B3LYP/6-311 + + G (2d, 2p)∥B3LYP/6-31 + G* level to estimate hydride affinities of five groups of aromatic carbonyl compounds. The detailed results are listed in Table 1.

  17. Targeting Reactive Carbonyl Species with Natural Sequestering Agents

    OpenAIRE

    Sung Won Hwang; Yoon-Mi Lee; Giancarlo Aldini; Kyung-Jin Yeum

    2016-01-01

    Reactive carbonyl species generated by the oxidation of polyunsaturated fatty acids and sugars are highly reactive due to their electrophilic nature, and are able to easily react with the nucleophilic sites of proteins as well as DNA causing cellular dysfunction. Levels of reactive carbonyl species and their reaction products have been reported to be elevated in various chronic diseases, including metabolic disorders and neurodegenerative diseases. In an effort to identify sequestering agents...

  18. Synthesis of furan from allenic sulfide derivatives

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    In this paper, we report the synthesis of furan derivatives from allenic sulfides. By the reaction with NaH, β-Hydroxyl allenic sulfides were found to generate furan products in excellent yields with the removal of phenylthio group. β-Aldehyde allenic sulfides were found to give similar furan products with one more substituent when treated with additional nucleophilic reagents. β-ketone allenic sulfides can also cyclize to give furan derivatives with the promotion of P2O5.

  19. Synthesis of furan from allenic sulfide derivatives

    Institute of Scientific and Technical Information of China (English)

    PENG LingLing; ZHANG Xiu; MA Jie; ZHONG ZhenZhen; ZHANG Zhe; ZHANG Yan; WANG JianBo

    2009-01-01

    In this paper, we report the synthesis of furan derivatives from allenic sulfides. By the reaction with NaH.,β-Hydroxyl allenic sulfides were found to generate furan products in excellent yields with the removal of phenylthio group.β-Aldehyde allenic sulfides were found to give similar furan products with one more substituent when treated with additional nucleophilic reagents. β-ketone allenic sulfides can also cyclize to give furan derivatives with the promotion of P2O5.

  20. Carbonyl species characteristics during the evaporation of essential oils

    Science.gov (United States)

    Chiang, Hsiu-Mei; Chiu, Hua-Hsien; Lai, Yen-Ming; Chen, Ching-Yen; Chiang, Hung-Lung

    2010-06-01

    Carbonyls emitted from essential oils can affect the air quality when they are used in indoors, especially under poor ventilation conditions. Lavender, lemon, rose, rosemary, and tea tree oils were selected as typical and popular essential oils to investigate in terms of composition, thermal characteristics and fifteen carbonyl constituents. Based on thermogravimetric (TG) analysis, the activation energy was 7.6-8.3 kcal mol -1, the reaction order was in the range of 0.6-0.7 and the frequency factor was 360-2838 min -1. Formaldehyde, acetaldehyde, acetone, and propionaldehyde were the dominant carbonyl compounds, and their concentrations were 0.034-0.170 ppm. The emission factors of carbonyl compounds were 2.10-3.70 mg g -1, and acetone, propionaldehyde, acetaldehyde, and formaldehyde accounted for a high portion of the emission factor of carbonyl compounds in essential oil exhaust. Some unhealthy carbonyl species such as formaldehyde and valeraldehyde, were measured at low-temperature during the vaporization of essential oils, indicating a potential effect on indoor air quality and human health.

  1. 30 CFR 250.808 - Hydrogen sulfide.

    Science.gov (United States)

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.808 Section 250.808... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Production Safety Systems § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of...

  2. 30 CFR 250.490 - Hydrogen sulfide.

    Science.gov (United States)

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.490 Section 250.490... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Drilling Operations Hydrogen Sulfide § 250.490 Hydrogen... black lettering as follows: Letter height Wording 12 inches Danger. Poisonous Gas. Hydrogen Sulfide....

  3. 30 CFR 250.604 - Hydrogen sulfide.

    Science.gov (United States)

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.604 Section 250.604... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Workover Operations § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or...

  4. 30 CFR 250.504 - Hydrogen sulfide.

    Science.gov (United States)

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.504 Section 250.504... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Completion Operations § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or...

  5. Traditional reactive carbonyl scavengers do not prevent the carbonylation of brain proteins induced by acute glutathione depletion

    OpenAIRE

    Zheng, J; Bizzozero, O. A.

    2010-01-01

    This study investigated the effect of reactive carbonyl species (RCS)-trapping agents on the formation of protein carbonyls during depletion of brain glutathione (GSH). To this end, rat brain slices were incubated with the GSH-depletor diethyl maleate in the absence or presence of chemically different RCS scavengers (hydralazine, methoxylamine, aminoguanidine, pyridoxamine, carnosine, taurine and z-histidine hydrazide). Despite their strong reactivity towards the most common RCS, none of the ...

  6. STUDY OF HYDROGEN SULFIDE REMOVAL FROM GROUNDWATER

    Directory of Open Access Journals (Sweden)

    T. Lupascu

    2013-06-01

    Full Text Available The process of the hydrogen sulfide removal from the underground water of the Hancesti town has been investigated. By oxygen bubbling through the water containing hydrogen sulfide, from the Hancesti well tube, sulfur is deposited in the porous structure of studied catalysts, which decreases their catalytic activity. Concomitantly, the process of adsorption / oxidation of hydrogen sulfide to sulfate take place. The kinetic research of the hydrogen sulfide removal from the Hancesti underground water, after its treatment by hydrogen peroxide, proves greater efficiency than in the case of modified carbonic adsorbents. As a result of used treatment, hydrogen sulfide is completely oxidized to sulfates

  7. Sulfide intrusion and detoxification in seagrasses ecosystems

    DEFF Research Database (Denmark)

    Hasler-Sheetal, Harald; Holmer, Marianne

    Sulfide intrusion in seagrasses represents a global threat to seagrasses and thereby an important parameter in resilience of seagrass ecosystems. In contrast seegrasses colonize and grow in hostile sediments, where they are constantly exposed to invasion of toxic gaseous sulfide. Remarkably little...... is known about the strategies of seagrasses to survive sulfide intrusion, their potential detoxification mechanisms and sulfur nutrition in general. By a global review of sulfide intrusion, coupled with a series of field studies and in situ experiments we elucidate sulfide intrusion and different...... strategies of seagrasses to sustain sulfide intrusion. Using stable isotope tracing, scanning electron microscopy with x-ray analysis, tracing sulfur compounds combined with ecosystem parameters we found different spatial, intraspecific and interspecific strategies to cope with sulfidic sediments. 1...

  8. Clinical features of schizophrenia with enhanced carbonyl stress.

    Science.gov (United States)

    Miyashita, Mitsuhiro; Arai, Makoto; Kobori, Akiko; Ichikawa, Tomoe; Toriumi, Kazuya; Niizato, Kazuhiro; Oshima, Kenichi; Okazaki, Yuji; Yoshikawa, Takeo; Amano, Naoji; Miyata, Toshio; Itokawa, Masanari

    2014-09-01

    Accumulating evidence suggests that advanced glycation end products, generated as a consequence of facilitated carbonyl stress, are implicated in the development of a variety of diseases. These diseases include neurodegenerative illnesses, such as Alzheimer disease. Pyridoxamine is one of the 3 forms of vitamin B6, and it acts by combating carbonyl stress and inhibiting the formation of AGEs. Depletion of pyridoxamine due to enhanced carbonyl stress eventually leads to a decrease in the other forms of vitamin B6, namely pyridoxal and pyridoxine. We previously reported that higher levels of plasma pentosidine, a well-known biomarker for advanced glycation end products, and decreased serum pyridoxal levels were found in a subpopulation of schizophrenic patients. However, there is as yet no clinical characterization of this subset of schizophrenia. In this study, we found that these patients shared many clinical features with treatment-resistant schizophrenia. These include a higher proportion of inpatients, low educational status, longer durations of hospitalization, and higher doses of antipsychotic medication, compared with patients without carbonyl stress. Interestingly, psychopathological symptoms showed a tendency towards negative association with serum vitamin B6 levels. Our results support the idea that treatment regimes reducing carbonyl stress, such as supplementation of pyridoxamine, could provide novel therapeutic benefits for this subgroup of patients. PMID:24062594

  9. Traditional reactive carbonyl scavengers do not prevent the carbonylation of brain proteins induced by acute glutathione depletion.

    Science.gov (United States)

    Zheng, J; Bizzozero, O A

    2010-03-01

    This study investigated the effect of reactive carbonyl species (RCS)-trapping agents on the formation of protein carbonyls during depletion of brain glutathione (GSH). To this end, rat brain slices were incubated with the GSH-depletor diethyl maleate in the absence or presence of chemically different RCS scavengers (hydralazine, methoxylamine, aminoguanidine, pyridoxamine, carnosine, taurine and z-histidine hydrazide). Despite their strong reactivity towards the most common RCS, none of the scavengers tested, with the exception of hydralazine, prevented protein carbonylation. These findings suggest that the majority of protein-associated carbonyl groups in this oxidative stress paradigm do not derive from stable lipid peroxidation products like malondialdehyde (MDA), acrolein and 4-hydroxynonenal (4-HNE). This conclusion was confirmed by the observation that the amount of MDA-, acrolein- and 4-HNE-protein adducts does not increase upon GSH depletion. Additional studies revealed that the efficacy of hydralazine at preventing carbonylation was due to its ability to reduce oxidative stress, most likely by inhibiting mitochondrial production of superoxide and/or by scavenging lipid free radicals. PMID:20001647

  10. Redox Biochemistry of Hydrogen Sulfide*

    OpenAIRE

    Kabil, Omer; Banerjee, Ruma

    2010-01-01

    H2S, the most recently discovered gasotransmitter, might in fact be the evolutionary matriarch of this family, being both ancient and highly reduced. Disruption of γ-cystathionase in mice leads to cardiovascular dysfunction and marked hypertension, suggesting a key role for this enzyme in H2S production in the vasculature. However, patients with inherited deficiency in γ-cystathionase apparently do not present vascular pathology. A mitochondrial pathway disposes sulfide and couples it to oxid...

  11. Infrared Photodissociation Spectroscopy of Metal Oxide Carbonyl Cations.

    Science.gov (United States)

    Brathwaite, Antonio D.; Duncan, Michael A.

    2013-06-01

    Mass selected metal oxide-carbonyl cations of the form MO_{m}(CO)_{n}^{+} are studied via infrared laser photodissociation spectroscopy, in the 600-2300cm^{1} region. Insight into the structure and bonding of these complexes is obtained from the number of infrared active bands, their relative intensities and their frequency positions. Density functional theory calculations are carried out in support of the experimental data. Insight into the bonding of CO ligands to metal oxides is obtained and the effect of oxidation on the carbonyl stretching frequency is revealed.

  12. Formation of vesicles with an organometallic amphiphilic bilayer by supramolecular arrangement of metal carbonyl metallosurfactants

    OpenAIRE

    Parera Piella, Elisabet; Comelles, Francesc; Barnadas Rodríguez, Ramon; Suades Ortuño, Joan

    2011-01-01

    Metallo-vesicles are formed in water medium as a result of the supramolecular arrangement of molybdenum carbonyl metallosurfactants. These new kind of surfactants contain a hydrophobic metal carbonyl fragment and are easily prepared from surfactant phosphine ligands

  13. Iron-Sulfur-Carbonyl and -Nitrosyl Complexes: A Laboratory Experiment.

    Science.gov (United States)

    Glidewell, Christopher; And Others

    1985-01-01

    Background information, materials needed, procedures used, and typical results obtained, are provided for an experiment on iron-sulfur-carbonyl and -nitrosyl complexes. The experiment involved (1) use of inert atmospheric techniques and thin-layer and flexible-column chromatography and (2) interpretation of infrared, hydrogen and carbon-13 nuclear…

  14. Comparing Carbonyl Chemistry in Comprehensive Introductory Organic Chemistry Textbooks

    Science.gov (United States)

    Nelson, Donna J.; Kumar, Ravi; Ramasamy, Saravanan

    2015-01-01

    Learning the chemistry of compounds containing carbonyl groups is difficult for undergraduate students partly because of a convolution of multiple possible reaction sites, competitive reactions taking place at those sites, different criteria needed to discern between the mechanisms of these reactions, and no straightforward selection method…

  15. Frustrated Lewis pairs-assisted reduction of carbonyl compounds

    DEFF Research Database (Denmark)

    Marek, Ales; Pedersen, Martin Holst Friborg

    2015-01-01

    An alternative and robust method for the reduction of carbonyl groups by frustrated Lewis pairs (FLPs) is reported in this paper. With its very mild reaction conditions, good to excellent yields, absolute regioselectivity and the non-metallic character of the reagent, it provides an excellent too...

  16. High throughput assay for evaluation of reactive carbonyl scavenging capacity ☆

    OpenAIRE

    N. Vidal; J.P. Cavaille; Graziani, F.; M. Robin; Ouari, O; Pietri, S.; Stocker, P.

    2014-01-01

    Many carbonyl species from either lipid peroxidation or glycoxidation are extremely reactive and can disrupt the function of proteins and enzymes. 4-hydroxynonenal and methylglyoxal are the most abundant and toxic lipid-derived reactive carbonyl species. The presence of these toxics leads to carbonyl stress and cause a significant amount of macromolecular damages in several diseases. Much evidence indicates trapping of reactive carbonyl intermediates may be a useful strategy for inhibiting or...

  17. Kinetic Studies of Sulfide Mineral Oxidation and Xanthate Adsorption

    OpenAIRE

    Mendiratta, Neeraj K.

    2000-01-01

    Sulfide minerals are a major source of metals; however, certain sulfide minerals, such as pyrite and pyrrhotite, are less desirable. Froth flotation is a commonly used separation technique, which requires the use of several reagents to float and depress different sulfide minerals. Xanthate, a thiol collector, has gained immense usage in sulfide minerals flotation. However, some sulfides are naturally hydrophobic and may float without a collector. Iron sulfides, such as pyrite and pyrrho...

  18. Hydrogen sulfide and vascular relaxation

    Institute of Scientific and Technical Information of China (English)

    SUN Yan; TANG Chao-shu; DU Jun-bao; JIN Hong-fang

    2011-01-01

    Objective To review the vasorelaxant effects of hydrogen sulfide (H2S) in arterial rings in the cardiovascular system under both physiological and pathophysiological conditions and the possible mechanisms involved.Data sources The data in this review were obtained from Medline and Pubmed sources from 1997 to 2011 using the search terms "hydrogen sulfide" and ""vascular relaxation".Study selection Articles describing the role of hydrogen sulfide in the regulation of vascular activity and its vasorelaxant effects were selected.Results H2S plays an important role in the regulation of cardiovascular tone.The vasomodulatory effects of H2S depend on factors including concentration,species and tissue type.The H2S donor,sodium hydrosulfide (NarS),causes vasorelaxation of rat isolated aortic rings in a dose-dependent manner.This effect was more pronounced than that observed in pulmonary arterial rings.The expression of KATP channel proteins and mRNA in the aortic rings was increased compared with pulmonary artery rings.H2S is involved in the pathogenesis of a variety of cardiovascular diseases.Downregulation of the endogenous H2S pathway is an important factor in the pathogenesis of cardiovascular diseases.The vasorelaxant effects of H2S have been shown to be mediated by activation of KATP channels in vascular smooth muscle cells and via the induction of acidification due to activation of the CI/HCO3 exchanger.It is speculated that the mechanisms underlying the vasoconstrictive function of H2S in the aortic rings involves decreased NO production and inhibition of cAMP accumulation.Conclusion H2S is an important endogenous gasotransmitter in the cardiovascular system and acts as a modulator of vascular tone in the homeostatic regulation of blood pressure.

  19. Optimized biotin-hydrazide enrichment and mass spectrometry analysis of peptide carbonyls

    DEFF Research Database (Denmark)

    Havelund, Jesper F.; Wojdyla, K; Jensen, O. N.; Møller, Ian Max; Rogowska-Wrzesinska, A.

    Irreversible cell damage through protein carbonylation is the result of reaction with reactive oxygen species (ROS) and has been coupled to many diseases. The precise molecular consequences of protein carbonylation, however, are still not clear. The localization of the carbonylated amino acid is ...

  20. Variation in sulfide tolerance of photosystem II in phylogenetically diverse cyanobacteria from sulfidic habitats

    Science.gov (United States)

    Miller, Scott R.; Bebout, Brad M.

    2004-01-01

    Physiological and molecular phylogenetic approaches were used to investigate variation among 12 cyanobacterial strains in their tolerance of sulfide, an inhibitor of oxygenic photosynthesis. Cyanobacteria from sulfidic habitats were found to be phylogenetically diverse and exhibited an approximately 50-fold variation in photosystem II performance in the presence of sulfide. Whereas the degree of tolerance was positively correlated with sulfide levels in the environment, a strain's phenotype could not be predicted from the tolerance of its closest relatives. These observations suggest that sulfide tolerance is a dynamic trait primarily shaped by environmental variation. Despite differences in absolute tolerance, similarities among strains in the effects of sulfide on chlorophyll fluorescence induction indicated a common mode of toxicity. Based on similarities with treatments known to disrupt the oxygen-evolving complex, it was concluded that sulfide toxicity resulted from inhibition of the donor side of photosystem II.

  1. New biologically active hydrogen sulfide donors.

    Science.gov (United States)

    Roger, Thomas; Raynaud, Francoise; Bouillaud, Frédéric; Ransy, Céline; Simonet, Serge; Crespo, Christine; Bourguignon, Marie-Pierre; Villeneuve, Nicole; Vilaine, Jean-Paul; Artaud, Isabelle; Galardon, Erwan

    2013-11-25

    Generous donors: The dithioperoxyanhydrides (CH3 COS)2 , (PhCOS)2 , CH3 COSSCO2 Me and PhCOSSCO2 Me act as thiol-activated hydrogen sulfide donors in aqueous buffer solution. The most efficient donor (CH3 COS)2 can induce a biological response in cells, and advantageously replace hydrogen sulfide in ex vivo vascular studies. PMID:24115650

  2. Sulfide stress cracking of pipeline steels

    International Nuclear Information System (INIS)

    The problem of the sulfide stress corrosion cracking of pipeline steels and their welded joints have been presented for pipeline steels. Results of hydrogen sulfide stress cracking inhibitors and corrosion inhibitors of three types protective actions on pipeline steels of two grades petroleum range of products are given. (author)

  3. Ammonia and hydrogen sulfide removal using biochar

    Science.gov (United States)

    Reducing ammonia and hydrogen sulfide emissions from livestock facilities is an important issue for many communities and livestock producers. Ammonia has been regarded as odorous, precursor for particulate matter (PM), and contributed to livestock mortality. Hydrogen sulfide is highly toxic at elev...

  4. An efficient synthesis of 2-[carbonyl-11C]acetamido-2-deoxy-D-glucopyranose (N-[carbonyl-11C]acetyl-D-glucosamine)

    International Nuclear Information System (INIS)

    A rapid chemical synthesis of 2-[carbonyl-11C]acetamido-2-deoxy-D-glucopyranose (N-[carbonyl-11C]acetyl-D-glucosamine) starting from [11C]carbon dioxide is described. The total time required for the synthesis, the radiochemical yield, and purity of the titled sugar are ca. 60 min, 49.5% (based on [carbonyl-11C] acetic acid), and >98%, respectively. (author)

  5. Regulation of nonadiabatic processes in the photolysis of some carbonyl compounds.

    Science.gov (United States)

    Lin, King-Chuen

    2016-03-14

    Carbonyl compounds studied are confined to acetyl halide (CH3COCl), acetyl cyanide (CH3COCN), acetyl sulfide (CH3COSH), acetaldehyde (CH3CHO), and methyl formate (HCOOCH3). They are asymmetrically substituted, but do not follow the well-known Norrish type I reactions. Each compound ejected in an effusive beam at about 300 K is commonly excited to the (1)(n, π*)CO lower state; that is, a nonbonding electron on O of the C[double bond, length as m-dash]O group is promoted to the antibonding orbital of π*CO. The photolysis experiments are conducted in the presence of Ar gas and the corresponding fragments are detected using time-resolved Fourier-transform Infrared (FTIR) emission spectroscopy. The enhancement of the collision-induced internal conversion or intersystem crossing facilitates the dissociation channels via highly vibrational states of the ground singlet (So) or triplet (T1) potential energy surfaces. In this manner, an alternative nonadiabatic channel is likely to open yielding different products, even if the diabatic coupling strength is strong between the excited state and the neighboring state. For instance, the photodissociation of CH3COCl at 248 nm produces HCl, CO, and CH2 fragments, in contrast to the supersonic jet experiments showing dominance of the Cl fragment eliminated from the excited state. If the diabatic coupling strength is weak, dissociation proceeds mainly through internal conversion, such as the cases of CH3COCN and CH3COSH. The photodissociation of CH3COCN at 308 nm has never been reported before, while for CH3COSH matrix-isolated photodissociation was conducted that shows a distinct spectral feature from the current FTIR method. The CH3CHO and HCOOCH3 molecules belong to the same type of carbonyl compounds, in which the molecular products, CO + CH4 and CO + CH3OH, are produced through both transition state and roaming pathways. Their products are characterized differently between molecular beam and current FTIR experiments. For

  6. Weathering of sulfides on Mars

    Science.gov (United States)

    Burns, Roger G.; Fisher, Duncan S.

    1987-01-01

    Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produce degradation products in the Martian regolith. By analogy and terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni, and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato-and hydroxo-complex ions and sols formed gossan above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite), and silica (opal). Underlying groundwater, now permafrost contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates, and phyllosilicates during dust storms on Mars.

  7. Measurement of dissolved sulfide in geothermal condensate

    Energy Technology Data Exchange (ETDEWEB)

    Chang, D.P.Y.; Corsi, R.L.; McNeece, C.

    1985-01-01

    The objective of this study was to develop a reliable method for determining the concentration of sulfide ions in laboratory solutions and in field samples containing geothermal condensate. A method based upon a sulfide selective ion electrode has been tested successfully on both. The method is straightforward to apply, involving collection of filtered samples into a sulfide anti-oxidant buffer (SAOB), subsequent measurement by electrodes and comparison with a calibration curve prepared from solutions containing known concentrations of sulfide ions. The importance of filtering the samples was demonstrated by a marked reduction of electrode potential after sample filtration. For replicate solutions of known composition containing greater than 1 x 10/sup -6/ M (0.032 ppm) of dissolved sulfide the estimated accuracy of the method was about 5%. For geothermal condensate of unknown composition, the mean of replicate samples was estimated to be within about 20% of the true value.

  8. Comparing forward and inverse models to estimate the seasonal variation of hemisphere-integrated fluxes of carbonyl sulfide

    Directory of Open Access Journals (Sweden)

    A. J. Kettle

    2002-01-01

    Full Text Available A simple inverse model is proposed to deduce hemisphere-integrated COS flux based on published time series of total column COS. The global atmosphere is divided into two boxes representing the Northern and Southern Hemispheres, and the total column COS data from several stations are used to calculate hemispheric COS loadings. The integrated flux within each hemisphere is calculated as a linear combination of a steady-state solution and time-varying perturbation. The nature of the time-varying perturbation is deduced using two different approaches: an analytic solution based on a cosine function that was fitted to the original total column COS measurement time series and a Simplex optimization with no underlying assumption about the functional form of the total column time series. The results suggest that there is a steady-state COS flux from the Northern to the Southern Hemisphere. There is a seasonal variation superimposed on this flux that in the Southern Hemisphere has a maximum rate of COS input into the atmosphere around January and a maximum rate of COS removal from the atmosphere around August--September. In the Northern Hemisphere, the maximum rate of COS input into the atmosphere is around May--June, and the maximum rate of COS removal is either August or January, depending on which station in the Northern Hemisphere is considered. The results of the inverse model are compared with the outcome of a forward approach on the temporal and spatial variation of the dominant global sources and sinks published earlier. In general, the deduced hemisphere-integrated flux estimates showed good agreement with the database estimates, though it remains uncertain whether COS removal from the atmosphere in the Northern Hemisphere is dominated by plant and soil uptake in the boreal summer or by oceanic uptake in boreal winter.

  9. Comparing forward and inverse models to estimate the seasonal variation of hemisphere-integrated fluxes of carbonyl sulfide

    Directory of Open Access Journals (Sweden)

    A. J. Kettle

    2002-06-01

    Full Text Available A simple inverse model is proposed to deduce hemisphere-integrated COS flux based on published time series of total column COS. The global atmosphere is divided into two boxes representing the Northern and Southern Hemispheres, and the total column COS data from several stations are used to deduce hemispheric COS loadings. The integrated flux within each hemisphere is calculated as a linear combination of a steady-state solution and time-varying perturbation. The nature of the time-varying perturbation is deduced using two different approaches: an analytic solution based on a cosine function that was fitted to the original total column COS measurement time series and a Simplex optimization with no underlying assumption about the functional form of the total column time series. The results suggest that there is a steady-state COS flux from the Northern to the Southern Hemisphere. There is a seasonal variation superimposed on this flux that in the Southern Hemisphere has a maximum rate of COS input into the atmosphere around January and a maximum rate of COS removal from the atmosphere around August--September. In the Northern Hemisphere, the maximum rate of COS input into the atmosphere is around May--June, and the maximum rate of COS removal is either August or January, depending on which station in the Northern Hemisphere is considered. The results of the inverse model are compared with the outcome of a forward approach on the temporal and spatial variation of the dominant global sources and sinks published earlier. In general, the deduced hemisphere-integrated flux estimates showed good agreement with the database estimates, though it remains uncertain whether COS removal from the atmosphere in the Northern Hemisphere is dominated by plant and soil uptake in the boreal summer or by oceanic uptake in boreal winter.

  10. Phenolic carbonyls undergo rapid aqueous photodegradation to form low-volatility, light-absorbing products

    Science.gov (United States)

    Smith, Jeremy D.; Kinney, Haley; Anastasio, Cort

    2016-02-01

    We investigated the aqueous photochemistry of six phenolic carbonyls - vanillin, acetovanillone, guaiacyl acetone, syringaldehyde, acetosyringone, and coniferyl aldehyde - that are emitted from wood combustion. The phenolic carbonyls absorb significant amounts of solar radiation and decay rapidly via direct photodegradation, with lifetimes (τ) of 13-140 min under Davis, CA winter solstice sunlight at midday (solar zenith angle = 62°). The one exception is guaiacyl acetone, where the carbonyl group is not directly connected to the aromatic ring: This species absorbs very little sunlight and undergoes direct photodegradation very slowly (τ > 103 min). We also found that the triplet excited states (3C*) of the phenolic carbonyls rapidly oxidize syringol (a methoxyphenol without a carbonyl group), on timescales of 1-5 h for solutions containing 5 μM phenolic carbonyl. The direct photodegradation of the phenolic carbonyls, and the oxidation of syringol by 3C*, both efficiently produce low volatility products, with SOA mass yields ranging from 80 to 140%. Contrary to most aliphatic carbonyls, under typical fog conditions we find that the primary sink for the aromatic phenolic carbonyls is direct photodegradation in the aqueous phase. In areas of significant wood combustion, phenolic carbonyls appear to be small but significant sources of aqueous SOA: over the course of a few hours, nearly all of the phenolic carbonyls will be converted to SOA via direct photodegradation, enhancing the POA mass from wood combustion by approximately 3-5%.

  11. [Carbonyl stress and oxidatively modified proteins in chronic renal failure].

    Science.gov (United States)

    Bargnoux, A-S; Morena, M; Badiou, S; Dupuy, A-M; Canaud, B; Cristol, J-P

    2009-01-01

    Oxidative stress is commonly observed in chronic renal failure patients resulting from an unbalance between overproduction of reactive oxygen species and impairement of defense mechanisms. Proteins appear as potential targets of uremia-induced oxidative stress and may undergo qualitative modifications. Proteins could be directly modified by reactive oxygen species which leads to amino acid oxydation and cross-linking. Proteins could be indirectly modified by reactive carbonyl compounds produced by glycoxidation and lipo-peroxidation. The resulting post-traductional modifications are known as carbonyl stress. In addition, thiols could be oxidized or could react with homocystein leading to homocysteinylation. Finally, tyrosin could be oxidized by myeloperoxidase leading to advanced oxidative protein products (AOPP). Oxidatively modified proteins are increased in chronic renal failure patients and may contribute to exacerbate the oxidative stress/inflammation syndrome. They have been involved in long term complications of uremia such as amyloidosis and accelerated atherosclerosis. PMID:19297289

  12. Role of Carbonyl Modifications on Aging-Associated Protein Aggregation

    Science.gov (United States)

    Tanase, Maya; Urbanska, Aleksandra M.; Zolla, Valerio; Clement, Cristina C.; Huang, Liling; Morozova, Kateryna; Follo, Carlo; Goldberg, Michael; Roda, Barbara; Reschiglian, Pierluigi; Santambrogio, Laura

    2016-01-01

    Protein aggregation is a common biological phenomenon, observed in different physiological and pathological conditions. Decreased protein solubility and a tendency to aggregate is also observed during physiological aging but the causes are currently unknown. Herein we performed a biophysical separation of aging-related high molecular weight aggregates, isolated from the bone marrow and splenic cells of aging mice and followed by biochemical and mass spectrometric analysis. The analysis indicated that compared to younger mice an increase in protein post-translational carbonylation was observed. The causative role of these modifications in inducing protein misfolding and aggregation was determined by inducing carbonyl stress in young mice, which recapitulated the increased protein aggregation observed in old mice. Altogether our analysis indicates that oxidative stress-related post-translational modifications accumulate in the aging proteome and are responsible for increased protein aggregation and altered cell proteostasis.

  13. Primordial Xenon in Allende Sulfides

    Science.gov (United States)

    Lee, J. T.; Manuel, O. K.

    1995-09-01

    The Allende C3V carbonaceous chondrite incorporated isotopically anomalous components of several medium-heavy elements (Z=36-62) from nucleosynthesis [1]. Isotopically distinct Xe (Z=54) has been found in grains ranging from several _ to a few mm in size. Diamond [2] is the host of Xe that is enriched in isotopes produced by the very rapid p- and r-processes in a supernova explosion [3]. Silicon carbide [4] is the host of Xe that is enriched in the middle isotopes, 128-132Xe, produced by slow neutron capture [3] before a star reaches the supernova stage. The present study was undertaken to identify the isotopic composition of primitive Xe initially trapped in sulfides of the Allende meteorite. Two FeS mineral separates were analyzed by stepwise heating. One sample was first irradiated in a neutron flux to generate a tracer isotope, 131*Xe, by the 130Te(n, gamma beta-)131*Xe reaction. The release pattern of this tracer isotope, 131*Xe, closely paralleled the release of primordial 132Xe up to 950 degrees C, when the sulfide melted and released the bulk of its trapped Xe (Figure 1). The Xe released from both samples at 950 deg C was terrestrial in isotopic composition, except for enrichments from spallogenic and radiogenic components (Figure 2). From the results of this and earlier analyses of Xe in meteoritic FeS [5, 6, 7], we conclude that terrestrial-type Xe was dominant in the central region of the protoplanetary nebula, and it remains a major component in the FeS of diverse meteorites and in the terrestrial planets that are rich in Fe, S [8]. References: [1] Begemann F. (1993) Origin and Evolution of the Elements (N. Prantzos et al., eds.), 518-527, Cambridge Univ. [2] Lewis R. S. and Anders E. (1988) LPS XIX, 679-680. [3] Burbidge et al. (1957) Rev. Modern Phys., 29, 547-650. [4] Tang M. and Anders E. (1988) GCA, 52, 1235-1244. [5] Niemeyer S. (1979) GCA, 43, 843-860. [6] Lewis et al. (1979) GCA, 43, 1743-1752. [7] Hwaung G. and Manuel O. K. (1982) Nature, 299

  14. Special Topic 3B: Acidity, Basicity, and Carbonyl Condensation Reactions

    OpenAIRE

    Christiansen, Mike A

    2012-01-01

    The purpose of this video is to help second-year organic chemistry students review the concepts and questions that most frequently appear on standardized entrance exams, like the MCAT, DAT, PCAT, and GRE. I'll here teach you how to sort molecules according to acidity and basicity. I'll also review the following carbonyl condensation and related reactions: the aldol reaction, the Claisen and intramolecular diketone condensations, and the malonic ester synthesis. --Dr. Mike Christiansen from Ut...

  15. Nucleophilic tetrafluoroethylation of carbonyl compounds with fluorinated sulfones

    Czech Academy of Sciences Publication Activity Database

    Václavík, Jiří; Chernykh, Yana; Jurásek, Bronislav; Beier, Petr

    2015-01-01

    Roč. 169, Jan (2015), s. 24-31. ISSN 0022-1139 R&D Projects: GA ČR GAP207/11/0421 Grant ostatní: GA MŠk(CZ) ED3.2.00/08.0144; GA MŠk(CZ) LM2010005 Institutional support: RVO:61388963 Keywords : fluorine * tetrafluoroethylation * sulfones * nucleophilic addition * carbonyl compounds Subject RIV: CC - Organic Chemistry Impact factor: 1.948, year: 2014

  16. Iron(III)-catalysed carbonyl-olefin metathesis.

    Science.gov (United States)

    Ludwig, Jacob R; Zimmerman, Paul M; Gianino, Joseph B; Schindler, Corinna S

    2016-05-19

    The olefin metathesis reaction of two unsaturated substrates is one of the most powerful carbon-carbon-bond-forming reactions in organic chemistry. Specifically, the catalytic olefin metathesis reaction has led to profound developments in the synthesis of molecules relevant to the petroleum, materials, agricultural and pharmaceutical industries. These reactions are characterized by their use of discrete metal alkylidene catalysts that operate via a well-established mechanism. While the corresponding carbonyl-olefin metathesis reaction can also be used to construct carbon-carbon bonds, currently available methods are scarce and severely hampered by either harsh reaction conditions or the required use of stoichiometric transition metals as reagents. To date, no general protocol for catalytic carbonyl-olefin metathesis has been reported. Here we demonstrate a catalytic carbonyl-olefin ring-closing metathesis reaction that uses iron, an Earth-abundant and environmentally benign transition metal, as a catalyst. This transformation accommodates a variety of substrates and is distinguished by its operational simplicity, mild reaction conditions, high functional-group tolerance, and amenability to gram-scale synthesis. We anticipate that these characteristics, coupled with the efficiency of this reaction, will allow for further advances in areas that have historically been enhanced by olefin metathesis. PMID:27120158

  17. Pelletizing of sulfide molybdenite concentrates

    Science.gov (United States)

    Palant, A. A.

    2007-04-01

    The results of a pelletizing investigation using various binding components (water, syrup, sulfite-alcohol distillery grains, and bentonite) of the flotation sulfide molybdenite concentrate (˜84% MoS2) from the Mongolian deposit are discussed. The use of syrup provides rather high-strength pellets (>3 N/pellet or >300 g/pellet) of the required size (2 3 mm) for the consumption of 1 kg binder per 100 kg concentrate. The main advantage of the use of syrup instead of bentonite is that the molybdenum cinder produced by oxidizing roasting of raw ore materials is not impoverished due to complete burning out of the syrup. This fact exerts a positive effect on the subsequent hydrometallurgical process, decreasing molybdenum losses related to dump cakes.

  18. Adequate hydrogen sulfide, healthy circulation

    Institute of Scientific and Technical Information of China (English)

    DU Jun-bao; CHEN Stella; JIN Hong-fang; TANG Chao-shu

    2011-01-01

    Previously,hydrogen sulfide (H2S) was considered to be a toxic gas.However,recently it was discovered that it could be produced in mammals and even in plants,throughtheproductionandmetabolismof sulfur-containing amino acids.In mammals,H2S is mainly catalyzed by cystathionine-γ-lyase (CSE),cystathionin-β-lyase (CBS) and 3-mercaptopyruvate sulfurtransferase (MPST) with the substrate of L-cysteine.Endogenous H2S exerts many important physiological and pathophysiological functions,including hypotensive action,vasorelaxation,myocardial dilation,inhibition of smooth muscle cell proliferation,and antioxidatve actions.Importantly,it plays a very important role in the pathogenesis of systemic hypertension,pulmonary hypertension,atherosclerosis,myocardialinjury,angiogenesis,hyperhomocysteinemi aandshock.Therefore,H2S is now being considered to be a novel gasotransmitter after nitric oxide and carbon monoxide in the regulation of circulatory system.

  19. How selection offsets sulfide corrosion

    International Nuclear Information System (INIS)

    Steels in Girdler heavy water plants are generally required to withstand wet hydrogen sulfide or its aqueous solution. The reasons for selecting various grades for various locations are explained. Information on welding methods is given, and the codes applicable are listed. Carbon steel can be used only where fluid velocity is low. Sections which fail completely if pitted are made of AISI 316 stainless steel. Diaphragms and other very thin parts located in the stagnant fluid are made of Inconel 625. Where solution-annealing of stainless steels at 1000 deg C after welding is not feasible, low-carbon grades (304L, 316L) are used. Some failures are depicted. All castings are completely radiographically examined. (N.D.H.)

  20. Structural studies in limestone sulfidation

    Energy Technology Data Exchange (ETDEWEB)

    Fenouil, L.A.; Lynn, S.

    1993-05-01

    This study investigates the sulfidation of limestone at high temperatures (700--900{degree}C) as the first step in the design of a High-Temperature Coal-Gas Clean-Up system using millimeter-size limestone particles. Several workers have found that the rate of this reaction significantly decreases after an initial 10 to 15% conversion of CaCO{sub 3} to CaS. The present work attempts to explain this feature. It is first established that millimeter-size limestone particles do not sinter at temperatures up to the CaCO{sub 3} calcination point (899{degree}C at 1.03 bar CO{sub 2} partial pressure). It is then shown that CaS sinters rapidly at 750 to 900{degree}C if CO{sub 2} is present in the gas phase. Scanning Electron Microscope (SEM) photographs and Electron Dispersive Spectroscopy (EDS) data reveal that the CaS product layer sinters and forms a quasi-impermeable coating around the CaCO{sub 3} grains that greatly hinders more H{sub 2}S from reaching the still unreacted parts of the stone. Moreover, most of the pores initially present within the limestone structure begin to disappear or, at least, are significantly reduced in size. From then on, subsequent conversion is limited by diffusion of H{sub 2}S through the CaS layer, possibly by S{sup 2{minus}} ionic diffusion. The kinetics is then adequately described by a shrinking-core model, in which a sharp front of completely converted limestone is assumed to progress toward the center of the pellet. Finally, experimental evidence and computer simulations using simple sintering models suggest that the CaS sintering, responsible for the sharp decrease in the sulfidation rate, is surface-diffusion controlled.

  1. Microbial control of hydrogen sulfide production

    Energy Technology Data Exchange (ETDEWEB)

    Montgomery, A.D.; Bhupathiraju, V.K.; Wofford, N.; McInerney, M.J. [Univ. of Oklahoma, Tulsa, OK (United States)] [and others

    1995-12-31

    A sulfide-resistant strain of Thiobacillus denitrificans, strain F, prevented the accumulation of sulfide by Desulfovibrio desulfuricans when both organisms were grown in liquid medium. The wild-type strain of T. denitrificans did not prevent the accumulation of sulfide produced by D. desulfuricans. Strain F also prevented the accumulation of sulfide by a mixed population of sulfate-reducing bacteria enriched from an oil field brine. Fermentation balances showed that strain F stoichiometrically oxidized the sulfide produced by D. desulfuricans and the oil field brine enrichment to sulfate. The ability of a strain F to control sulfide production in an experimental system of cores and formation water from the Redfield, Iowa, natural gas storage facility was also investigated. A stable, sulfide-producing biofilm was established in two separate core systems, one of which was inoculated with strain F while the other core system (control) was treated in an identical manner, but was not inoculated with strain F. When formation water with 10 mM acetate and 5 mM nitrate was injected into both core systems, the effluent sulfide concentrations in the control core system ranged from 200 to 460 {mu}M. In the test core system inoculated with strain F, the effluent sulfide concentrations were lower, ranging from 70 to 110 {mu}M. In order to determine whether strain F could control sulfide production under optimal conditions for sulfate-reducing bacteria, the electron donor was changed to lactate and inorganic nutrients (nitrogen and phosphate sources) were added to the formation water. When nutrient-supplemented formation water with 3.1 mM lactate and 10 mM nitrate was used, the effluent sulfide concentrations of the control core system initially increased to about 3,800 {mu}M, and then decreased to about 1,100 {mu}M after 5 weeks. However, in the test core system inoculated with strain F, the effluent sulfide concentrations were much lower, 160 to 330 {mu}M.

  2. Phase Engineering of 2D Tin Sulfides.

    OpenAIRE

    Mutlu, Z; Wu, RJ; Wickramaratne, D.; Shahrezaei, S; Liu, C; Temiz, S; Patalano, A; M Ozkan; Lake, RK; Mkhoyan, KA; Ozkan, CS

    2016-01-01

    Tin sulfides can exist in a variety of phases and polytypes due to the different oxidation states of Sn. A subset of these phases and polytypes take the form of layered 2D structures that give rise to a wide host of electronic and optical properties. Hence, achieving control over the phase, polytype, and thickness of tin sulfides is necessary to utilize this wide range of properties exhibited by the compound. This study reports on phase-selective growth of both hexagonal tin (IV) sulfide SnS2...

  3. The sulfide oxidation in an electrolytic sulfide oxidizing bioreactor using graphite anode

    International Nuclear Information System (INIS)

    The goal of the present research was the direct conversion of sulfide (an important contaminant in various industrial wastewaters) to sulfate, whose discharge limits are much less stringent than those for sulfide. The electrolysis of sodium sulfide was investigated under different conditions such as: ph, current density and working area etc. along with cyclic voltammetry. By the use of a graphite anode, we achieved near-quantitative electrochemical conversion of sulfide ions to sulfate with current efficiency of 88%. Kinetically, the reaction is first order in current density. The experimental results revealed that the sulfide removal rate of more than 88% could be achieved under the conditions T=30 deg. C, ph = 7, current density of 1 mA/cm/sup 2/ at anode area of 225 cm/sup 2/.The process can be practically coupled with bioreactor for an effective sulfide removal. (author)

  4. Beads,Necklaces, Chains and Strings in Capping Carbonyl Clusters

    Directory of Open Access Journals (Sweden)

    Enos Masheija Kiremire

    2015-09-01

    Full Text Available The paper attempts to explain at length the close relationship between transition metal carbonyl clusters with main group clusters especially the boranes using the 14n and 4n rules. When the ‘shielding’ electrons are removed from a transition metal carbonyl cluster and becomes ‘naked’, it resembles a corresponding one in the main group elements. A an expanded table of osmium carbonyl clusters was constructed using the capping fragment Os(CO2(14n-2 and the fragment Os(CO3 (14n+0. The table reveals the fact that the known series such closo, nido and arachno are part and parcel of a wide range of series especially the capping series 14n+q, where q takes up negative multiple integers of two including 0 such as such = 0, -2,-4, -6, and so on. The linkage between capping series in transition metal carbonyl clusters has also been identified. Apart from the capping series generated in the table, there is another type of series where the skeletal cluster elements remained the same but the number of carbonyl ligands successively decreased. These types of series are referred to as stripping series. Mapping generating functions were also derived which produces any cluster formula or series required. Also the table shows that many clusters form utilizing some of its atoms as closo nucleus around which the larger ones are built and thus forming clusters within larger clusters. The table may be used to categorize a given cluster formula that falls within its range. Otherwise, using the 14n rule or 4n rule can be used for cluster classification. Furthermore, the table indicated that atoms, fragments and molecules can be classified into series. Through this approach of using series, Hoffmann’s important isolobal relationship of chemical species can splendidly be explained.Using the 14n rule and 4n rules creates a framework under which chemical species such as atoms, fragments, molecules and ions some of which may appear unrelated from main group

  5. Carbonyl compounds in gas and particle phases of mainstream cigarette smoke

    International Nuclear Information System (INIS)

    Carbonyl compounds (carbonyls) are important constituents of cigarette smoke and some are toxic and may be carcinogenic or mutagenic to humans. In this study carbonyl emissions in the gas and particle phases of mainstream cigarette smoke were assessed by GC-MS with pentafluorophenyl hydrazine (PFPH) derivatization. Seven brands of cigarettes and one brand of cigar common in the UK market and having differing nicotine, tar and carbon monoxide yields were investigated. Sixteen carbonyl components were identified in gaseous emissions and twenty in the particle phase. In the gaseous emissions, acetaldehyde presented as the predominant species, followed by formaldehyde, 2-propenal, and pentanal. In the particulate emissions, 1-hydroxy-2-propanone was the most abundant followed by formaldehyde, benzaldehyde, and 2,5-dimethylbenzaldehyde. Significant differences were found in carbonyl emissions among the brands of cigarettes. The gaseous carbonyl emissions varied in the range of 216-405 μg cigarette-1 (μg cig-1) and the particulate carbonyl emissions varied in the range of 23-127 μg cig-1. Positive correlations were found between the total emission of carbonyls, tar yield and carbon monoxide yield. Similar gas/particle (G/P) partitioning ratios of carbonyls were found among all cigarettes, which implies that G/P partitions of carbonyls in smoke mainly depend on the physical properties of the carbonyls. The gaseous carbonyl emissions were enhanced by 40% to 130% when some of the water, accounting for 8-12% of cigarettes in mass, was removed from the tobacco. Non-filtered cigarettes showed significantly higher carbonyl emissions compared to their filtered equivalents. Carbonyl particulate accounted for 11-19% by mass of total particulate matter from tobacco smoke. The cigar generated 806 μg cig-1 gaseous and 141 μg cig-1 particulate carbonyls, which is 2-4 times greater than the cigarettes. - Highlights: → Carbonyl emission factors in both gas (16 species) and

  6. Carbonyl compounds in gas and particle phases of mainstream cigarette smoke

    Energy Technology Data Exchange (ETDEWEB)

    Pang, Xiaobing, E-mail: pangxbyuanj@gmail.com [Department of Chemistry, University of York, Heslington, York, YO10 5DD (United Kingdom); Lewis, Alastair C., E-mail: ally.lewis@york.ac.uk [National Centre for Atmospheric Science, University of York, Heslington, York, YO10 5DD (United Kingdom)

    2011-11-01

    Carbonyl compounds (carbonyls) are important constituents of cigarette smoke and some are toxic and may be carcinogenic or mutagenic to humans. In this study carbonyl emissions in the gas and particle phases of mainstream cigarette smoke were assessed by GC-MS with pentafluorophenyl hydrazine (PFPH) derivatization. Seven brands of cigarettes and one brand of cigar common in the UK market and having differing nicotine, tar and carbon monoxide yields were investigated. Sixteen carbonyl components were identified in gaseous emissions and twenty in the particle phase. In the gaseous emissions, acetaldehyde presented as the predominant species, followed by formaldehyde, 2-propenal, and pentanal. In the particulate emissions, 1-hydroxy-2-propanone was the most abundant followed by formaldehyde, benzaldehyde, and 2,5-dimethylbenzaldehyde. Significant differences were found in carbonyl emissions among the brands of cigarettes. The gaseous carbonyl emissions varied in the range of 216-405 {mu}g cigarette{sup -1} ({mu}g cig{sup -1}) and the particulate carbonyl emissions varied in the range of 23-127 {mu}g cig{sup -1}. Positive correlations were found between the total emission of carbonyls, tar yield and carbon monoxide yield. Similar gas/particle (G/P) partitioning ratios of carbonyls were found among all cigarettes, which implies that G/P partitions of carbonyls in smoke mainly depend on the physical properties of the carbonyls. The gaseous carbonyl emissions were enhanced by 40% to 130% when some of the water, accounting for 8-12% of cigarettes in mass, was removed from the tobacco. Non-filtered cigarettes showed significantly higher carbonyl emissions compared to their filtered equivalents. Carbonyl particulate accounted for 11-19% by mass of total particulate matter from tobacco smoke. The cigar generated 806 {mu}g cig{sup -1} gaseous and 141 {mu}g cig{sup -1} particulate carbonyls, which is 2-4 times greater than the cigarettes. - Highlights: {yields} Carbonyl

  7. Ambient levels of carbonyl compounds and their sources in Guangzhou, China

    Science.gov (United States)

    Feng, Yanli; Wen, Sheng; Chen, Yingjun; Wang, Xinming; Lü, Huixiong; Bi, Xinhui; Sheng, Guoying; Fu, Jiamo

    Ambient levels of carbonyl compounds and their possible sources, vehicular exhaust and cooking exhaust, were studied at seven places in Guangzhou, including five districts (a residential area, an industrial area, a botanical garden, a downtown area and a semi-rural area), a bus station and a restaurant during the period of June-September 2003. Nineteen carbonyl compounds were identified in the ambient air, of which acetone was the most abundant carbonyl, followed by formaldehyde and acetaldehyde. Only little changes were found in carbonyl concentration levels in the five different districts because of their dispersion and mixture in the atmosphere in summer. The lower correlations between the carbonyls' concentrations might result from the mixture of carbonyls derived from different sources, including strong photochemical reactions at noon in summer. Formaldehyde and acetaldehyde were the main carbonyls in bus station, while straight-chain carbonyls were comparatively abundant in cooking exhaust. Besides vehicular exhaust, cooking might be another major source of carbonyl compounds in Guangzhou City, especially for high molecular weight carbonyls.

  8. Indoor carbonyl compounds in an academic building in Beijing, China: concentrations and influencing factors

    Institute of Scientific and Technical Information of China (English)

    Chuanjia JIANG; Pengyi ZHANG

    2012-01-01

    Carbonyl compounds in indoor air are of great concern for their adverse health effects. Between February and May, 2009, concentrations of 13 carbonyl compounds were measured in an academic building in Beijing, China. Total concentration of the detected carbonyls ranged from 20.7 to 189.1 I.tg.m3, and among them acetone and formaldehyde were the most abundant, with mean concentrations of 26.4 and 22.6gg.m-3, respectively. Average indoor concentrations of other carbonyls were below I 0 gg. m~3. Principal component analysis identified a combined effect of common indoor carbonyl sources and ventilation on indoor carbonyl levels. Diurnal variations of the carbonyl compounds were investigated in one office room, and carbonyl concentrations tended to be lower in the daytime than at night, due to enhanced ventilation. Average concentrations of carbonyl compounds in the office room were generally higher in early May than in late February, indicating the influence of temperature. Carbo- nyl source emission rates from both the room and human occupants were estimated during two lectures, based on one-compartment mass balance model. The influence of human occupants on indoor carbonyl concentrations varies with environmental conditions, and may become signifi- cant in the case of a large human occupancy.

  9. Formation of Copper Sulfide Artifacts During Electrolytic Dissolution of Steel

    Science.gov (United States)

    Tan, Jia; Pistorius, P. Chris

    2013-06-01

    Based on equilibrium considerations, copper sulfide is not expected to form in manganese-containing steel, yet previous workers reported finding copper sulfide in transmission electron microscope samples which had been prepared by electropolishing. It is proposed that copper sulfide can form during electrolytic dissolution because of the much greater stability of copper sulfide relative to manganese sulfide in contact with an electrolyte containing copper and manganese cations. This mechanism has been demonstrated with aluminum-killed steel samples.

  10. High temperature sulfide corrosion and transport properties of transition metal sulfides

    International Nuclear Information System (INIS)

    An overview is presented of the role of the defect and transport properties of transition metal sulfides on the kinetics and mechanism of high-temperature sulfide corrosion of metals and alloys. It has been shown that due to the very high concentration of defects in common metal sulfides, not only pure metals but also conventional high-temperature alloys (chromia and alumina formers) undergo very rapid degradation in highly sulfidizing environments. Refractory metals (Mo, Nb), on the other hands, are highly resistant to sulfide corrosion, their sulfidation rates being comparable with the oxidation rate of chromium. Also, alloying of common metals by niobium and molybdenum improve considerably corrosion resistance with respect to highly sulfidizing atmospheres. It has demonstrated that Al.-Mo and Al.-Mo-Si alloys shown excellent resistant to sulfidizing environments, these materials being also simultaneously oxidation resistant. Thus, new prospects have been created for the development of a new generation of coating materials, resistant to multicomponent sulfidizing-oxidizing atmospheres, often encountered in many branches of modern technology. (author)

  11. Managing hydrogen sulfide the natural way

    Energy Technology Data Exchange (ETDEWEB)

    Beasley, T.; Abry, R.G.F. [New Paradigm Gas Processing Ltd., Calgary, AB (Canada)

    2003-07-01

    This paper explores the benefits and costs associated with acid gas injection versus flaring and venting. It provides an update of Shell Paques biological gas desulfurization technology and the world's first high pressure application of the technology at the EnCana Bantry Project. The process is particularly well suited to treat sour (acid) natural gases that are currently being flared. It can also be used as an alternative to acid gas injection. Complete removal of hydrogen sulfide can be achieved by selective biotechnological conversion of hydrogen sulfide to elemental sulfur. Compared to conventional processes, this breakthrough technology achieves greater savings in terms of capital and operational costs. The Shell-Paque process produces up to 50 tonnes of sulfur per day with virtually complete conversion of hydrogen sulfide to elemental sulfur, resulting in no hydrogen sulfide based airborne emissions. 2 refs., 2 tabs., 35 figs.

  12. Inorganic sorbents for concentration of hydrogen sulfide

    International Nuclear Information System (INIS)

    Present work is devoted to application of inorganic sorbents for concentration of hydrogen sulfide. The elaboration of method is conducted under controlled concentrations of hydrogen sulphide from 1.00 til 0.01 mg/l.

  13. The Search for Interstellar Sulfide Grains

    Science.gov (United States)

    Keller, Lindsay P.; Messenger, Scott

    2010-01-01

    The lifecycle of sulfur in the galaxy is poorly understood. Fe-sulfide grains are abundant in early solar system materials (e.g. meteorites and comets) and S is highly depleted from the gas phase in cold, dense molecular cloud environments. In stark contrast, sulfur is essentially undepleted from the gas phase in the diffuse interstellar medium, indicating that little sulfur is incorporated into solid grains in this environment. It is widely believed that sulfur is not a component of interstellar dust grains. This is a rather puzzling observation unless Fe-sulfides are not produced in significant quantities in stellar outflows, or their lifetime in the ISM is very short due to rapid destruction. Fe sulfide grains are ubiquitous in cometary samples where they are the dominant host of sulfur. The Fe-sulfides (primarily pyrrhotite; Fe(1-x)S) are common, both as discrete 0.5-10 micron-sized grains and as fine (5-10 nm) nanophase inclusions within amorphous silicate grains. Cometary dust particles contain high abundances of well-preserved presolar silicates and organic matter and we have suggested that they should contain presolar sulfides as well. This hypothesis is supported by the observation of abundant Fe-sulfides grains in dust around pre- and post-main sequence stars inferred from astronomical spectra showing a broad 23 micron IR feature due to FeS. Fe-sulfide grains also occur as inclusions in bona fide circumstellar amorphous silicate grains and as inclusions within deuterium-rich organic matter in cometary dust samples. Our irradiation experiments show that FeS is far more resistant to radiation damage than silicates. Consequently, we expect that Fe sulfide stardust should be as abundant as silicate stardust in solar system materials.

  14. Mechanism of mechanical activation for sulfide ores

    Institute of Scientific and Technical Information of China (English)

    HU Hui-ping; CHEN Qi-yuan; YIN Zhou-lan; HE Yue-hui; HUANG Bai-yun

    2007-01-01

    Structural changes for mechanically activated pyrite, sphalerite, galena and molybdenite with or without the exposure to ambient air, were systematically investigated using X-ray diffraction analysis(XRD), particle size analysis, gravimetrical method, X-ray photo-electron spectroscopy(XPS) and scanning electron microscopy(SEM), respectively. Based on the above structural changes for mechanically activated sulfide ores and related reports by other researchers, several qualitative rules of the mechanisms and the effects of mechanical activation for sulfide ores are obtained. For brittle sulfide ores with thermal instability, and incomplete cleavage plane or extremely incomplete cleavage plane, the mechanism of mechanical activation is that a great amount of surface reactive sites are formed during their mechanical activation. The effects of mechanical activation are apparent. For brittle sulfide ores with thermal instability, and complete cleavage plane, the mechanism of mechanical activation is that a great amount of surface reactive sites are formed, and lattice deformation happens during their mechanical activation. The effects of mechanical activation are apparent. For brittle sulfide ores with excellent thermal stability, and complete cleavage plane, the mechanism of mechanical activation is that lattice deformation happens during their mechanical activation. The effects of mechanical activation are apparent. For sulfide ores with high toughness, good thermal stability and very excellent complete cleavage plane, the mechanism of mechanical activation is that lattice deformation happens during their mechanical activation, but the lattice deformation ratio is very small. The effects of mechanical activation are worst.

  15. Air-water transfer of hydrogen sulfide

    DEFF Research Database (Denmark)

    Yongsiri, C.; Vollertsen, J.; Rasmussen, M. R.;

    2004-01-01

    The emissions process of hydrogen sulfide was studied to quantify air–water transfer of hydrogen sulfide in sewer networks. Hydrogen sulfide transfer across the air–water interface was investigated at different turbulence levels (expressed in terms of the Froude number) and pH using batch...... experiments. By means of the overall mass–transfer coefficient (KLa), the transfer coefficient of hydrogen sulfide (KLaH2S), referring to total sulfide, was correlated to that of oxygen (KLaO2) (i.e., the reaeration coefficient). Results demonstrate that both turbulence and pH in the water phase play...... a significant role for KLaH2S. An exponential expression is a suitable representation for the relationship between KLaH2S and the Froude number at all pH values studied (4.5 to 8.0). Because of the dissociation of hydrogen sulfide, KLaH2S increased with decreasing pH at a constant turbulence level. Relative...

  16. Carbonyl-twisted 6-acyl-2-dialkylaminonaphthalenes as solvent acidity sensors

    OpenAIRE

    Green, Amy M.; Naughton, Hannah R.; Nealy, Zachariah B.; Robert D. Pike; Abelt, Christopher J.

    2012-01-01

    Derivatives of 2-propionyl-6-dimethylaminonaphthalene (PRODAN) with twisted carbonyl groups were investigated as highly responsive sensors of H-bond donating ability. The PRODAN derivative bearing a pivaloyl group (4) was prepared. The torsion angle between the carbonyl and naphthalene is 26° in the crystal. It shows solvatochromism that is similar to five other PRODAN derivatives (1-3, 5-6). Twisted-carbonyl derivatives 3, 4 and 6 show strong fluorescence quenching in protic solvents. The or...

  17. Determination of carbonyl compounds in air by HPLC

    International Nuclear Information System (INIS)

    A method for the determination of seven carbonyl compounds in air is presented. The procedure involve sampling of air by a Sep-Pak cartridge impregnated with 2,4-dinitrophenylhydrazine. Elution was done with 3 mL of acetonitrile and the eluate was diluted to 5 mL. The analysis was done by HPLC with UV detection and external standard method quantification. It has been achieved relative standard deviations about 5% and detection limits of 80 ng/cartridge for formaldehyde, acetaldehyde and acetone+acrolein. Three different types of samples (rural, urban, petrol emission) were successfully analyzed

  18. Sulfide response analysis for sulfide control using a pS electrode in sulfate reducing bioreactors.

    Science.gov (United States)

    Villa-Gomez, D K; Cassidy, J; Keesman, K J; Sampaio, R; Lens, P N L

    2014-03-01

    Step changes in the organic loading rate (OLR) through variations in the influent chemical oxygen demand (CODin) concentration or in the hydraulic retention time (HRT) at constant COD/SO4(2-) ratio (0.67) were applied to create sulfide responses for the design of a sulfide control in sulfate reducing bioreactors. The sulfide was measured using a sulfide ion selective electrode (pS) and the values obtained were used to calculate proportional-integral-derivative (PID) controller parameters. The experiments were performed in an inverse fluidized bed bioreactor with automated operation using the LabVIEW software version 2009(®). A rapid response and high sulfide increment was obtained through a stepwise increase in the CODin concentration, while a stepwise decrease to the HRT exhibited a slower response with smaller sulfide increment. Irrespective of the way the OLR was decreased, the pS response showed a time-varying behavior due to sulfide accumulation (HRT change) or utilization of substrate sources that were not accounted for (CODin change). The pS electrode response, however, showed to be informative for applications in sulfate reducing bioreactors. Nevertheless, the recorded pS values need to be corrected for pH variations and high sulfide concentrations (>200 mg/L). PMID:24361702

  19. Analysis of dynamic protein carbonylation in rice embryo during germination through AP-SWATH.

    Science.gov (United States)

    Zhang, Hui; He, Dongli; Yu, Jianlan; Li, Ming; Damaris, Rebecca Njeri; Gupta, Ravi; Kim, Sun Tae; Yang, Pingfang

    2016-03-01

    Seed germination is an important aspect of the plant life cycle, during which, reactive oxygen species (ROS) accumulate. The accumulation of ROS results in an increase in protein oxidation of which carbonylation is the most canonical one. However, there is insufficient information concerning protein oxidation, especially carbonylation and its contribution to seed germination. In this study, biotin hydrazide labeled chromatography combined with sequential window acquisition of all theoretical fragment ion spectra (SWATH) method was used to analyze the dynamic pattern of protein carbonylation in rice embryos during germination. A total of 1872 unique proteins were quantified, among which 288 carbonylated peptides corresponding to 144 proteins were determined based on the filtering through mass shifts of modified amino acids. In addition, 66 carbonylated proteins were further analyzed based on their carbonylation intensity in four stages of germination. These identified carbonylated proteins were mainly involved in maintaining the levels of ROS, abscisic acid and seed reserves. Remarkably, a peroxiredoxin was found with 23 unique carbonylated peptides, and the expression of which was consistent with its increased activity. This study describes the dynamic pattern of carbonylated proteins during seed germination, and may help to further understand the biochemical mechanisms on this process. PMID:26801057

  20. The carbonyl oxide-aldehyde complex: a new intermediate of the ozonolysis reaction

    Science.gov (United States)

    Cremer, Dieter; Kraka, Elfi; McKee, M. L.; Radharkrishnan, T. P.

    1991-12-01

    MP4(SDQ)/6-31G (d,p) calculations suggest that the ozonolysis of alkenes in solution phase does not proceed via carbonyl oxide, but via a dipole complex between aldehyde and carbonyl oxide, which is 9 kcal/mol more stable than the separated molecules. The dipole complex is probably formed in the solvent cage upon decomposition of primary ozonide to aldehyde and carbonyl oxide. Rotation of either aldehyde or carbonyl oxide in the solvent cage leads to an antiparallel alignment of molecular dipole moments and dipole-dipole attraction.

  1. Two-dimensional gel electrophoretic detection of protein carbonyls derivatized with biotin-hydrazide.

    Science.gov (United States)

    Wu, Jinzi; Luo, Xiaoting; Jing, Siqun; Yan, Liang-Jun

    2016-04-15

    Protein carbonyls are protein oxidation products that are often used to measure the magnitude of protein oxidative damage induced by reactive oxygen or reactive nitrogen species. Protein carbonyls have been found to be elevated during aging and in age-related diseases such as stroke, diabetes, and neurodegenerative diseases. In the present article, we provide detailed protocols for detection of mitochondrial protein carbonyls labeled with biotin-hydrazide followed by 2-dimensional isoelectric focusing (IEF)/SDS-PAGE and Western blotting probed with horse-radish peroxidase-conjugated streptavidin. The presented procedures can also be modified for detection of carbonylation of non-mitochondrial proteins. PMID:26590475

  2. Fluorescence labeling of carbonylated lipids and proteins in cells using coumarin-hydrazide

    Directory of Open Access Journals (Sweden)

    Venukumar Vemula

    2015-08-01

    Full Text Available Carbonylation is a generic term which refers to reactive carbonyl groups present in biomolecules due to oxidative reactions induced by reactive oxygen species. Carbonylated proteins, lipids and nucleic acids have been intensively studied and often associated with onset or progression of oxidative stress related disorders. In order to reveal underlying carbonylation pathways and biological relevance, it is crucial to study their intracellular formation and spatial distribution. Carbonylated species are usually identified and quantified in cell lysates and body fluids after derivatization using specific chemical probes. However, spatial cellular and tissue distribution have been less often investigated. Here, we report coumarin-hydrazide, a fluorescent chemical probe for time- and cost-efficient labeling of cellular carbonyls followed by fluorescence microscopy to evaluate their intracellular formation both in time and space. The specificity of coumarin-hydrazide was confirmed in time- and dose-dependent experiments using human primary fibroblasts stressed with paraquat and compared with conventional DNPH-based immunocytochemistry. Both techniques stained carbonylated species accumulated in cytoplasm with strong perinuclear clustering. Using a complimentary array of analytical methods specificity of coumarin-hydrazide probe towards both protein- and lipid-bound carbonyls has been shown. Additionally, co-distribution of carbonylated species and oxidized phospholipids was demonstrated.

  3. trans-Di-μ-carbonyl-bis{carbonyl[η5-2,3,4,5-tetramethyl-1-(5-methyl-2-furylcyclopentadienyl]ruthenium(I}(Ru—Ru

    Directory of Open Access Journals (Sweden)

    Jin Lin

    2009-08-01

    Full Text Available In the crystal structure of the title compound, [Ru2(C14H17O2(CO4], each RuI atom is connected to one end-on and two bridging carbonyl groups and one cyclopentadienyl ring. The two Ru atoms are connected into binuclear complexes via two bridging carbonyl groups, forming four-membered rings which are located on centres of inversion. The Ru—Ru distance of 2.7483 (11 Å corresponds to a single bond. The two carbonyl groups in these binuclear complexes are trans-oriented.

  4. Reactivity of Ir(III) carbonyl complexes with water: alternative by-product formation pathways in catalytic methanol carbonylation

    OpenAIRE

    Haynes, A.; Elliott, P. I. P.; Haak, S; Meijer, A.J.H.M.; Sunley, G.J

    2013-01-01

    The reactions of water with a number of iridium(III) complexes relevant to the mechanism for catalytic methanol carbonylation are reported. The iridium acetyl, [Ir(CO)2I3(COMe)]−, reacts with water under mild conditions to release CO2 and CH4, rather than the expected acetic acid. Isotopic labeling and kinetic experiments are consistent with a mechanism involving nucleophilic attack by water on a terminal CO ligand of [Ir(CO)2I3(COMe)]− to give an (undetected) hydroxycarbonyl spec...

  5. Prosthetic iodination methods for radiolabeling of carbonyl moieties

    International Nuclear Information System (INIS)

    The demonstrable need for an indirect, prosthetic-group, radioiodination of carbonyl-containing biomolecules such as ketosteroids, carbohydrates, gangliosides, glycoproteins and aldehydo- and keto-drugs. This need has been addressed by developing a route to iodinated (radioiodination) aryl hydrazides which are subsequently condensed with carbonyl-containing moieties. This dissertation is directed at improving the utility of this reaction and at comparing the hydrolytic stability of the resulting hydrazones to that of similar tyramine imines, a type presently employed in indirect radioiodinations. The aryl carboxylic acid hydrazones were virtually inert to hydrolysis under simulated physiological conditions which caused imine bond rupture. Further improvements to this new prosthetic labeling method were sought in simplifying its two-step, acid-catalyzed cleavage of triazenooxadiazoles (the protected, pre-labeling form of the aryl carboxylic acid hydrazides) to the iodinated hydrazide. Synthetic procedures were explored which might yield non-conjugated aryl oxadiazoles--bearing methylenes inserted between the phenyl and the heterocyclic ring--in the expectation that these substances would be less stable and would hydrolyze in a single-acid-catalyzed step. Four synthetic pathways to amino (or nitro) aryl-methyl oxadiazoles could not be advanced beyond the open-chain precursors of the heterocyclics. Pyrolysis, thermolysis, and catalyzed cyclization reagents could not effect ring closure. A method was developed, however, to an oxadiazolone which can serve as a protective functionality for the iodinated aryl acid hydrazides

  6. IRC analysis of methanol carbonylation reaction catalyzed by rhodium complex

    Institute of Scientific and Technical Information of China (English)

    HAO Maorong; FENG Wenlin; JI Yongqiang; LEI Ming

    2004-01-01

    In the reaction cycle for methanol carbonylation catalyzed by Rh complex, the structure geometries of the reactant, intermediates, transition states and product of each elemental reaction have been studied by using the energy gradient method at HF/LANL2DZ level, and the changes of their potential profiles have also been calculated. Through IRC analyses of the transition states for each elemental reaction, it is confirmed that the various structure geometries obtained are stationary points on the cycle reaction pathway of methanol carbonylation catalyzed by Rh complex, and the changes are given in energies and structure geometries of the reactant molecules along the reaction pathway of lowest energy. It has been proposed that the geometrical conversions of intermediates play an important role during the cycle reaction. Through analyses of structure geometries, it has been suggested that, in addition to cis- and trans- structure exchange linkage of catalysis reactive species, the two pathways, cis- and trans-cata- lyzed cycle reactions, can also be linked through geometrical conversion of intermediates, of which the activation energy is 49.79 kJ/mol. Moreover, the reductive elimination elemental reaction may be neither cis-cycle nor trans- one, showing that the cycle reaction can be achieved through various pathways. However different the pathway, the oxidative addition elemental reaction of CH3I is the rate-controlling step.

  7. Hydrogen Sulfide and Urogenital Tract.

    Science.gov (United States)

    di Villa Bianca, Roberta d'Emmanuele; Cirino, Giuseppe; Sorrentino, Raffaella

    2015-01-01

    In this chapter the role played by H2S in the physiopathology of urogenital tract revising animal and human data available in the current relevant literature is discussed. H2S pathway has been demonstrated to be involved in the mechanism underlying penile erection in human and experimental animal. Both cystathionine-β synthase (CBS) and cystathionine-γ lyase (CSE) are expressed in the human corpus cavernosum and exogenous H2S relaxes isolated human corpus cavernosum strips in an endothelium-independent manner. Hydrogen sulfide pathway also accounts for the direct vasodilatory effect operated by testosterone on isolated vessels. Convincing evidence suggests that H2S can influence the cGMP pathway by inhibiting the phosphodiesterase 5 (PDE-5) activity. All these findings taken together suggest an important role for the H2S pathway in human corpus cavernosum homeostasis. However, H2S effect is not confined to human corpus cavernosum but also plays an important role in human bladder. Human bladder expresses mainly CBS and generates in vitro detectable amount of H2S. In addition the bladder relaxant effect of the PDE-5 inhibitor sildenafil involves H2S as mediator. In conclusion the H2S pathway is not only involved in penile erection but also plays a role in bladder homeostasis. In addition the finding that it involved in the mechanism of action of PDE-5 inhibitors strongly suggests that modulation of this pathway can represent a therapeutic target for the treatment of erectile dysfunction and bladder diseases. PMID:26162831

  8. Terahertz spectroscopy of hydrogen sulfide

    International Nuclear Information System (INIS)

    Pure rotational transitions of hydrogen sulfide (H2S) in its ground and first excited vibrational states have been recorded at room temperature. The spectrum comprises an average of 1020 scans at 0.005 cm−1 resolution recorded in the region 45–360 cm−1 (1.4 to 10.5 THz) with a globar continuum source using a Fourier transform spectrometer located at the AILES beamline of the SOLEIL synchrotron. Over 2400 rotational lines have been detected belonging to ground vibrational state transitions of the four isotopologues H232S, H233S, H234S, and H236S observed in natural abundance. 65% of these lines are recorded and assigned for the first time, sampling levels as high as J=26 and Ka=17 for H232S. 320 pure rotational transitions of H232S in its first excited bending vibrational state are recorded and analysed for the first time and 86 transitions for H234S, where some of these transitions belong to new experimental energy levels. Rotational constants have been fitted for all the isotopologues in both vibrational states using a standard effective Hamiltonian approach. Comprehensive comparisons are made with previously available data as well as the data available in HITRAN, CDMS, and JPL databases. The 91 transitions assigned to H236S give the first proper characterization of its pure rotational spectrum. -- Highlights: • Over 2400 lines are measured and assigned in the 45–360 cm−1 region. • New rotational transitions are assigned for four isotopologues of H2S. • Rotational transitions within the first excited state of H2S are assigned for the first time. • An improved rotational line list is presented

  9. Transition-metal-catalyzed carbonylation reactions of olefins and alkynes: a personal account.

    Science.gov (United States)

    Wu, Xiao-Feng; Fang, Xianjie; Wu, Lipeng; Jackstell, Ralf; Neumann, Helfried; Beller, Matthias

    2014-04-15

    Carbon monoxide was discovered and identified in the 18th century. Since the first applications in industry 80 years ago, academic and industrial laboratories have broadly explored CO's use in chemical reactions. Today organic chemists routinely employ CO in organic chemistry to synthesize all kinds of carbonyl compounds. Despite all these achievements and a century of carbonylation catalysis, many important research questions and challenges remain. Notably, apart from academic developments, industry applies carbonylation reactions with CO on bulk scale. In fact, today the largest applications of homogeneous catalysis (regarding scale) are carbonylation reactions, especially hydroformylations. In addition, the vast majority of acetic acid is produced via carbonylation of methanol (Monsanto or Cativa process). The carbonylation of olefins/alkynes with nucleophiles, such as alcohols and amines, represent another important type of such reactions. In this Account, we discuss our work on various carbonylations of unsaturated compounds and related reactions. Rhodium-catalyzed isomerization and hydroformylation reactions of internal olefins provide straightforward access to higher value aldehydes. Catalytic hydroaminomethylations offer an ideal way to synthesize substituted amines and even heterocycles directly. More recently, our group has also developed so-called alternative metal catalysts based on iridium, ruthenium, and iron. What about the future of carbonylation reactions? CO is already one of the most versatile C1 building blocks for organic synthesis and is widely used in industry. However, because of CO's high toxicity and gaseous nature, organic chemists are often reluctant to apply carbonylations more frequently. In addition, new regulations have recently made the transportation of carbon monoxide more difficult. Hence, researchers will need to develop and more frequently use practical and benign CO-generating reagents. Apart from formates, alcohols, and metal

  10. Phase Engineering of 2D Tin Sulfides.

    Science.gov (United States)

    Mutlu, Zafer; Wu, Ryan J; Wickramaratne, Darshana; Shahrezaei, Sina; Liu, Chueh; Temiz, Selcuk; Patalano, Andrew; Ozkan, Mihrimah; Lake, Roger K; Mkhoyan, K A; Ozkan, Cengiz S

    2016-06-01

    Tin sulfides can exist in a variety of phases and polytypes due to the different oxidation states of Sn. A subset of these phases and polytypes take the form of layered 2D structures that give rise to a wide host of electronic and optical properties. Hence, achieving control over the phase, polytype, and thickness of tin sulfides is necessary to utilize this wide range of properties exhibited by the compound. This study reports on phase-selective growth of both hexagonal tin (IV) sulfide SnS2 and orthorhombic tin (II) sulfide SnS crystals with diameters of over tens of microns on SiO2 substrates through atmospheric pressure vapor-phase method in a conventional horizontal quartz tube furnace with SnO2 and S powders as the source materials. Detailed characterization of each phase of tin sulfide crystals is performed using various microscopy and spectroscopy methods, and the results are corroborated by ab initio density functional theory calculations. PMID:27099950

  11. Functional consortium for denitrifying sulfide removal process

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Chuan [Harbin Inst. of Technology (CN). State Key Lab. of Water Resource and Environment (SKLWRE); Harbin Inst. of Technology (China). School of Municipal and Environmental Engineering; Ren, Nanqi; Wang, Aijie [Harbin Inst. of Technology (CN). State Key Lab. of Water Resource and Environment (SKLWRE); Liu, Lihong [Harbin Inst. of Technology (China). School of Municipal and Environmental Engineering; Lee, Duu-Jong [Harbin Inst. of Technology (CN). State Key Lab. of Water Resource and Environment (SKLWRE); National Taiwan Univ., Taipei (China). Dept. of Chemical Engineering

    2010-03-15

    Denitrifying sulfide removal (DSR) process simultaneously converts sulfide, nitrate, and chemical oxygen demand from industrial wastewaters to elemental sulfur, nitrogen gas, and carbon dioxide, respectively. This investigation utilizes a dilution-to-extinction approach at 10{sup -2} to 10{sup -6} dilutions to elucidate the correlation between the composition of the microbial community and the DSR performance. In the original suspension and in 10{sup -2} dilution, the strains Stenotrophomonas sp., Thauera sp., and Azoarcus sp. are the heterotrophic denitrifiers and the strains Paracoccus sp. and Pseudomonas sp. are the sulfide-oxidizing denitrifers. The 10{sup -4} dilution is identified as the functional consortium for the present DSR system, which comprises two functional strains, Stenotrophomonas sp. strain Paracoccus sp. At 10{sup -6} dilution, all DSR performance was lost. The functions of the constituent cells in the DSR granules were discussed based on data obtained using the dilution-to-extinction approach. (orig.)

  12. Transition Metal Catalyzed Synthesis of Aryl Sulfides

    Directory of Open Access Journals (Sweden)

    Chad C. Eichman

    2011-01-01

    Full Text Available The presence of aryl sulfides in biologically active compounds has resulted in the development of new methods to form carbon-sulfur bonds. The synthesis of aryl sulfides via metal catalysis has significantly increased in recent years. Historically, thiolates and sulfides have been thought to plague catalyst activity in the presence of transition metals. Indeed, strong coordination of thiolates and thioethers to transition metals can often hinder catalytic activity; however, various catalysts are able to withstand catalyst deactivation and form aryl carbon-sulfur bonds in high-yielding transformations. This review discusses the metal-catalyzed arylation of thiols and the use of disulfides as metal-thiolate precursors for the formation of C-S bonds.

  13. Solar thermal extraction of copper from sulfides

    Energy Technology Data Exchange (ETDEWEB)

    Winkel, L.; Guesdon, C.; Sturzenegger, M.

    2003-03-01

    With the aim to develop a solar-driven process for the extraction of copper from sulfide concentrates re-search on the decomposition of copper sulfides under inert atmospheres has been initiated. Thermogravimetric measurements on chalcocite (Cu{sub 2}S) revealed that copper is formed already at 1823 K. Chalcopyrite (CuFeS{sub 2}) also disintegrates at this temperature, although at a lower rate. Copper and iron have been identified in the solid residue. The results confirm the feasibility of copper extraction by direct decomposition of sulfides under atmospheric pressure. The decomposition under inert atmosphere prevents generation of SO{sub 2}, and is beneficial to the removal of volatile impurities. Chemical equilibrium calculations for CuFeS{sub 2} contaminated with enargite (Cu{sub 3}AsS{sub 4}) have shown that the absence of an oxidic slag allows for a complete evaporation of arsenic and subsequent separation. (author)

  14. Iron-sulfide crystals in probe deposits

    DEFF Research Database (Denmark)

    Laursen, Karin; Frandsen, Flemming

    1998-01-01

    Iron-sulfides were observed in deposits collected on a probe inserted at the top of the furnace of a coal-fired power station in Denmark. The chemical composition of the iron-sulfides is equivalent to pyrrhotite (FeS). The pyrrhotites are present as crystals and, based on the shape of the crystals......, it was deduced that they were not deposited but instead grew within the deposit. The presence of unburned char particles within the deposits supports the concept that a reducing environment existed in the deposits. Two processes are proposed for explaining the existence of pyrrhotite crystals within...... a deposit: (1) impact of low viscous droplets of iron sulfide; and (2) sulfur diffusion. Previous research on the influence of pyrite on slagging focused on the decomposition of pyrite into pyrrhotite and especially on the oxidation stage of this product during impact on the heat transfer surfaces...

  15. Evaluation of carbonyl compounds formed during gamma irradiation of maize starch

    International Nuclear Information System (INIS)

    Changes in the levels of radionduced carbonyl compounds were analysed as a function of irradiation conditions (dose, dose rate, temperature, atmosphere), starch properties (water content) and post irradiation treatments (storage, autoclaving). The percentages of identified and unknown carbonyl fractions were respectively 40 and 60%. The half unknown fraction was linked on the radiodextrins (polysaccharides formed during irradiation of starch). (orig.)

  16. Protective mechanisms of Cucumis sativus in diabetes-related modelsof oxidative stress and carbonyl stress

    Science.gov (United States)

    Heidari, Himan; Kamalinejad, Mohammad; Noubarani, Maryam; Rahmati, Mokhtar; Jafarian, Iman; Adiban, Hasan; Eskandari, Mohammad Reza

    2016-01-01

    Introduction: Oxidative stress and carbonyl stress have essential mediatory roles in the development of diabetes and its related complications through increasing free radicals production and impairing antioxidant defense systems. Different chemical and natural compounds have been suggested for decreasing such disorders associated with diabetes. The objectives of the present study were to investigate the protective effects of Cucumis sativus (C. sativus) fruit (cucumber) in oxidative and carbonyl stress models. These diabetes-related models with overproduction of reactive oxygen species (ROS) and reactive carbonyl species (RCS) simulate conditions observed in chronic hyperglycemia. Methods: Cytotoxicity induced by cumene hydroperoxide (oxidative stress model) or glyoxal (carbonyl stress model) were measured and the protective effects of C. sativus were evaluated using freshly isolated rat hepatocytes. Results: Aqueous extract of C. sativus fruit (40 μg/mL) prevented all cytotoxicity markers in both the oxidative and carbonyl stress models including cell lysis, ROS formation, membrane lipid peroxidation, depletion of glutathione, mitochondrial membrane potential decline, lysosomal labialization, and proteolysis. The extract also protected hepatocytes from protein carbonylation induced by glyoxal. Our results indicated that C. sativus is able to prevent oxidative stress and carbonyl stress in the isolated hepatocytes. Conclusion: It can be concluded that C. sativus has protective effects in diabetes complications and can be considered a safe and suitable candidate for decreasing the oxidative stress and carbonyl stress that is typically observed in diabetes mellitus.

  17. Preparation and microwave shielding property of silver-coated carbonyl iron powder

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Xiao Guo, E-mail: xgcao@gdut.edu.cn [School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, Guangdong (China); Ren, Hao [Guangzhou Research Institute of O-M-E Technology, Guangzhou 510006, Guangdong (China); Zhang, Hai Yan [School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, Guangdong (China)

    2015-05-15

    Highlights: • The silver-coated carbonyl iron powder is prepared by the electroless plating process. • The silver-coated carbonyl iron powder is a new kind of conductive filler. • The reflection and absorption dominate the shielding mechanism of the prepared powder. • Increasing the thickness of electroconductive adhesive will increase the SE. - Abstract: Electroless silver coating of carbonyl iron powder is demonstrated in the present investigation. The carbonyl iron powders are characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), and X-ray diffraction analysis (XRD) before and after the coating process. The relatively uniform and continuous silver coating is obtained under the given coating conditions. In this paper, the electromagnetic interference (EMI) shielding mechanism of the silver-coated carbonyl iron powder is suggested. The reflection of silver coating and absorption of carbonyl iron powder dominate the shielding mechanism of the silver-coated carbonyl iron powder. The silver-coated carbonyl iron powders are used as conductive filler in electroconductive adhesive for electromagnetic interference shielding applications. The effect of the thickness of electroconductive adhesive on the shielding effectiveness (SE) is investigated. The results indicate that the SE increases obviously with the increase of the thickness of electroconductive adhesive. The SE of the electroconductive adhesive with 0.35 mm thickness is above 38 dB across the tested frequency range.

  18. AminoxyTMT: A novel multi-functional reagent for characterization of protein carbonylation.

    Science.gov (United States)

    Afiuni-Zadeh, Somaieh; Rogers, John C; Snovida, Sergei I; Bomgarden, Ryan D; Griffin, Timothy J

    2016-01-01

    Protein carbonylation is a common oxidative stress (OS)-driven post-translational modification (PTM). Proteome-wide carbonylation events can best be characterized using a combination of analytical approaches. Immunoblotting of carbonylated proteins provides data on the extent of modifications within complex samples, as well as a broad comparison of carbonylation profiles between different biological states (e.g., disease versus control), while mass spectrometry (MS)-based analysis provides information on proteins susceptible to carbonylation, as well as the potential for quantitative characterization of specific sites of amino acid modification. Here, we present a novel use for aminoxyTMT, a derivative of the Tandem Mass Tag (TMT) isobaric labeling reagent, which utilizes an aminooxy functional group for covalent labeling of reactive carbonyls in proteins. When coupled with anti-TMT antibody, we demonstrate the use of aminoxyTMT for immunoblot profiling of protein carbonylation in complex mixtures, as well as enrichment of modified peptides from these mixtures. Proof-of-principle experiments also show the amenability of aminoxyTMT-labeled carbonylated peptides enriched from complex mixtures to identification using tandem MS (MS/MS) and database searching, as well as quantitative analysis using TMT-based reporter ion intensity measurements. PMID:27071607

  19. Preparation and microwave shielding property of silver-coated carbonyl iron powder

    International Nuclear Information System (INIS)

    Highlights: • The silver-coated carbonyl iron powder is prepared by the electroless plating process. • The silver-coated carbonyl iron powder is a new kind of conductive filler. • The reflection and absorption dominate the shielding mechanism of the prepared powder. • Increasing the thickness of electroconductive adhesive will increase the SE. - Abstract: Electroless silver coating of carbonyl iron powder is demonstrated in the present investigation. The carbonyl iron powders are characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), and X-ray diffraction analysis (XRD) before and after the coating process. The relatively uniform and continuous silver coating is obtained under the given coating conditions. In this paper, the electromagnetic interference (EMI) shielding mechanism of the silver-coated carbonyl iron powder is suggested. The reflection of silver coating and absorption of carbonyl iron powder dominate the shielding mechanism of the silver-coated carbonyl iron powder. The silver-coated carbonyl iron powders are used as conductive filler in electroconductive adhesive for electromagnetic interference shielding applications. The effect of the thickness of electroconductive adhesive on the shielding effectiveness (SE) is investigated. The results indicate that the SE increases obviously with the increase of the thickness of electroconductive adhesive. The SE of the electroconductive adhesive with 0.35 mm thickness is above 38 dB across the tested frequency range

  20. Protein carbonylation and metal-catalyzed protein oxidation in a cellular perspective

    DEFF Research Database (Denmark)

    Møller, Ian Max; Rogowska-Wrzesinska, Adelina; Rao, R S P

    2011-01-01

    be relevant in physiological processes, irreversible oxidative modifications are known to contribute to cellular damage and disease. The most well-studied irreversible protein oxidation is carbonylation. In this work we first examine how protein carbonylation occurs via metal-catalyzed oxidation (MCO...

  1. Modeling of Sulfide Microenvironments on Mars

    Science.gov (United States)

    Schwenzer, S. P.; Bridges, J. C.; McAdam, A.; Steer, E. D.; Conrad, P. G.; Kelley, S. P.; Wiens, R. C.; Mangold, N.; Grotzinger, J.; Eigenbrode, J. L.; Franz, H. B.; Sutter, B.

    2016-01-01

    Yellowknife Bay (YKB; sol 124-198) is the second site that the Mars Science Laboratory Rover Curiosity investigated in detail on its mission in Gale Crater. YKB represents lake bed sediments from an overall neutral pH, low salinity environment, with a mineralogical composition which includes Ca-sulfates, Fe oxide/hydroxides, Fe-sulfides, amorphous material, and trioctahedral phyllosilicates. We investigate whether sulfide alteration could be associated with ancient habitable microenvironments in the Gale mudstones. Some textural evidence for such alteration may be pre-sent in the nodules present in the mudstone.

  2. Sol-gel processing of metal sulfides

    Science.gov (United States)

    Stanic, Vesha

    Metal sulfides were synthesised via a sol-gel process using various metal alkoxides and hydrogen sulfide in toluene. Colloidal gels were prepared from germanium ethoxide, germanium isopropoxide, zinc tert-butoxide and tungsten (VI) ethoxide, whereas colloidal powder was produced from tungsten (V) dichloride ethoxide. Special precautions were necessary to protect the reaction mixture from water contamination which produced metal oxides. Results indicated that the main source of water is the hydrogen sulfide gas. In addition, synthesis of metal sulfides from a mixture of metal oxide and sulfide was demonstrated by the example of monoclinic germanium disulfide. It was produced by reaction of the sol-gel product with sulfur. Heat treatment of the sol-gel product and sulfur yielded single phase GeSsb2. The sol-gel prepared materials and their heat treated products were characterized by various methods. A chemical kinetics study of the functional groups -OR, -SH and Ssp{2-} was carried out for the sol-gel processing of GeSsb2 from of hydrogen sulfide and two different alkoxides, germanium ethoxide and germanium isopropoxide. The study was performed for different concentrations of precursors at different molar ratios and temperatures. The results indicate that the proposed reaction mechanism was simplified under appropriate reaction conditions. Experimentally determined rate constants of thiolysis and condensations demonstrate that thiolysis is slow and that condensations are fast steps, regardless of the studied reaction conditions. A study of the temperature effect on the reaction rate constant shows that it increases with temperature in accord with both Arrhenius law and transition-state theory. Activation energies, Esba, and activation parameters DeltaSsp{ddagger}, DeltaHsp{ddagger} and DeltaGsp{ddagger}, were determined for thiolysis and condensation reactions. The potentiometric tiration method was used for quantitative determination of germanium sulfide and

  3. Protein carbonylation after traumatic brain injury: cell specificity, regional susceptibility, and gender differences.

    Science.gov (United States)

    Lazarus, Rachel C; Buonora, John E; Jacobowitz, David M; Mueller, Gregory P

    2015-01-01

    Protein carbonylation is a well-documented and quantifiable consequence of oxidative stress in several neuropathologies, including multiple sclerosis, Alzheimer׳s disease, and Parkinson׳s disease. Although oxidative stress is a hallmark of traumatic brain injury (TBI), little work has explored the specific neural regions and cell types in which protein carbonylation occurs. Furthermore, the effect of gender on protein carbonylation after TBI has not been studied. The present investigation was designed to determine the regional and cell specificity of TBI-induced protein carbonylation and how this response to injury is affected by gender. Immunohistochemistry was used to visualize protein carbonylation in the brains of adult male and female Sprague-Dawley rats subjected to controlled cortical impact (CCI) as an injury model of TBI. Cell-specific markers were used to colocalize the presence of carbonylated proteins in specific cell types, including astrocytes, neurons, microglia, and oligodendrocytes. Results also indicated that the injury lesion site, ventral portion of the dorsal third ventricle, and ventricular lining above the median eminence showed dramatic increases in protein carbonylation after injury. Specifically, astrocytes and limited regions of ependymal cells adjacent to the dorsal third ventricle and the median eminence were most susceptible to postinjury protein carbonylation. However, these patterns of differential susceptibility to protein carbonylation were gender dependent, with males showing significantly greater protein carbonylation at sites distant from the lesion. Proteomic analyses were also conducted and determined that the proteins most affected by carbonylation in response to TBI include glial fibrillary acidic protein, dihydropyrimidase-related protein 2, fructose-bisphosphate aldolase C, and fructose-bisphosphate aldolase A. Many other proteins, however, were not carbonylated by CCI. These findings indicate that there is both regional

  4. Membrane for hydrogen recovery from streams containing hydrogen sulfide

    Science.gov (United States)

    Agarwal, Pradeep K.

    2007-01-16

    A membrane for hydrogen recovery from streams containing hydrogen sulfide is provided. The membrane comprises a substrate, a hydrogen permeable first membrane layer deposited on the substrate, and a second membrane layer deposited on the first layer. The second layer contains sulfides of transition metals and positioned on the on a feed side of the hydrogen sulfide stream. The present invention also includes a method for the direct decomposition of hydrogen sulfide to hydrogen and sulfur.

  5. Impact of HVAC filter on indoor air quality in terms of ozone removal and carbonyls generation

    Science.gov (United States)

    Lin, Chi-Chi; Chen, Hsuan-Yu

    2014-06-01

    This study aims at detecting ozone removal rates and corresponding carbonyls generated by ozone reaction with HVAC filters from various building, i.e., shopping mall, school, and office building. Studies were conducted in a small-scale environmental chamber. By examining dust properties including organic carbon proportion and specific surface area of dusts adsorbed on filters along with ozone removal rates and carbonyls generation rate, the relationship among dust properties, ozone removal rates, and carbonyls generation was identified. The results indicate a well-defined positive correlation between ozone removal efficiency and carbonyls generation on filters, as well as a positive correlation among the mass of organic carbon on filters, ozone removal efficiency and carbonyls generations.

  6. Development of an automatic sampling device for the continuous measurement of atmospheric carbonyls compounds

    International Nuclear Information System (INIS)

    Two sampling strategies were studied to develop an automatic instrument for the continuous measurement of atmospheric carbonyl compounds. Because of its specificity towards carbonyls compounds, sampling by using a transfer of gaseous phase in a liquid phase associated with a simultaneous chemical derivatization of the trapped compounds was first studied. However, this method do not allow a quantitative sampling of all studied carbonyl compounds, nor a continuous measurement in the field. To overcome the difficulties, a second strategy was investigated: the cryogenic adsorption onto solid adsorbent followed by thermodesorption and a direct analysis by GC/MS. Collection efficiency using different solid adsorbents was found greater than 95% for carbonyl compounds consisting of 1 to 7 carbons. This work is a successful first step towards the realization of the automatic sampling device for a continuous measurement of atmospheric carbonyls compounds. (author)

  7. The effect of sulfide inhibition on the ANAMMOX process.

    Science.gov (United States)

    Jin, Ren-Cun; Yang, Guang-Feng; Zhang, Qian-Qian; Ma, Chun; Yu, Jin-Jin; Xing, Bao-Shan

    2013-03-01

    The feasibility of anaerobic ammonium oxidation (ANAMMOX) process to treat wastewaters containing sulfide was studied in this work. Serum bottles were used as experimental containers in batch tests to analyze the short-term response of the ANAMMOX process under sulfide stress. The IC(50) of sulfide-S for ANAMMOX biomass was substrates-dependent and was calculated to be 264 mg L(-1) at an initial total nitrogen level of 200 mg L(-1) (molar ratio of ammonium and nitrite was 1:1). The long-term effects and the performance recovery under sulfide stress were continuously monitored and evaluated in an upflow anaerobic sludge blanket reactor. The performance of the ANAMMOX system was halved at an sulfide-S level of 32 mg L(-1) within 13 days; however, the nitrogen removal rate (NRR) decreased by only 17.2% within 18 days at an sulfide-S concentration of 40 mg L(-1) after long-time acclimatization of sludge in the presence of sulfide. The ANAMMOX performance recovered under sulfide-S level of 8 mg L(-1) with a steady NRR increasing speed, linear relationship between the NRR and operation time. The synchronic reduce in the specific ANAMMOX activity and the biomass extended the apparent doubling time of the nitrogen removal capacity and decreased biomass growth rate. PMID:23273856

  8. T.O.C.S. : Hydrogen Sulfide Remission System

    OpenAIRE

    ECT Team, Purdue

    2007-01-01

    BioEnviroTech, Inc., (BET) developed Toxicity Odor Corrosion Sulfides (T.O.C.S.) Remission System for hydrogen sulfide reduction in municipal and industrial wastewater sewer, lift stations and force mains. This safe and cost effective biotreatment technology uses safe and natural bacteria to interrupt sulfide generation.

  9. Direct Vapor Phase Carbonylation of Methanol over NiCl2/C Catalyst

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    @@ Introduction The carbonylation of alcohols via homogenous catalysis is important in manufacturing acetic acid and higher carboxylic acids and their esters[1,2]. The main route to produce acetic acid is to make methanol carbonylated by means of the Monsanto and BP process in which a homogeneous rhodium catalyst is used. Although the homogeneous carbonylation of methanol is a highly selective process, it is affected by the disadvantages associated with a highly corrosive reaction medium due to the use of methyl iodide as the promoter, and the difficulty of the product separation[3]. The use of a heterogeneous catalyst seems very interesting and attractive to us[4], especially the direct vapor phase carbonylation of methanol without a halide promoter is of considerable importance and is strong incentive economically. There has, however, been very little success in finding either heterogeneous or homogeneous catalysts that can catalyze the reaction effectively without the addition of a promoter[5,6]. According to the known carbonylation mechanism[7,8], the methyl iodide directly carbonylates with CO to from MeCOI which interacts with methanol(MeOH) to produce methyl acetate(MeCOOMe) and HI, and then MeOH reacts with HI to from CH3I. In fact, this carbonylation reaction is the indirect catalytic carbonylation of methanol[9]. In this work, a novel catalyst for the direct vapor phase carbonylation of methanol without the addition of any halide in the feed as a promoter was investigated. Compared to the known liquid phase methanol carbonylation process, some advantages of this vapor phase reaction are as follows:

  10. Synthesis, characterization and bioactivities of N,O-carbonylated chitosan.

    Science.gov (United States)

    Liu, Hongli; Liu, Xiaoli; Yue, Lin; Jiang, Qixing; Xia, Wenshui

    2016-10-01

    N,O-Carbonylated chitosan derivative (NTCS) was synthesized via oxidation and substitution reaction, respectively. The carboxyethylation of the polysaccharide was identified by Fourier transform infrared (FTIR), (1)H nuclear magnetic resonance (NMR), X-ray diffraction analysis (XRD), Zeta potential measurement and Thermogravimetric analysis (TGA). It is revealed that compared with chitosan (CS), NTCS exhibited an excellent solubility in distilled water, high in vitro bile acid binding capacity, as well as a low viscosity. The in vitro bile acid binding capacity reached 17.21mg/g, which was 4.5-fold higher than that of CS. The results suggest that NTCS may be useful as a potential functional food supplement in food industry or a key ingredient in the pharmaceutical industry. These findings provide important supports for developing new food additive, and expand the scope of application of CS in the food industry. PMID:27189702

  11. SILP catalysis in gas-phase hydroformylation and carbonylation

    Energy Technology Data Exchange (ETDEWEB)

    Riisager, A.; Fehrmann, R. [Technical Univ. of Denmark, Lyngby (Denmark). Dept. of Chemistry; Haumann, M.; Wasserscheid, P. [Univ. Erlangen-Nuernberg (Germany). Lehrstuhl fuer Chemische Reaktionstechnik

    2006-07-01

    Supported ionic liquid phase (SILP) catalysts are new materials consisting of an ionic liquid-metal catalyst solution highly dispersed on a porous support. The use of a non-volatile, ionic liquid catalyst phase in SILP catalysts results in a stable heterogeneous-type material with selectivity and efficiency like homogeneous catalysts. The silica-supported SILP Rh-bisphosphine hydroformylation catalyst exhibited good activities and excellent selectivities in gas phase hydroformylation with stability exceeding 700 hours time-on-stream. Spectroscopic and kinetic data confirmed the homogeneous nature of the catalyst. In the Rh- SILP catalysed carbonylation of methanol the formation of undesired by-products could be suppressed by variation of residence time and gas pressure. (orig.)

  12. Measurement and biological significance of the volatile sulfur compounds hydrogen sulfide, methanethiol and dimethyl sulfide in various biological matrices

    NARCIS (Netherlands)

    Tangerman, Albert

    2009-01-01

    This review deals with the measurement of the volatile Sulfur compounds hydrogen sulfide, methanethiol and dimethyl sulfide in various biological matrices of rats and humans (blood, serum, tissues, urine, breath, feces and flatus). Hydrogen sulfide and methanethiol both contain the active thiol (-SH

  13. The diagenesis of carbohydrates by hydrogen sulfide

    Science.gov (United States)

    Mango, Frank D.

    1983-08-01

    Carbohydrates react with hydrogen sulfide under low temperature (100° to 200°C) yielding a variety of organosulfur compounds including thiophenes, thiols, sulfides and sulfones. A polymer is also produced, whose elemental composition is within the range of natural coals. When reductive dehydration is carried out in the presence of hydrocarbon, organosulfur compounds are formed in the carbon number range of the hydrocarbon used. In these processes, an active hydrogen transfer catalyst is produced which facilitates the passage of hydrogen between normal paraffins and saccharide units, distributing sulfur between these two families primarily in the form of thiophene rings. The simplicity of these systems - H 2S, carbohydrates, H 2O, hydrocarbon - and the facility of the chemistry would suggest that the carbohydrates and hydrogen sulfide may be important agents in the diagenetic processes leading to petroleum and coal. Carbohydrate reduction by hydrogen sulfide may constitute an important route through which certain organosulfur compounds found in petroleum and coal entered these materials in early diagenesis.

  14. Support Effect in Hydrodesulfurization over Ruthenium Sulfide

    Czech Academy of Sciences Publication Activity Database

    Gulková, Daniela; Kaluža, Luděk; Vít, Zdeněk; Zdražil, Miroslav

    Prague : JHI, 2008, s. 58-s. 59. [Symposium on Catalysis /40./. Prague (CZ), 03.11.2008-05.11.2008] R&D Projects: GA ČR GA104/06/0705 Institutional research plan: CEZ:AV0Z40720504 Keywords : ruthenium sulfide * hydrodesulfurization * support Subject RIV: CF - Physical ; Theoretical Chemistry

  15. Support Effect in Hydrodesulfurization over Ruthenium Sulfide

    Czech Academy of Sciences Publication Activity Database

    Gulková, Daniela; Kaluža, Luděk; Vít, Zdeněk; Zdražil, Miroslav

    2009-01-01

    Roč. 51, č. 2 (2009), s. 146-149. ISSN 1337-7027 R&D Projects: GA ČR GA104/06/0705 Institutional research plan: CEZ:AV0Z40720504 Keywords : ruthenium sulfide * hydrodesulfurization * support effect Subject RIV: CC - Organic Chemistry

  16. Monitoring sulfide and sulfate-reducing bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Tanner, R.S.

    1995-12-31

    Simple yet precise and accurate methods for monitoring sulfate-reducing bacteria (SRB) and sulfide remain useful for the study of bacterial souring and corrosion. Test kits are available to measure sulfide in field samples. A more precise methylene blue sulfide assay for both field and laboratory studies is described here. Improved media, compared to that in API RP-38, for enumeration of SRB have been formulated. One of these, API-RST, contained cysteine (1.1 mM) as a reducing agent, which may be a confounding source of sulfide. While cysteine was required for rapid enumeration of SRB from environmental samples, the concentration of cysteine in medium could be reduced to 0.4 mM. It was also determined that elevated levels of yeast extract (>1 g/liter) could interfere with enumeration of SRB from environmental samples. The API-RST medium was modified to a RST-11 medium. Other changes in medium composition, in addition to reduction of cysteine, included reduction of the concentration of phosphate from 3.4 mM to 2.2 mM, reduction of the concentration of ferrous iron from 0.8 mM to 0.5 mM and preparation of a stock mineral solution to ease medium preparation. SRB from environmental samples could be enumerated in a week in this medium.

  17. Reaction between Hydrogen Sulfide and Limestone Calcines

    Czech Academy of Sciences Publication Activity Database

    Hartman, Miloslav; Svoboda, Karel; Trnka, Otakar; Čermák, Jiří

    2002-01-01

    Roč. 41, č. 10 (2002), s. 2392-2398. ISSN 0888-5885 R&D Projects: GA AV ČR IAA4072711; GA AV ČR IAA4072801 Keywords : hydrogen sulfide * limestone calcines * desulfurization Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.247, year: 2002

  18. Variation of ambient carbonyl levels in urban Beijing between 2005 and 2012

    Science.gov (United States)

    Chen, Wentai; Shao, Min; Wang, Ming; Lu, Sihua; Liu, Ying; Yuan, Bin; Yang, Yudong; Zeng, Limin; Chen, Zhongming; Chang, Chih-Chung; Zhang, Qian; Hu, Min

    2016-03-01

    Carbonyl compounds are important precursors of secondary air pollutants. With the rapid economic development and the implementation of stricter control measures in Beijing, the sources of carbonyls possibly changed. Based on measurement data obtained at an urban site in Beijing between 2005 and 2012, we investigated annual variations in carbonyl levels and sources during these years. In summer, formaldehyde and acetaldehyde levels decreased significantly at a rate of 9.1%/year and 7.2%/year, respectively, while acetone levels increased at a rate of 4.3%/year. In winter, formaldehyde levels increased and acetaldehyde levels decreased. We also investigated the factors driving the variation in carbonyls levels during summer by determination of emission ratios for carbonyls and their precursors, and calculation of photochemical formation of carbonyls. The relative declines for primary formaldehyde and acetaldehyde levels were larger than those for secondary formation. This is possibly due to the increasing usage of natural gas and liquefied petroleum gas which could result in the rise of carbonyl precursor emission ratios. The increase in acetone levels might be related to the rising solvent usage in Beijing during these years. The influences of these sources should be paid more attention in future research.

  19. Electroless plating preparation and electromagnetic properties of Co-coated carbonyl iron particles/polyimide composite

    Science.gov (United States)

    Zhou, Yingying; Zhou, Wancheng; Li, Rong; Qing, Yuchang; Luo, Fa; Zhu, Dongmei

    2016-03-01

    To solve the serious electromagnetic interference problems at elevated temperature, one thin microwave-absorbing sheet employing Co-coated carbonyl iron particles and polyimide was prepared. The Co-coated carbonyl iron particles were successfully prepared using an electroless plating method. The microstructure, composition, phase and static magnetic properties of Co-coated carbonyl iron particles were characterized by combination of scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD) and vibrating sample magnetometer (VSM). The electromagnetic parameters of Co-coated carbonyl iron particles/polyimide composite were measured in the frequency range of 2-18 GHz, and the electromagnetic loss mechanism of the material-obtained was discussed. The microwave absorption properties of composites before and after heat treatment at 300 °C for 100 h were characterized in 2-18 GHz frequency range. It was established that composites based on Co-coated carbonyl iron demonstrate thermomagnetic stability, indicating that Co coating reduces the oxidation of carbonyl iron. Thus, Co-coated carbonyl iron particles/polyimide composites are useful in the design of microwave absorbers operating at temperatures up to 300 °C.

  20. Microbial oxidation of mixtures of methylmercaptan and hydrogen sulfide.

    Science.gov (United States)

    Subramaniyan, A; Kolhatkar, R; Sublette, K L; Beitle, R

    1998-01-01

    Refinery spent-sulfidic caustic, containing only inorganic sulfides, has previously been shown to be amenable to biotreatment with Thiobacillus denitrificans strain F with complete oxidation of sulfides to sulfate. However, many spent caustics contain mercaptans that cannot be metabolized by this strict autotroph. An aerobic enrichment culture was developed from mixed Thiobacilli and activated sludge that was capable of simultaneous oxidation of inorganic sulfide and mercaptans using hydrogen sulfide (H2S) and methylmercaptan (MeSH) gas feeds used to simulate the inorganic and organic sulfur of a spent-sulfidic caustic. The enrichment culture was also capable of biotreatment of an actual mercaptan-containing, spent-sulfidic caustic but at lower rates than predicted by operation on MeSH and H2S fed to the culture in the gas phase, indicating that the caustic contained other inhibitory components. PMID:18576062

  1. Behaviour of protein carbonyl groups in juvenile myocardial infarction.

    Science.gov (United States)

    Caimi, Gregorio; Canino, Baldassare; Incalcaterra, Egle; Ferrera, Eleonora; Montana, Maria; Lo Presti, Rosalia

    2013-01-01

    Acute myocardial infarction (AMI) is accompanied by oxidative stress, and protein oxidation is among the consequences of oxidative stress. We examined the plasma concentration of protein carbonyl groups (PC), a marker of protein oxidation, in a group of young subjects with AMI (45 men and 5 women; mean age 40.4 ± 4.8 yrs). We found a significant increase of PC (p < 0.001) in comparison with normal controls. No difference was observed between patients with AMI characterized by elevated ST segment and those without elevation of ST segment. There was no correlation between the ejection fraction and PC in the whole group nor in the subgroups of STEMI and non-STEMI patients. Subdividing the whole group of AMI patients according to the number of risk factors and the number of stenosed coronary vessels, the difference in PC level was not statistically significant among the subgroups. This study showed an increased protein oxidation in young subjects with recent AMI. Further investigation is needed to ascertain whether this can be a target of therapeutic intervention. PMID:22504219

  2. Aldol Condensation of Volatile Carbonyl Compounds in Acidic Aerosols

    Science.gov (United States)

    Noziere, B.; Esteve, W.

    2003-12-01

    Reactions of volatile organic compounds in acidic aerosols have been shown recently to be potentially important for organic aerosol formation and growth. Aldol condensation, the acid-catalyzed polymerization of carbonyl compounds, is a likely candidate to enhance the flux of organic matter from the gas phase to the condensed phase in the atmosphere. Until now these reactions have only been characterized for conditions relevant to synthesis (high acidities and liquid phase systems) and remote from atmospheric ones. In this work, the uptake of gas-phase acetone and 2,4\\-pentanedione by sulfuric acid solutions has been measured at room temperature using a Rotated Wetted Wall Reactor coupled to a Mass Spectrometer. The aldol condensation rate constants for 2,4\\-pentanedione measured so far for sulfuric acid solutions between 96 and 70 % wt. display a variation with acidity in agreement with what predicted in the organic chemical literature. The values of these constants, however, are much lower than expected for this compound, and comparable to the ones of acetone. Experiments are underway to complete this study to lower acidities and understand the discrepancies with the predicted reactivity.

  3. Teratogenicity and embryotoxicity of nickel carbonyl in Syrian hamsters

    Energy Technology Data Exchange (ETDEWEB)

    Sunderman, F.W. Jr.; Shen, S.K.; Reid, M.C.; Allpass, P.R.

    1980-01-01

    Nickel carbonyl was administered to groups of pregnant hamsters by inhalation on days 4, 5, 6, 7, or 8 of gestation. The dams were killed on day 15 of gestation, and the fetuses were examined for malformations. Exposure to Ni(CO)/sub 4/ on days 4 or 5 of gestation resulted in malformation in 5.5% and 5.8% of the progeny, respectively. Progeny included 9 fetuses with cystic lungs, 7 fetuses with exencephaly, 1 fetus with exencephaly plus fused rib and 1 fetus with anophthalmia plus cleft palate. Hemorrhages into serious cavities were found. In progeny of dams exposed to Ni(CO)/sub 4/ on days 6 or 7 of gestation, there was 1 fetus with fused ribs and there were 2 fetuses with hydronephrosis. In another experiment, pregnant hamsters were exposed to inhalation of Ni(CO)/sub 4/ on day 5 of gestation; these dams were permitted to deliver their litters and to nurse their pups. There was no significant difference in the average number of live pups in the Ni(CO)/sub 4/-exposed litters compared to control litters. Neonatal mortality was increased in Ni(CO)/sub 4/-exposed litters. This study demonstrates that Ni(CO)/sub 4/ is teratogenic and embryotoxic in Syrian hamsters.

  4. Human TTR conformation altered by rhenium tris-carbonyl derivatives.

    Science.gov (United States)

    Ciccone, Lidia; Policar, Clotilde; Stura, Enrico A; Shepard, William

    2016-09-01

    Transthyretin (TTR) is a 54 kDa homotetrameric serum protein that transports thyroxine (T4) and retinol. TTR is potentially amyloidogenic due to homotetramer dissociation into monomeric intermediates that self-assemble as amyloid deposits and insoluble fibrils. Most crystallographic structures, including those of amyloidogenic variants show the same tetramer without major variations in the monomer-monomer interface nor in the volume of the interdimeric cavity. Soaking TTR crystals in a solution containing rhenium tris-carbonyl derivatives yields a TTR conformer never observed before. Only one of the two monomers of the crystallographic dimer is significantly altered, and the inner part of the T4 binding cavity is expanded at one end and shrunk at the other. The result redefines the mechanism of allosteric communication between the two sites, suggesting that negative cooperativity is a function of dimer asymmetry, which can be induced through internal or external binding. An aspect that remains unexplained is why the conformational changes are ubiquitous throughout the crystal although the heavy metal content of the derivatized crystals is relatively low. The conformational changes observed, which include Leu(82), may represent a form of TTR better at scavenging β-Amyloid. At a resolution of 1.69Å, with excellent refinement statistics and well defined electron density for all parts of the structure, it is possible to envisage answering important questions that range from protein cooperative behavior to heavy atom induced protein conformational modifications that can result in crystallographic non-isomorphism. PMID:27402536

  5. Sulfide Intrusion and Detoxification in the Seagrass Zostera marina.

    Directory of Open Access Journals (Sweden)

    Harald Hasler-Sheetal

    Full Text Available Gaseous sulfide intrusion into seagrasses growing in sulfidic sediments causes little or no harm to the plant, indicating the presence of an unknown sulfide tolerance or detoxification mechanism. We assessed such mechanism in the seagrass Zostera marina in the laboratory and in the field with scanning electron microscopy coupled to energy dispersive X-ray spectroscopy, chromatographic and spectrophotometric methods, and stable isotope tracing coupled with a mass balance of sulfur compounds. We found that Z. marina detoxified gaseous sediment-derived sulfide through incorporation and that most of the detoxification occurred in underground tissues, where sulfide intrusion was greatest. Elemental sulfur was a major detoxification compound, precipitating on the inner wall of the aerenchyma of underground tissues. Sulfide was metabolized into thiols and entered the plant sulfur metabolism as well as being stored as sulfate throughout the plant. We conclude that avoidance of sulfide exposure by reoxidation of sulfide in the rhizosphere or aerenchyma and tolerance of sulfide intrusion by incorporation of sulfur in the plant are likely major survival strategies of seagrasses in sulfidic sediments.

  6. The Evolution of Sulfide Tolerance in the Cyanobacteria

    Science.gov (United States)

    Miller, Scott R.; Bebout, Brad M.; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    Understanding how the function of extant microorganisms has recorded both their evolutionary histories and their past interactions with the environment is a stated goal of astrobiology. We are taking a multidisciplinary approach to investigate the diversification of sulfide tolerance mechanisms in the cyanobacteria, which vary both in their degree of exposure to sulfide and in their capacity to tolerate this inhibitor of photosynthetic electron transport. Since conditions were very reducing during the first part of Earth's history and detrital sulfides have been found in Archean sediments, mechanisms conferring sulfide tolerance may have been important for the evolutionary success of the ancestors of extant cyanobacteria. Two tolerance mechanisms have been identified in this group: (1) resistance of photosystem II, the principal target of sulfide toxicity; and (2) maintenance of the ability to fix carbon despite photosystem II inhibition by utilizing sulfide as an electron donor in photosystem I - dependent, anoxygenic photosynthesis. We are presently collecting comparative data on aspects of sulfide physiology for laboratory clones isolated from a variety of habitats. These data will be analyzed within a phylogenetic framework inferred from molecular sequence data collected for these clones to test how frequently different mechanisms of tolerance have evolved and which tolerance mechanism evolved first. In addition, by analyzing these physiological data together with environmental sulfide data collected from our research sites using microelectrodes, we can also test whether the breadth of an organism's sulfide tolerance can be predicted from the magnitude of variation in environmental sulfide concentration it has experienced in its recent evolutionary past and whether greater average sulfide concentration and/or temporal variability in sulfide favors the evolution of a particular mechanism of sulfide tolerance.

  7. Iron-sulfide redox flow batteries

    Science.gov (United States)

    Xia, Guan-Guang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

    2013-12-17

    Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

  8. Iron-sulfide redox flow batteries

    Energy Technology Data Exchange (ETDEWEB)

    Xia, Guanguang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L

    2016-06-14

    Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

  9. Nanostructured palladium tailored via carbonyl chemical route towards oxygen reduction reaction

    International Nuclear Information System (INIS)

    Graphical Abstract: Mass-depending morphologies of nanostructured Palladium obtained via the carbonyl chemical route. Display Omitted -- Highlights: •Mass-depending morphology was observed in nanostructured palladium supported on carbon prepared by the carbonyl chemical route. •The Morphological effect of carbon supported Pd was investigated towards ORR. -- Abstract: Carbon supported palladium nanostructures were synthesized via the carbonyl chemical route. Compared with nanostructured platinum, prepared via carbonyl chemical route, Pd nanomaterials showed mass-loading morphology, whereas particle size and morphology of Pt nanostructures was constant. The oxygen reduction reaction (ORR) on nanostructured Pd, with different morphology in both acid and alkaline medium was investigated. A relationship, based on X-ray diffraction structural analysis pattern, transmission electron microscope, with the Pd morphological effect on ORR activity was identified

  10. Structure and Bonding in Binuclear Metal Carbonyls. Classical Paradigms vs. Insights from Modern Theoretical Calculations

    Czech Academy of Sciences Publication Activity Database

    Ponec, Robert

    2015-01-01

    Roč. 1053, SI (2015), s. 195-213. ISSN 2210-271X Institutional support: RVO:67985858 Keywords : binuclear metal carbonyls * DAFH analysis * 18-electron rule Subject RIV: CC - Organic Chemistry Impact factor: 1.545, year: 2014

  11. Comparison of sampling methods for radiocarbon dating of carbonyls in air samples via accelerator mass spectrometry

    Science.gov (United States)

    Schindler, Matthias; Kretschmer, Wolfgang; Scharf, Andreas; Tschekalinskij, Alexander

    2016-05-01

    Three new methods to sample and prepare various carbonyl compounds for radiocarbon measurements were developed and tested. Two of these procedures utilized the Strecker synthetic method to form amino acids from carbonyl compounds with either sodium cyanide or trimethylsilyl cyanide. The third procedure used semicarbazide to form crystalline carbazones with the carbonyl compounds. The resulting amino acids and semicarbazones were then separated and purified using thin layer chromatography. The separated compounds were then combusted to CO2 and reduced to graphite to determine 14C content by accelerator mass spectrometry (AMS). All of these methods were also compared with the standard carbonyl compound sampling method wherein a compound is derivatized with 2,4-dinitrophenylhydrazine and then separated by high-performance liquid chromatography (HPLC).

  12. Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

    Science.gov (United States)

    Pierantozzi, Ronald

    1985-01-01

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  13. Synthesis of 2-Cyclopentenone Derivatives via Palladium-Catalyzed Intramolecular Carbonyl α-Alkenylation.

    Science.gov (United States)

    Chen, Panpan; Meng, Yinggao; Wang, Han; Han, Feipeng; Wang, Yulong; Song, Chuanjun; Chang, Junbiao

    2016-08-01

    2-Cyclopentenone derivatives have been efficiently synthesized from 5-bromo-5-hexen-2-ones via palladium-catalyzed intramolecular carbonyl α-alkenylation followed by double-bond migration under mild reaction conditions. PMID:27463262

  14. Efficient and selective α-bromination of carbonyl compounds with N-bromosuccinimide under microwave

    KAUST Repository

    Guan, Xiao-Yu

    2014-02-07

    A highly efficient method for the synthesis of α-halocarbonyl compounds has been achieved via selective monobromination of aromatic and aliphatic carbonyl compounds with N-bromosuccinimide catalyzed by p-toluenesulfonic acid under microwave irradiation within 30 min.

  15. Subsurface heaters with low sulfidation rates

    Energy Technology Data Exchange (ETDEWEB)

    John, Randy Carl; Vinegar, Harold J

    2013-12-10

    A system for heating a hydrocarbon containing formation includes a heater having an elongated ferromagnetic metal heater section. The heater is located in an opening in a formation. The heater section is configured to heat the hydrocarbon containing formation. The exposed ferromagnetic metal has a sulfidation rate that goes down with increasing temperature of the heater, when the heater is in a selected temperature range.

  16. Hydrogen sulfide prodrugs-a review.

    Science.gov (United States)

    Zheng, Yueqin; Ji, Xingyue; Ji, Kaili; Wang, Binghe

    2015-09-01

    Hydrogen sulfide (H2S) is recognized as one of three gasotransmitters together with nitric oxide (NO) and carbon monoxide (CO). As a signaling molecule, H2S plays an important role in physiology and shows great potential in pharmaceutical applications. Along this line, there is a need for the development of H2S prodrugs for various reasons. In this review, we summarize different H2S prodrugs, their chemical properties, and some of their potential therapeutic applications. PMID:26579468

  17. Hydrogen sulfide prodrugs—a review

    Directory of Open Access Journals (Sweden)

    Yueqin Zheng

    2015-09-01

    Full Text Available Hydrogen sulfide (H2S is recognized as one of three gasotransmitters together with nitric oxide (NO and carbon monoxide (CO. As a signaling molecule, H2S plays an important role in physiology and shows great potential in pharmaceutical applications. Along this line, there is a need for the development of H2S prodrugs for various reasons. In this review, we summarize different H2S prodrugs, their chemical properties, and some of their potential therapeutic applications.

  18. Efficiently Dispersing Carbon Nanotubes in Polyphenylene Sulfide

    OpenAIRE

    Sommer, Kevin M; Pipes, R. Byron

    2013-01-01

    Thermal plastics are replacing conventional metals in the aerospace, sporting, electronics, and other industries. Thermal plastics are able to withstand relatively high temperatures, have good fatigue properties, and are lighter than metals. Unfortunately, they are not very electrically conductive. However, adding carbon nanotubes to thermal plastics such as polyphenylene sulfide (PPS) can drastically increase the plastic's conductivity at a low weight percent of nanotubes called the percolat...

  19. Protein carbonylation and aggregation precede neuronal apoptosis induced by partial glutathione depletion

    Directory of Open Access Journals (Sweden)

    Jianzheng Zheng

    2012-04-01

    Full Text Available While the build-up of oxidized proteins within cells is believed to be toxic, there is currently no evidence linking protein carbonylation and cell death. In the present study, we show that incubation of nPC12 (neuron-like PC12 cells with 50 μM DEM (diethyl maleate leads to a partial and transient depletion of glutathione (GSH. Concomitant with GSH disappearance there is increased accumulation of PCOs (protein carbonyls and cell death (both by necrosis and apoptosis. Immunocytochemical studies also revealed a temporal/spatial relationship between carbonylation and cellular apoptosis. In addition, the extent of all three, PCO accumulation, protein aggregation and cell death, augments if oxidized proteins are not removed by proteasomal degradation. Furthermore, the effectiveness of the carbonyl scavengers hydralazine, histidine hydrazide and methoxylamine at preventing cell death identifies PCOs as the toxic species. Experiments using well-characterized apoptosis inhibitors place protein carbonylation downstream of the mitochondrial transition pore opening and upstream of caspase activation. While the study focused mostly on nPC12 cells, experiments in primary neuronal cultures yielded the same results. The findings are also not restricted to DEM-induced cell death, since a similar relationship between carbonylation and apoptosis was found in staurosporine- and buthionine sulfoximine-treated nPC12 cells. In sum, the above results show for the first time a causal relationship between carbonylation, protein aggregation and apoptosis of neurons undergoing oxidative damage. To the best of our knowledge, this is the first study to place direct (oxidative protein carbonylation within the apoptotic pathway.

  20. Proteomic analysis and protein carbonylation profile in trained and untrained rat muscle

    OpenAIRE

    F.Magherini; P.M. Abruzzo; Puglia, M.; Bini, L.; T. Gamberi; Esposito, F; A. Veicsteinas; Marini, M.; Fiorillo, C; Gulisano, M; Modesti, A

    2012-01-01

    Understanding the relationship between physical exercise, reactive oxygen species and skeletal muscle modification is important in order to better identify the benefits or the damages that appropriate or inappropriate exercise can induce. Unbalanced ROS levels can lead to oxidation of cellular macromolecules and a major class of protein oxidative modification is carbonylation. The aim of this investigation was to study muscle protein expression and carbonylation patterns in tra...

  1. Proteomic and Carbonylation Profile Analysis of Rat Skeletal Muscles following Acute Swimming Exercise

    OpenAIRE

    F. Magherini; T. Gamberi; Pietrovito, L; T. Fiaschi; L. Bini; Esposito, F; M. Marini; P.M. Abruzzo; Gulisano, M; Modesti, A

    2013-01-01

    Previous studies by us and other groups characterized protein expression variation following long-term moderate training, whereas the effects of single bursts of exercise are less known. Making use of a proteomic approach, we investigated the effects of acute swimming exercise (ASE) on protein expression and carbonylation patterns in two hind limb muscles: the Extensor Digitorum Longus (EDL) and the Soleus, mostly composed of fast-twitch and slow-twitch fibres, respectively. Carbonylation is ...

  2. Fabrication and electromagnetic characteristics of microwave absorbers containing PPY and carbonyl iron composite

    Energy Technology Data Exchange (ETDEWEB)

    Li Dengao, E-mail: lidengao123@163.com [College of Information Engineering, Taiyuan University of Technology, Taiyuan 030024 (China); Wang Hongbin; Zhao Jumin [College of Information Engineering, Taiyuan University of Technology, Taiyuan 030024 (China); Yang Xiaoli [Department of Electrical and Computer Engineering, Purdue University Calumet, IN 46323-2094 (United States)

    2011-10-17

    Highlights: {yields} Polypyrrole powders are prepared by in situ polymerization method. {yields} Then PPY-carbonyl iron composite with different mixture ratios have been prepared. {yields} The effect of the mass ratio of PPY-carbonyl iron on the microwave loss properties of the composites is investigated. {yields} A possible microwave absorbing mechanism of PPY-carbonyl iron composite has been proposed. - Abstract: The objective of this study is to develop microwave absorbers using both dielectric and magnetic lossy materials. Polypyrrole (PPY) is used as dielectric lossy materials and carbonyl iron particles is used as magnetic lossy materials. Polypyrrole powders are prepared by in situ polymerization method. Then PPY-carbonyl iron composite with different mixture ratios have been prepared by as-prepared material. The structure, morphology and properties of the composites are characterized with IR, XRD, scanning electron microscope (SEM), Net-work Anlyzer. The complex permittivity ({epsilon}{sup '}{sub r}-j{epsilon}{sup ''}{sub r}) and reflection loss (dB) of the composites have been measured at different microwave frequencies in S-band and C-band (30-6000 MHz) employing vector network analyzer model HP 8722ET vector. The effect of the mass ratio of PPY-carbonyl iron on the microwave loss properties of the composites is investigated. A possible microwave absorbing mechanism of PPY-carbonyl iron composite has been proposed. The PPY-carbonyl iron composite can find applications in suppression of electromagnetic interference (EMI), and reduction of radar signature.

  3. COMPARATIVE STUDY OF EFFICACY OF FERROUS SULPHATE AND CARBONYL IRON IN ANEMIA OF ANTENATAL WOMEN

    Directory of Open Access Journals (Sweden)

    Radhika

    2015-03-01

    Full Text Available Iron deficiency anemia is the most common and important public health problem all over the world in the risk group of antenatal women. Research is going on to improve the iron status of the pregnant women with different forms of iron available. In this regard, Carbonyl Iron is showing promising results in improving the red cell mass with better compliance. 120 antenatal women were recruited in this study. The study comprised of 6weeks for each patient. They were given Carbonyl Iron 100 mg/day and FeS04 100gm/day . Before and after treatment all the baseline and specific investigations were one. Results were tabulated, comparison and significance were tested by unpaired student ’s’ test and their 'p' value was calculated. Results were shown graphically also. Carbonyl Iron showed improvement in hemoglobin, PCV and better than ferrous Sulphate (P <0.001. Incidence of side effects were less with Carbonyl Iron than Ferrous Sulphate, better compliance was seen with Carbonyl Iron. In conclusion, the present study s howed that Carbonyl Iron had better efficacy and safety in the management of Iron deficiency anemia in antenatal women than ferrous Sulphate

  4. Oxidative Stress and Carbonyl Lesions in Ulcerative Colitis and Associated Colorectal Cancer

    Directory of Open Access Journals (Sweden)

    Zhiqi Wang

    2016-01-01

    Full Text Available Oxidative stress has long been known as a pathogenic factor of ulcerative colitis (UC and colitis-associated colorectal cancer (CAC, but the effects of secondary carbonyl lesions receive less emphasis. In inflammatory conditions, reactive oxygen species (ROS, such as superoxide anion free radical (O2∙-, hydrogen peroxide (H2O2, and hydroxyl radical (HO∙, are produced at high levels and accumulated to cause oxidative stress (OS. In oxidative status, accumulated ROS can cause protein dysfunction and DNA damage, leading to gene mutations and cell death. Accumulated ROS could also act as chemical messengers to activate signaling pathways, such as NF-κB and p38 MAPK, to affect cell proliferation, differentiation, and apoptosis. More importantly, electrophilic carbonyl compounds produced by lipid peroxidation may function as secondary pathogenic factors, causing further protein and membrane lesions. This may in turn exaggerate oxidative stress, forming a vicious cycle. Electrophilic carbonyls could also cause DNA mutations and breaks, driving malignant progression of UC. The secondary lesions caused by carbonyl compounds may be exceptionally important in the case of host carbonyl defensive system deficit, such as aldo-keto reductase 1B10 deficiency. This review article updates the current understanding of oxidative stress and carbonyl lesions in the development and progression of UC and CAC.

  5. Microaeration for hydrogen sulfide removal in UASB reactor.

    Science.gov (United States)

    Krayzelova, Lucie; Bartacek, Jan; Kolesarova, Nina; Jenicek, Pavel

    2014-11-01

    The removal of hydrogen sulfide from biogas by microaeration was studied in Up-flow Anaerobic Sludge Blanket (UASB) reactors treating synthetic brewery wastewater. A fully anaerobic UASB reactor served as a control while air was dosed into a microaerobic UASB reactor (UMSB). After a year of operation, sulfur balance was described in both reactors. In UASB, sulfur was mainly presented in the effluent as sulfide (49%) and in biogas as hydrogen sulfide (34%). In UMSB, 74% of sulfur was detected in the effluent (41% being sulfide and 33% being elemental sulfur), 10% accumulated in headspace as elemental sulfur and 9% escaped in biogas as hydrogen sulfide. The efficiency of hydrogen sulfide removal in UMSB was on average 73%. Microaeration did not cause any decrease in COD removal or methanogenic activity in UMSB and the elemental sulfur produced by microaeration did not accumulate in granular sludge. PMID:25270045

  6. Simultaneous removal of sulfide, nitrate and acetate: Kinetic modeling

    International Nuclear Information System (INIS)

    Biological removal of sulfide, nitrate and chemical oxygen demand (COD) simultaneously from industrial wastewaters to elementary sulfur (S0), N2, and CO2, or named the denitrifying sulfide (DSR) process, is a cost effective and environmentally friendly treatment process for high strength sulfide and nitrate laden organic wastewater. Kinetic model for the DSR process was established for the first time on the basis of Activated Sludge Model No. 1 (ASM1). The DSR experiments were conducted at influent sulfide concentrations of 200-800 mg/L, whose results calibrate the model parameters. The model correlates well with the DSR process dynamics. By introducing the switch function and the inhibition function, the competition between autotrophic and heterotrophic denitrifiers is quantitatively described and the degree of inhibition of sulfide on heterotrophic denitrifiers is realized. The model output indicates that the DSR reactor can work well at 0.5 1000 mg/L influent sulfide, however, the DSR system will break down.

  7. Study on the sulfidation behavior of smithsonite

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Dandan; Wen, Shuming, E-mail: shmwen@126.com; Deng, Jiushuai, E-mail: dengshuai689@163.com; Liu, Jian; Mao, Yingbo

    2015-02-28

    Highlights: • Zeta potential showed that the pH{sub IEP} of smithsonite decreased from 7.7 to 6. • ICP test showed the gradual reduction of C{sub S} in the solution. • SEM showed that the mineral surface was partially changed to ZnS film. • XPS indicated that the presence of a characteristic signal peak of sulfur ions. - Abstract: Zinc extraction from low-grade mineral resources of oxidized zinc has recently become a focus of study. Sulfidation is an important process in oxidized ore flotation. In this study, the influence of sulfur ion adsorption on smithsonite surface was investigated with the use of zeta potential, inductively coupled plasma (ICP), scanning electron microscope (SEM), and X-ray photoelectron spectroscopic studies. Zeta potential measurements of sodium sulfide showed that sulfur ions were adsorbed onto the surface of pure smithsonite, as evidenced by the increased negative charge and the decrease in the pH{sub IEP} of smithsonite from 7.7 to 6 after sodium sulfide treatment. The ICP test revealed the gradual reduction in sulfur ion adsorption onto the surface of smithsonite in pulp sulfur. After 30 min of absorption, C{sub S} in the solution declined from 1000 × 10{sup −6} mol/L to 1.4 × 10{sup −6} mol/L. SEM results showed that the mineral surface was partially changed to ZnS film after sodium sulfide treatment, whereas EDS analysis results showed that 2% S is contained on the smithsonite surface. X-ray photoelectron spectroscopy results indicated the presence of a characteristic signal peak of sulfur ions after sulfidation. Sulfur concentration increased to 11.89%, whereas oxygen concentration decreased from 42.31% to 13.74%. Sulfur ions were not only present during chemical adsorption, but were also incorporated into the crystal lattices of minerals by the exchange reaction between S{sup 2−} and CO{sub 3}{sup 2−} ions.

  8. Protein carbonylation, protein aggregation and neuronal cell death in a murine model of multiple sclerosis

    Science.gov (United States)

    Dasgupta, Anushka

    Many studies have suggested that oxidative stress plays an important role in the pathophysiology of both multiple sclerosis (MS) and its animal model experimental autoimmune encephalomyelitis (EAE). Yet, the mechanism by which oxidative stress leads to tissue damage in these disorders is unclear. Recent work from our laboratory has revealed that protein carbonylation, a major oxidative modification caused by severe and/or chronic oxidative stress conditions, is elevated in MS and EAE. Furthermore, protein carbonylation has been shown to alter protein structure leading to misfolding/aggregation. These findings prompted me to hypothesize that carbonylated proteins, formed as a consequence of oxidative stress and/or decreased proteasomal activity, promote protein aggregation to mediate neuronal apoptosis in vitro and in EAE. To test this novel hypothesis, I first characterized protein carbonylation, protein aggregation and apoptosis along the spinal cord during the course of myelin-oligodendrocyte glycoprotein (MOG)35-55 peptide-induced EAE in C57BL/6 mice [Chapter 2]. The results show that carbonylated proteins accumulate throughout the course of the disease, albeit by different mechanisms: increased oxidative stress in acute EAE and decreased proteasomal activity in chronic EAE. I discovered not only that there is a temporal correlation between protein carbonylation and apoptosis but also that carbonyl levels are significantly higher in apoptotic cells. A high number of juxta-nuclear and cytoplasmic protein aggregates containing the majority of the oxidized proteins are also present during the course of EAE, which seems to be due to reduced autophagy. In chapter 3, I show that when gluthathione levels are reduced to those in EAE spinal cord, both neuron-like PC12 (nPC12) cells and primary neuronal cultures accumulate carbonylated proteins and undergo cell death (both by necrosis and apoptosis). Immunocytochemical and biochemical studies also revealed a temporal

  9. Effects of dispersed sulfides in bronze under line contact conditions

    Directory of Open Access Journals (Sweden)

    Tomohiro Sato

    2016-03-01

    Full Text Available A sintered bronze system is applied to plane bearings with some lubricants. A bronze-based, sulfide-dispersed Cu alloy was developed via sintering. Sulfides had some functions, reduction of friction resistance, preventing scoring and seizure. Effects of the developed sulfide-containing bronze were investigated using a journal-type testing apparatus in wet conditions; results indicate that the developed bronze may have some anti-scoring properties.

  10. Extraction of Nanosized Cobalt Sulfide from Spent Hydrocracking Catalyst

    OpenAIRE

    Samia A. Kosa; Hegazy, Eman Z.

    2013-01-01

    The processes used for the extraction of metals (Co, Mo, and Al) from spent hydrotreating catalysts were investigated in this study. A detailed mechanism of the metal extraction process is described. Additionally, a simulation study was performed to understand the sulfidizing mechanism. The suggested separation procedure was effective and achieved an extraction of approximately 80–90%. In addition, the sulfidization mechanism was identified. This sulfidizing process for Co was found to involv...

  11. Metabolism of bupropion by carbonyl reductases in liver and intestine.

    Science.gov (United States)

    Connarn, Jamie N; Zhang, Xinyuan; Babiskin, Andrew; Sun, Duxin

    2015-07-01

    Bupropion's metabolism and the formation of hydroxybupropion in the liver by cytochrome P450 2B6 (CYP2B6) has been extensively studied; however, the metabolism and formation of erythro/threohydrobupropion in the liver and intestine by carbonyl reductases (CR) has not been well characterized. The purpose of this investigation was to compare the relative contribution of the two metabolism pathways of bupropion (by CYP2B6 and CR) in the subcellular fractions of liver and intestine and to identify the CRs responsible for erythro/threohydrobupropion formation in the liver and the intestine. The results showed that the liver microsome generated the highest amount of hydroxybupropion (Vmax = 131 pmol/min per milligram, Km = 87 μM). In addition, liver microsome and S9 fractions formed similar levels of threohydrobupropion by CR (Vmax = 98-99 pmol/min per milligram and Km = 186-265 μM). Interestingly, the liver has similar capability to form hydroxybupropion (by CYP2B6) and threohydrobupropion (by CR). In contrast, none of the intestinal fractions generate hydroxybupropion, suggesting that the intestine does not have CYP2B6 available for metabolism of bupropion. However, intestinal S9 fraction formed threohydrobupropion to the extent of 25% of the amount of threohydrobupropion formed by liver S9 fraction. Enzyme inhibition and Western blots identified that 11β-dehydrogenase isozyme 1 in the liver microsome fraction is mainly responsible for the formation of threohydrobupropion, and in the intestine AKR7 may be responsible for the same metabolite formation. These quantitative comparisons of bupropion metabolism by CR in the liver and intestine may provide new insight into its efficacy and side effects with respect to these metabolites. PMID:25904761

  12. New Ir Bis-Carbonyl Precursor for Water Oxidation Catalysis.

    Science.gov (United States)

    Huang, Daria L; Beltrán-Suito, Rodrigo; Thomsen, Julianne M; Hashmi, Sara M; Materna, Kelly L; Sheehan, Stafford W; Mercado, Brandon Q; Brudvig, Gary W; Crabtree, Robert H

    2016-03-01

    This paper introduces Ir(I)(CO)2(pyalc) (pyalc = (2-pyridyl)-2-propanoate) as an atom-efficient precursor for Ir-based homogeneous oxidation catalysis. This compound was chosen to simplify analysis of the water oxidation catalyst species formed by the previously reported Cp*Ir(III)(pyalc)OH water oxidation precatalyst. Here, we present a comparative study on the chemical and catalytic properties of these two precursors. Previous studies show that oxidative activation of Cp*Ir-based precursors with NaIO4 results in formation of a blue Ir(IV) species. This activation is concomitant with the loss of the placeholder Cp* ligand which oxidatively degrades to form acetic acid, iodate, and other obligatory byproducts. The activation process requires substantial amounts of primary oxidant, and the degradation products complicate analysis of the resulting Ir(IV) species. The species formed from oxidation of the Ir(CO)2(pyalc) precursor, on the other hand, lacks these degradation products (the CO ligands are easily lost upon oxidation) which allows for more detailed examination of the resulting Ir(pyalc) active species both catalytically and spectroscopically, although complete structural analysis is still elusive. Once Ir(CO)2(pyalc) is activated, the system requires acetic acid or acetate to prevent the formation of nanoparticles. Investigation of the activated bis-carbonyl complex also suggests several Ir(pyalc) isomers may exist in solution. By (1)H NMR, activated Ir(CO)2(pyalc) has fewer isomers than activated Cp*Ir complexes, allowing for advanced characterization. Future research in this direction is expected to contribute to a better structural understanding of the active species. A diol crystallization agent was needed for the structure determination of 3. PMID:26901517

  13. Organometallic and Bioorganometallic Chemistry - Ferrocene and Metal Carbonyls

    Directory of Open Access Journals (Sweden)

    Čakić Semenčić, M.

    2011-02-01

    Full Text Available Organometallic chemistry deals with compounds containing metal-carbon bonds. Basic organometallics derived from the s- and p-block metals (containing solely σ-bonds were understood earlier, while organometallic chemistry of the d- and f-block has developed much more recently. These compounds are characterized by three types of M-C bonds (σ, π and δand their structures are impossible to deduce by chemical means alone; fundamental advances had to await the development of X-ray diffraction, as well as IR- and NMR-spectroscopy. On the other hand, elucidation of the structure of e. g. vitamin B12 and ferrocene (discovered in 1951 contributed to progress in these instrumental analytical methods, influencing further phenomenal success of transition-metal organometallic chemistry in the second half of the twentieth century. The most thoroughly explored fields of application of organometallics were in the area of catalysis, asymmetric synthesis, olefin metathesis, as well as organic synthesis and access to new materials and polymers.The most usual ligands bound to d- and f-metals are carbon monoxide, phosphines, alkyls, carbenes and arenes, and in this review the bonding patterns in the metal carbonyls and ferrocene are elaborated. The common characteristics of these two classes are two-component bonds. The CO-M bonds include (i donation from ligand HOMO to vacant M d-orbitals (σ-bond, and (ii back-donation from the filled M d-orbitals in the ligand LUMO (π-bond. Similar (but much more complicated ferrocene contains delocalized bonds consisting of electron donation from Cp to Fe (σ-bonds- and π-bonding and δ-back-bonding from metal to Cp. In such a way ferrocene, i. e. (η5-Cp2Fe contains 18 bonding electrons giving to this compound "superaromatic" properties in the sense of stability and electrophilic substitution. In contrast to benzenoid aromatic compounds reactions in two Cp-rings can occur giving homo- and heteroannularly mono-, two-… per

  14. Investigation into leaching of indium-containing sulfide cake

    International Nuclear Information System (INIS)

    Data are given of laboratory investigations into indium leaching from commercial-grade sulfide cake. Two indium extraction methods are studied: exchange sulfide decomposition by blue vitriol treatment, sulfide destruction by means of an oxidizer where manganese ore containing manganese dioxide and zinc cake containing zinc ferrite have been used. The influence of the reagent consumption temperature, duration of leaching on the indium extraction is estimated as well as into on the Copper and arsenic transport into the solution. Optimal conditions for the indium extraction from sulfide cake under salt leaching and oxidizing treatment are established

  15. Limitation of Sulfide Capacity Concept for Molten Slags

    Science.gov (United States)

    Jung, In-Ho; Moosavi-Khoonsari, Elmira

    2016-04-01

    The sulfide capacity concept has been widely used in pyrometallurgy to define sulfur removal capacities of slags. Typically, the sulfide capacity is considered to be a unique slag property depending only on temperature regardless of partial pressures of oxygen and sulfur. In the present study, it is demonstrated that sulfide capacities of slags in particular those of Na2O-containing slags can vary with partial pressures of oxygen and sulfur due to large solubility of sulfide in Na2O-containing slag systems.

  16. Recent findings on sinks for sulfide in gravity sewer networks

    DEFF Research Database (Denmark)

    Nielsen, Asbjørn Haaning; Hvitved-Jacobsen, Thorkild; Vollertsen, Jes

    2006-01-01

    Sulfide buildup in sewer networks is associated with several problems, including health impacts, corrosion of sewer structures and odor nuisance. In recent years, significant advances in the knowledge of the major processes governing sulfide buildup in sewer networks have been made. This paper...... summarizes this newly obtained knowledge and emphasizes important implications of the findings. Model simulations of the in-sewer processes important for the sulfur cycle showed that sulfide oxidation in the wetted biofilm is typically the most important sink for dissolved sulfide in gravity sewers. However...

  17. Carbon steel protection in G.S. (Girlder sulfide) plants. Iron sulfide scales formation conditions. Pt. 1

    International Nuclear Information System (INIS)

    An ASTM A 516 degree 60 carbon steel superficial protection technique submitted to a hydrogen-water sulfide corrosive medium at 2 MPa of pressure and 40-125 deg C forming on itself an iron sulfide layer was tested. Studies on pH influence, temperature, passivating mean characteristics and exposure time as well as the mechanical resistance of sulfide layers to erosion are included. (Author)

  18. MEASURING METAL SULFIDE COMPLEXES IN OXIC RIVER WATERS WITH SQUARE WAVE VOLTAMMETRY. (R825395)

    Science.gov (United States)

    A sulfide identification protocol was developed to quantify specific metal sulfides that could exist in river water. Using a series of acid additions, nitrogen purges, and voltammetric analyses, metal sulfides were identified and semiquantified in three specific gr...

  19. Proteomic identification of carbonylated proteins in F344 rat hippocampus after 1-bromopropane exposure

    International Nuclear Information System (INIS)

    1-Bromopropane (1-BP) is neurotoxic in both experimental animals and humans. Previous proteomic analysis of rat hippocampus implicated alteration of protein expression in oxidative stress, suggesting that oxidative stress plays a role in 1-BP-induced neurotoxicity. To understand this role at the protein level, we exposed male F344 rats to 1-BP at 0, 400, or 1000 ppm for 8 h/day for 1 week or 4 weeks by inhalation and quantitated changes in hippocampal protein carbonyl using a protein carbonyl assay, two-dimensional gel electrophoresis (2-DE), immunoblotting, and matrix-assisted laser-desorption ionization time-of-flight mass spectrometry (MALDI-TOF-TOF/MS). Hippocampal reactive oxygen species and protein carbonyl were significantly increased, demonstrating 1-BP-associated induction of oxidative stress and protein damage. MALDI-TOF-TOF/MS identified 10 individual proteins with increased carbonyl modification (p < 0.05; fold-change ≥ 1.5). The identified proteins were involved in diverse biological processes including glycolysis, ATP production, tyrosine catabolism, GTP binding, guanine degradation, and neuronal metabolism of dopamine. Hippocampal triosephosphate isomerase (TPI) activity was significantly reduced and negatively correlated with TPI carbonylation (p < 0.001; r = 0.83). Advanced glycation end-product (AGE) levels were significantly elevated both in the hippocampus and plasma, and hippocampal AGEs correlated negatively with TPI activity (p < 0.001; r = 0.71). In conclusion, 1-BP-induced neurotoxicity in the rat hippocampus seems to involve oxidative damage of cellular proteins, decreased TPI activity, and elevated AGEs. -- Highlights: ► 1-BP increases hippocampal ROS levels and hippocampal and plasma protein carbonyls. ► 1-BP increases TPI carbonylation and decreases TPI activity in the hippocampus. ► 1-BP increases hippocampal and plasma AGE levels.

  20. Normal State of the Metallic Hydrogen Sulfide

    OpenAIRE

    Kudryashov, Nikolay A.; Kutukov, Alexander A.; Mazur, Evgeny A.

    2016-01-01

    Generalized theory of the normal properties of the metal in the case of the electron-phonon (EP) systems with not constant density of electronic states is used to examine the normal state of the SH3 and SH2 phase of the hydrogen sulfide at different pressures. The frequency dependence of the real and imaginary part of the self-energy part (SP) of the electron Green's function, the real and imaginary part of the complex renormalization of the electron mass, the real and imaginary part of the c...

  1. Solubility of hydrogen sulfide in water

    International Nuclear Information System (INIS)

    The solubility of hydrogen sulfide in water, which is of importance in the design and analysis of the dual temperature process for the production of heavy water, has been measured in the temperature range 100 - 1800C at pressures up to 6670 kPa or the hydrate/H2S-rich liquid locus, whichever is lower at the particular temperature. Limited vapor phase data at 900, 1200, and 1500C were also obtained. Henry's coefficients have been determined from the experimental data. (orig./HK)

  2. Quantitative Proteomic Profiling of Muscle Type-Dependent and Age-Dependent Protein Carbonylation in Rat Skeletal Muscle Mitochondria

    OpenAIRE

    Feng, Juan; Xie, Hongwei; Meany, Danni L.; Thompson, LaDora V.; Arriaga, Edgar A.; Griffin, Timothy J.

    2008-01-01

    Carbonylation is a highly prevalent protein modification in skeletal muscle mitochondria, possibly contributing to its functional decline with age. Using quantitative proteomics, we identified mitochondrial proteins susceptible to carbonylation in a muscle type (slow- vs fast-twitch)-dependent and age-dependent manner from Fischer 344 rat skeletal muscle. Fast-twitch muscle contained twice as many carbonylated mitochondrial proteins than did slow-twitch muscle, with 22 proteins showing signif...

  3. Purification and characterization of a novel carbonyl reductase isolated from Rhodococcus erythropolis.

    Science.gov (United States)

    Zelinski, T; Peters, J; Kula, M R

    1994-04-15

    During growth on n-tetradecane a novel NADH-dependent carbonyl reductase is induced in the Gram-positive bacterium Rhodococcus erythropolis (Peters, P., Zelinski, T. and Kula, M.R. (1992) Appl. Microbiol. Biotechnol. 38, 334-340). The enzyme has been purified to homogeneity using fractional pH precipitation, anion exchange chromatography and affinity chromatography. The isoelectric point of the oxidoreductase is 4.4. The apparent molecular mass of the native enzyme is 161 kDa, that of the subunits 40 kDa as determined by SDS gel electrophoresis. A tetrameric structure of the carbonyl reductase is consistent with these results. Important biochemical data concerning the application of the reductase are: a broad pH-optimum, temperature optimum at 40 degrees C and stability at room temperature for more than 5 days. The oxidoreductase accepted as substrate aliphatic and aromatic ketones, keto esters (esters of keto carboxylic acids) and halogenated carbonyl compounds and reduced them to the corresponding hydroxyl compounds with (S)-configuration with more than 98% enantiomeric excess. The NAD(+)-dependent oxidation of primary alcohols was not catalyzed by the carbonyl reductase, whereas secondary alcohols and hydroxy acid esters were oxidized to the corresponding carbonyl compounds at about 10-fold slower reaction rates compared to the reduction. PMID:7764739

  4. 21 CFR 73.2995 - Luminescent zinc sulfide.

    Science.gov (United States)

    2010-04-01

    ... coloring externally applied facial makeup preparations and nail polish included under § 720.4(c)(7)(ix) and... zinc sulfide in facial makeup preparations shall not exceed 10 percent by weight of the final product. (2) Facial makeup preparations containing luminescent zinc sulfide are intended for use only...

  5. Effect of Soluble Sulfide on the Activity of Luminescent Bacteria

    Directory of Open Access Journals (Sweden)

    Feng Wang

    2012-05-01

    Full Text Available Sulfide is an important water pollutant widely found in industrial waste water that has attracted much attention. S2−, as a weak acidic anion, is easy hydrolyzed to HS and H2S in aqueous solution. In this study, biological tests were performed to establish the toxicity of sulfide solutions on luminescent bacteria. Considering the sulfide solution was contained three substances—S2−, HS and H2S—the toxicity test was performed at different pH values to investigate which form of sulfide increased light emission and which reduced light emission. It was shown that the EC50 values were close at pH 7.4, 8.0 and 9.0 which were higher than pH 5 and 10. The light emission and sulfide concentrations displayed an inverse exponential dose-response relationship within a certain concentration range at pH 5, 6.5 and 10. The same phenomenon occurred for the high concentration of sulfide at pH 7.4, 8 and 9, in which the concentration of sulfide was HS >> H2S > S2−. An opposite hormesis-effect appeared at the low concentrations of sulfide.

  6. 40 CFR 425.03 - Sulfide analytical methods and applicability.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Sulfide analytical methods and applicability. 425.03 Section 425.03 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... § 425.03 Sulfide analytical methods and applicability. (a) The potassium ferricyanide titration...

  7. First detection of doubly deuterated hydrogen sulfide

    CERN Document Server

    Vastel, C; Ceccarelli, C; Pearson, J

    2003-01-01

    This work was carried out with using the Caltech Submillimeter Observatory and presents the observational study of HDS and D2S towards a sample of Class 0 sources, and dense cores. We report the first detection of doubly deuterated hydrogen sulfide (D2S) in two dense cores and analyze the chemistry of these molecules aiming to help understand the deuteration processes in the interstellar medium. The observed values of the D2S/HDS ratio, and upper limits, require an atomic D/H ratio in the accreting gas of 0.1-1. The study presented in this Letter supports the hypothesis that formaldehyde, methanol and hydrogen sulfide are formed on the grain surfaces, during the cold pre-stellar core phase, where the CO depleted gas has large atomic D/H ratios. The high values for the D/H ratios are consistent with the predictions of a recent gas-phase chemical model that includes H3+ and its deuterated isotopomers, H2D+, D2H+ and D3+ (Roberts et al. 2003).

  8. Hydrogen Sulfide and Polysulfides as Biological Mediators

    Directory of Open Access Journals (Sweden)

    Hideo Kimura

    2014-10-01

    Full Text Available Hydrogen sulfide (H2S is recognized as a biological mediator with various roles such as neuromodulation, regulation of the vascular tone, cytoprotection, anti-inflammation, oxygen sensing, angiogenesis, and generation of mitochondrial energy. It is produced by cystathionine β-synthase (CBS, cystathionine γ-lyase (CSE, and 3-mercaptopyruvate sulfurtransferase (3MST. The activity of CBS is enhanced by S-adenosyl methionine (SAM and glutathionylation, while it is inhibited by nitric oxide (NO and carbon monoxide (CO. The activity of CSE and cysteine aminotransferase (CAT, which produces the 3MST substrate 3-mercaptopyruvate (3MP, is regulated by Ca2+. H2S is oxidized to thiosulfate in mitochondria through the sequential action of sulfide quinone oxidoreductase (SQR, sulfur dioxygenase, and rhodanese. The rates of the production and clearance of H2S determine its cellular concentration. Polysulfides (H2Sn have been found to occur in the brain and activate transient receptor potential ankyrin 1 (TRPA1 channels, facilitate the translocation of nuclear factor erythroid 2-related factor 2 (Nrf2 to the nucleus, and suppress the activity of phosphatase and tensin homolog (PTEN by sulfurating (sulfhydrating the target cysteine residues. A cross talk between H2S and NO also plays an important role in cardioprotection as well as regulation of the vascular tone. H2S, polysulfides, and their cross talk with NO may mediate various physiological and pathophysiological responses.

  9. Hierarchical Architecturing for Layered Thermoelectric Sulfides and Chalcogenides

    Directory of Open Access Journals (Sweden)

    Priyanka Jood

    2015-03-01

    Full Text Available Sulfides are promising candidates for environment-friendly and cost-effective thermoelectric materials. In this article, we review the recent progress in all-length-scale hierarchical architecturing for sulfides and chalcogenides, highlighting the key strategies used to enhance their thermoelectric performance. We primarily focus on TiS2-based layered sulfides, misfit layered sulfides, homologous chalcogenides, accordion-like layered Sn chalcogenides, and thermoelectric minerals. CS2 sulfurization is an appropriate method for preparing sulfide thermoelectric materials. At the atomic scale, the intercalation of guest atoms/layers into host crystal layers, crystal-structural evolution enabled by the homologous series, and low-energy atomic vibration effectively scatter phonons, resulting in a reduced lattice thermal conductivity. At the nanoscale, stacking faults further reduce the lattice thermal conductivity. At the microscale, the highly oriented microtexture allows high carrier mobility in the in-plane direction, leading to a high thermoelectric power factor.

  10. Physical and microstructural aspects of iron sulfide degradation in concrete

    International Nuclear Information System (INIS)

    The microstructural aspects of iron sulfide degradation in dam concrete were investigated by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) in both dam concrete samples and laboratory concrete. The results show that iron sulfide inclusions with a diameter of a few micrometers in the aggregates are reactive and appear to generate expansion first in the aggregates and consequently in the cement paste. The expansion from the iron sulfides is a consequence of the increase in volume of the reaction products formed. The types of iron sulfide present in the aggregate, mainly pyrrhotite (FeS) and pyrite (FeS2), show similar reaction behavior in the aggregates. The released sulfate can lead to a secondary ettringite formation in the concrete matrix, but the degradation associated with this appears to be minor. The reaction of the iron sulfides was found to be very slow even when laboratory samples were exposed to elevated temperatures.

  11. Influence of Water Salinity on Air Purification from Hydrogen Sulfide

    Directory of Open Access Journals (Sweden)

    Leybovych L.I.

    2015-12-01

    Full Text Available Mathematical modeling of «sliding» water drop motion in the air flow was performed in software package FlowVision. The result of mathematical modeling of water motion in a droplet with diameter 100 microns at the «sliding» velocity of 15 m/s is shown. It is established that hydrogen sulfide oxidation occurs at the surface of phases contact. The schematic diagram of the experimental setup for studying air purification from hydrogen sulfide is shown. The results of the experimental research of hydrogen sulfide oxidation by tap and distilled water are presented. The dependence determining the share of hydrogen sulfide oxidized at the surface of phases contact from the dimensionless initial concentration of hydrogen sulfide in the air has been obtained.

  12. Sulindac Sulfide, but Not Sulindac Sulfone, Inhibits Colorectal Cancer Growth

    Directory of Open Access Journals (Sweden)

    Christopher S. Williams

    1999-06-01

    Full Text Available Sulindac sulfide, a metabolite of the nonsteroidal antiinflammatory drug (NSAID sulindac sulfoxide, is effective at reducing tumor burden in both familial adenomatous polyposis patients and in animals with colorectal cancer. Another sulindac sulfoxide metabolite, sulindac sulfone, has been reported to have antitumor properties without inhibiting cyclooxygenase activity. Here we report the effect of sulindac sulfone treatment on the growth of colorectal carcinoma cells. We observed that sulindac sulfide or sulfone treatment of HCA-7 cells led to inhibition of prostaglandin E2 production. Both sulindac sulfide and sulfone inhibited HCA-7 and HCT-116 cell growth in vitro. Sulindac sulfone had no effect on the growth of either HCA-7 or HCT-116 xenografts, whereas the sulfide derivative inhibited HCA-7 growth in vivo. Both sulindac sulfide and sulfone inhibited colon carcinoma cell growth and prostaglandin production in vitro, but sulindac sulfone had no effect on the growth of colon cancer cell xenografts in nude mice.

  13. Advanced zirconia-coated carbonyl-iron particles for acidic magnetorheological finishing of chemical-vapor-deposited ZnS and other IR materials

    Science.gov (United States)

    Salzman, S.; Giannechini, L. J.; Romanofsky, H. J.; Golini, N.; Taylor, B.; Jacobs, S. D.; Lambropoulos, J. C.

    2015-10-01

    We present a modified version of zirconia-coated carbonyl-iron (CI) particles that were invented at the University of Rochester in 2008. The amount of zirconia on the coating is increased to further protect the iron particles from corrosion when introduced to an acidic environment. Five low-pH, magnetorheological (MR) fluids were made with five acids: acetic, hydrochloric, nitric, phosphoric, and hydrofluoric. All fluids were based on the modified zirconia-coated CI particles. Off-line viscosity and pH stability were measured for all acidic MR fluids to determine the ideal fluid composition for acidic MR finishing of chemical-vapor-deposited (CVD) zinc sulfide (ZnS) and other infrared (IR) optical materials, such as hot-isostatic-pressed (HIP) ZnS, CVD zinc selenide (ZnSe), and magnesium fluoride (MgF2). Results show significant reduction in surface artifacts (millimeter-size, pebble-like structures on the finished surface) for several standard-grade CVD ZnS substrates and good surface roughness for the non-CVD MgF2 substrate when MR finished with our advanced acidic MR fluid.

  14. DISSOLUTION OF PLUTONIUM CONTAINING CARRIER PRECIPITATE BY CARBONATE METATHESIS AND SEPARATION OF SULFIDE IMPURITIES THEREFROM BY SULFIDE PRECIPITATION

    Science.gov (United States)

    Duffield, R.B.

    1959-07-14

    A process is described for recovering plutonium from foreign products wherein a carrier precipitate of lanthanum fluoride containing plutonium is obtained and includes the steps of dissolving the carrier precipitate in an alkali metal carbonate solution, adding a soluble sulfide, separating the sulfide precipitate, adding an alkali metal hydroxide, separating the resulting precipitate, washing, and dissolving in a strong acid.

  15. Mechanistic differences between methanol and dimethyl ether carbonylation in side pockets and large channels of mordenite.

    Science.gov (United States)

    Boronat, Mercedes; Martínez, Cristina; Corma, Avelino

    2011-02-21

    The activity and selectivity towards carbonylation presented by Brønsted acid sites located inside the 8MR pockets or in the main 12MR channels of mordenite is studied by means of quantum-chemical calculations, and the mechanistic differences between methanol and DME carbonylation are investigated. The selectivity towards carbonylation is higher inside the 8MR pockets, where the competitive formation of DME and hydrocarbons that finally leads to catalyst deactivation is sterically impeded. Moreover, inclusion of dispersion interactions in the calculations leads to agreement between the calculated activation barriers for the rate determining step and the experimentally observed higher reactivity of methoxy groups located inside the 8MR channels. PMID:21249237

  16. Increased carbonylation, protein aggregation and apoptosis in the spinal cord of mice with experimental autoimmune encephalomyelitis

    Directory of Open Access Journals (Sweden)

    Nora I. Perrone‑Bizzozero

    2013-04-01

    Full Text Available Previous work from our laboratory implicated protein carbonylation in the pathophysiology of both MS (multiple sclerosis and its animal model EAE (experimental autoimmune encephalomyelitis. Subsequent in vitro studies revealed that the accumulation of protein carbonyls, triggered by glutathione deficiency or proteasome inhibition, leads to protein aggregation and neuronal cell death. These findings prompted us to investigate whether their association can be also established in vivo. In the present study, we characterized protein carbonylation, protein aggregation and apoptosis along the spinal cord during the course of MOG (myelin-oligodendrocyte glycoprotein35–55 peptide-induced EAE in C57BL/6 mice. The results show that protein carbonyls accumulate throughout the course of the disease, albeit by different mechanisms: increased oxidative stress in acute EAE and decreased proteasomal activity in chronic EAE. We also show a temporal correlation between protein carbonylation (but not oxidative stress and apoptosis. Furthermore, carbonyl levels are significantly higher in apoptotic cells than in live cells. A high number of juxta-nuclear and cytoplasmic protein aggregates containing the majority of the oxidized proteins are present during the course of EAE. The LC3 (microtubule-associated protein light chain 3-II/LC3-I ratio is significantly reduced in both acute and chronic EAE indicating reduced autophagy and explaining why aggresomes accumulate in this disorder. Taken together, the results of the present study suggest a link between protein oxidation and neuronal/glial cell death in vivo, and also demonstrate impaired proteostasis in this widely used murine model of MS.

  17. Carbon steel protection in G.S. (Girlder sulfide) plants. Pressure influence on iron sulfide scales formation. Pt. 5

    International Nuclear Information System (INIS)

    In order to protect carbon steel towers and piping of Girlder sulfide (G.S.) experimental heavy water plants against corrosion produced by the action of aqueous solutions of hydrogen sulfide, a method, previously published, was developed. Carbon steel, exposed to saturated aqueous solutions of hydrogen sulfide, forms iron sulfide scales. In oxygen free solutions evolution of corrosion follows the sequence: mackinawite → cubic ferrous sulfide → troilite → pyrrotite → pyrite. Scales formed by pyrrotite-pyrite or pyrite are the most protective layers (these are obtained at 130 deg C, 2MPa, for periods of 14 days). Experiments, at 125 deg C and periods of 10-25 days, were performed in two different ways: 1- constant pressure operations at 0.5 and 1.1 MPa. 2- variable pressure operation between 0.3-1 MPa. In all cases pyrrotite-pyrite scales were obtained. (Author)

  18. Synthesis of diversely substituted 2-(furan-3-yl)acetates from allenols through cascade carbonylations.

    Science.gov (United States)

    He, Yan; Zhang, Xinying; Fan, Xuesen

    2015-11-21

    Novel synthesis of diversely substituted 2-(furan-3-yl)acetates via palladium-catalyzed one-pot multi-component reactions of allenols, aryl iodides, alcohols, and carbon monoxide has been developed. Notably, the formation of the title compounds features a cascade process combining carbonylation of aryl iodide, alcohoxyl carbonylation of the in situ formed allyl palladium complex, and intramolecular condensation of the α-hydroxyl enone intermediate. Moreover, the 2-(furan-3-yl)acetates obtained herein were found to be ready intermediates for the construction of the biologically significant naphtho[1,2-b]furan-5-ol scaffold. PMID:26399394

  19. Improvement on stability of square planar rhodium (Ⅰ) complexes for carbonylation of methanol to acetic acid

    Institute of Scientific and Technical Information of China (English)

    蒋华; 潘平来; 袁国卿; 陈新滋

    1999-01-01

    A series of square planar cis-dicarbonyl polymer coordinated rhodium complexes with uncoordinated donors near the central rhodium atoms for carbonylation of methanol to acetic acid are reported. Data of IR, XPS and thermal analysis show that these complexes are very stable. The intramolecular substitution reaction is proposed for their high stability. These complexes show excellent catalytic activity, selectivity and less erosion to the equipment for the methanol carbonylation to acetic acid. The distillation process may be used instead of flash vaporization in the manufacture of acetic acid, which reduces the investment on the equipment.

  20. First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation

    DEFF Research Database (Denmark)

    Riisager, Anders; Jørgensen, Betina; Wasserscheid, Peter

    2006-01-01

    A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)(2)I-2]-[BMIM]I -SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation.......A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)(2)I-2]-[BMIM]I -SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation....

  1. Activation of Carbonyl-Containing Molecules with Solid Lewis Acids in Aqueous Media

    Energy Technology Data Exchange (ETDEWEB)

    Román-Leshkov, Yuriy [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Chemical Engineering; Davis, Mark E. [California Inst. of Technology (CalTech), Pasadena, CA (United States). Chemical Engineering

    2011-09-28

    Current interest in reacting carbonyl-containing molecules in aqueous media is primarily due to the growing emphasis on conversion of biomass to fuels and chemicals. Recently, solid Lewis acids have been shown to perform catalytic reactions with carbonyl-containing molecules such as sugars in aqueous media. Here, catalysis mediated by Lewis acids is briefly discussed, Lewis acid solids that perform catalysis in aqueous media are then described, and the review is concluded with a few comments on the outlook for the future.

  2. Synthesis of carbonyl-/sup 14/C labelled 'acetochlor'

    Energy Technology Data Exchange (ETDEWEB)

    Jablonkai, I.; Marton, A.F.; Dutka, F. (Hungarian Academy of Sciences, Budapest. Central Research Inst. for Physics)

    1982-09-20

    Carbonyl-/sup 14/C labelled 'acetochlor' (2-chloro-N-ethoxymethyl-N-(2-ethyl-6-methylphenyl)acetamide) was prepared by chlorination of acetic-1-/sup 14/C acid obtained from barium radiocarbonate to monochloroacetic-1-/sup 14/C acid which was further chlorinated to monochloroacetyl-1-/sup 14/C chloride. The addition reaction of this latter with 2-ethyl-6-methylene aniline gave a chloromethyl derivative the ethanolysis of which resulted in 'acetochlor' labelled in its carbonyl carbon. The overall radiochemical yield is 51%.

  3. Kinetics of Vapor—Phase Carbonylation of Ethanol on Ni—Zn/C Catalyst

    Institute of Scientific and Technical Information of China (English)

    PENGFeng

    2002-01-01

    A novel heterogeneous Ni-Zn/C catalyst was used for vapor-phase carbonylation of ethanol under atmospheric pressure.Experiments were designed with the elimination of mass-transfer resistances.The data of primary reaction in the carbonylation were collected with a differential tubular reactor.Power law rate models were emplyed to express the conversion of ethanol and the yields of ethyl propionated and diethyl ether.The results obtained with the models were in agreement with the experimental data.

  4. Atomic layer deposition of aluminum sulfide thin films using trimethylaluminum and hydrogen sulfide

    International Nuclear Information System (INIS)

    Sequential exposures of trimethylaluminum and hydrogen sulfide are used to deposit aluminum sulfide thin films by atomic layer deposition (ALD) in the temperature ranging from 100 to 200 °C. Growth rate of 1.3 Å per ALD cycle is achieved by in-situ quartz crystal microbalance measurements. It is found that the growth rate per ALD cycle is highly dependent on the purging time between the two precursors. Increased purge time results in higher growth rate. Surface limited chemistry during each ALD half cycle is studied by in-situ Fourier transformed infrared vibration spectroscopy. Time of flight secondary ion-mass spectroscopy measurement is used to confirm elemental composition of the deposited films

  5. Banded sulfide-magnetite ores of Mauk copper massive sulfide deposit, Central Urals: Composition and genesis

    Science.gov (United States)

    Safina, N. P.; Maslennikov, V. V.; Maslennikova, S. P.; Kotlyarov, V. A.; Danyushevsky, L. V.; Large, R. R.; Blinov, I. A.

    2015-05-01

    The results of investigation of metamorphosed sulfide-magnetite ores from the Mauk deposit located within the Main Ural Fault at the junction of Tagil and Magnitogorsk massive sulfide zones are discussed. The ore-hosting sequence comprises metamorphic rocks formed from basalt, carbonaceous and carbonaceous-cherty siltstone, and lenticular serpentinized ultramafic bodies. The ores of the deposit are represented by banded varieties and less frequent breccia. The clastic origin of the banded ore is indicated by load casts at the bottom of sulfide beds, alternation of sulfide and barren beds, and the truncation of the growth zones of pyrite crystals. Pyrite, pyrrhotite, chalcopyrite, sphalerite, and magnetite are the major minerals of the banded ores. The internal structure of the listed minerals testifies to the deep metamorphic recrystallization of primary hydrothermal-sedimentary ores accompanied with deformation. Cubanite, pyrrhotite, mackinawite, greigite, and gold are enclosed in metacrysts of pyrite, magnetite, and chalcopyrite. The accessory minerals of the Pb-Bi-Te, Bi-Te, and Ag-Te systems as well as uraninite have been found at the Mauk deposit for the first time. Magnetite predominantly replaces pyrite and less frequently chalcopyrite, pyrrhotite, and gangue minerals. It was established that the major carriers of As and Co are crystals of metamorphic pyrite. Chalcopyrite is the major carrier of Zn, Sn, Te, Pb, Bi, and Ag. Admixture of Fe and Cu is typical of sphalerite, and Se and Ni are characteristic of pyrrhotite. Ti, V, Mn, Sb, As, Ba, and U are concentrated in magnetite. The banded ores of the Mauk deposit are suggested as having been transformed in several stages: diagenesis, anadiagenesis, epidiagenesis ( t 500°C).

  6. Azo dye decolorization assisted by chemical and biogenic sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Prato-Garcia, Dorian [Laboratory for Research on Advanced Processes for Water Treatment, Unidad Académica Juriquilla, Instituto de Ingeniería, Universidad Nacional Autónoma de México, Blvd. Juriquilla 3001, Querétaro 76230 (Mexico); Cervantes, Francisco J. [División de Ciencias Ambientales, Instituto Potosino de Investigación Científica y Tecnológica, Camino a la Presa de San José 2055, San Luis Potosí 78216 (Mexico); Buitrón, Germán, E-mail: gbuitronm@ii.unam.mx [Laboratory for Research on Advanced Processes for Water Treatment, Unidad Académica Juriquilla, Instituto de Ingeniería, Universidad Nacional Autónoma de México, Blvd. Juriquilla 3001, Querétaro 76230 (Mexico)

    2013-04-15

    Highlights: ► Azo dyes were reduced efficiently by chemical and biogenic sulfide. ► Biogenic sulfide was more efficient than chemical sulfide. ► There was no competition between dyes and sulfate for reducing equivalents. ► Aromatic amines barely affected the sulfate-reducing process. -- Abstract: The effectiveness of chemical and biogenic sulfide in decolorizing three sulfonated azo dyes and the robustness of a sulfate-reducing process for simultaneous decolorization and sulfate removal were evaluated. The results demonstrated that decolorization of azo dyes assisted by chemical sulfide and anthraquinone-2,6-disulfonate (AQDS) was effective. In the absence of AQDS, biogenic sulfide was more efficient than chemical sulfide for decolorizing the azo dyes. The performance of sulfate-reducing bacteria in attached-growth sequencing batch reactors suggested the absence of competition between the studied azo dyes and the sulfate-reducing process for the reducing equivalents. Additionally, the presence of chemical reduction by-products had an almost negligible effect on the sulfate removal rate, which was nearly constant (94%) after azo dye injection.

  7. Azo dye decolorization assisted by chemical and biogenic sulfide

    International Nuclear Information System (INIS)

    Highlights: ► Azo dyes were reduced efficiently by chemical and biogenic sulfide. ► Biogenic sulfide was more efficient than chemical sulfide. ► There was no competition between dyes and sulfate for reducing equivalents. ► Aromatic amines barely affected the sulfate-reducing process. -- Abstract: The effectiveness of chemical and biogenic sulfide in decolorizing three sulfonated azo dyes and the robustness of a sulfate-reducing process for simultaneous decolorization and sulfate removal were evaluated. The results demonstrated that decolorization of azo dyes assisted by chemical sulfide and anthraquinone-2,6-disulfonate (AQDS) was effective. In the absence of AQDS, biogenic sulfide was more efficient than chemical sulfide for decolorizing the azo dyes. The performance of sulfate-reducing bacteria in attached-growth sequencing batch reactors suggested the absence of competition between the studied azo dyes and the sulfate-reducing process for the reducing equivalents. Additionally, the presence of chemical reduction by-products had an almost negligible effect on the sulfate removal rate, which was nearly constant (94%) after azo dye injection

  8. Sulfide elimination by intermittent nitrate dosing in sewer sediments

    Institute of Scientific and Technical Information of China (English)

    Yanchen Liu; Chen Wu; Xiaohong Zhou; David Z.Zhu; Hanchang Shi

    2015-01-01

    The formation of hydrogen sulfide in biofilms and sediments in sewer systems can cause severe pipe corrosions and health hazards,and requires expensive programs for its prevention.The aim of this study is to propose a new control strategy and the optimal condition for sulfide elimination by intermittent nitrate dosing in sewer sediments.The study was carried out based on lab-scale experiments and batch tests using real sewer sediments.The intermittent nitrate dosing mode and the optimal control condition were investigated.The results indicated that the sulfide-intermittent-elimination strategy by nitrate dosing is advantageous for controlling sulfide accumulation in sewer sediment.The oxidation-reduction potential is a sensitive indicator parameter that can reflect the control effect and the minimum N/S (nitrate/sulfide)ratio with slight excess nitrate is necessary for optimal conditions ofefficient sulfide control with lower carbon source loss.The opth-nal control condition is feasible for the sulfide elimination in sewer systems.

  9. DEVELOPMENT AND APPLICATION OF A SENSITIVE METHOD TO DETERMINE CONCENTRATIONS OF ACROLEIN AND OTHER CARBONYLS IN AMBIENT AIR

    Science.gov (United States)

    The sampler developed by Charles and Cahill, with Dr. Vincent Seaman, consists of a custom-built glass mist chamber in which air enters at a high flow rate and carbonyls are trapped in a solution of sodium bisulfite as carbonyl-bisulfite adducts. This reaction is rapid (on ...

  10. Enhanced antioxidation and electromagnetic properties of Co-coated flaky carbonyl iron particles prepared by electroless plating

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Yingying, E-mail: zyzlchappy1989@163.com [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China); Zhou, Wancheng [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China); Li, Rong [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China); No. 603 Faculty, Xi’an Institute of High Technology, Xi’an 710025 (China); Mu, Yang; Qing, Yuchang [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China)

    2015-07-15

    Highlights: • Co-coated carbonyl iron particles were prepared by electroless plating method. • The obvious weight gain of carbonyl iron was deferred to 400 °C after Co-coated. • The permeability of the Co-coated particle composite kept almost invariable. • Co-coated carbonyl iron composite reserves a better absorption after heat treatment. - Abstract: Co was successfully coated on the surface of flaky carbonyl iron particles using an electroless plating method. The morphologies, composition, as well as magnetic, antioxidation and electromagnetic properties of the samples were characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), vibrating sample magnetometer (VSM), thermogravimetric (TG) and microwave network analyzer. TG curve shows that the obvious weight gain of carbonyl iron was deferred from 300 to 400 °C after Co-coated. In contrast to raw carbonyl iron, the Co-coated carbonyl iron shows better stability on electromagnetic properties after 300 °C heat treatment for 10 h, demonstrating that the Co coating can act as the protection of carbonyl iron.

  11. Green Synthesis and Regioselective Control of Sn/I2 Mediated Allylation of Carbonyl Compounds with Crotyl Halide in Water

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Yan; ZHA,Zhang-Gen; ZHOU,Yu-Qing; WANG,Zhi-Yong

    2004-01-01

    @@ Barbier-type carbonyl allylation is particularly useful due to ease of operation and the availability and tractability of allylic substrates,[1] Metals such as indium, zinc and tin are often used as the mediator. Here we present a green approach toward the synthesis, that is, Sn/I2 mediated allylation of carbonyl compounds with crotyl halide in water.

  12. Photopromoted carbonylation of olefins with carbon dioxide and labelling studies with 13CO2 and 13CH3OH

    Institute of Scientific and Technical Information of China (English)

    YIN Jingmei; GAO Dabin; HU Jiehan; ZHOU Guangyun; JIA Yingping; WANG Xiangsheng

    2003-01-01

    Photopromoted carbonylation of olefins with carbon dioxide can be completed in ambient conditions (room temperatures and atmospheric pressure) by Co(OAc)2 catalysis. It was found that in carbonyl carbons of methyl ester of aliphatic acid 50% is from CO2 and the other 50% from CH3OH by labelling experimental with 13CO2 and 13CH3OH.

  13. Hydrogen bonding to carbonyl oxygen of nitrogen-pyramidalized amide - detection of pyramidalization direction preference by vibrational circular dichroism spectroscopy.

    Science.gov (United States)

    Wang, Siyuan; Taniguchi, Tohru; Monde, Kenji; Kawahata, Masatoshi; Yamaguchi, Kentaro; Otani, Yuko; Ohwada, Tomohiko

    2016-03-01

    Nitrogen-pyramidalization of amide increases electron density on nitrogen and decreases that on carbonyl oxygen. We identified hydrogen-bonding to carbonyl of nitrogen-pyramidalized bicyclic β-proline derivatives by crystallography, and by NMR and vibrational circular dichroism (VCD) spectroscopy in solution. Such hydrogen-bonding can switch the preferred nitrogen-pyramidalization direction, as detected by VCD spectroscopy. PMID:26889607

  14. On the pelletizing of sulfide molybdenite concentrate

    International Nuclear Information System (INIS)

    Investigation results are discussed on the process of pelletizing with the use of various binders (water, syrup, sulfite-alcoholic residue and bentonite) for flotation sulfide molybdenite concentrate (∼84 % MoS2) of the Mongolian deposit. It is established that with the use of syrup rather strong pellets (>300 g/p) of desired size (2-3 mm) can be obtained at a binder flowrate of 1 kg per 100 kg of concentrate. The main advantage of using syrup instead of bentonite lies in the fact that in this instance no depletion of a molybdenum calcine obtained by oxidizing roasting of raw ore takes place due to syrup complete burning out. This affects positively subsequent hydrometallurgical conversion because of decreasing molybdenum losses with waste cakes

  15. Role of iron sulfides in uranium deposition

    International Nuclear Information System (INIS)

    The role of iron mono- and disulfides in uranium infiltrated orogenesis is considered on the basis of the results of experimental and mineral-geochemical investigations. it is shown that pyrrhotite decomposing in a weak-acid medium with hydrogen sulfide and hydrogen emission precipitates actively uranium from oxygen-containing waters. Pyrrhotite in oxygen-free medium - when hydrogoethite is absent (probably due to partial proportionalization of Fe2+, SO42- and H2S and electron release causes Eh decrease at the mineral solution boundary up to values - 250 mV and correspondingly recovery uranium deposition. Regions of near-the fracture and over-the-break rock pyritization are of great importance when forecasting and prospecting infiltrated uranium deposits

  16. Chemical foundations of hydrogen sulfide biology.

    Science.gov (United States)

    Li, Qian; Lancaster, Jack R

    2013-11-30

    Following nitric oxide (nitrogen monoxide) and carbon monoxide, hydrogen sulfide (or its newer systematic name sulfane, H2S) became the third small molecule that can be both toxic and beneficial depending on the concentration. In spite of its impressive therapeutic potential, the underlying mechanisms for its beneficial effects remain unclear. Any novel mechanism has to obey fundamental chemical principles. H2S chemistry was studied long before its biological relevance was discovered, however, with a few exceptions, these past works have received relatively little attention in the path of exploring the mechanistic conundrum of H2S biological functions. This review calls attention to the basic physical and chemical properties of H2S, focuses on the chemistry between H2S and its three potential biological targets: oxidants, metals and thiol derivatives, discusses the applications of these basics into H2S biology and methodology, and introduces the standard terminology to this youthful field. PMID:23850631

  17. Responsive lanthanide coordination polymer for hydrogen sulfide.

    Science.gov (United States)

    Liu, Baoxia; Chen, Yang

    2013-11-19

    Metal organic coordination polymers have received great attention because of their flexible compositions and architecture. Here, we report the design and synthesis of a responsive lanthanide coordination polymer (LCP) for hydrogen sulfide (H2S), utilizing self-assembling of biomolecule nucleotide with luminescent terbium ion (Tb(3+)) and sensitizing silver ion (Ag(+)) in aqueous solution. LCP is highly fluorescent due to the inclusion of Ag(+) ions, which sensitized the fluorescence of Tb(3+) ions. H2S can strongly quench the fluorescence of LCP through its high affinity for Ag(+) ions. Such configurated LCP material from initial building blocks showed high sensitivity and selectivity for H2S and was applied to the determination of H2S in human serum. LCP with Tb(3+) ions also has a long fluorescence lifetime, which allows for time-resolved fluorescence assays, possessing particular advantages to probing H2S in biological systems with autofluorescence. PMID:24191713

  18. Modulation of hydrogen sulfide by vascular hypoxia

    Directory of Open Access Journals (Sweden)

    Osmond JM

    2014-08-01

    Full Text Available Jessica M Osmond, Nancy L KanagyVascular Physiology Group, Department of Cell Biology and Physiology, University of New Mexico Health Sciences Center, Albuquerque, NM, USAAbstract: Hydrogen sulfide (H2S has emerged as a key regulator of cardiovascular function. This gasotransmitter is produced in the vasculature and is involved in numerous processes that promote vascular homeostasis, including vasodilation and endothelial cell proliferation. Although H2S plays a role under physiological conditions, it has become clear in recent years that hypoxia modulates the production and action of H2S. Furthermore, there is growing evidence that H2S is cytoprotective in the face of hypoxic insults. This review focuses on the synthesis and signaling of H2S in hypoxic conditions in the vasculature, and highlights recent studies providing evidence that H2S is a potential therapy for preventing tissue damage in hypoxic conditions.Keywords: H2S, cystathionine γ-lyase, vascular smooth muscle, endothelium

  19. Hydrogen sulfide production from subgingival plaque samples.

    Science.gov (United States)

    Basic, A; Dahlén, G

    2015-10-01

    Periodontitis is a polymicrobial anaerobe infection. Little is known about the dysbiotic microbiota and the role of bacterial metabolites in the disease process. It is suggested that the production of certain waste products in the proteolytic metabolism may work as markers for disease severity. Hydrogen sulfide (H2S) is a gas produced by degradation of proteins in the subgingival pocket. It is highly toxic and believed to have pro-inflammatory properties. We aimed to study H2S production from subgingival plaque samples in relation to disease severity in subjects with natural development of the disease, using a colorimetric method based on bismuth precipitation. In remote areas of northern Thailand, adults with poor oral hygiene habits and a natural development of periodontal disease were examined for their oral health status. H2S production was measured with the bismuth method and subgingival plaque samples were analyzed for the presence of 20 bacterial species with the checkerboard DNA-DNA hybridization technique. In total, 43 subjects were examined (age 40-60 years, mean PI 95 ± 6.6%). Fifty-six percent had moderate periodontal breakdown (CAL > 3  7 mm) on at least one site. Parvimonas micra, Filifactor alocis, Porphyromonas endodontalis and Fusobacterium nucleatum were frequently detected. H2S production could not be correlated to periodontal disease severity (PPD or CAL at sampled sites) or to a specific bacterial composition. Site 21 had statistically lower production of H2S (p = 0.02) compared to 16 and 46. Betel nut chewers had statistically significant lower H2S production (p = 0.01) than non-chewers. Rapid detection and estimation of subgingival H2S production capacity was easily and reliably tested by the colorimetric bismuth sulfide precipitation method. H2S may be a valuable clinical marker for degradation of proteins in the subgingival pocket. PMID:25280920

  20. The electrochemical behavior of sulfide ions in molten cryolite

    International Nuclear Information System (INIS)

    The electrochemical behavior of sulfide ions in molten cryolite (Na3A1F6) has been studied by cyclic voltammetry using graphite electrodes at 1323 K. The oxidation of sulfide ions is found to proceed via a quasi-reversible mechanism, i.e., one in which the current is controlled by both diffusion and charge transfer kinetics. The transfer coefficient BETA and the standard rate constant k /SUB s/ are estimated to be 0.5 and 0.0042 cm/sec, respectively. The apparent diffusion coefficient for sulfide ions in cryolite at 1323 K is about 3.93 x 10-5 cm2/sec

  1. Effect of Soluble Sulfide on the Activity of Luminescent Bacteria

    OpenAIRE

    Feng Wang; Ling-Ling Wu; Hong-Wen Gao; Ying Shao

    2012-01-01

    Sulfide is an important water pollutant widely found in industrial waste water that has attracted much attention. S2−, as a weak acidic anion, is easy hydrolyzed to HS and H2S in aqueous solution. In this study, biological tests were performed to establish the toxicity of sulfide solutions on luminescent bacteria. Considering the sulfide solution was contained three substances—S2−, HS

  2. Optimization of the superconducting phase of hydrogen sulfide

    International Nuclear Information System (INIS)

    The electron and phonon spectra, as well as the densities of electron and phonon states of the SH3 phase and the stable orthorhombic structure of hydrogen sulfide SH2, are calculated for the pressure interval 100–225 GPa. It is found that the I4/mmm phase can be responsible for the superconducting properties of metallic hydrogen sulfide along with the SH3 phase. Sequential stages for obtaining and conservation of the SH2 phase are proposed. The properties of two (SH2 and SH3) superconducting phases of hydrogen sulfide are compared

  3. Optimization of the superconducting phase of hydrogen sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Degtyarenko, N. N.; Masur, E. A., E-mail: eugen-mazur@mail.ru [National Research Nuclear University MEPhI (Russian Federation)

    2015-12-15

    The electron and phonon spectra, as well as the densities of electron and phonon states of the SH{sub 3} phase and the stable orthorhombic structure of hydrogen sulfide SH{sub 2}, are calculated for the pressure interval 100–225 GPa. It is found that the I4/mmm phase can be responsible for the superconducting properties of metallic hydrogen sulfide along with the SH{sub 3} phase. Sequential stages for obtaining and conservation of the SH{sub 2} phase are proposed. The properties of two (SH{sub 2} and SH{sub 3}) superconducting phases of hydrogen sulfide are compared.

  4. Adsorbate thermodynamics as a determinant of reaction mechanism: Pentamethylene sulfide on Mo(110)

    Energy Technology Data Exchange (ETDEWEB)

    Wiegand, B.C.; Friend, C.M.; Roberts, J.T. (Harvard Univ., Cambridge, MA (USA))

    The reactions of the totally unstrained, six-membered cyclic sulfide pentamethylene sulfide on Mo(110) have been investigated by using temperature-programmed reaction spectroscopy and X-ray photoelectron spectroscopy in an effort to identify the roles of ring size and strain in dictating reaction selectivity. Four gases products are detected in the temperature-programmed reaction of pentamethylene sulfide: dihydrogen at 380 and 590 K, pentane at 350 K, pentene at 345 K, and pentamethylene sulfide at 190 and 280 K. The kinetics for hydrocarbon production from pentamethylene sulfide are qualitatively different than for the four- and five-membered cyclic sulfides, trimethylene sulfide and tetrahydrothiophene.

  5. Sulfide Intrusion and Detoxification in the Seagrass Zostera marina

    DEFF Research Database (Denmark)

    Hasler-Sheetal, Harald; Holmer, Marianne

    2015-01-01

    Gaseous sulfide intrusion into seagrasses growing in sulfidic sediments causes little or no harm to the plant, indicating the presence of an unknown sulfide tolerance or detoxification mechanism. We assessed such mechanism in the seagrass Zostera marina in the laboratory and in the field with...... well as being stored as sulfate throughout the plant. We conclude that avoidance of sulfide exposure by reoxidation of sulfide in the rhizosphere or aerenchyma and tolerance of sulfide intrusion by incorporation of sulfur in the plant are likely major survival strategies of seagrasses in sulfidic...

  6. Ultraviolet absorption cross sections of carbonyl sulfide isotopologues OC32S, OC33S, OC34S and O13CS: isotopic fractionation in photolysis and atmospheric implications

    Directory of Open Access Journals (Sweden)

    N. Yoshida

    2011-07-01

    Full Text Available We report measurements of the ultraviolet absorption cross sections of OC32S, OC33S, OC34S and O13CS from 195 to 260 nm. The OCS isotopologues were synthesized from isotopically-enriched elemental sulfur by reaction with carbon monoxide. The measured cross section of OC32S is consistent with literature spectra recorded using natural abundance samples. Relative to the spectrum of the most abundant isotopologue, substitution of heavier rare isotopes has two effects. First, as predicted by the reflection principle, the Gaussian-based absorption envelope becomes slightly more narrow and blue-shifted. Second, as predicted by Franck-Condon considerations, the weak vibrational structure is red-shifted. Sulfur isotopic fractionation constants (33ε, 34ε as a function of wavelength are not highly structured, and tend to be close to zero on average on the high energy side and negative on the low energy side. Since OCS photolysis occurs in the lower stratosphere, the integrated photolysis rate of each isotopologue at 20 km was calculated. Sulfur isotopic fractionation constants at 20 km altitude are (−3.7 ± 4.5 ‰ and (1.1 ± 4.2 ‰ for 33ε and 34ε, respectively, which is inconsistent with the previously estimated large fractionation of over 73 ‰ in 34ε. This demonstrates that OCS photolysis does not produce sulfur isotopic fractionation of more than ca. 5 ‰, suggesting OCS may be the source of background stratospheric sulfate aerosols. Finally, the predicted isotopic fractionation constant for 33S excess (33E in OCS photolysis is (−4.2 ± 6.6 ‰, and thus photolysis of OCS is not expected to be the source of the non-mass-dependent signature observed in modern and Archaean samples.

  7. Magnetically Recoverable Supported Ruthenium Catalyst for Hydrogenation of Alkynes and Transfer Hydrogenation of Carbonyl Compounds

    Science.gov (United States)

    A ruthenium (Ru) catalyst supported on magnetic nanoparticles (NiFe2O4) has been successfully synthesized and used for hydrogenation of alkynes at room temperature as well as transfer hydrogenation of a number of carbonyl compounds under microwave irradiation conditions. The cata...

  8. Magnetic Silica-Supported Ruthenium Nanoparticles: An Efficient Catalyst for Transfer Hydrogenation of Carbonyl Compounds

    Science.gov (United States)

    One-pot synthesis of ruthenium nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium nano particles immobilization; the hydration of nitriles and transfer hydrogenation of carbonyl compounds occurs in hi...

  9. An Eco-Friendly System for Oximation of Organic Carbonyl Compounds Under Microwave Irradiation

    OpenAIRE

    Hana Batmani; Davood Setamdideh

    2014-01-01

    The oximation of a variety of organic carbonyl compounds was efficiently carried out with NH2OH·HCl under microwave irradiation. The reactions were performed in water or water-ethanol as green solvents to give Z-aldoxime isomers from the corresponding aldehydes and E-ketoxime isomers from the corresponding ketones in a perfect selectively with excellent yields.

  10. α-Regioselective Barbier Reaction of Carbonyl Compounds and Allyl Halides Mediated by Praseodymium.

    Science.gov (United States)

    Wu, San; Li, Ying; Zhang, Songlin

    2016-09-01

    The first utility of praseodymium as a mediating metal in the Barbier reaction of carbonyl compounds with allyl halides was reported in this paper. In contrast to the traditional metal-mediated or catalyzed Barbier reactions, exclusive α-adducts were obtained in this one-pot reaction with a broad scope of substrates and feasible reaction conditions. PMID:27490708

  11. Effect of carotenoid structure on excited-state dynamics of carbonyl carotenoids

    Czech Academy of Sciences Publication Activity Database

    Chábera, P.; Fuciman, M.; Hříbek, P.; Polívka, Tomáš

    2009-01-01

    Roč. 11, - (2009), s. 8795-8703. ISSN 1463-9076 R&D Projects: GA AV ČR IAA608170604 Institutional research plan: CEZ:AV0Z50510513 Keywords : excited-state dynamics * carbonyl carotenoids * femtosecond spectroscopy Subject RIV: BO - Biophysics Impact factor: 4.116, year: 2009

  12. Proteomic and carbonylation profile analysis of rat skeletal muscles following acute swimming exercise.

    Directory of Open Access Journals (Sweden)

    Francesca Magherini

    Full Text Available Previous studies by us and other groups characterized protein expression variation following long-term moderate training, whereas the effects of single bursts of exercise are less known. Making use of a proteomic approach, we investigated the effects of acute swimming exercise (ASE on protein expression and carbonylation patterns in two hind limb muscles: the Extensor Digitorum Longus (EDL and the Soleus, mostly composed of fast-twitch and slow-twitch fibres, respectively. Carbonylation is one of the most common oxidative modifications of proteins and a marker of oxidative stress. In fact, several studies suggest that physical activity and the consequent increase in oxygen consumption can lead to increase in reactive oxygen and nitrogen species (RONS production, hence the interest in examining the impact of RONS on skeletal muscle proteins following ASE. Results indicate that protein expression is unaffected by ASE in both muscle types. Unexpectedly, the protein carbonylation level was reduced following ASE. In particular, the analysis found 31 and 5 spots, in Soleus and EDL muscles respectively, whose carbonylation is reduced after ASE. Lipid peroxidation levels in Soleus were markedly reduced as well. Most of the decarbonylated proteins are involved either in the regulation of muscle contractions or in the regulation of energy metabolism. A number of hypotheses may be advanced to account for such results, which will be addressed in future studies.

  13. Ketene as a Reaction Intermediate in the Carbonylation of Dimethyl Ether to Methyl Acetate over Mordenite

    DEFF Research Database (Denmark)

    Rasmussen, Dominik Bjørn; Christensen, Jakob Munkholt; Temel, Burcin;

    2015-01-01

    Unprecedented insight into the carbonylation of dimethyl ether over Mordenite is provided through the identification of ketene (CH2CO) as a reaction intermediate. The formation of ketene is predicted by detailed DFT calculations and verified experimentally by the observation of doubly deuterated ...

  14. NMR Studies of Structure-Reactivity Relationships in Carbonyl Reduction: A Collaborative Advanced Laboratory Experiment

    Science.gov (United States)

    Marincean, Simona; Smith, Sheila R.; Fritz, Michael; Lee, Byung Joo; Rizk, Zeinab

    2012-01-01

    An upper-division laboratory project has been developed as a collaborative investigation of a reaction routinely taught in organic chemistry courses: the reduction of carbonyl compounds by borohydride reagents. Determination of several trends regarding structure-activity relationship was possible because each student contributed his or her results…

  15. [pi] Backbonding in Carbonyl Complexes and Carbon-Oxygen Stretching Frequencies: A Molecular Modeling Exercise

    Science.gov (United States)

    Montgomery, Craig D.

    2007-01-01

    An exercise is described that has illustrated the effect of various factors on [pi] backbonding to carbonyl ligands, where the students can view the molecular orbitals corresponding to the M-CO [pi] interaction as well as the competing interaction between the metal and co-ligands. The visual and hands-on nature of the modeling exercise has helped…

  16. Temporal variation of carbonyl compound concentrations at a semi-rural site in Denmark

    DEFF Research Database (Denmark)

    Christensen, C.S.; Skov, H.; Nielsen, T.; Lohse, C.

    2000-01-01

    for PAN and ozone during high-pressure episodes also indicated that photochemical production was a major controlling factor. Here the highest concentrations of carbonyl compounds were observed in air masses with the highest photochemical age (PCA) and a likely source was determined to be the oxidation...

  17. Heterogeneous Chemistry of Carbonyls and Alcohols With Sulfuric Acid: Implications for Secondary Organic Aerosol Formation

    Science.gov (United States)

    Zhao, J.; Levitt, N.; Zhang, R.

    2006-12-01

    Recent environmental chamber studies have suggested that acid-catalyzed particle-phase reactions of organic carbonyls lead to multifold increases in secondary organic aerosol (SOA) mass and acid-catalyzed reactions between alcohols and aldehydes in the condensed phase lead to the formation of hemiacetals and acetals, also enhancing secondary organic aerosol growth. The kinetics and mechanism of the heterogeneous chemistry of carbonyls and alcohols with sulfuric acid, however, remain largely uncertain. In this talk, we present measurements of heterogeneous uptake of several carbonyls and alcohols on liquid H2SO4 in a wide range of acid concentrations and temperatures. The results indicate that uptake of larger carbonyls is explained by aldol condensation. For small dicarbonyls, heterogeneous reactions are shown to decrease with acidity and involve negligible formation of sulfate esters. Hydration and polymerization likely explain the measured uptake of such small dicarbonyls on H2SO4 and the measurements do not support an acid- catalyzed uptake. Atmospheric implications from our findings will be discussed.

  18. Synthesis, spectroscopic characterizations, crystal structures and DFT studies of nalidixic acid carbonyl hydrazones derivatives

    Science.gov (United States)

    Bergamini, F. R. G.; Ribeiro, M. A.; Lancellotti, M.; Machado, D.; Miranda, P. C. M. L.; Cuin, A.; Formiga, A. L. B.; Corbi, P. P.

    2016-09-01

    This article describes the synthesis and characterization of the 1-ethyl-7-methyl-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carbohydrazide (hzd) and six carbonyl hydrazones derivatives of the nalidixic with 1H-pyrrol-2-ylmethylidene (hpyrr), 1H-imidazol-2-ylmethylidene (h2imi), pyridin-2-ylmethylidene (h2py), pyridin-3-ylmethylidene (h3py), pyridin-4-ylmethylidene(h4py) and (2-hydroxyphenyl)methylidene (hsali). The carbonyl hydrazones were characterized by elemental and ESI-QTOF-MS analyses, IR and detailed NMR spectroscopic measurements. The 2D NMR experiments allowed the unambiguous assignment of the hydrogen, carbon and nitrogen atoms, which have not been reported for nalidixic acid carbonyl hydrazone derivatives so far. Crystal structures of hzd and the new carbonyl hydrazones h2imi, hpyrr and h3py were determined by X-ray diffraction studies. Although the synthesis of hzd was reported decades ago, the hzd crystal structure have not been reported yet. Geometric optimizations of all the characterized structures were performed with the aid of DFT studies. Despite the fact that the hydrazones with 2-pyridine carboxylic acid (h2py) and salicyl aldehyde (hsali) were already reported by literature, a detailed spectroscopic study followed by DFT studies are also reported for such compounds in this manuscript. Antimicrobial studies of the compounds are also presented.

  19. Carbonylative Heck Reactions Using CO Generated ex Situ in a Two-Chamber System

    DEFF Research Database (Denmark)

    Hermange, Philippe; Gøgsig, Thomas; Lindhardt, Anders Thyboe; Taaning, Rolf Hejle; Skrydstrup, Troels

    2011-01-01

    A carbonylative Heck reaction of aryl iodides and styrene derivatives employing a two-chamber system using a stable, crystalline, and nontransition metal based carbon monoxide source is reported. By applying near-stoichiometric amounts of the carbon monoxide precursor, an effective exploitation of...

  20. Specificity of sites within eight-membered ring zeolite channels for carbonylation of methyls to acetyls.

    Science.gov (United States)

    Bhan, Aditya; Allian, Ayman D; Sunley, Glenn J; Law, David J; Iglesia, Enrique

    2007-04-25

    The acid-catalyzed formation of carbon-carbon bonds from C1 precursors via CO insertion into chemisorbed methyl groups occurs selectively within eight-membered ring (8-MR) zeolite channels. This elementary step controls catalytic carbonylation rates of dimethyl ether (DME) to methyl acetate. The number of O-H groups within 8-MR channels was measured by rigorous deconvolution of the infrared bands for O-H groups in cation-exchanged and acid forms of mordenite (M,H-MOR) and ferrierite (H-FER) after adsorption of basic probe molecules of varying size. DME carbonylation rates are proportional to the number of O-H groups within 8-MR channels. Na+ cations selectively replaced protons within 8-MR channels and led to a disproportionate decrease in carbonylation turnover rates (per total H+). These conclusions are consistent with the low or undetectable rates of carbonylation on zeolites without 8-MR channels (H-BEA, H-FAU, H-MFI). Such specificity of methyl reactivity upon confinement within small channels appears to be unprecedented in catalysis by microporous solids, which typically select reactions by size exclusion of bulkier transition states. PMID:17397162

  1. Palladium-catalyzed carbonylative sonogashira coupling of aryl bromides using near stoichiometric carbon monoxide

    DEFF Research Database (Denmark)

    Neumann, Karoline T.; Laursen, Simon R.; Lindhardt, Anders T.;

    2014-01-01

    A general procedure for the palladium-catalyzed carbonylative Sonogashira coupling of aryl bromides is reported, using near stoichiometric amounts of carbon monoxide. The method allows a broad substrate scope in moderate to excellent yields. The formed alkynone motive serves as a platform for...

  2. Direct photolysis of carbonyl compounds dissolved in cloud and fog~droplets

    Science.gov (United States)

    Epstein, S. A.; Tapavicza, E.; Furche, F.; Nizkorodov, S. A.

    2013-09-01

    Gas-phase photolysis is an important tropospheric sink for many carbonyl compounds; however the significance of direct photolysis of these compounds dissolved in cloud and fog droplets is uncertain. We develop a theoretical approach to assess the importance of aqueous photolysis for a series of carbonyls that possess carboxyl and hydroxyl functional groups by comparison with rates of other atmospheric processes. We use computationally and experimentally derived effective Henry's law constants, hydration equilibrium parameters, aqueous hydroxyl radical (OH) rate constants, and optical extinction coefficients to identify types of compounds that will (or will not) have competitive aqueous photolysis rates. We also present molecular dynamics simulations designed to estimate gas- and aqueous-phase extinction coefficients of unstudied atmospherically relevant compounds found in d-limonene and isoprene secondary organic aerosol. In addition, experiments designed to measure the photolysis rate of glyceraldehyde, an atmospherically relevant water-soluble organic compound, reveal that aqueous quantum yields are highly molecule-specific and cannot be extrapolated from measurements of structurally similar compounds. We find that only two out of the 92 carbonyl compounds investigated, pyruvic acid and acetoacetic acid, may have aqueous photolysis rates that exceed the rate of oxidation by dissolved OH. For almost all carbonyl compounds lacking α,β-conjugation that were investigated, atmospheric removal by direct photolysis in cloud and fog droplets can be neglected under typical atmospheric conditions.

  3. The Palladium-Catalyzed Vinylation and Carbonylation of Bromoindoles and N-Acety1-bromoindoline

    OpenAIRE

    Kasahara, Akira; Izumi, Taeko; Ogata, Hideaki

    1989-01-01

    Abstracts The palladium-catalyzed vinylic substitution reaction of alkenes has been shown to proceed in moderate yields with 5- and 6-bromoindols, and N-acetyl-5-bromoindoline. 4-, 5-, 6-, and 7-Bromoindoles also undergo facile palladium-assisted carbonylation with carbon monoxide in methanol to produce methoxycarbonylindoles in moderate yields.

  4. Palladium-Catalyzed Carbonylation of Primary Amines in Supercritical Carbon Dioxide

    Institute of Scientific and Technical Information of China (English)

    李金恒; 江焕峰; 陈鸣才

    2001-01-01

    The chemoselectity of the palladimm-catalyzed carbonylation of amines was affected by the addition of MeOH in supercritical carbon dioxide. The results show different selectivity in supercritical carbon dioxide CO2(sc) from that in alcohol.Methyl carbamate and its derivatives were obtained in high yields in CO2(sc).

  5. Oxalyl chloride as a practical carbon monoxide source for carbonylation reactions

    DEFF Research Database (Denmark)

    Hansen, Steffen V F; Ulven, Trond

    2015-01-01

    A method for generation of high-quality carbon monoxide by decomposition of oxalyl chloride in an aqueous hydroxide solution is described. The usefulness of the method is demonstrated in the synthesis of heterocycles and for hydroxy-, alkoxy-, amino-, and reductive carbonylation reactions, in sev...

  6. Efficient and selective α-bromination of carbonyl compounds with N-bromosuccinimide under microwave

    Directory of Open Access Journals (Sweden)

    Xiao-Yu Guan

    2015-11-01

    Full Text Available A highly efficient method for the synthesis of α-halocarbonyl compounds has been achieved via selective monobromination of aromatic and aliphatic carbonyl compounds with N-bromosuccinimide catalyzed by p-toluenesulfonic acid under microwave irradiation within 30 min.

  7. Synthesis of an Epoxide Carbonylation Catalyst: Exploration of Contemporary Chemistry for Advanced Undergraduates

    Science.gov (United States)

    Getzler, Yutan D. Y. L.; Schmidt, Joseph A. R.; Coates, Geoffrey W.

    2005-01-01

    A class of highly active, well-defined compounds for the catalytic carbonylation of epoxides and aziridines to beta-lactones and beta-lactams are introduced. The synthesis of one of the catalysts involves a simple imine condensation to form the ligand followed by air-sensitive metalation and salt metathesis steps.

  8. A selective palladium-catalyzed carbonylative arylation of aryl ketones to give vinylbenzoate compounds.

    Science.gov (United States)

    Schranck, Johannes; Tlili, Anis; Neumann, Helfried; Alsabeh, Pamela G; Stradiotto, Mark; Beller, Matthias

    2012-12-01

    Preparation of enols: when treated with [{Pd(cinnamyl)Cl}(2)]/cataCXium A (nBuPAd(2), Ad=adamantyl) under an atmosphere of CO, aryl ketones react with aryl halides in a carbonylative C-O coupling reaction to form (Z)-vinyl benzoates. PMID:23143936

  9. Sulfide mineralization in ultramafic rocks of the Faryab ophiolite complex, southern Kerman

    OpenAIRE

    Mohammad Ali Rajabzadeh; Fatemeh Al Sadi

    2015-01-01

    Introduction Worldwide, Ni-Cu and PGE magmatic sulfide deposits are confined to the lower parts of stratiform mafic and ultramafic complexes. However, ophiolite mafic and ultramafic complexes have been rarely explored for sulfide deposits despite the fact that they have been extensively explored and exploited for chromite. Sulfide saturation during magmatic evolution is necessary for sulfide mineralization, in which sulfide melts scavenge chalcophile metals from the parent magma and conc...

  10. Sulfide oxidizing activity as a survival strategy in mangrove clam Polymesoda erosa (Solander, 1786)

    Digital Repository Service at National Institute of Oceanography (India)

    Clemente, S.; Ingole, B.S.; Sumati, M.; Goltekar, R.

    strategies of sulfide detoxification appear to be common in animals in normoxia. First, sulfide can be bound to blood proteins (Bagarinao and Vetter 1992). Second, sulfide is frequently oxidized to less toxic or nontoxic sulfur compounds, either... with the help of bacterial symbionts (Wilmot and Vetter 1990) or in the animal tissue (Vetter et al. 1987). As a group, thiotrophic (sulfide-utilizing) bacteria employ various enzymatic pathways for conversion of sulfide into energy, including the oxidation...

  11. Functional Analysis of Three Sulfide:Quinone Oxidoreductase Homologs in Chlorobaculum tepidum▿ †

    OpenAIRE

    Chan, Leong-Keat; Morgan-Kiss, Rachael M; Hanson, Thomas E.

    2008-01-01

    Sulfide:quinone oxidoreductase (SQR) catalyzes sulfide oxidation during sulfide-dependent chemo- and phototrophic growth in bacteria. The green sulfur bacterium Chlorobaculum tepidum (formerly Chlorobium tepidum) can grow on sulfide as the sole electron donor and sulfur source. C. tepidum contains genes encoding three SQR homologs: CT0117, CT0876, and CT1087. This study examined which, if any, of the SQR homologs possess sulfide-dependent ubiquinone reduction activity and are required for gro...

  12. Co-settling of Chromite and Sulfide Melt Droplets and Trace Element Partitioning between Sulfide and Silicate Melts

    Science.gov (United States)

    Manoochehri, S.; Schmidt, M. W.; Guenther, D.

    2013-12-01

    Gravitational settling of immiscible, dense sulfide melt droplets together with other cumulate phases such as chromite, combined with downward percolation of these droplets through a cumulate pile, is thought to be one of the possible processes leading to the formation of PGE rich sulfide deposits in layered mafic intrusions. Furthermore some chromitite seams in the Merensky Reef (Bushveld Complex) are considered to be acting as a filter or barrier for further downward percolation of sulfide melts into footwall layers. To investigate the feasibility of such mechanical processes and to study the partitioning behavior of 50 elements including transition metals and REEs (but not PGEs) between a silicate and a sulfide melt, two separate series of high temperature (1250-1380 °C) centrifuge-assisted experiments at 1000 g, 0.4-0.6 GPa were conducted. A synthetic silicate glass with a composition representative of the parental magma of the Bushveld Complex (~ 55 wt% SiO2) was mixed with pure FeS powder. For the first series of experiments, 15 or 25 wt% natural chromite with average grain sizes of ~ 5 or 31 μm were added to a mixture of silicate glass and FeS (10 wt%) adding 1 wt% water. For the second series, a mixture of the same glass and FeS was doped with 50 trace elements. These mixtures were first statically equilibrated and then centrifuged. In the first experimental series, sulfide melt droplets settled together with, but did not segregate from chromite grains even after centrifugation at 1000 g for 12 hours. A change in initial chromite grain size and proportions didn't have any effect on segregation. Without chromite, the starting mixture resulted in the formation of large sulfide melt pools together with finer droplets still disseminated through the silicate glass and both at the bottom of the capsule. The incomplete segregation of sulfide melt is interpreted as being due to high interfacial energies between sulfide and silicate melts/crystals which hinder

  13. Oxi-DIGE: A novel proteomic approach for detecting and quantifying carbonylated proteins.

    Science.gov (United States)

    Baraibar, Martin; Ladouce, Romain; Friguet, Bertrand

    2014-10-01

    Proteins are involved in key cellular functions and our health and wellness depends on their quality. Accumulation of oxidatively damaged proteins is a hallmark of deleterious processes such increased oxidative stress, chronic inflammation, ageing and age-related diseases. Thus, quantifying and identifying oxidized proteins is a biomarker of choice for monitoring biological ageing and/or the efficiency of anti-oxidant, ant-inflammatory and anti-ageing therapies. However, the absence of reliable tools for analyses has inhibited its establishment as the gold standard for measuring the efficacy of anti-ageing and age related diseases interventions. Herein, we present a novel proteomics technology, named Oxi-DIGE?, which provides a significant improvement in terms of specificity, reproducibility and statistical support for proteomic analysis of carbonylated proteins. In Oxi-DIGE, protein carbonyls are labelled with fluorescent hydrazide probes that bind specifically to carbonyl groups in proteins. Experimental groups (e.g. control and experimental samples) are labelled with different flurophore-binded hydrazides that fluoresce light at different wavelengths, producing different colour fluorescence. Thus samples from different experimental groups are co-resolved on a single 2D gel. Increased accuracy is provided due to: (i) reduced false positives by using an exogenous synthetic fluorescent tag; (ii) multiplexing, that is the possibility to run multiple samples on the same gel, (iii) the use of an internal standard on each gel which eliminates inter-gel variations and provides an increased statistical confidence. In addition, the resolution of the carbonyl groups is improved, forming distinct spots that can be identified by mass spectrometry. ?Patent Application (M. Baraibar, R. Ladouce., B. Friguet, A method for detecting and/or quantifying carbonylated proteins (WO/2012/175519) filed by UPMC and referring to the technology described in this abstract. PMID:26461312

  14. Evaluation of hazardous airborne carbonyls on a university campus in southern China.

    Science.gov (United States)

    Ho, Steven Sai Hang; Ip, Ho Sai Simon; Ho, Kin Fai; Ng, Louisa Pan Ting; Dai, W T; Cao, Junji; Chan, Chi Sing; Ho, Legolas Baggio

    2014-08-01

    A comprehensive assessment of indoor carbonyl compounds for the academic staff workers, and students was conducted on a university campus in Xiamen, China. A total of 15 representative environment categories, including 12 indoor workplaces and three residential units, were selected. The potential indoor pollution sources were identified based on the variability in the molar compositions and correlation analyses for the target carbonyls. Furnishing materials, cooking emissions, and electronic equipment, such as photocopiers, can generate various carbonyls in the workplace. Comparison studies were conducted in the clerical offices, demonstrating that off-gases from wooden furniture and lacquer coatings, environmental tobacco smoke (ETS), and the use of cleaning reagents elevated the indoor carbonyl levels. The measured concentrations of formaldehyde and acetaldehyde in most locations surpassed the exposure limit levels. The lifetime cancer hazard risk (R) associated with formaldehyde was above the concern risk level (1 x 10(-6)) in all of the workplaces. The results indicate that formaldehyde exposure is a valid occupational health and safety concern. Wooden furniture and refurbishing materials can pose serious health threats to occupants. The information in this study could act as a basis for future indoor air quality monitoring in Mainland China. Implications: A university campus represents a microscale city environment consisting of all the working, living, and commercial needs of staff and students. The scope of this investigation covers 21 hazardous carbonyl species based on samples collected from 15 categories of workplaces and residential building in a university campus in southern China. Findings of the study provide a comprehensive assessment of indoor air quality with regards to workers' health and safety. No similar study has been carried out in China. PMID:25185393

  15. Preliminary air pollution survey of hydrogen sulfide: a literature review

    Energy Technology Data Exchange (ETDEWEB)

    Miner, S.

    1969-10-01

    This is a preliminary literature review representing present knowledge of hydrogen sulfide and its effects on humans, animals, plants and materials. Hydrogen sulfide is a colorless gas that has an obnoxious odor at low concentrations. The odor threshold is in the g/cu m range. In higher concentrations, the gas is toxic to humans and animals and corrosive to many metals. It will tarnish silver and react with heavy metals in points to discolor the paint. In humans, it will cause headache, conjunctivitis, sleeplessness, pain in the eyes, and similar symptoms at low air concentrations and death at high air concentrations. However, the majority of the complaints arising from hydrogen sulfide air pollution are due to its obnoxious odor in extremely low air concentrations. Air pollution by hydrogen sulfide is not a widespread urban problem but is generally localized in the vicinity of an emitter such as kraft paper mills, industrial waste disposal ponds, sewage plants, refineries, and coke oven plants.

  16. [Activity of hydrogen sulfide production enzymes in kidneys of rats].

    Science.gov (United States)

    Mel'nyk, A V; Pentiuk, O O

    2009-01-01

    An experimental research of activity and kinetic descriptions of enzymes participating in formation of hydrogen sulfide in the kidney of rats has been carried out. It was established that cystein, homocystein and thiosulphate are the basic substrates for hydrogen sulfide synthesis. The higest activity for hydrogen sulfide production belongs to thiosulfate-dithiolsulfurtransferase and cysteine aminotransferase, less activity is characteristic of cystathionine beta-synthase and cystathio-nine gamma-lyase. The highest affinity to substrate is registered for thiosulfate-dithiolsulfurtransferase and cystathionine gamma-lyase. It is discovered that the substrate inhibition is typical of all hydrogen sulfide formation enzymes, although this characteristic is the most expressed thiosulfat-dithiolsulfurtransferase. PMID:20387629

  17. Micro-PIXE Analysis of Trace Elements in Sulfides

    International Nuclear Information System (INIS)

    Micro-scale Proton-induced X-ray Emission (PIXE) of trace elements (TE) in sulfides provides insights into geologic processes including magmatic system evolution, ore forming events, and fluid-flow processes. The Los Alamos nuclear microprobe was used to determine TE concentrations and ratios in sulfides from diverse geologic environments including hydrothermal ore deposits, coal seams, and metamorphic rocks. Pyrrhotite (Po) from silicic volcanics contains high Cu and Ni; Po from the Clear Lake volcanic field has higher Mo than does Po from other volcanic fields. Coal pyrites contain high Cu, As, Se, Mo and Pb, and show high As/Se and Mo/Se in marine influenced sulfides from the Lower Kittanning coal, but not in other marine-influenced coals. Sulfides are amenable to micro-PIXE studies because of the difficulties in obtaining the homogeneous standards required for many other TE microanalytical techniques

  18. Hydrogen Sulfide Micro-Sensor for Biomass Fouling Detection Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Hydrogen Sulfide (H2S)is the leading chemical agent causing human fatalities following inhalation exposures. The overall aim of this project is to develop and...

  19. The hydrogen sulfide metabolite trimethylsulfonium is found in human urine

    Science.gov (United States)

    Lajin, Bassam; Francesconi, Kevin A.

    2016-06-01

    Hydrogen sulfide is the third and most recently discovered gaseous signaling molecule following nitric oxide and carbon monoxide, playing important roles both in normal physiological conditions and disease progression. The trimethylsulfonium ion (TMS) can result from successive methylation reactions of hydrogen sulfide. No report exists so far about the presence or quantities of TMS in human urine. We developed a method for determining TMS in urine using liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI-QQQ), and applied the method to establish the urinary levels of TMS in a group of human volunteers. The measured urinary levels of TMS were in the nanomolar range, which is commensurate with the steady-state tissue concentrations of hydrogen sulfide previously reported in the literature. The developed method can be used in future studies for the quantification of urinary TMS as a potential biomarker for hydrogen sulfide body pools.

  20. Oxidation and Precipitation of Sulfide in Sewer Networks

    DEFF Research Database (Denmark)

    Nielsen, A. H.

    are integrated at a more detailed level in the extended WATS model. This allows effects of pH, temperature and hydraulic conditions on the individual processes to be accounted for. For several of the processes, model parameters were found to be highly site specific. A sound and reliable use of complex models....... The effect of temperature on oxidation kinetics was described by the widely used Arrhenius equation. Rates of chemical and biological sulfide oxidation in the wastewater were found to double with temperature increases of 10 and 7C, respectively. The biofilm experiments indicated a smaller dependency...... on temperature in that the biofilm sulfide oxidation rate was found to double with a temperature increase of approximately 23C. The pH dependency of chemical sulfide oxidation in wastewater represented the dissociation of sulfide, with the hydrosulfide ion being more rapidly oxidized than molecular hydrogen...

  1. A new mechanism for the aerobic catabolism of dimethyl sulfide.

    OpenAIRE

    Visscher, P T; Taylor, B F

    1993-01-01

    Aerobic degradation of dimethyl sulfide (DMS), previously described for thiobacilli and hyphomicrobia, involves catabolism to sulfide via methanethiol (CH3SH). Methyl groups are sequentially eliminated as HCHO by incorporation of O2 catalyzed by DMS monooxygenase and methanethiol oxidase. H2O2 formed during CH3SH oxidation is destroyed by catalase. We recently isolated Thiobacillus strain ASN-1, which grows either aerobically or anaerobically with denitrification on DMS. Comparative experimen...

  2. DLC coatings in high temperature hydrogen sulfide environment

    OpenAIRE

    Liskiewicz, T; Al-Borno, A; A. Neville; Zhao, H

    2015-01-01

    Surface protection in high temperature hydrogen sulfide environment remains a significant challenge with limited number of materials providing adequate protection. Diamond-like carbon (DLC) thin films are recognized across different sectors as a promising way of controlling wear and the corrosion performance of components. The aim of this paper is to test the hypothesis that thin DLC coatings may act as an efficient corrosion barrier for steel components in high temperature hydrogen sulfide e...

  3. Biogeographic congruency among bacterial communities from terrestrial sulfidic springs

    OpenAIRE

    BrendanHeadd

    2014-01-01

    Terrestrial sulfidic springs support diverse microbial communities by serving as stable conduits for geochemically diverse and nutrient-rich subsurface waters. Microorganisms that colonize terrestrial springs likely originate from groundwater, but may also be sourced from the surface. As such, the biogeographic distribution of microbial communities inhabiting sulfidic springs should be controlled by a combination of spring geochemistry and surface and subsurface transport mechanisms, and not ...

  4. Alternating current electroluminescent properties of zinc sulfide powders

    OpenAIRE

    Salimian, Alireza

    2012-01-01

    In order to investigate the alternating current electroluminescent properties of zinc sulfide powders the following experiments were conducted: synthesis of zinc sulfide phosphors (comprised of zinc, sulfur and copper dopant); thermal shocking of phosphor materials (sudden cooling, using liquid nitrogen, of phosphor particles heated up to 500oC) and analysis of their alternating current electroluminescent properties as well as studies of particle crystal structures by synchrotron and conventi...

  5. No facilitator required for membrane transport of hydrogen sulfide

    OpenAIRE

    Mathai, John C.; Missner, Andreas; Kügler, Philipp; Saparov, Sapar M.; Zeidel, Mark L.; Lee, John K.; Pohl, Peter

    2009-01-01

    Hydrogen sulfide (H2S) has emerged as a new and important member in the group of gaseous signaling molecules. However, the molecular transport mechanism has not yet been identified. Because of structural similarities with H2O, it was hypothesized that aquaporins may facilitate H2S transport across cell membranes. We tested this hypothesis by reconstituting the archeal aquaporin AfAQP from sulfide reducing bacteria Archaeoglobus fulgidus into planar membranes and by monitoring the resulting fa...

  6. INVESTIGATIONS ON BIOCHEMICAL PURIFICATION OF GROUND WATER FROM HYDROGEN SULFIDE

    Directory of Open Access Journals (Sweden)

    Yu. P. Sedlukho

    2015-01-01

    Full Text Available The paper considers problems and features of biochemical removal of hydrogen sulfide from ground water. The analysis of existing methods for purification of ground water from hydrogen sulfide has been given in the paper. The paper has established shortcomings of physical and chemical purification of ground water. While using aeration methods for removal of hydrogen sulfide formation of colloidal sulfur that gives muddiness and opalescence to water occurs due to partial chemical air oxidation. In addition to this violation of sulfide-carbonate equilibrium taking place in the process of aeration due to desorption of H2S and CO2, often leads to clogging of degasifier nozzles with formed CaCO3 that causes serious operational problems. Chemical methods require relatively large flow of complex reagent facilities, storage facilities and transportation costs.In terms of hydrogen sulfide ground water purification the greatest interest is given to the biochemical method. Factors deterring widespread application of the biochemical method is its insufficient previous investigation and necessity to execute special research in order to determine optimal process parameters while purifying groundwater of a particular water supply source. Biochemical methods for oxidation of sulfur compounds are based on natural biological processes that ensure natural sulfur cycle. S. Vinogradsky has established a two-stage mechanism for oxidation of hydrogen sulfide with sulfur bacteria (Beggiatoa. The first stage presupposes oxidation of hydrogen sulphide to elemental sulfur which is accumulating in the cytoplasm in the form of globules. During the second stage sulfur bacteria begin to oxidize intracellular sulfur to sulfuric acid due to shortage of hydrogen sulfide.The paper provides the results of technological tests of large-scale pilot plants for biochemical purification of groundwater from hydrogen sulfide in semi-industrial conditions. Dependences of water quality

  7. An eco-friendly oxidation of sulfide compounds

    Indian Academy of Sciences (India)

    RAVINDRA B WAGH; SITARAM H GUND; JAYASHREE M NAGARKAR

    2016-08-01

    An improved green route has been developed for the oxidation of sulfide compounds. Albendazole is converted to ricobendazole or albendazole sulfone using H₂O₂ as an oxidant and H₂O as the solvent. High yields of the corresponding products were obtained by carrying out the reaction at room temperature. This synthetic method is environmentally clean and safe, operationally simple for the oxidation of other benzimidazole anthelmintics and various sulfide compounds.

  8. The hydrogen sulfide metabolite trimethylsulfonium is found in human urine

    OpenAIRE

    Bassam Lajin; Francesconi, Kevin A

    2016-01-01

    Hydrogen sulfide is the third and most recently discovered gaseous signaling molecule following nitric oxide and carbon monoxide, playing important roles both in normal physiological conditions and disease progression. The trimethylsulfonium ion (TMS) can result from successive methylation reactions of hydrogen sulfide. No report exists so far about the presence or quantities of TMS in human urine. We developed a method for determining TMS in urine using liquid chromatography-electrospray ion...

  9. Lithium-aluminum/iron sulfide batteries

    Science.gov (United States)

    Henriksen, G. L.; Vissers, D. R.

    Lithium-alloy/metal sulfide batteries have been under development at Argonne National Laboratory since 1972. ANL's technology employs a two-phase Li alloy negative electrode, low-melting point LiCl-rich LiCl-LiBr-KBr molten salt electrolyte, and either an FeS or an upper-plateau (UP) FeS 2 positive electrode. These components are assembled in an 'electrolyte-starved' bipolar cell configuration. Use of the multi-phase Li alloy ((α+β)-Li-Al and Li 5Al 5Fe 2) negative electrode provides in situ overcharge tolerance that renders the bipolar design viable. Employing LiCl-rich LiCl-LiBr-KBr electrolyte is 'electrolyte-starved" cells achieves low-burdened cells that possess low area-specific impedance, comparable with that of flooded cells using LiCl-LiBr-KBr eutectic electrolyte. The combination of dense UP FeS 2 electrodes and low-melting electrolyte produces a stable and reversible couple, achieving over 1000 cycles in flooded cells, with high power capabilities. In addition, a new class of stable chalcogenide ceramic/sealant materials was developed. These materials produce high-strength bonds between a variety of metals and ceramics, which make fabrication of lithium/iron sulfide bipolar stacks practical. Bipolar Li-Al/FeS and Li-Al/FeS 2 cells and four-cell stacks using these seals have been built and tested for electric vehicle (EV) applications. When cell performance characteristics are used to model full-scale EV ad hybrid vehicle (HV) batteries, they are projected to meet or exceed the performance requirements for a large variety of EV and HV applications. In 1992, the US Advanced Battery Consortium awarded contracts to ANL and SAFT America to continue the development of the bipolar Li-Al/FeS 2 battery to meet their long-term criteria. Both ANL and sAFT are working together to refine this technology for EV applications and scale it up to larger stacks and fully integrated battery modules.

  10. Identification, quantification, and functional aspects of skeletal muscle protein-carbonylation in vivo during acute oxidative stress.

    Science.gov (United States)

    Fedorova, Maria; Kuleva, Nadezhda; Hoffmann, Ralf

    2010-05-01

    Reactive oxidative species (ROS) play important roles in cellular signaling but can also modify and often functionally inactivate other biomolecules. Thus, cells have developed effective enzymatic and nonenzymatic strategies to scavenge ROS. However, under oxidative stress, ROS production is able to overwhelm the scavenging systems, increasing the levels of functionally impaired proteins. A major class of irreversible oxidative modifications is carbonylation, which refers to reactive carbonyl-groups. In this investigation, we have studied the production and clearance rates for skeletal muscle proteins in a rat model of acute oxidative stress over a time period of 24 h using a gel-based proteomics approach. Optimized ELISA and Western blots with 10-fold improved sensitivities showed that the carbonylation level was stable at 4 nmol per mg protein 3 h following ROS induction. The carbonylation level then increased 3-fold over 6 h and then remained stable. In total, the oxidative stress changed the steady state levels of 20 proteins and resulted in the carbonylation of 38 skeletal muscle proteins. Carbonylation of these proteins followed diverse kinetics with some proteins being highly carbonylated very quickly, whereas others peaked in the 9 h sample or continued to increase up to 24 h after oxidative stress was induced. PMID:20377239

  11. Anisotropic Optical Properties of Layered Germanium Sulfide

    CERN Document Server

    Tan, Dezhi; Wang, Feijiu; Mohamed, Nur Baizura; Mouri, Shinichiro; Sandhaya, Koirala; Zhang, Wenjing; Miyauchi, Yuhei; Ohfuchi, Mari; Matsuda, Kazunari

    2016-01-01

    Two-dimensional (2D) layered materials, transition metal dichalcogenides and black phosphorus, have attracted much interest from the viewpoints of fundamental physics and device applications. The establishment of new functionalities in anisotropic layered 2D materials is a challenging but rewarding frontier, owing to their remarkable optical properties and prospects for new devices. Here, we report the anisotropic optical properties of layered 2D monochalcogenide of germanium sulfide (GeS). Three Raman scattering peaks corresponding to the B3g, A1g, and A2g modes with strong polarization dependence are demonstrated in the GeS flakes, which validates polarized Raman spectroscopy as an effective method for identifying the crystal orientation of anisotropic layered GeS. Photoluminescence (PL) is observed with a peak at around 1.66 eV that originates from the direct optical transition in GeS at room temperature. Moreover, determination of the polarization dependent characteristics of the PL and absorption reveals...

  12. Hydrogen Sulfide and Endothelium-Dependent Vasorelaxation

    Directory of Open Access Journals (Sweden)

    Jerzy Bełtowski

    2014-12-01

    Full Text Available In addition to nitric oxide and carbon monoxide, hydrogen sulfide (H2S, synthesized enzymatically from l-cysteine or l-homocysteine, is the third gasotransmitter in mammals. Endogenous H2S is involved in the regulation of many physiological processes, including vascular tone. Although initially it was suggested that in the vascular wall H2S is synthesized only by smooth muscle cells and relaxes them by activating ATP-sensitive potassium channels, more recent studies indicate that H2S is synthesized in endothelial cells as well. Endothelial H2S production is stimulated by many factors, including acetylcholine, shear stress, adipose tissue hormone leptin, estrogens and plant flavonoids. In some vascular preparations H2S plays a role of endothelium-derived hyperpolarizing factor by activating small and intermediate-conductance calcium-activated potassium channels. Endothelial H2S signaling is up-regulated in some pathologies, such as obesity and cerebral ischemia-reperfusion. In addition, H2S activates endothelial NO synthase and inhibits cGMP degradation by phosphodiesterase 5 thus potentiating the effect of NO-cGMP pathway. Moreover, H2S-derived polysulfides directly activate protein kinase G. Finally, H2S interacts with NO to form nitroxyl (HNO—a potent vasorelaxant. H2S appears to play an important and multidimensional role in endothelium-dependent vasorelaxation.

  13. Interplay of carbonyl-carbonyl, Csbnd H⋯O and Csbnd H⋯π interactions in hierarchical supramolecular assembly of tartaric anhydrides - Tartaric acid and its O-acyl derivatives: Part 11

    Science.gov (United States)

    Madura, Izabela D.; Zachara, Janusz; Hajmowicz, Halina; Synoradzki, Ludwik

    2012-06-01

    The detailed analysis of molecular and crystal structure of the O-acyltartaric anhydrides is presented. The role of both intra- and intermolecular weak interactions is discussed. The Hirshfeld surfaces analysis in form of dnorm representation and decomposed finger print plots was used to find out the types of weak but directional carbonyl-carbonyl, Csbnd H⋯O and Csbnd H⋯π interactions. The major interactions at the subsequent levels of the crystal architecture were identified. The interplay between carbonyl-carbonyl interactions and Csbnd H⋯O hydrogen bonds both at the molecular level as well as in basic supramolecular motives was analyzed. In all cases the primary supramolecular motif was found to be the ribbon showing the p21 rod group symmetry. The key role of the ribbon motif is reflected in the hexagonal packing of rods.

  14. Selenium content of sulfide ores related to ophiolites of Greece.

    Science.gov (United States)

    Economou-Eliopoulos, M; Eliopoulos, D G

    1998-01-01

    Several deposits of sulfide mineralization have been described in the ophiolites of Greece. Based on their mineralogical and chemical composition and the host rocks, two types can be distinguished: (1) the Fe-Cu-Ni-Co type consisting of pyrrhotite, chalcopyrite, Co-pentlandite, pyrite, magnetite + arsenides, +/- chromite, hosted in serpentinites, gabbros or diabases, which have variable geochemical characteristics, and (2) sulfide mineralization of the Cyprus type containing variable proportions of pyrite, chalcopyrite, bornite, and sphalerite. The spatial association with shear zones and fault systems, which is a common feature in both types of mineralization, provided the necessary permeability for the circulation of the responsible mineralized hydrothermal fluids. The selenium (Se) content in representative samples of both types of mineralization from the ophiolites of Pindos (Kondro, Perivoli, and Neropriona), Othrys (Eretria and A. Theodoroi), Veria (Trilofon), and Argolis (Ermioni) shows a wide variation. The highest values of Se (130 to 1900 ppm) were found in massive Fe-Cu sulfide ores from Kondro, in particular the Cu-rich portions (average 1300 ppm Se). The average values of Se for the Othrys sulfides are low (< 40 ppm Se). The Se content in a diabase breccia pipe (50 x 200 m) with disseminated pyrite mineralization (Neropriona) ranges from < 1 to 35 ppm Se. The highest values were noted in strongly altered samples that also exhibited a significant enrichment in platinum (1 ppm Pt). Sulfide mineralization (irregular to lens-like masses and stringers) associated with magnetite, hosted in gabbros exposed in the Perivoli area (Tsouma hill), shows a content ranging from 40 to 350 ppm Se. The distribution of Se in the studied type of the sulfide mineralization may be of genetic significance, indicating that the Se level, which often is much higher than in typical magmatic sulfides related to mafic-ultramafic rocks (average 90-100 ppm Se), may positively affect

  15. Recherches récentes sur le cobalt carbonyle et ses dérivés Recent Studies of Cobalt Carbonyl and Its Derivatives

    Directory of Open Access Journals (Sweden)

    Poilblanc R.

    2006-11-01

    Full Text Available Faisant le point sur l'ensemble de leurs résultats obtenus au cours des dernières années, les auteurs développent divers aspects relatifs aux synthèses, à la physico-chimie et aux structures des complexes dérivés des cobalt carbonyle. L'étude concerne essentiellement : - les dérivés de simple substitution de l'octacarbonyle dicobalt et la tautomérie des complexes dinucléaires; - les dérivés mononucléaires ioniques et leur relation avec les formes alkyle et acétyle du cobalt (I; - le bis (tétracarbonyle cobalt mercure et ses dérivés de substitution ; - les dérivés tétranucléaires et le phénomène de « migration intramoléculaire » des ligands. Les caractéristiques spectrographiques de quelque soixante-dix complexes sont fournies en annexe. The authors review their findings concerning the synthesis, physico-chemical properties and structural nature of cobalt carbonyl derivatives. The article deals with : - Normal substitution of Col (CO,, and tautomerism of binuclear complexes; - lonic mononuclear derivatives in relation with alkyl and acetylcobaltcarbonyls ; - Bis (tetracarbonylcobalt mercury and its substituted derivatives ; - Tetranuclear cobalt complexes exhibiting intramolecular scrambling. Spectrographic data of some 70 compounds are given.

  16. Analysis of protein carbonylation-pitfalls and promise in commonly used methods

    DEFF Research Database (Denmark)

    Rogowska-Wrzesinska, Adelina; Wojdyla, K; Nedić, O;

    2014-01-01

    that research scientists are becoming more eager to be able to measure accurately the level of oxidized protein in biological materials, and to determine the precise site of the oxidative attack on the protein, in order to get insights into the molecular mechanisms involved in the progression of diseases....... Several methods for measuring protein carbonylation have been implemented in different laboratories around the world. However, to date no methods prevail as the most accurate, reliable, and robust. The present paper aims at giving an overview of the common methods used to determine protein carbonylation...... in biological material as well as to highlight the limitations and the potential. The ultimate goal is to give quick tips for a rapid decision making when a method has to be selected and taking into consideration the advantage and drawback of the methods....

  17. Analysis of protein carbonylation - pitfalls and promise in commonly used methods

    DEFF Research Database (Denmark)

    Rogowska-Wrzesinska, A.; Wojdyla, K.; Nedic, O.;

    2014-01-01

    that research scientists are becoming more eager to be able to measure accurately the level of oxidized protein in biological materials, and to determine the precise site of the oxidative attack on the protein, in order to get insights into the molecular mechanisms involved in the progression of diseases....... Several methods for measuring protein carbonylation have been implemented in different laboratories around the world. However, to date no methods prevail as the most accurate, reliable, and robust. The present paper aims at giving an overview of the common methods used to determine protein carbonylation...... in biological material as well as to highlight the limitations and the potential. The ultimate goal is to give quick tips for a rapid decision making when a method has to be selected and taking into consideration the advantage and drawback of the methods....

  18. Crystallization and preliminary X-ray crystallographic studies of pig heart carbonyl reductase

    International Nuclear Information System (INIS)

    Pig heart carbonyl reductase has been crystallized in the presence of NADPH. Diffraction data have been collected using synchrotron radiation. Pig heart carbonyl reductase (PHCR), which belongs to the short-chain dehydrogenase/reductase (SDR) family, has been crystallized by the hanging-drop vapour-diffusion method. Two crystal forms (I and II) have been obtained in the presence of NADPH. Form I crystals belong to the tetragonal space group P42, with unit-cell parameters a = b = 109.61, c = 94.31 Å, and diffract to 1.5 Å resolution. Form II crystals belong to the tetragonal space group P41212, with unit-cell parameters a = b = 120.10, c = 147.00 Å, and diffract to 2.2 Å resolution. Both crystal forms are suitable for X-ray structure analysis at high resolution

  19. Polar [3 + 2] cycloaddition of ketones with electrophilically activated carbonyl ylides. Synthesis of spirocyclic dioxolane indolinones.

    Science.gov (United States)

    Bentabed-Ababsa, Ghenia; Derdour, Aicha; Roisnel, Thierry; Sáez, Jose A; Domingo, Luis R; Mongin, Florence

    2008-09-01

    The [3 + 2] cycloaddition reaction between carbonyl ylides generated from epoxides and ketones (ethyl pyruvate, ethyl phenylglyoxylate, isatin, N-methylisatin and 5-chloroisatin) to give substituted dioxolanes and spirocyclic dioxolane indolinones was investigated. The effect of microwave irradiation on the outcome of the reaction was studied. The thermal reaction between 2,2-dicyano-3-phenyloxirane and N-methylisatin was theoretically studied using DFT methods. This reaction is a domino process that comprises two steps. The first is the thermal ring opening of the epoxide to yield a carbonyl ylide intermediate, whereas the second step is a polar [3 + 2] cycloaddition to yield the final spiro cycloadducts. The cycloaddition presents a low stereoselectivity and a large regio- and chemoselectivity. Analysis of the electrophilicity values and the Fukui functions of the reagents involved in the cycloaddition step allowed the chemical outcome to be explained. PMID:18698474

  20. Amino acid decarboxylations produced by lipid-derived reactive carbonyls in amino acid mixtures.

    Science.gov (United States)

    Hidalgo, Francisco J; León, M Mercedes; Zamora, Rosario

    2016-10-15

    The formation of 2-phenylethylamine and phenylacetaldehyde in mixtures of phenylalanine, a lipid oxidation product, and a second amino acid was studied to determine the role of the second amino acid in the degradation of phenylalanine produced by lipid-derived reactive carbonyls. The presence of the second amino acid usually increased the formation of the amine and reduced the formation of the Strecker aldehyde. The reasons for this behaviour seem to be related to the α-amino group and the other functional groups (mainly amino or similar groups) present in the side-chain of the amino acid. These groups are suggested to modify the lipid-derived reactive carbonyl but not the reaction mechanism because the Ea of formation of both 2-phenylethylamine and phenylacetaldehyde remained unchanged in all studied systems. All these results suggest that the amine/aldehyde ratio obtained by amino acid degradation can be modified by adding free amino acids during food formulation. PMID:27173560

  1. Influence of gamma radiation reaction on the hydroesterification of butenes catalyzed by metal carbonyls

    International Nuclear Information System (INIS)

    In the hydro carboxylation reaction, which first has been studied by Reppe, olefine and acetylene compounds are processed with carbon monoxide and water at high pressures and high temperatures in the presence of metal carbonyls. This reaction can be enhanced considerably by application of ionizing radiation. Lower pressures and in particular lower temperatures can be used if gamma irradiation is performed during carboxylation. For the experiments a mixture of buten-1 and buten-2 as well as pure buten-1 and pure buten-2 has been used to study the behaviour of these olefines with respect to the isomerization of the reaction products and to the olefines not transformed in the reaction process. Replacing water, methanol has been used as a reaction component, thus obtaining directly the respective carbonyl acid esters, which can be analysed quantitatively and qualitatively with respect to their isomeric composition by gaschromatography. (orig./HK)

  2. Determination of protein carbonyls in plasma, cell extracts, tissue homogenates, isolated proteins

    DEFF Research Database (Denmark)

    Weber, Daniela; Davies, Michael J.; Grune, Tilman

    2015-01-01

    the most relevant methods to detect protein carbonyls after derivatization with 2,4-dinitrophenylhydrazine with an emphasis on measurement in plasma, cells, organ homogenates, isolated proteins and organelles. Sample preparation, derivatization conditions and protein handling are presented for the...... different reactive oxygen species in blood, tissues and cells. Sample preparation and stabilization are key steps in the accurate quantification of oxidation-related products and examination of physiological/pathological processes. This review therefore focuses on the sample preparation processes used in...... spectrophotometric and HPLC method as well as for immunoblotting and ELISA. An extensive overview covering these methods in previously published articles is given for researchers who plan to measure protein carbonyls in different samples....

  3. Contribution to radiation-chemically catalyzed hydroformylation of butenes in the presence of metal carbonyls

    International Nuclear Information System (INIS)

    In this paper a study is presented of the influence of gamma-radiation on the catalytic hydroformylation of olefines. As model olefines buten-1 and buten-2 as well as their mixtures have been used together with the catalysts di-cobalt octacarbonyle and rhodium (I) tristri phenyl-phosphine carbonyle hydride. In addition the catalytic activity of the VI. side group carbonyles Cr(CO)6, Mo(CO)6 and W(CO)6 has been studied under radiation chemical conditions. For this purpose a mixture of olefine, solvent (cyclo hexane) and calalyst has been pressurized and processed in a mixing autoklave together with a Co and H2 (1:1) mixture, variing the reaction variables within certain limits. (orig.)

  4. Design and fabrication of microfluidic mixer from carbonyl iron–PDMS composite membrane

    KAUST Repository

    Li, Jiaxing

    2010-10-12

    This paper introduces a carbonyl iron-PDMS (CI-PDMS) composite magnetic elastomer in which carbonyl iron (CI) particles are uniformly distributed in a PDMS matrix. The CI particles and the PDMS were mixed at different weight ratios and tested to determine the influence of CI concentration. The magnetic and mechanical properties of the magnetic elastomers were characterized, respectively, by vibrating-sample magnetometer and by tensile testing using a mechanical analyzer. The elastomer was found to exhibit high magnetization and good mechanical flexibility. The morphology and deformation of the CI-PDMS membrane also were observed. A magnetically actuated microfluidic mixer (that is, a micromixer) integrated with CI-PDMS elastomer membranes was successfully designed and fabricated. The high efficiency and quality of the mixing makes possible the impressive potential applications of this unique CI-PDMS material in microfluidic systems. © Springer-Verlag 2010.

  5. The Pharmacological Activities of the Metabolites of N-[(Trimethylamineboryl)-Carbonyl]-L-Phenylalanine Methyl Ester

    OpenAIRE

    Miller, M. C.III; Sood, A.; Spielvogel, B. F.; Shrewsbury, R. P.; Hall, I. H.

    1996-01-01

    The metabolites of N-[(trimethylamineboryl)-carbonyl]-L-phenylalanine methyl ester 1 proved to be active in a number of pharmacological screens where the parent had previously demonstrated potent activity. The proposed metabolites demonstrated significant activity as cytotoxic, hypolipidemic, and anti-inflammatory agents. In cytotoxicity screens several of the proposed metabolites afforded better activity than the parent compound against the growth of suspended and solid tumor cell lines. Eva...

  6. Formation of Small Gas Phase Carbonyls from Heterogeneous Oxidation of Polyunsaturated Fatty Acids (PUFA)

    Science.gov (United States)

    Zhou, S.; Zhao, R.; Lee, A.; Gao, S.; Abbatt, J.

    2011-12-01

    Fatty acids (FAs) are emitted into the atmosphere from gas and diesel powered vehicles, cooking, plants, and marine biota. Field measurements have suggested that FAs, including polyunsaturated fatty acids (PUFA), could make up an important contribution to the organic fraction of atmospheric aerosols. Due to the existence of carbon-carbon double bonds in their molecules, PUFA are believed to be highly reactive towards atmospheric oxidants such as OH and NO3 radicals and ozone, which will contribute to aerosol hygroscopicity and cloud condensation nuclei activity. Previous work from our group has shown that small carbonyls formed from the heterogeneous reaction of linoleic acid (LA) thin films with gas-phase O3. It is known that the formation of small carbonyls in the atmosphere is not only relevant to the atmospheric budget of volatile organic compounds but also to secondary organic aerosol formation. In the present study, using an online proton transfer reaction mass spectrometry (PTR-MS) and off-line gas chromatography-mass spectrometry (GC-MS) we again investigated carbonyl formation from the same reaction system, i.e. the heterogeneous ozonolysis of LA film. In addition to the previously reported carbonyls, malondialdehyde (MDA), a source of reactive oxygen species that is mutagenic, has been identified as a product for the first time. Small dicarbonyls, e.g. glyoxal, are expected to be formed from the further oxidation of MDA. In this presentation, the gas-phase chemistry of MDA with OH radicals using a newly built Teflon chamber in our group will also be presented.

  7. Synthesis and Insecticidal Activity of Novel N-Pyridylpyrazole Carbonyl Thioureas

    Institute of Scientific and Technical Information of China (English)

    王宝雷; 马翼; 熊丽霞; 李正名

    2012-01-01

    A series of novel N-pyridylpyrazole carbonyl thioureas were designed and synthesized. Their structures were characterized by melting points, 1H NMR, IR and elemental analysis or HRMS. The bioassay tests indicated that some of these compounds exhibited moderate insecticidal activity against Mythirnna separata Walker and Culex pipiens pallens. Among 17 compounds, 5n and 5p showed 100% larvicidal activity against Mythimna separata Walker at the test concentration of 100 mg/L.

  8. Influence of carbonyl stress on rheological alterations of blood materials and decarbonylation effect of glutathione

    Institute of Scientific and Technical Information of China (English)

    彭密军; 蔡建光; 贺洪; 龚萍; 李国林; 汤婷; 朱泽瑞; 印大中

    2008-01-01

    The effects of various toxic carbonyls such as malondialdehyde(MDA),a secondary product of lipid peroxidation,and other aldehydes on rheological parameters and their relationship with aging-associated alterations were studied.Both MDA and glutaraldehyde(Glu) in different concentrations significantly increase viscosity,plastic viscosity and yield stress of human plasma and erythrocyte suspensions.MDA(20 mmol/L) reduces sharply the typical fluorescence of proteins(excitation 280 nm/emission 350 nm),and produces age pigment-like fluorescence with a strong emission peak at 460 nm when excites at 395 nm by only being incubated for some hours.In contrast,Glu decreases merely the fluorescence of proteins without producing age pigment-like fluorescence.These data suggest interestingly that the MDA-induced gradual protein cross linking seems to form from different mechanisms compared to the fast rheological changes of blood materials which may take place either in acute and chronic diseases or during aging.On the other hand,MDA induces various deleterious alterations of erythrocytes whereas glutathione(GSH) inhibits the MDA-related carbonyl stress in a concentration-dependent manner.The results indicate that carbonyl-amino reaction exists in the blood widely and GSH has the ability to interrupt or reverse this reaction in a certain way.It implies that carbonyl stress may be one of the important factors in blood stasis and suggests a theoretical and practical approach in anti-stresses and anti-aging.

  9. Polar [3 + 2] cycloaddition of ketones with electrophilically activated carbonyl ylides. Synthesis of spirocyclic dioxolane indolinones.

    OpenAIRE

    Bentabed-Ababsa, Ghenia; Derdour, Aicha; Roisnel, Thierry; Sáez, Jose A.; Luis R. Domingo; Mongin, Florence

    2008-01-01

    The [3 + 2] cycloaddition reaction between carbonyl ylides generated from epoxides and ketones (ethyl pyruvate, ethyl phenylglyoxylate, isatin, N-methylisatin and 5-chloroisatin) to give substituted dioxolanes and spirocyclic dioxolane indolinones was investigated. The effect of microwave irradiation on the outcome of the reaction was studied. The thermal reaction between 2,2-dicyano-3-phenyloxirane and N-methylisatin was theoretically studied using DFT methods. This reaction is a domino proc...

  10. COMPARATIVE STUDY OF EFFICACY OF FERROUS SULPHATE AND CARBONYL IRON IN ANEMIA OF ANTENATAL WOMEN

    OpenAIRE

    Radhika; Souris

    2015-01-01

    Iron deficiency anemia is the most common and important public health problem all over the world in the risk group of antenatal women. Research is going on to improve the iron status of the pregnant women with different forms of iron available. In this regard, Carbonyl Iron is showing promising results in improving the red cell mass with better compliance. 120 antenatal women were recruited in this study. The study comprised of 6weeks fo...

  11. Proteomic identification of carbonylated proteins in the kidney of trichloroethene-exposed MRL+/+ mice

    OpenAIRE

    Fan, Xiuzhen; WANG, GANGDUO; English, Robert D.; Khan, M. Firoze

    2013-01-01

    Trichloroethene (TCE), a common environmental and occupational pollutant, is associated with multi-organ toxicity. Kidney is one of major target organs affected as a result of TCE exposure. Our previous studies have shown that exposure to TCE causes increased protein oxidation (protein carbonylation) in the kidneys of autoimmune-prone MRL +/+ mice, and suggested a potential role of protein oxidation in TCE-mediated nephrotoxicity. To assess the impact of chronic TCE exposure on protein oxidat...

  12. Influence of shape anisotropy on microwave complex permeability in carbonyl iron flakes/epoxy resin composites

    Institute of Scientific and Technical Information of China (English)

    Wen Fu-Sheng; Qiao Liang; Zhou Dong; Zuo Wen-Liang; Yi Hai-Bo; Li Fa-Shen

    2008-01-01

    To explore the mechanism of carbonyl iron flake composites for microwave complex permeability, this paper investigates the feature of the flakes. The shape anisotropy was certified by the results of the magnetization hysteresis loops and the Mossbauer spectra. Furthermore, the shape anisotropy was used to explain the origin of composite microwave performance, and the calculated results agree with the experiment. It is believed that the shape anisotropy dominates microwave complex permeability, and the natural resonance plays main role in flake.

  13. Oxidative Stress and Carbonyl Lesions in Ulcerative Colitis and Associated Colorectal Cancer

    OpenAIRE

    Zhiqi Wang; Sai Li; Yu Cao; Xuefei Tian; Rong Zeng; Duan-Fang Liao; Deliang Cao

    2016-01-01

    Oxidative stress has long been known as a pathogenic factor of ulcerative colitis (UC) and colitis-associated colorectal cancer (CAC), but the effects of secondary carbonyl lesions receive less emphasis. In inflammatory conditions, reactive oxygen species (ROS), such as superoxide anion free radical (O2 ∙−), hydrogen peroxide (H2O2), and hydroxyl radical (HO∙), are produced at high levels and accumulated to cause oxidative stress (OS). In oxidative status, accumulated ROS can cause protein dy...

  14. Novel Routes to Ethylene Glycol Synthesis via Acid-Catalyzed Carbonylation of Formaldehyde and Dimethoxymethane

    OpenAIRE

    Celik, Fuat Emin

    2010-01-01

    Carbon-carbon bond forming carbonylation reactions were investigated as candidates to replace ethene epoxidation as the major source of ethylene glycol production. This work was motivated by the potentially lower cost of carbon derived from synthesis gas as compared to ethylene. Synthesis gas can be produced from relatively abundant and cheap natural gas, coal, and biomass resources whereas ethylene is derived from increasingly scarce and expensive crude oil. From synthesis gas, a range of...

  15. DETERMINATION OF PROTEIN CARBONYL LEVELS IN PATIENTS WITH CHRONIC ALCOHOLICS AND EVALUATION TOGETHER WITH OTHER PARAMETERS

    OpenAIRE

    YALCIN, Serap

    2011-01-01

    Investigation of the impact of oxidative stress, of which chronic alcohol consumption is an important indicator, on proteins and lipids. In this study, in order to evaluate oxidative damage, blood samples of 40 alcoholic patients, lying in the psychiatry clinic of Ankara University with the diagnosis of alcoholism, and 20 healthy people have been worked with spectrophotometric method. Malondialdehyde (MDA), lipid peroxidation product, and protein carbonyl (PCO) levels observed as statisticall...

  16. The interaction of metal carbonyl compounds with organic polymers and monomers

    OpenAIRE

    Lyons, Michael P.

    1993-01-01

    The photochemistry of W(CO)6, Mo(CO)6, and Cr(CO)6 in the presence of monomeric and polymeric triphenylphosphine ligands was investigated in toluene solution, using laser flash photolysis with 355nm excitation. The mechanism and kinetics of interaction of the primary photoproducts M(CO)5(toluene) (M = W, Mo, or Cr) with the various monomeric ligands were investigated. Interaction of the metal carbonyl photofragments with various homopolymers is also discussed. The polymerisation methods used ...

  17. Doxorubicin-induced carbonylation and degradation of cardiac myosin binding protein C promote cardiotoxicity

    OpenAIRE

    Aryal, Baikuntha; Jeong, Jinsook; Rao, V. Ashutosh

    2014-01-01

    Doxorubicin is one of the most successful anticancer agents. However, 10–30% of all treated patients experience a dose-limiting cardiac adverse event. Oxidative stress is partly responsible for the cardiotoxicity because the heart does not possess required antioxidant mechanisms. Protein oxidation by carbonylation is irreversible and marks proteins for loss of function and degradation. Using proteomics and MS, we identified and investigated cardiac myosin binding protein (MyBPC) as being sele...

  18. Density functional theory study of electroreductive hydrocoupling of alpha,beta-unsaturated carbonyl compounds.

    Science.gov (United States)

    Kise, Naoki

    2006-11-24

    [reaction: see text] The electroreductive hydrocoupling of methyl cinnamate, methyl crotonate, cumarin, and benzalacetone was studied by DFT (B3LYP/6-311++ G**) calculations. The computational outcomes for the transition states in the hydrocoupling of anion radicals generated by a one-electron transfer to the alpha,beta-unsaturated carbonyl compounds well agree with the diastereoselectivities in the experimental results previously reported. PMID:17109548

  19. Synthesis and complexing properties of carbonyl-containing thiacalyx[4]arenes

    International Nuclear Information System (INIS)

    Stereoisomers of unsubstituted by upper rim of thiacalyx(4)arenes containing four carbonyl fragments have been prepared for the first time, their structure has been investigated by one- and two-dimensional spectroscopy, NMR, IR-spectroscopy and mass-spectrometry. Complexing properties of macrocycles concerning alkali metal cations (Li+, Na+, K+, Cs+) is evaluated by picrate extraction. Lack of the preorganization in the case of unsubstituted by upper rim thiacalyxarenes accounts for sudden decreasing extraction ability

  20. A carnosine intervention study in overweight human volunteers: bioavailability and reactive carbonyl species sequestering effect

    OpenAIRE

    Luca Regazzoni; Barbora de Courten; Davide Garzon; Alessandra Altomare; Cristina Marinello; Michaela Jakubova; Silvia Vallova; Patrik Krumpolec; Marina Carini; Jozef Ukropec; Barbara Ukropcova; Giancarlo Aldini

    2016-01-01

    Carnosine is a natural dipeptide able to react with reactive carbonyl species, which have been recently associated with the onset and progression of several human diseases. Herein, we report an intervention study in overweight individuals. Carnosine (2 g/day) was orally administered for twelve weeks in order to evaluate its bioavailability and metabolic fate. Two carnosine adducts were detected in the urine samples of all subjects. Such adducts are generated from a reaction with acrolein, whi...

  1. Hydrogen sulfide and nervous system regulation

    Institute of Scientific and Technical Information of China (English)

    ZHOU Cheng-fang; TANG Xiao-qing

    2011-01-01

    Objective This review discusses the current status and progress in studies on the roles of hydrogen sulfide (H2S) in regulation of neurotoxicity,neuroprotection,and neuromodulator,as well as its therapeutic potential for neurodegenerative disorders.Data sources The data used in this review were mainly from Medline and PubMed published in English from 2001 to August 2011.The search terms were “hydrogen sulfide”,“neuron”,and “neurodegenerative disorders”.Study selection Articles regarding the regulation of neuronal function,the protection against neuronal damage and neurological diseases,and their possible cellular and molecular mechanisms associated with H2S were selected.Results The inhibited generation of endogenous H2S is implicated in 1-methy-4-phenylpyridinium ion,6-OHDA,and homocysteine-triggered neurotoxicity.H2S elicits neuroprotection in Alzheimer's disease and Parkinson's disease models as well as protecting neurons against oxidative stress,ischemia,and hypoxia-induced neuronal death.H2S offers anti-oxidant,anti-inflammatory and anti-apoptotic effects,as well as activates ATP-sensitive potassium channels and cystic fibrosis transmembrane conductance regulator Cl- channels.H2S regulates the long-term potentiation (LTP) and GABAB receptors in the hippocampus,as well as intracellular calcium and pH homeostasis in neurons and glia cells.Conclusions These articles suggest that endogenous H2S may regulate the toxicity of neurotoxin.H2S not only acts as a neuroprotectant but also serves as a novel neuromodulator.

  2. Mitochondrial ascorbate-glutathione cycle and proteomic analysis of carbonylated proteins during tomato (Solanum lycopersicum) fruit ripening.

    Science.gov (United States)

    López-Vidal, O; Camejo, D; Rivera-Cabrera, F; Konigsberg, M; Villa-Hernández, J M; Mendoza-Espinoza, J A; Pérez-Flores, L J; Sevilla, F; Jiménez, A; Díaz de León-Sánchez, F

    2016-03-01

    In non-photosynthetic tissues, mitochondria are the main source of energy and of reactive oxygen species. Accumulation of high levels of these species in the cell causes damage to macromolecules including several proteins and induces changes in different metabolic processes. Fruit ripening has been characterized as an oxidative phenomenon; therefore, control of reactive oxygen species levels by mitochondrial antioxidants plays a crucial role on this process. In this work, ascorbate-glutathione cycle components, hydrogen peroxide levels and the proteomic profile of carbonylated proteins were analyzed in mitochondria isolated from tomato (Solanum lycopersicum) fruit at two ripening stages. A significant increase on most ascorbate-glutathione cycle components and on carbonylated proteins was observed in mitochondria from breaker to light red stage. Enzymes and proteins involved in diverse cellular and mitochondrial metabolic pathways were identified among the carbonylated proteins. These results suggest that protein carbonylation is a post-translational modification involved in tomato fruit ripening regulation. PMID:26471654

  3. Hydrogen bond and protonation during interaction of transition metal carbonyl complexes with HCl and perfluoro-tert-butanol

    International Nuclear Information System (INIS)

    Using the method of IR-spectrometry HCl interaction with some carbonyl complexes of transition metals: (Et5C5)Re(CO)3, (η6 - Me3C6H3)M(CO)3, where M = Cr, Mo, W at low temperatures in solution of liquid xenon, as well as interaction of certain complexes of Arene M (CO)L2 type with perfluoro-tert-butanol, have been investigated. It is ascertained that HCl is able to form H-bond with carbonyl Π-complexes by transition metals via oxygen atom of carbonyl group at metal atom in xenon solution. The protonation of carbonyl complexes of transition metals to metal atom can proceed via the stage of hydrogen bond formation to oxygen atom of CO group

  4. Effect of carbonyl inhibitors and their H₂O₂ detoxification on lactic acid fermentation.

    Science.gov (United States)

    Li, Jing; Zhu, Caiqing; Tu, Maobing; Han, Pingping; Wu, Yonnie

    2015-04-01

    Biomass degradation compounds significantly inhibit biochemical conversion of biomass prehydrolysates to biofuels and chemicals, such as lactic acid. To characterize the structure-activity relationship of carbonyl inhibition on lactic acid fermentation, we examined effects of eight carbonyl compounds (furfural, 5-hydroxymethyl furfural, vanillin, syringaldehyde, 4-hydroxybenzaldehyde, phthalaldehyde, benzoic acid, and pyrogallol aldehyde) and creosol on lactic acid production by Lactobacillus delbrueckii. Pyrogallol aldehyde reduced the cell growth rate by 35 % at 1.0 mM and inhibited lactic acid production completely at 2.0 mM. By correlating the molecular descriptors to the inhibition constants in lactic acid fermentation, we found a good relationship between the hydrophobicity (Log P) of aldehydes and their inhibition constants in fermentation. The inhibitory effect of carbonyl inhibitors appeared to correlate with their thiol reactivity as well. In addition, we found that H2O2 detoxified pyrogallol aldehyde and phthalaldehyde inhibitory activity. H2O2 detoxification was applied to real biomass prehydrolysates in lactic acid fermentation. PMID:25666370

  5. Gas chromatographic analysis of reactive carbonyl compounds formed from lipids upon UV-irradiation

    International Nuclear Information System (INIS)

    Peroxidation of lipids produces carbonyl compounds; some of these, e.g., malonaldehyde and 4-hydroxynonenal, are genotoxic because of their reactivity with biological nucleophiles. Analysis of the reactive carbonyl compounds is often difficult. The methylhydrazine method developed for malonaldehyde analysis was applied to simultaneously measure the products formed from linoleic acid, linolenic acid, arachidonic acid, and squalene upon ultraviolet-irradiation (UV-irradiation). The photoreaction products, saturated monocarbonyl, alpha,beta-unsaturated carbonyls, and beta-dicarbonyls, were derivatized with methylhydrazine to give hydrazones, pyrazolines, and pyrazoles, respectively. The derivatives were analyzed by gas chromatography and gas chromatography-mass spectrometry. Lipid peroxidation products identified included formaldehyde, acetaldehyde, acrolein, malonaldehyde, n-hexanal, and 4-hydroxy-2-nonenal. Malonaldehyde levels formed upon 4 hr of irradiation were 0.06 micrograms/mg from squalene, 2.4 micrograms/mg from linolenic acid, and 5.7 micrograms/mg from arachidonic acid. Significant levels of acrolein (2.5 micrograms/mg) and 4-hydroxy-2-nonenal (0.17 micrograms/mg) were also produced from arachidonic acid upon 4 hr irradiation

  6. Role of Protein Carbonylation in Skeletal Muscle Mass Loss Associated with Chronic Conditions

    Directory of Open Access Journals (Sweden)

    Esther Barreiro

    2016-05-01

    Full Text Available Muscle dysfunction, characterized by a reductive remodeling of muscle fibers, is a common systemic manifestation in highly prevalent conditions such as chronic heart failure (CHF, chronic obstructive pulmonary disease (COPD, cancer cachexia, and critically ill patients. Skeletal muscle dysfunction and impaired muscle mass may predict morbidity and mortality in patients with chronic diseases, regardless of the underlying condition. High levels of oxidants may alter function and structure of key cellular molecules such as proteins, DNA, and lipids, leading to cellular injury and death. Protein oxidation including protein carbonylation was demonstrated to modify enzyme activity and DNA binding of transcription factors, while also rendering proteins more prone to proteolytic degradation. Given the relevance of protein oxidation in the pathophysiology of many chronic conditions and their comorbidities, the current review focuses on the analysis of different studies in which the biological and clinical significance of the modifications induced by reactive carbonyls on proteins have been explored so far in skeletal muscles of patients and animal models of chronic conditions such as COPD, disuse muscle atrophy, cancer cachexia, sepsis, and physiological aging. Future research will elucidate the specific impact and sites of reactive carbonyls on muscle protein content and function in human conditions.

  7. Uncertainties of polynuclear aromatic hydrocarbon and carbonyl measurements in heavy-duty diesel emission.

    Science.gov (United States)

    Mabilia, Rosanna; Cecinato, Angelo; Guerriero, Ettore; Possanzini, Massimiliano

    2006-02-01

    In this note we describe the speciated particle-phase PM2.5 polynuclear aromatic hydrocarbon (PAH) and gas-phase carbonyl emissions as collected from a heavy-duty diesel bus outfitted with an oxidation catalyst for exhaust after-treatment. The vehicle was run on a chassis dynamometer during a transient cycle test reproducing a typical city bus route (Azienda Tramviaria Municipalizzata cycle). The diluted tailpipe emissions were sampled for PAH using a 2.5 microm cut size cyclone glass fiber filter assembly, while carbonyls were absorbed onto dinitrophenyl hydrazine-coated silica cartridges. The former compounds were analysed by CGC-MS, the latter by HPLC-UV. Combining the two sets of speciation data resulting from 15 identical dynamometer tests provided a profile of both unregulated organic emissions. PAH emission rates decreased with the number of benzene fused rings. Fluoranthene and pyrene amounted to 90% of total PAHs quantified; six-ring PAHs accounted only for 0.5%. Similarly, formaldehyde and acetaldehyde accounted for approximately 80% of the total carbonyl emissions. Uncertainties of the method in the determination of individual emission factors were calculated. Statistical data processing revealed that all the measurements were quite unaffected by systematic errors and repeatability percentages did not exceed 50% for the majority of components of both groups. PMID:16524107

  8. Gas chromatographic analysis of reactive carbonyl compounds formed from lipids upon UV-irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Dennis, K.J.; Shibamoto, T. (Univ. of California, Davis (USA))

    1990-08-01

    Peroxidation of lipids produces carbonyl compounds; some of these, e.g., malonaldehyde and 4-hydroxynonenal, are genotoxic because of their reactivity with biological nucleophiles. Analysis of the reactive carbonyl compounds is often difficult. The methylhydrazine method developed for malonaldehyde analysis was applied to simultaneously measure the products formed from linoleic acid, linolenic acid, arachidonic acid, and squalene upon ultraviolet-irradiation (UV-irradiation). The photoreaction products, saturated monocarbonyl, alpha,beta-unsaturated carbonyls, and beta-dicarbonyls, were derivatized with methylhydrazine to give hydrazones, pyrazolines, and pyrazoles, respectively. The derivatives were analyzed by gas chromatography and gas chromatography-mass spectrometry. Lipid peroxidation products identified included formaldehyde, acetaldehyde, acrolein, malonaldehyde, n-hexanal, and 4-hydroxy-2-nonenal. Malonaldehyde levels formed upon 4 hr of irradiation were 0.06 micrograms/mg from squalene, 2.4 micrograms/mg from linolenic acid, and 5.7 micrograms/mg from arachidonic acid. Significant levels of acrolein (2.5 micrograms/mg) and 4-hydroxy-2-nonenal (0.17 micrograms/mg) were also produced from arachidonic acid upon 4 hr irradiation.

  9. Vapor phase carbonylation of dimethyl ether and methyl acetate with supported transition metal catalysts

    International Nuclear Information System (INIS)

    The synthesis of acetic acid (AcOH) from methanol (MeOH) and carbon monoxide has been performed industrially in the liquid phase using a rhodium complex catalyst and an iodide promoter. The selectivity to AcOH is more than 99% under mild conditions (1750C, 28 atm). The homogeneous rhodium catalyst has been also effective for the synthesis of acetic anhydride (Ac2O) by carbonylation of dimethyl ether (DME) or methyl acetate (AcOMe). However, rhodium is one of the most expensive metals and its proved reserves are quite limited. It is highly desired, therefore, to develop a new catalyst as a substitute for rhodium. The authors have already reported that nickel supported on active carbon exhibits an excellent activity for the vapor phase carbonylation of MeOh in the presence of iodide promoter and under moderately pressurized conditions. In addition, corrosive attack on reactors by iodide compounds is expected to be negligible in the vapor phase system. In the present work, vapor phase carbonylation of DME and AcOMe on nickel-active carbon (Ni/A.C.) and molybdenum-active carbon (Mo/A.C.) catalysts was studied

  10. Synthesis, structural and vibrational properties of 1-(adamantane-1-carbonyl)-3-halophenyl thioureas

    Science.gov (United States)

    Saeed, Aamer; Erben, Mauricio F.; Bolte, Michael

    2013-02-01

    1-(Adamantane-1-carbonyl)-3-(2,4-dichlorophenyl)thiourea (1) and 1-(adamantane-1-carbonyl)-3-(2-bromo-4,6-difluorophenyl)thiourea (2) were synthesized by the reaction of adamantane-1-carbonyl chloride with ammonium thiocyanate to afford the adamantane-1-carbonylisothiocyanate in situ followed by treatment with suitable halogenated anilines. The structures of the products were established by elemental analyses, Fourier transform infrared spectroscopy (FTIR), 1H, 13C nuclear magnetic resonance (NMR), mass spectroscopy and single crystal X-ray diffraction study. Bond lengths and angles show the usual values. All of three condensed cyclohexane rings of the adamantane residues adopt the usual chair conformation. The molecular conformation of 1 and 2 is stabilized by an intramolecular (Nsbnd H⋯Odbnd C) hydrogen bond which forms a pseudo-six-membered ring. Structural features have been complemented with the joint analysis of the FTIR and FT-Raman spectra along with quantum chemical calculations at the B3LYP/6-311++G** level.

  11. A carnosine intervention study in overweight human volunteers: bioavailability and reactive carbonyl species sequestering effect

    Science.gov (United States)

    Regazzoni, Luca; de Courten, Barbora; Garzon, Davide; Altomare, Alessandra; Marinello, Cristina; Jakubova, Michaela; Vallova, Silvia; Krumpolec, Patrik; Carini, Marina; Ukropec, Jozef; Ukropcova, Barbara; Aldini, Giancarlo

    2016-06-01

    Carnosine is a natural dipeptide able to react with reactive carbonyl species, which have been recently associated with the onset and progression of several human diseases. Herein, we report an intervention study in overweight individuals. Carnosine (2 g/day) was orally administered for twelve weeks in order to evaluate its bioavailability and metabolic fate. Two carnosine adducts were detected in the urine samples of all subjects. Such adducts are generated from a reaction with acrolein, which is one of the most toxic and reactive compounds among reactive carbonyl species. However, neither carnosine nor adducts have been detected in plasma. Urinary excretion of adducts and carnosine showed a positive correlation although a high variability of individual response to carnosine supplementation was observed. Interestingly, treated subjects showed a significant decrease in the percentage of excreted adducts in reduced form, accompanied by a significant increase of the urinary excretion of both carnosine and carnosine-acrolein adducts. Altogether, data suggest that acrolein is entrapped in vivo by carnosine although the response to its supplementation is possibly influenced by individual diversities in terms of carnosine dietary intake, metabolism and basal production of reactive carbonyl species.

  12. Electrochemical Behavior Of Copper Electrode In Potassium Sulfide Solutions

    Directory of Open Access Journals (Sweden)

    I. Zaafarany

    2014-09-01

    Full Text Available The electro chemical behavior of copper electrode in 2M potassium sulfide solution was studied using cyclic voltammograms and potentiostatic polarization techniques. The morphology studies were applied using scanning electron microscope (SEM and energy dispersive analysis of X-rays (EDAX and X-ray powder diffraction. Three anodic peaks were observed in the anodic scan of cyclic voltammograms. SEM and EDAX analysis show the formation of an anodic copper sulfide layer on the surface of copper. Chemical sulfidization of the copper shown to be an important layer growth pathway. The sulfide layers do not passivate copper and the formation of passivating oxide layer is suppressed. The sulfide layer on copper has a Cu2S stoichiometry with roxybyite and digenite structure and it grows by a nucleation. A small patches were consistent with a CuS composition. The formation of KCu7S4 or any other ternary compound could not be observed. Only a presumable polysulfide phase very similar to KCuS4 could be detected.

  13. Cytoprotective Effects of Hydrophilic and Lipophilic Extracts of Pistacia vera against Oxidative Versus Carbonyl Stress in Rat Hepatocytes

    OpenAIRE

    Shahraki, Jafar; Zareh, Mona; Kamalinejad, Mohammad; Pourahmad, Jalal

    2014-01-01

    This study was conducted to evaluate the cytoprotection of various extracts and bioactive compounds found in Pistacia vera againts cytotoxicity, ROS formation, lipid peroxidation, protein carbonylation, mitochondrial and lysosomal membrane damages in cell toxicity models of diabetes related carbonyl (glyoxal) and oxidative stress (hydroperoxide). Methanol, water and ethyl acetate were used to prepare crude pistachios extracts, which were then used to screen for in-vitro cytoprotection of fres...

  14. Asymmetric Conjugate Alkynylation of Cyclic α,β-Unsaturated Carbonyl Compounds with a Chiral Diene Rhodium Catalyst.

    Science.gov (United States)

    Dou, Xiaowei; Huang, Yinhua; Hayashi, Tamio

    2016-01-18

    Asymmetric conjugate alkynylation of cyclic α,β-unsaturated carbonyl compounds (ketones, esters, and amides) was realized by use of diphenyl[(triisopropylsilyl)ethynyl]methanol as an alkynylating reagent in the presence of a rhodium catalyst coordinated with a new chiral diene ligand (Fc-bod; bod=bicyclo[2.2.2]octa-2,5-diene, Fc=ferrocenyl) to give high yields of the corresponding β-alkynyl-substituted carbonyl compounds with 95-98% ee. PMID:26636764

  15. Spatial distributions of and diurnal variations in low molecular weight carbonyl compounds in coastal seawater, and the controlling factors

    International Nuclear Information System (INIS)

    We studied the spatial distributions of and the diurnal variations in four low molecular weight (LMW) carbonyl compounds, formaldehyde, acetaldehyde, propionaldehyde, and glyoxal, in coastal seawater. The samples were taken from the coastal areas of Hiroshima Bay, the Iyo Nada, and the Bungo Channel, western Japan. The formaldehyde, acetaldehyde, and glyoxal concentrations were higher in the northern part of Hiroshima Bay than at offshore sampling points in the Iyo Nada and the Bungo Channel. These three compounds were found at much higher concentrations in the surface water than in deeper water layers in Hiroshima Bay. It is noteworthy that propionaldehyde was not detected in any of the seawater samples, the concentrations present being lower than the detection limit (1 nanomole per liter (nM)) of the high performance liquid chromatography (HPLC) system we used. Photochemical and biological experiments were performed in the laboratory to help understand the characteristic distributions and fates of the LMW carbonyl compounds. The primary process controlling their fate in the coastal environment appears to be their biological consumption. The direct photo degradation of propionaldehyde, initiated by ultraviolet (UV) absorption, was observed, although formaldehyde and acetaldehyde were not degraded by UV irradiation. Our results suggest that the degradation of the LMW carbonyl compounds by photochemically formed hydroxyl radicals is relatively insignificant in the study area. Atmospheric deposition is a possible source of soluble carbonyl compounds in coastal surface seawater, but it may not influence the carbonyl concentrations in offshore waters. - Highlights: • Low molecular weight (LMW) carbonyl compounds in coastal seawater were determined. • Photochemical productions of LMW carbonyl compounds in seawater were observed. • LMW carbonyl compounds were largely consumed biologically. • Photochemical degradation was relatively insignificant in the study area

  16. Synthesis of beta-lactones by the regioselective, cobalt and Lewis acid catalyzed carbonylation of simple and functionalized epoxides.

    Science.gov (United States)

    Lee, J T; Thomas, P J; Alper, H

    2001-08-10

    The PPNCo(CO)(4) and BF(3) x Et(2)O catalyzed carbonylation of simple and functionalized epoxides in DME gives the corresponding beta-lactones regioselectively in good to high yields. The carbonylation occurred selectively at the unsubstituted C-O bond of the epoxide ring, and this reaction tolerates various functional groups such as alkenyl, halide, hydroxy, and alkyl ether. PMID:11485465

  17. Simultaneous removal of sulfide, nitrate and acetate under denitrifying sulfide removal condition: Modeling and experimental validation

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Xijun; Chen, Chuan; Wang, Aijie; Guo, Wanqian; Zhou, Xu [State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090 (China); Lee, Duu-Jong, E-mail: djlee@ntu.edu.tw [State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090 (China); Department of Chemical Engineering, National Taiwan University, Taipei 106, Taiwan (China); Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei 106, Taiwan (China); Ren, Nanqi, E-mail: rnq@hit.edu.cn [State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090 (China); Chang, Jo-Shu [Research Center for Energy Technology and Strategy, National Cheng Kung University, Tainan, Taiwan (China)

    2014-01-15

    Graphical abstract: Model evaluation applied to case study 1: (A-G) S{sup 2−}, NO{sub 3}{sup −}-N, NO{sub 2}{sup −}-N, and Ac{sup −}-C profiles under initial sulfide concentrations of 156.2 (A), 539 (B), 964 (C), 1490 (D), 342.7 (E), 718 (F), and 1140.7 (G) mg L{sup −1}. The solid line represents simulated result and scatter represents experimental result. -- Highlights: • This work developed a mathematical model for DSR process. • Kinetics of sulfur–nitrogen–carbon and interactions between denitrifiers were studied. • Kinetic parameters of the model were estimated via data fitting. • The model described kinetic behaviors of DSR processes over wide parametric range. -- Abstract: Simultaneous removal of sulfide (S{sup 2−}), nitrate (NO{sub 3}{sup −}) and acetate (Ac{sup −}) under denitrifying sulfide removal process (DSR) is a novel biological wastewater treatment process. This work developed a mathematical model to describe the kinetic behavior of sulfur–nitrogen–carbon and interactions between autotrophic denitrifiers and heterotrophic denitrifiers. The kinetic parameters of the model were estimated via data fitting considering the effects of initial S{sup 2−} concentration, S{sup 2−}/NO{sub 3}{sup −}-N ratio and Ac{sup −}-C/NO{sub 3}{sup −}-N ratio. Simulation supported that the heterotrophic denitratation step (NO{sub 3}{sup −} reduction to NO{sub 2}{sup −}) was inhibited by S{sup 2−} compared with the denitritation step (NO{sub 2}{sup −} reduction to N{sub 2}). Also, the S{sup 2−} oxidation by autotrophic denitrifiers was shown two times lower in rate with NO{sub 2}{sup −} as electron acceptor than that with NO{sub 3}{sup −} as electron acceptor. NO{sub 3}{sup −} reduction by autotrophic denitrifiers occurs 3–10 times slower when S{sup 0} participates as final electron donor compared to the S{sup 2−}-driven pathway. Model simulation on continuous-flow DSR reactor suggested that the adjustment of

  18. Gas phase carbonyl compounds in ship emissions: Differences between diesel fuel and heavy fuel oil operation

    Science.gov (United States)

    Reda, Ahmed A.; Schnelle-Kreis, J.; Orasche, J.; Abbaszade, G.; Lintelmann, J.; Arteaga-Salas, J. M.; Stengel, B.; Rabe, R.; Harndorf, H.; Sippula, O.; Streibel, T.; Zimmermann, R.

    2014-09-01

    Gas phase emission samples of carbonyl compounds (CCs) were collected from a research ship diesel engine at Rostock University, Germany. The ship engine was operated using two different types of fuels, heavy fuel oil (HFO) and diesel fuel (DF). Sampling of CCs was performed from diluted exhaust using cartridges and impingers. Both sampling methods involved the derivatization of CCs with 2,4-Dinitrophenylhydrazine (DNPH). The CCs-hydrazone derivatives were analyzed by two analytical techniques: High Performance Liquid Chromatography-Diode Array Detector (HPLC-DAD) and Gas Chromatography-Selective Ion Monitoring-Mass Spectrometry (GC-SIM-MS). Analysis of DNPH cartridges by GC-SIM-MS method has resulted in the identification of 19 CCs in both fuel operations. These CCs include ten aliphatic aldehydes (formaldehyde, acetaldehyde, propanal, isobutanal, butanal, isopentanal, pentanal, hexanal, octanal, nonanal), three unsaturated aldehydes (acrolein, methacrolein, crotonaldehyde), three aromatic aldehyde (benzaldehyde, p-tolualdehyde, m,o-molualdehyde), two ketones (acetone, butanone) and one heterocyclic aldehyde (furfural). In general, all CCs under investigation were detected with higher emission factors in HFO than DF. The total carbonyl emission factor was determined and found to be 6050 and 2300 μg MJ-1 for the operation with HFO and DF respectively. Formaldehyde and acetaldehyde were found to be the dominant carbonyls in the gas phase of ship engine emission. Formaldehyde emissions factor varied from 3500 μg MJ-1 in HFO operation to 1540 μg MJ-1 in DF operation, which is 4-30 times higher than those of other carbonyls. Emission profile contribution of CCs showed also a different pattern between HFO and DF operation. The contribution of formaldehyde was found to be 58% of the emission profile of HFO and about 67% of the emission profile of DF. Acetaldehyde showed opposite behavior with higher contribution of 16% in HFO compared to 11% for DF. Heavier carbonyls

  19. A monotonic increase of formal metal–metal bond orders from one to five upon loss of carbonyl groups from binuclear benzene chromium carbonyls

    International Nuclear Information System (INIS)

    Highlights: • Density functional theory studies on (C6H6)2Cr2(CO)n (n = 5, 4, 3, 2, 1) are reported. • The predicted Cr–Cr distances in (C6H6)2Cr2(CO)n (n = 5, 4, 3, 2, 1) decrease monotonically as CO groups are lost. • The formal Cr–Cr bond orders in (C6H6)2Cr2(CO)n (n = 5, 4, 3, 2, 1) increase monotonically from 1 to 5 as CO groups are lost. • Comparison of the (C6H6)2Cr2(CO)n and (C5H5)2Mn2(CO)n systems are made. - Abstract: Benzene forms a binuclear chromium carbonyl derivative (η6-C6H6)2Cr2(μ-CO)3, shown by X-ray crystallography to have a very short Cr≡Cr distance, suggesting the formal triple bond required to give each chromium atom the favored 18-electron configuration. We now describe theoretical studies on the entire series of binuclear benzene chromium carbonyls (C6H6)2Cr2(CO)n (n = 5, 4, 3, 2, 1). The predicted Cr–Cr distances in the lowest energy singlet structures determined by the BP86 method decrease monotonically as carbonyl groups are lost starting from 2.95 Å in (C6H6)2Cr2(CO)5 to 1.95 Å in (C6H6)2Cr2(CO) corresponding to a steady increase in the formal bond order from one to five. This increase in formal Cr–Cr bond order is also supported by a monotonic increase in the Wiberg bond indices ranging from 0.29 for the single bond in (C6H6)2Cr2(CO)5 to ∼2 for the formal quintuple bond in (C6H6)2Cr2(CO)

  20. Re-Os geochronology on sulfides from the Tudun Cu-Ni sulfide deposit, Eastern Tianshan, and its geological significance

    Science.gov (United States)

    Wang, Minfang; Wang, Wei; Gutzmer, Jens; Liu, Kun; Li, Chao; Michałak, Przemysław P.; Xia, Qinlin; Guo, Xiaonan

    2015-11-01

    The Tudun deposit is a medium-sized Cu-Ni sulfide deposit, located at the westernmost edge of the Huangshan-Jing'erquan Belt in the northern part of Eastern Tianshan, NW China. Sulfide separates including pentlandite, pyrrhotite and chalcopyrite from the Tudun deposit, contain Re, common Os and 187Os ranging from 40.46 to 201.2, 0.8048 to 6.246 and 0.1709 to 0.9977 ppb, respectively. They have very low 187Os/188Os ratios of 1.224-2.352. The sulfides yield a Re-Os isochron age of 270.0 ± 7.5 Ma (MSWD = 1.3), consistent within uncertainty with the SHRIMP zircon U-Pb age for the Tudun mafic intrusion (gabbro) of 280.0 ± 3.0 Ma. The calculated initial 187Os/188Os ratio is 0.533 ± 0.022, and γOs values range from 283 to 307, with a mean of 297, indicating significant crustal contamination of the parent melt prior to sulfide saturation. The Tudun deposit shares the same age and Re-Os isotopic compositions with other orthomagmatic Cu-Ni sulfide deposits in Huangshan-Jing'erquan Belt, suggesting that they have formed in Early Permian.

  1. Sulfide Catalysts Supported on Porous Aromatic Frameworks for Naphthalene Hydroprocessing

    Directory of Open Access Journals (Sweden)

    Eduard Karakhanov

    2016-08-01

    Full Text Available This paper describes the first example of using porous aromatic frameworks as supports for sulfide catalysts for the hydrogenation of aromatic hydrocarbons. The synthesis of bimetallic Ni-W and Ni-Mo sulfides was performed by in situ decomposition of [(n-Bu4N]2[Ni(MeS42] (Me = W, Mo complexes, supported on mesoporous aromatic framework with a diamond-like structure. It is shown that the highest naphthalene conversions were achieved in the case of additional sulfidation with sulfur. After the reaction, catalysts were characterized by X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy. The activity of synthesized catalysts has been studied using naphthalene as a model substrate. The materials used in this study were substantially active in hydrogenation and slightly in hydrocracking of naphthalene.

  2. Investigation of chemical suppressants for inactivation of sulfide ores

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    In order to investigate the effective control method of spontaneous combustion in the mining of sulfide ore deposits, This paper presents the testing results of several selected chemicals (water glass, calcium chloride, calcium oxide, magnesium oxide and their composites) as oxidation suppressants for sulfide ores. A weight increment scaling method was used to measure suppressant performance, and this method proved to be accurate, simple and convenient. Based on a large number of experiments, the test results show that four types of chemical mixtures demonstrate a good performance in reducing the oxidation rate of seven active sulfide ore samples by up to 27% to 100% during an initial 76 d period. The mixtures of water glass mixed with calcium chloride and magnesium oxide mixed with calcium chloride can also act as fire suppressants when used with fire sprinkling systems.

  3. Diverse sulfur metabolisms from two subterranean sulfidic spring systems.

    Science.gov (United States)

    Rossmassler, Karen; Hanson, Thomas E; Campbell, Barbara J

    2016-08-01

    In sulfidic environments, microbes oxidize reduced sulfur compounds via several pathways. We used metagenomics to investigate sulfur metabolic pathways from microbial mat communities in two subterranean sulfidic streams in Lower Kane Cave, WY, USA and from Glenwood Hot Springs, CO, USA. Both unassembled and targeted recA gene assembly analyses revealed that these streams were dominated by Epsilonproteobacteria and Gammaproteobacteria, including groups related to Sulfurovum, Sulfurospirillum, Thiothrix and an epsilonproteobacterial group with no close cultured relatives. Genes encoding sulfide:quinone oxidoreductase (SQR) were abundant at all sites, but the specific SQR type and the taxonomic affiliation of each type differed between sites. The abundance of thiosulfate oxidation pathway genes (Sox) was not consistent between sites, although overall they were less abundant than SQR genes. Furthermore, the Sox pathway appeared to be incomplete in all samples. This work reveals both variations in sulfur metabolism within and between taxonomic groups found in these systems, and the presence of novel epsilonproteobacterial groups. PMID:27324397

  4. Mechanism of sulfide effect on viscosity of HPAM polymer solution

    Institute of Scientific and Technical Information of China (English)

    康万利; 周阳; 王志伟; 孟令伟; 刘述忍; 白宝君

    2008-01-01

    The effect of sulfide on HPAM solution viscosity was studied using BROOKFIELD DV-II viscometer,and the interaction mechanism was discussed.The HPAM solution viscosity was investigated through fully reducing sulfide by the addition of hydrogen peroxide oxidation,and the mechanism of increasing polymer viscosity was investigated.The experimental results also show that there is a critical concentration of 15 mg/L.Below it,the loss rate of HPAM solution viscosity increases more rapidly,but becomes slowly above the critical concentration.A theoretical guidance for oilfields to prepare polymer solution using sewage-water by eliminating sulfide,and it is also importance to prepare polymer solution using sewage-water and save fresh water.

  5. Extraction of Nanosized Cobalt Sulfide from Spent Hydrocracking Catalyst

    Directory of Open Access Journals (Sweden)

    Samia A. Kosa

    2013-01-01

    Full Text Available The processes used for the extraction of metals (Co, Mo, and Al from spent hydrotreating catalysts were investigated in this study. A detailed mechanism of the metal extraction process is described. Additionally, a simulation study was performed to understand the sulfidizing mechanism. The suggested separation procedure was effective and achieved an extraction of approximately 80–90%. In addition, the sulfidization mechanism was identified. This sulfidizing process for Co was found to involve an intermediate, the structure of which was proposed. This proposed intermediate was confirmed through simulations. Moreover, the activities of the spent and the regenerated catalyst were examined in the cracking of toluene. The modification of the spent catalyst through the use of different iron oxide loadings improved the catalytic activity.

  6. Laser cleaning of sulfide scale on compressor impeller blade

    Science.gov (United States)

    Tang, Q. H.; Zhou, D.; Wang, Y. L.; Liu, G. F.

    2015-11-01

    Sulfide scale on the surface of a compressor impeller blade can considerably reduce the impeller performance and its service life. To prepare for subsequent remanufacturing, such as plasma spraying, it needs to be removed completely. In the corrosion process on an FV(520)B stainless steel, sulfide scale is divided into two layers because of different outward diffusion rates of Cr, Ni and Fe. In this paper, the cleaning threshold values of the upper and inner layers and the damage threshold value of the substrate were investigated using a pulsed fiber laser. To obtain experimental evidence, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and 3D surface profilometry were employed to investigate the two kinds of sulfide layers on specimens before, during, and after laser cleaning.

  7. Mathematical model for microbial oxidation of pure lead sulfide by Thiobacillus ferrooxidans.

    Science.gov (United States)

    Kargi, F

    1989-08-01

    A shrinking-core mathematical model describing bioleaching of lead sulfide is developed considering the deposition of insoluble bio-oxidation products on metal sulfide particle surfaces. Variations in particle size are considered as it affects diffusion limitations. PMID:18588129

  8. Thermodynamics of Complex Sulfide Inclusion Formation in Ca-Treated Al-Killed Structural Steel

    Science.gov (United States)

    Guo, Yin-tao; He, Sheng-ping; Chen, Gu-jun; Wang, Qian

    2016-05-01

    Controlling the morphology of the sulfide inclusion is of vital importance in enhancing the properties of structural steel. Long strip-shaped sulfides in hot-rolled steel can spherize when, instead of the inclusion of pure single-phase MnS, the guest is a complex sulfide, such as an oxide-sulfide duplex and a solid-solution sulfide particle. In this study, the inclusions in a commercial rolled structural steel were investigated. Spherical and elongated oxide-sulfide duplex as well as single-phase (Mn,Ca)S solid solution inclusions were observed in the steel. A thermodynamic equilibrium between the oxide and sulfide inclusions was proposed to understand the oxide-sulfide duplex inclusion formation. Based on the equilibrium solidification principle, thermodynamic discussions on inclusion precipitation during the solidification process were performed for both general and resulfurized structural steel. The predicted results of the present study agreed well with the experimental ones.

  9. Morphology and thermal studies of zinc sulfide and cadmium sulfide nanoparticles in polyvinyl alcohol matrix

    Science.gov (United States)

    Osuntokun, Jejenija; Ajibade, Peter A.

    2016-09-01

    Zn(II) and Cd(II) metal complexes of 1-cyano-1-carboethoxyethylene-2,2-dithiolato-κS,S'-bis(N,N-dimethylthiourea-κS) have been synthesized and characterized with analytical and spectroscopic techniques. The complexes were thermolysed in hexadecylamine at 200 °C to prepare ZnS and CdS nanoparticles. The nanoparticles were characterized with scanning electron microscope (SEM), transmission electron microscope (TEM), and powder X-ray diffraction (p-XRD). TEM images showed spherically shaped nanoparticles, whose sizes are in the range 4.33-7.21 nm for ZnS and 4.95-7.7 nm CdS respectively and XRD confirmed cubic crystalline phases for the nanoparticles. The optical band gap energy evaluated from the absorption spectra are 2.88 eV (430 nm) and 2.81 eV (440 nm) for the ZnS and CdS nanoparticles respectively. The as-prepared metal sulfide nanoparticles were further incorporated into polyvinyl alcohol (PVA) to give ZnS/PVA and CdS/PVA composites. The polymer nanocomposites were studied to investigate their morphology and thermal properties relative to the pure PVA. XRD diffractions indicated that the crystalline phases of the nanoparticles and the sizes in PVA matrices remained unaltered. Infra-red spectra studies revealed interactions between the PVA and the metal sulfide nanoparticles and TGA studies show that the ZnS/PVA and CdS/PVA nanocomposites exhibit better thermal stability than the pure PVA.

  10. Application of Borehole SIP Technique to Sulfide Mineral Exploration

    Science.gov (United States)

    Kim, Changryol; Park, Mi Kyung; Park, Samgyu; Sung, Nak Hoon; Shin, Seung Wook

    2016-04-01

    In the study, SIP (Spectral Induced Polarization) well logging probe system was developed to rapidly locate the metal ore bodies with sulfide minerals in the boreholes. The newly developed SIP logging probe employed the non-polarizable electrodes, consisting of zinc chloride (ZnCl2), sodium chloride (NaCl), gypsum (CaSO4·2H2O), and water (H2O), instead of existing copper electrodes, leading to eliminating the EM coupling effect in the IP surveys as much as possible. In addition, the SIP logging system is designed to make measurements down to maximum 500 meters in depth in the boreholes. The SIP well logging was conducted to examine the applicability of the SIP probe system to the boreholes at the ore mine in Jecheon area, Korea. The boreholes used in the SIP logging are known to have penetrated the metal ore bodies with sulfide minerals from the drilling investigations. The ore mine of the study area is the scarn deposits surrounded by the limestone or lime-silicate rocks in Ordovician period. The results of the SIP well logging have shown that the borehole segments with limestone or lime-silicate rocks yielded the insignificant SIP responses while the borehole segments with sulfide minerals (e.g. pyrite) provided the significant phase shifts of the SIP responses. The borehole segments penetrating the metal ore body, so-called cupola, have shown very high response of the phase shift, due to the high contents of the sulfide mineral pyrite. The phase shifts of the SIP response could be used to estimate the grade of the ore bodies since the higher contents of the sulfide minerals, the higher magnitudes of the phase shifts in the SIP responses. It is, therefore, believed that the borehole SIP technique can be applied to investigate the metal ore bodies with sulfide minerals, and that could be used to estimate the ore grades as a supplementary tool in the future.

  11. Hydrogen evolution from water through metal sulfide reactions

    International Nuclear Information System (INIS)

    Transition metal sulfides play an important catalytic role in many chemical reactions. In this work, we have conducted a careful computational study of the structures, electronic states, and reactivity of metal sulfide cluster anions M2SX− (M = Mo and W, X = 4–6) using density functional theory. Detailed structural analysis shows that these metal sulfide anions have ground state isomers with two bridging sulfide bonds, notably different in some cases from the corresponding oxides with the same stoichiometry. The chemical reactivity of these metal sulfide anions with water has also been carried out. After a thorough search on the reactive potential energy surface, we propose several competitive, energetically favorable, reaction pathways that lead to the evolution of hydrogen. Selectivity in the initial water addition and subsequent hydrogen migration are found to be the key steps in all the proposed reaction channels. Initial adsorption of water is most favored involving a terminal metal sulfur bond in Mo2S4− isomers whereas the most preferred orientation for water addition involves a bridging metal sulfur bond in the case of W2S4− and M2S5− isomers. In all the lowest energy H2 elimination steps, the interacting hydrogen atoms involve a metal hydride and a metal hydroxide (or thiol) group. We have also observed a higher energy reaction channel where the interacting hydrogen atoms in the H2 elimination step involve a thiol (–SH) and a hydroxyl (–OH) group. For all the reaction pathways, the Mo sulfide reactions involve a higher barrier than the corresponding W analogues. We observe for both metals that reactions of M2S4− and M2S5− clusters with water to liberate H2 are exothermic and involve modest free energy barriers. However, the reaction of water with M2S6− is highly endothermic with a considerable barrier due to saturation of the local bonding environment

  12. Vegetation successfully prevents oxidization of sulfide minerals in mine tailings.

    Science.gov (United States)

    Li, Yang; Sun, Qingye; Zhan, Jing; Yang, Yang; Wang, Dan

    2016-07-15

    The oxidization of metal sulfide in tailings causes acid mine drainage. However, it remains unclear whether vegetation prevents the oxidization of metal sulfides. The oxidization characteristics and microbial indices of the tailings in the presence of various plant species were investigated to explore the effects of vegetation on the oxidization of sulfide minerals in tailings. The pH, reducing sulfur, free iron oxides (Fed), chemical oxygen consumption (COC) and biological oxygen consumption (BOC) were measured. Key iron- and sulfur-oxidizing bacteria (Acidithiobacillus spp., Leptospirillum spp. and Thiobacillus spp.) were quantified using real-time PCR. The results indicate that vegetation growing on tailings can effectively prevent the oxidization of sulfide minerals in tailings. A higher pH and reducing-sulfur content and lower Fed were observed in the 0-30 cm depth interval in the presence of vegetation compared to bare tailings (BT). The COC gradually decreased with depth in all of the soil profiles; specifically, the COC rapidly decreased in the 10-20 cm interval in the presence of vegetation but gradually decreased in the BT profiles. Imperata cylindrica (IC) and Chrysopogon zizanoides (CZ) profiles contained the highest BOC in the 10-20 cm interval. The abundance of key iron- and sulfur-oxidizing bacteria in the vegetated tailings were significantly lower than in the BT; in particular, IC was associated with the lowest iron- and sulfur-oxidizing bacterial abundance. In conclusion, vegetation successfully prevented the oxidization of sulfide minerals in the tailings, and Imperata cylindrica is the most effective in reducing the number of iron- and sulfur-oxidizing bacteria and helped to prevent the oxidization of sulfide minerals in the long term. PMID:27093236

  13. The use of biodiesel blends on a non-road generator and its impacts on ozone formation potentials based on carbonyl emissions

    International Nuclear Information System (INIS)

    In this study, emissions of carbonyl compounds from the use B50 and B100 were measured with a non-road diesel generator. A total of 25 carbonyl compounds were identified in the exhaust, including 10 with laboratory-synthesized standards. Formaldehyde, acetaldehyde, and acrolein were found as the most abundant carbonyl compounds emitted for both diesel and biodiesel. The sulphur content of diesel fuels and the source of biodiesel fuels were not found to have a significant impact on the emission of carbonyl compounds. The overall maximum incremental reactivity (MIR) was the highest at 0 kW and slightly increased from 25 to 75 kW. The MIR of B100 was the highest, followed by diesel and B50, which is consistent with the emission rates of total carbonyl compounds. This suggests that the use of biodiesel blends may be more beneficial to the environment than using pure biodiesel. -- Highlights: •Carbonyl compound emission from biodiesel blends combustion on a non-road generator. •25 compounds were identified, including 10 by laboratory-synthesized standards. •Sources of biodiesel have insignificant impacts on carbonyl compounds emission. •Sulphur contents have insignificant impacts on carbonyl compounds emission. •MIR of emitted carbonyls decreases in the following order: B100, diesel, B50. -- The study found that B50 resulted in lower total carbonyl emission rates and ozone formation potential resultant from these compounds, whereas both increased with B100

  14. Experimental constraints on gold and silver solubility in iron sulfides

    Energy Technology Data Exchange (ETDEWEB)

    Pal' yanova, Galina [Institute of Geology and Mineralogy, Siberian Branch of the Russian Academy of Sciences, 3, Koptyuga, Novosibirsk, 630090 (Russian Federation); Novosibirsk State University, Russia, 2, Pirogova, Novosibirsk, 630090 (Russian Federation); Mikhlin, Yuri [Institute of Chemistry and Chemical Technology, Siberian Branch of the Russian Academy of Sciences, Akademgorodok, 50/24, Krasnoyarsk, 660036 (Russian Federation); Kokh, Konstantin, E-mail: k.a.kokh@gmail.com [Institute of Geology and Mineralogy, Siberian Branch of the Russian Academy of Sciences, 3, Koptyuga, Novosibirsk, 630090 (Russian Federation); Novosibirsk State University, Russia, 2, Pirogova, Novosibirsk, 630090 (Russian Federation); Siberian Physical–Technical Institute of Tomsk State University, 1, Novosobornaya, Tomsk, 634050 (Russian Federation); Karmanov, Nick [Institute of Geology and Mineralogy, Siberian Branch of the Russian Academy of Sciences, 3, Koptyuga, Novosibirsk, 630090 (Russian Federation); Seryotkin, Yurii [Institute of Geology and Mineralogy, Siberian Branch of the Russian Academy of Sciences, 3, Koptyuga, Novosibirsk, 630090 (Russian Federation); Novosibirsk State University, Russia, 2, Pirogova, Novosibirsk, 630090 (Russian Federation)

    2015-11-15

    Experiments were performed to determine crystallization of Fe,S-melts (pyriti≿ and troilitic with molar ratio S/Fe ratios of 2 and 1, respectively) containing traces of gold and silver at (Ag/Au){sub wt} ratios varying from 10 to 0.1. The solid products were studied by optical microscopy, scanning electron microscopy, X-ray powder diffraction (XRD), microprobe analysis, and X-ray photoelectron spectroscopy (XPS) in order to reveal the concentration limits of “invisible” gold and silver in magmatic iron sulfides, and to determine the influence of sulfur on forms of precious metals in the Fe–S system with different Ag/Au ratios. Au–Ag phases do not form inclusions but instead concentrate on the grain boundaries in the synthetic pyrrhotite and troilite, while pyrite comprises micro- (1–5 μm) and macroinclusions of Au–Ag alloys and Au–Ag sulfides. In “pyriti≿” systems, the fineness of alloys increases from 650 to 970‰ and the composition of sulfides changes from acanthite (Ag{sub 2}S) to uytenbogaardtite (Ag{sub 3}AuS{sub 2}) and petrovskaite (AgAuS) as the Ag/Au ratio decreases. The concentrations of “invisible” precious metals revealed in troilite were 0.040 ± 0.013 wt.% Au and 0.079 ± 0.016 wt.% Ag. Measured concentrations in pyrite and pyrrhotite were <0.024 wt.% Au and <0.030 wt.% Ag. The surface layers of iron sulfides probed with XPS were enriched in the precious metals, and in silver relative to gold, especially in the systems with Fe/S = 1, probably, due to depletion of the metallic alloy surfaces with gold. Au- and Ag-bearing iron sulfides crystallized primarily from melts may be the source of redeposited phases in hydrothermal and hypergene processes. - Highlights: • The samples of Fe–S–Au–Ag system were synthesized. • Coupled solubility of gold and silver in iron sulfides was specified. • Ag–Au inclusions on surfaces of iron sulfides are likely to be enriched in silver. • Au–Ag sulfides can exist along with

  15. Kinetic studies of cadmium sulfide precipitation from aqueous thiourea solutions

    International Nuclear Information System (INIS)

    Kinetics of cadmium sulfide precipitation by thiourea from aqueous solutions containing ammonia complexes of cadmium(II) under conditions of spontaneous initiation of solid phase within solution volume at temperatures of 298-318 K was studied. It was ascertained that the process activation energy is 77843 J/mol, while the reaction order by initial cadmium complex equals unity. Kinetic equation, which permits control over cadmium sulfide precipitation and preparation of CdS films of desired morphology was derived on the basis of the experimental data

  16. Non-hydrolytic Sol-gel Synthesis of Tin Sulfides

    Science.gov (United States)

    Kaur, Rajvinder

    The non-hydrolytic sol-gel (NHSG) process is an effective low temperature route well known for preparing homogeneous metal oxides. Thermodynamically as well as kinetically favored products, which cannot be prepared with the traditional solid-state routes, can be produced using NHSG. This project is focused on the exploration of NHSG synthesis of binary tin sulfides. In the past few years, metal sulfides have been the subject of significant interest. Much effort has been devoted to understand these materials because of their potential applications in electronic, optical, and superconductor devices.4 Among these materials, tin sulfides are materials of technological importance, which are being explored as semiconductors, anode materials for Li ion batteries, photoconductors, photocatalysts and absorber layer materials in photovoltaic solar cell devices. All of these applications depend upon features like homogeneity, oxidation state, high surface area and purity of the materials. These properties can be difficult to achieve by employing traditional synthetic routes, which require high temperatures due to slow diffusion, limiting the products to thermodynamically stable phases and prohibiting control over properties like particle size and surface area. A variety of low temperature methods are being explored due to the increased demand for such advanced materials. This project is focused on exploring the NHSG approach to synthesize binary tin sulfides, with the main goal of establishing conditions for the targeted synthesis of different tin sulfide polymorphs with controlled particle size. Being non-oxide materials, tin sulfides can be air sensitive, which requires special attention in handling. All reactions were carried out in absence of oxygen. This project explores the reaction of tin halides with thioethers in a dry solvent medium, leading to the formation of tin sulfides. There are a number of synthetic parameters that can be varied for the NHSG approach. A

  17. Experimental constraints on gold and silver solubility in iron sulfides

    International Nuclear Information System (INIS)

    Experiments were performed to determine crystallization of Fe,S-melts (pyriti≿ and troilitic with molar ratio S/Fe ratios of 2 and 1, respectively) containing traces of gold and silver at (Ag/Au)wt ratios varying from 10 to 0.1. The solid products were studied by optical microscopy, scanning electron microscopy, X-ray powder diffraction (XRD), microprobe analysis, and X-ray photoelectron spectroscopy (XPS) in order to reveal the concentration limits of “invisible” gold and silver in magmatic iron sulfides, and to determine the influence of sulfur on forms of precious metals in the Fe–S system with different Ag/Au ratios. Au–Ag phases do not form inclusions but instead concentrate on the grain boundaries in the synthetic pyrrhotite and troilite, while pyrite comprises micro- (1–5 μm) and macroinclusions of Au–Ag alloys and Au–Ag sulfides. In “pyriti≿” systems, the fineness of alloys increases from 650 to 970‰ and the composition of sulfides changes from acanthite (Ag2S) to uytenbogaardtite (Ag3AuS2) and petrovskaite (AgAuS) as the Ag/Au ratio decreases. The concentrations of “invisible” precious metals revealed in troilite were 0.040 ± 0.013 wt.% Au and 0.079 ± 0.016 wt.% Ag. Measured concentrations in pyrite and pyrrhotite were <0.024 wt.% Au and <0.030 wt.% Ag. The surface layers of iron sulfides probed with XPS were enriched in the precious metals, and in silver relative to gold, especially in the systems with Fe/S = 1, probably, due to depletion of the metallic alloy surfaces with gold. Au- and Ag-bearing iron sulfides crystallized primarily from melts may be the source of redeposited phases in hydrothermal and hypergene processes. - Highlights: • The samples of Fe–S–Au–Ag system were synthesized. • Coupled solubility of gold and silver in iron sulfides was specified. • Ag–Au inclusions on surfaces of iron sulfides are likely to be enriched in silver. • Au–Ag sulfides can exist along with native gold in pyrite

  18. Dithiocarbamate Complexes as Single Source Precursors to Metal Sulfide Nanoparticles for Applications in Catalysis

    OpenAIRE

    Roffey, A. R.

    2014-01-01

    Herein we report the solvothermal decomposition of a range of metal dithiocarbamate complexes for the synthesis of metal sulfide nanoparticles. Metal sulfides exist in a variety of structural phases, some of which are known to be catalytically active towards various processes. The aim of this work was to synthesise a variety of different metal sulfide phases for future catalysis testing, particularly the iron sulfide greigite (Fe3S4, a thiospinel containing Fe2+ and Fe3+) which is to be teste...

  19. The solubility of iron sulfides and their role in mass transport in Girdler-Sulfide heavy water plants

    International Nuclear Information System (INIS)

    The solubilities of several iron sulfides, mackinawite FeSsub((1-x)), troilite FeS, pyrrhotite Fesub((1-x))S (monoclinic and hexagonal), and pyrite FeS2 have been determined in aqueous H2S solution at 0.1 MPa and 1.8 MPa H2S pressures between 25 deg and 125 deg C. The dependence of solubility on the pH of the medium has also been studied. It is concluded that since mackinawite is the most soluble of the iron sulfides, and has the highest dissolution rate and the steepest decline in solubility with temperature, its prolonged formation during plant operation should be avoided to minimize iron transport from lower to higher temperature areas in Girdler-Sulfide (G.S.) heavy water plants. This can be achieved by a preconditioning of carbon steel surfaces to convert mackinawite to pyrrhotite and pyrite

  20. Identifying the Prospective Area of Sulfide Groundwater within the Area of Palvantash Oil and Gas Deposit

    Directory of Open Access Journals (Sweden)

    M. R. Zhurayev

    2014-03-01

    Full Text Available This paper describes the methodology of prospecting for sulfide groundwater in the area of Palvantash oil fields. In result of study allowed determining the favorable conditions for the sulfide waters formation, and mapping the areas of different sulfide water concentration. The relatively permeable areas were established and the water borehole positions were recommended.

  1. Sulfide-iron interactions in domestic wastewater from a gravity sewer

    NARCIS (Netherlands)

    Nielsen, A.H.; Lens, P.N.L.; Vollertsen, J.; Hvitved-Jacobsen, Th.

    2005-01-01

    Interactions between iron and sulfide in domestic wastewater from a gravity sewer were investigated with particular emphasis on redox cycling of iron and iron sulfide formation. The concentration ranges of iron and total sulfide in the experiments were 0.4-5.4 mg Fe L-1 and 0-5.1 mg S L-1, respectiv

  2. Thermochemical hydrogen production via a cycle using barium and sulfur - Reaction between barium sulfide and water

    Science.gov (United States)

    Ota, K.; Conger, W. L.

    1977-01-01

    The reaction between barium sulfide and water, a reaction found in several sulfur based thermochemical cycles, was investigated kinetically at 653-866 C. Gaseous products were hydrogen and hydrogen sulfide. The rate determining step for hydrogen formation was a surface reaction between barium sulfide and water. An expression was derived for the rate of hydrogen formation.

  3. 76 FR 64022 - Hydrogen Sulfide; Community Right-to-Know Toxic Chemical Release Reporting

    Science.gov (United States)

    2011-10-17

    ... rule (December 1, 1993, 58 FR 63500). Hydrogen sulfide was listed under the criteria of EPCRA section... EPCRA section 313(d)(2)(B) (see 59 FR 61432, 61433, 61440-61442). Hydrogen sulfide has also been... adding hydrogen sulfide to the EPCRA section 313 list of toxic chemicals (58 FR 63500) (effective...

  4. H2S exposure elicits differential expression of candidate genes in fish adapted to sulfidic and non-sulfidic environments.

    Science.gov (United States)

    Tobler, Michael; Henpita, Chathurika; Bassett, Brandon; Kelley, Joanna L; Shaw, Jennifer H

    2014-09-01

    Disentangling the effects of plasticity, genetic variation, and their interactions on organismal responses to environmental stressors is a key objective in ecological physiology. We quantified the expression of five candidate genes in response to hydrogen sulfide (H2S) exposure in fish (Poecilia mexicana, Poeciliidae) from a naturally sulfide-rich environment as well as an ancestral, non-sulfidic population to test for constitutive and environmentally dependent population differences in gene expression patterns. Common garden raised individuals that had never encountered environmental H2S during their lifetime were subjected to short or long term H2S exposure treatments or respective non-sulfidic controls. The expression of genes involved in responses to H2S toxicity (cytochrome c oxidase, vascular endothelial growth factor, and cytochrome P450-2J6), H2S detoxification (sulfide:quinone oxidoreductase), and endogenous H2S production (cystathionine γ lyase) was determined in both gill and liver tissues by real time PCR. The results indicated complex changes in expression patterns that--depending on the gene--not only differed between organs and populations, but also on the type of H2S exposure. Populations differences, both constitutive and H2S exposure dependent (i.e., plastic), in gene expression were particularly evident for sulfide:quinone oxidoreductase, vascular endothelial growth factor, and to a lesser degree for cytochrome P450-2J6. Our study uncovered putatively adaptive modifications in gene regulation that parallel previously documented adaptive changes in phenotypic traits. PMID:24813672

  5. The structure of Aquifex aeolicus sulfide:quinone oxidoreductase, a basis to understand sulfide detoxification and respiration

    OpenAIRE

    Marcia, Marco; Ermler, Ulrich; Peng, Guohong; Michel, Hartmut

    2009-01-01

    Sulfide:quinone oxidoreductase (SQR) is a flavoprotein with homologues in all domains of life except plants. It plays a physiological role both in sulfide detoxification and in energy transduction. We isolated the protein from native membranes of the hyperthermophilic bacterium Aquifex aeolicus, and we determined its X-ray structure in the “as-purified,” substrate-bound, and inhibitor-bound forms at resolutions of 2.3, 2.0, and 2.9 Å, respectively. The structure is composed of 2 Rossmann doma...

  6. Carbonyl compounds in dining areas, kitchens and exhaust streams in restaurants with varying cooking methods in Kaohsiung, Taiwan.

    Science.gov (United States)

    Cheng, Jen-Hsuan; Lee, Yi-Shiun; Chen, Kang-Shin

    2016-03-01

    Eighteen carbonyl species in C1-C10 were measured in the dining areas, kitchens and exhaust streams of six different restaurant types in Kaohsiung, southern Taiwan. Measured results in the dining areas show that Japanese barbecue (45.06ppb) had the highest total carbonyl concentrations (sum of 18 compounds), followed by Chinese hotpot (38.21ppb), Chinese stir-frying (8.99ppb), Western fast-food (8.22ppb), Chinese-Western mixed style (7.38ppb), and Chinese buffet (3.08ppb), due to their different arrangements for dining and cooking spaces and different cooking methods. On average, low carbon-containing species (C1-C4), e.g., formaldehyde, acetaldehyde, acetone and butyraldehyde were dominant and contributed 55.01%-94.52% of total carbonyls in the dining areas of all restaurants. Meanwhile, Chinese-Western mixed restaurants (45.48ppb) had high total carbonyl concentrations in kitchens mainly because of its small kitchen and poor ventilation. However, high carbon-containing species (C5-C10) such as hexaldehyde, heptaldehyde and nonanaldehyde (16.62%-77.00% of total carbonyls) contributed comparatively with low carbon-containing compounds (23.01%-83.39% of total carbonyls) in kitchens. Furthermore, Chinese stir-frying (132.10ppb), Japanese barbecue (125.62ppb), Western fast-food (122.67ppb), and Chinese buffet (119.96ppb) were the four restaurant types with the highest total carbonyl concentrations in exhaust streams, indicating that stir-frying and grilling are inclined to produce polluted gases. Health risk assessments indicate that Chinese hotpot and Japanese barbecue exceeded the limits of cancer risk (10(-6)) and hazard index (=1), mainly due to high concentrations of formaldehyde. The other four restaurants were below both limits. PMID:26969068

  7. Protein conjugated with aldehydes derived from lipid peroxidation as an independent parameter of the carbonyl stress in the kidney damage

    Directory of Open Access Journals (Sweden)

    Medina-Navarro Rafael

    2011-11-01

    Full Text Available Abstract Background One of the well-defined and characterized protein modifications usually produced by oxidation is carbonylation, an irreversible non-enzymatic modification of proteins. However, carbonyl groups can be introduced into proteins by non-oxidative mechanisms. Reactive carbonyl compounds have been observed to have increased in patients with renal failure. In the present work we have described a procedure designed as aldehyde capture to calculate the protein carbonyl stress derived solely from lipid peroxidation. Methods Acrolein-albumin adduct was prepared as standard at alkaline pH. Rat liver microsomal membranes and serum samples from patients with diabetic nephropathy were subjected to the aldehyde capture procedure and aldol-protein formation. Before alkalinization and incubation, samples were precipitated and redisolved in 6M guanidine. The absorbances of the samples were read with a spectrophotometer at 266 nm against a blank of guanidine. Results Evidence showed abundance of unsaturated aldehydes derived from lipid peroxidation in rat liver microsomal membranes and in the serum of diabetic patients with advanced chronic kidney disease. Carbonyl protein and aldol-proteins resulted higher in the diabetic nephropathy patients (p Conclusion The aldehyde-protein adduct represents a non oxidative component of carbonyl stress, independent of the direct amino acid oxidation and could constitute a practical and novelty strategy to measure the carbonyl stress derived solely from lipid peroxidation and particularly in diabetic nephropathy patients. In addition, we are in a position to propose an alternative explanation of why alkalinization of urine attenuates rhabdomyolysis-induced renal dysfunction.

  8. Alloy selection for sulfidation: oxidation resistance in coal gasification environments

    Energy Technology Data Exchange (ETDEWEB)

    Bradshaw, R.W.; Stoltz, R.E.

    1980-01-01

    A series of iron-nickel-chromium and nickel-chromium alloys were studied for their combined sulfidation-oxidation resistance in simulated coal gasification environments. All alloys contained a minimum of 20 w/o chromium, and titanium and aluminum in the range 0 to 4 w/o. Corrosion resistance was evaluated at 1255/sup 0/K (1800/sup 0/F) in both high BTU and low BTU coal gasification atmospheres with 1 v/o H/sub 2/S. Titanium at levels greater than 1 w/o imparted significant sulfidation resistance due to an adherent, solid solution chromium-titanium oxide layer which prevented sulfur penetration. Aluminum was less effective in preventing sulfidation since surface scales were not adherent. Of the commercial alloys tested, Nimomic 81, Pyromet 31, IN801, and IN825 exhibited the best overall corrosion resistance. However, futher alloy development, tailored to produce solid solution chromium-titanium oxide scales, may lead to alloys with greater sulfidation-oxidation resistance than those investigated here.

  9. Adsorption characteristics of thiobacillus ferrooxidans on surface of sulfide minerals

    Institute of Scientific and Technical Information of China (English)

    LIU Jian-she; XIE Xue-hui; LI Bang-mei; DONG Qing-hai

    2005-01-01

    By using thiobacillus ferrooxidans (T.f) from Qixiashan, Hubei Province, China, the adsorption characteristics of T.f on surface of sulfide mineral were studied. The influences of adsorption time, pH value, temperature, initial inoculated concentration of bacteria, concentration of sulfide mineral powder, and variety of minerals on the adsorption characteristics were firstly investigated by using the ninhydrin colorimetric method, and the changes of contact angles and Zeta potentials of mineral surface during the bacterial adsorption were then determined. The results show that when the leaching experiments are performed for a long time from several days to a month, the maximal quantity of adsorption of T.f on the surface of pyrite is obtained under the following conditions: leaching for 20 d, pH value in range of 1-2 and temperature at 30 ℃, respectively; when the bio-leaching experiments are performed for a shorter leaching time, the maximal quantity of adsorption is obtained under the conditions: bio-leaching for 2 h, at 2.4×10 7 cell/mL of initial inoculated bacteria concentration, and at 10% of mineral powder concentration; and the adsorption quantities are different form one sulfide mineral to another, and the adsorption of T.f on the surface of sulfide minerals includes three phases: increasing phase, stationary phase and decreasing phase.

  10. Synthesis and photovoltaic application of coper (I) sulfide nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Yue; Wadia, Cyrus; Ma, Wanli; Sadtler, Bryce; Alivisatos, A.Paul

    2008-06-24

    We present the rational synthesis of colloidal copper(I) sulfide nanocrystals and demonstrate their application as an active light absorbing component in combination with CdS nanorods to make a solution-processed solar cell with 1.6percent power conversion efficiency on both conventional glass substrates and flexible plastic substrates with stability over a 4 month testing period.

  11. 40 CFR 721.5075 - Mixed methyltin mercaptoester sulfides.

    Science.gov (United States)

    2010-07-01

    ... sulfides (PMN P-92-177) is subject to reporting under this section for the significant new uses described.... Requirements as specified in § 721.85 (a)(1) and (a)(2) (only in a facility permitted to landfill Resources Conservation and Recovery Act (RCRA) hazardous wastes with the landfill operated in accordance with subtitle...

  12. Solar thermal extraction of copper and zinc from sulfides

    Energy Technology Data Exchange (ETDEWEB)

    Guesdon, C.; Sturzenegger, M.

    2002-03-01

    A novel approach for extracting metals from metal sulfides is proposed. Key feature is the use of concentrated solar radiation to directly convert metal sulfides into the metal and sulfur. Such processes have the potential to produce metals with virtually zero emission of SO{sub 2} and CO{sub 2}. The feasibility of such a solar thermal extraction has been evaluated for zinc sulfide (Zn S) and copper(I)sulfide Cu{sub 2}S. Thermodynamic calculations suggest that for both processes heat recovery from the hot product is required to implement a viable process. Decomposition experiments have indicated that the high reactivity of Zn and S is not compatible with the energy requirement of heat recovery and that quenching will likely be needed to collect Zn. As an alternative, the addition of a mixture of O{sub 2} and steam (chemical quenching) is discussed. The extraction of Cu from Cu{sub 2}S appears less critical: Experiments under N{sub 2} revealed the formation of metallic Cu already at 1323 K. Natural separation of gaseous S from liquid Cu successfully prevents recombination of the two products and at least partial heat recovery can be envisaged. (author)

  13. ISE Analysis of Hydrogen Sulfide in Cigarette Smoke

    Science.gov (United States)

    Li, Guofeng; Polk, Brian J.; Meazell, Liz A.; Hatchett, David W.

    2000-08-01

    Many advanced undergraduate analytical laboratory courses focus on exposing students to various modern instruments. However, students rarely have the opportunity to construct their own analytical tools for solving practical problems. We designed an experiment in which students are required to build their own analytical module, a potentiometric device composed of a Ag/AgCl reference electrode, a Ag/Ag2S ion selective electrode (ISE), and a pH meter used as voltmeter, to determine the amount of hydrogen sulfide in cigarette smoke. Very simple techniques were developed for constructing these electrodes. Cigarette smoke is collected by a gas washing bottle into a 0.1 M NaOH solution. The amount of sulfide in the cigarette smoke solution is analyzed by standard addition of sulfide solution while monitoring the response of the Ag/Ag2S ISE. The collected data are further evaluated using the Gran plot technique to determine the concentration of sulfide in the cigarette smoke solution. The experiment has been successfully incorporated into the lab course Instrumental Analysis at Georgia Institute of Technology. Students enjoy the idea of constructing an analytical tool themselves and applying their classroom knowledge to solve real-life problems. And while learning electrochemistry they also get a chance to visualize the health hazard imposed by cigarette smoking.

  14. A coumarin-based colorimetric fluorescent probe for hydrogen sulfide

    Indian Academy of Sciences (India)

    Yanqiu Yang; Yu Liu; Liang Yang; Jun Liu; Kun Li; Shunzhong Luo

    2015-03-01

    A coumarin-based fluorescent probe for selective detection of hydrogen sulfide (H2S) is presented. This `off–on’ probe exhibited high selectivity towards H2S in aqueous solution with a detection limit of 30 nM. Notably, because of its dual nucleophilicity, the probe could avoid the interference of thiols and other sulfur containing compounds.

  15. Potential Applications of Hydrogen Sulfide-Induced Suspended Animation

    NARCIS (Netherlands)

    H. Aslami; M.J. Schultz; N.P. Juffermans

    2009-01-01

    A suspended animation-like state has been induced in rodents with the use of hydrogen sulfide, resulting in hypothermia with a concomitant reduction in metabolic rate. Also oxygen demand was reduced, thereby protecting against hypoxia. Several therapeutic applications of induction of a hibernation-l

  16. Carbon-supported iron and iron-molybdenum sulfide catalysts

    International Nuclear Information System (INIS)

    The main objective was to describe the relations between the characteristics (composition and dispersion) of the actual sulfide phase and the catalytic activity. Attention was also paid to the influence of preparational aspects on these characteristics. The catalysts were characterized using in-situ Moessbauer spectroscopy down to 2.0 K. 254 refs.; 47 figs.; 22 tabs

  17. Hydrogen sulfide release from dairy manure storages containing gypsum bedding

    Science.gov (United States)

    Recycled gypsum products can provide a cost-effective bedding alternative for dairy producers. Manufacturers report reduced odors, moisture and bacteria in the stall environment when compared to traditional bedding. Gypsum provides a sulfate source that can be converted to hydrogen sulfide under ana...

  18. Luminescence in Sulfides: A Rich History and a Bright Future

    Directory of Open Access Journals (Sweden)

    Philippe F. Smet

    2010-04-01

    Full Text Available Sulfide-based luminescent materials have attracted a lot of attention for a wide range of photo-, cathodo- and electroluminescent applications. Upon doping with Ce3+ and Eu2+, the luminescence can be varied over the entire visible region by appropriately choosing the composition of the sulfide host. Main application areas are flat panel displays based on thin film electroluminescence, field emission displays and ZnS-based powder electroluminescence for backlights. For these applications, special attention is given to BaAl2S4:Eu, ZnS:Mn and ZnS:Cu. Recently, sulfide materials have regained interest due to their ability (in contrast to oxide materials to provide a broad band, Eu2+-based red emission for use as a color conversion material in white-light emitting diodes (LEDs. The potential application of rare-earth doped binary alkaline-earth sulfides, like CaS and SrS, thiogallates, thioaluminates and thiosilicates as conversion phosphors is discussed. Finally, this review concludes with the size-dependent luminescence in intrinsic colloidal quantum dots like PbS and CdS, and with the luminescence in doped nanoparticles.

  19. 40 CFR 425.04 - Applicability of sulfide pretreatment standards.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Applicability of sulfide pretreatment standards. 425.04 Section 425.04 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS LEATHER TANNING AND FINISHING POINT SOURCE CATEGORY General Provisions § 425.04 Applicability of...

  20. Estimation of bacterial hydrogen sulfide production in vitro

    Directory of Open Access Journals (Sweden)

    Amina Basic

    2015-06-01

    Full Text Available Oral bacterial hydrogen sulfide (H2S production was estimated comparing two different colorimetric methods in microtiter plate format. High H2S production was seen for Fusobacterium spp., Treponema denticola, and Prevotella tannerae, associated with periodontal disease. The production differed between the methods indicating that H2S production may follow different pathways.

  1. Support Effect in the Hydrodesulfurization of Thiophene over Rhodium Sulfide

    Czech Academy of Sciences Publication Activity Database

    Kaluža, Luděk; Vít, Zdeněk; Zdražil, Miroslav

    2010-01-01

    Roč. 101, č. 1 (2010), s. 63-72. ISSN 1878-5190 R&D Projects: GA ČR GA104/09/0751 Institutional research plan: CEZ:AV0Z40720504 Keywords : hydrodesulfurization * thiophene * rhodium sulfide Subject RIV: CI - Industrial Chemistry, Chemical Engineering

  2. Sulfide Oxidation in the Anoxic Black-Sea Chemocline

    DEFF Research Database (Denmark)

    JØRGENSEN, BB; FOSSING, H.; WIRSEN, CO; JANNASCH, HW

    1991-01-01

    The depth distributions of O2 and H2S and of the activity of chemical or bacterial sulfide oxidation were studied in the chemocline of the central Black Sea. Relative to measurements from earlier studies, the sulfide zone had moved upwards by 20-50 m and was now (May 1988) situated at a depth of 81...... per day, occurred in anoxic water at the top of the sulfide zone concurrent with the highest rates of dark CO2 assimilation. The main soluble oxidized products of sulfide were thiosulfate (68-82%) and sulfate. Indirect evidence was presented for the formation of elemental sulfur which accumulated to a...... that the measured H2S oxidation rates were 4-fold higher than could be explained by the downward flux of organic carbon and too high to balance the availability of electron acceptors such as oxidized iron or manganese. A nitrate maximum at the lower boundary of the O2 zone did not extend down to the...

  3. New Findings in Hydrogen Sulfide Related Corrosion of Concrete Sewers

    DEFF Research Database (Denmark)

    Nielsen, Asbjørn Haaning; Jensen, Henriette Stokbro; Hvitved-Jacobsen, Thorkild;

    2009-01-01

    This paper summarizes major findings of a long-term study of hydrogen sulfide gas (H2S) adsorption and oxidation on concrete and plastic sewer pipe surfaces. The processes have been studied using a pilot-scale setup designed to replicate conditions in a gravity sewer located downstream of a force...

  4. Formation and emissions of carbonyls during and following gas-phase ozonation of indoor materials

    Science.gov (United States)

    Poppendieck, D. G.; Hubbard, H. F.; Weschler, C. J.; Corsi, R. L.

    Ozone concentrations that are several orders of magnitude greater than typical urban ambient concentrations are necessary for gas-phase ozonation of buildings, either for deodorization or for disinfection of biological agents. However, there is currently no published literature on the interaction of building materials and ozone under such extreme conditions. It would be useful to understand, for example in the case of building re-occupation planning, what types and amounts of reaction products may form and persist in a building after ozonation. In this study, 24 materials were exposed to ozone at concentrations of 1000 ppm in the inlet stream of experimental chambers. Fifteen target carbonyls were selected and measured as building ozonation by-products (BOBPs). During the 36 h that include the 16 h ozonation and 20 h persistence phase, the total BOBP mass released from flooring and wall coverings ranged from 1 to 20 mg m -2, with most of the carbonyls being of lower molecular weight (C 1-C 4). In contrast, total BOBP mass released from wood-based products ranged from 20 to 100 mg m -2, with a greater fraction of the BOBPs being heavier carbonyls (C 5-C 9). The total BOBP mass released during an ozonation event is a function of both the total surface area of the material and the BOBP emission rate per unit area of material. Ceiling tile, carpet, office partition, and gypsum wallboard with flat latex paint often have large surface areas in commercial buildings and these same materials exhibited relatively high BOBP releases. The greatest overall BOBP mass releases were observed for three materials that building occupants might have significant contact with: paper, office partition, and medium density fiberboard, e.g., often used in office furniture. These materials also exhibited extended BOBP persistence following ozonation; some BOBPs (e.g., nonanal) persist for months or more at emission rates large enough to result in indoor concentrations that exceed their odor

  5. Sol–gel method as a way of carbonyl iron powder surface modification for interaction improvement

    Energy Technology Data Exchange (ETDEWEB)

    Małecki, P., E-mail: pawel.malecki@pwr.edu.pl [Polymer Engineering and Technology Division, W-3, Wrocław University of Technology, Smoluchowskiego 25, 50 370 Wrocław (Poland); Kolman, K.; Pigłowski, J. [Polymer Engineering and Technology Division, W-3, Wrocław University of Technology, Smoluchowskiego 25, 50 370 Wrocław (Poland); Kaleta, J. [Department of Mechanics, Materials Science and Engineering, W-10, Wrocław University of Technology, Smoluchowskiego 25, 50-370 Wrocław (Poland); Krzak, J., E-mail: justyna.krzak@pwr.edu.pl [Department of Mechanics, Materials Science and Engineering, W-10, Wrocław University of Technology, Smoluchowskiego 25, 50-370 Wrocław (Poland)

    2015-03-15

    This article presents a method for modification of carbonyl iron particles’ surface (CIP), (d{sub 50}=4–9 µm) by silica coatings obtained using the sol–gel method. Reaction parameters were determined to obtain dry magnetic powder with homogeneous silica coatings without further processing and without any by-product in the solid or liquid phase. This approach is new among the commonly used methods of silica coating of iron particles. No attempt has been made to cover a carbonyl iron surface by silica in a waste-free method, up to date. In the current work two different silica core/shell structures were made by the sol–gel process, based on different silica precursors: tetraethoxy-silane (TEOS) and tetramethoxy-silane (TMOS). The dependence between the synthesis procedure and thickness of silica shell covering carbonyl iron particles has been described. Surface morphology of the modified magnetic particles and the coating thickness were characterized with the use of scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Determination of the physicochemical structure of the obtained materials was performed by the energy-dispersive X-ray spectroscope (EDS), and the infrared technique (IR). The surface composition was analyzed using X-ray photoelectron spectroscopy (XPS). Additionally, distribution of particle size was measured using light microscopy. The new, efficient process of covering micro-size CIP with a nanometric silica layer was shown. Results of a performed analysis confirm the effectiveness of the presented method. - Highlights: • Proper covering CIP by sol–gel silica layer avoids agglomeration. • A new solid waste-free method of CIP coating is proposed. • Examination of the properties of modified CIP in depends on washing process. • Coatings on CIP particles doesn’t change the magnetic properties of particles.

  6. Sol–gel method as a way of carbonyl iron powder surface modification for interaction improvement

    International Nuclear Information System (INIS)

    This article presents a method for modification of carbonyl iron particles’ surface (CIP), (d50=4–9 µm) by silica coatings obtained using the sol–gel method. Reaction parameters were determined to obtain dry magnetic powder with homogeneous silica coatings without further processing and without any by-product in the solid or liquid phase. This approach is new among the commonly used methods of silica coating of iron particles. No attempt has been made to cover a carbonyl iron surface by silica in a waste-free method, up to date. In the current work two different silica core/shell structures were made by the sol–gel process, based on different silica precursors: tetraethoxy-silane (TEOS) and tetramethoxy-silane (TMOS). The dependence between the synthesis procedure and thickness of silica shell covering carbonyl iron particles has been described. Surface morphology of the modified magnetic particles and the coating thickness were characterized with the use of scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Determination of the physicochemical structure of the obtained materials was performed by the energy-dispersive X-ray spectroscope (EDS), and the infrared technique (IR). The surface composition was analyzed using X-ray photoelectron spectroscopy (XPS). Additionally, distribution of particle size was measured using light microscopy. The new, efficient process of covering micro-size CIP with a nanometric silica layer was shown. Results of a performed analysis confirm the effectiveness of the presented method. - Highlights: • Proper covering CIP by sol–gel silica layer avoids agglomeration. • A new solid waste-free method of CIP coating is proposed. • Examination of the properties of modified CIP in depends on washing process. • Coatings on CIP particles doesn’t change the magnetic properties of particles

  7. Deep-blue phosphorescence from perfluoro carbonyl-substituted iridium complexes.

    Science.gov (United States)

    Lee, Sunghun; Kim, Seul-Ong; Shin, Hyun; Yun, Hui-Jun; Yang, Kiyull; Kwon, Soon-Ki; Kim, Jang-Joo; Kim, Yun-Hi

    2013-09-25

    The new deep-blue iridium(III) complexes, (TF)2Ir(pic), (TF)2Ir(fptz), (HF)2Ir(pic), and (HF)2Ir(fptz), consisting of 2',4″-difluororphenyl-3-methylpyridine with trifluoromethyl carbonyl or heptafluoropropyl carbonyl at the 3' position as the main ligand and a picolinate or a trifluoromethylated-triazole as the ancillary ligand, were synthesized and characterized for applications in organic light-emitting diodes (OLEDs). Density function theory (DFT) calculations showed that these iridium complexes had a wide band gap, owing to the introduction of the strong electron withdrawing perfluoro carbonyl group. Time-dependent DFT (TD-DFT) calculations suggested that their lowest triplet excited state was dominated by a HOMO → LUMO transition and that the contribution of the metal-to-ligand charge transfer (MLCT) was higher than 34% for all four complexes, indicating that strong spin-orbit coupling exists in the complexes. The 10 wt % (TF)2Ir(pic) doped 9-(3-(9H-carbazole-9-yl)phenyl)-3-(dibromophenylphosphoryl)-9H-carbazole (mCPPO1) film exhibited the highest photoluminescence quantum yield of 74 ± 3% among the films based on the four complexes. Phosphorescent OLEDs based on (TF)2Ir(pic) and (TF)2Ir(fptz) exhibited maximum external quantum efficiencies of 17.1% and 8.4% and Commission Internationale de l'Eclairage (CIE) coordinates of (0.141, 0.158) and (0.147, 0.116), respectively. These CIE coordinates represent some of the deepest blue emissions ever achieved from phosphorescent OLEDs with considerably high EQEs. PMID:23998654

  8. STUDY OF CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE OVER A BIDENTATE POLYMER BOUND CIS-DICARBONYLRHODIUM COMPLEX AS CATALYST

    Institute of Scientific and Technical Information of China (English)

    WANG Xiaojun; LIU Zhongyang; PAN Pinglai; YUAN Guoqing

    1996-01-01

    Copolymer of 2-vinylpyridine and vinylacetate coordinated with dicarbonylrhodium used as a catalyst for carbonylation of methanol to acetic acid and anhydride has been studied. The structural characteristics of the copolymer ligand and complex, and the influences of the reaction conditions on the carbonylation catalyzed by this polymer complex have been investigated. In comparison with small molecule catalyst of Rh complex, the bidentate copolymer coordinated complex has better thermal stability. The reaction mechanism of the carbonylation reaction is also illustrated.

  9. A green synthesis of α,β-unsaturated carbonyl compounds from glyceraldehyde acetonide

    Directory of Open Access Journals (Sweden)

    Cláudia O. Veloso

    2011-01-01

    Full Text Available The catalytic behavior of Cs-exchanged and Cs-impregnated zeolites (X and Y was studied using the Knoevenagel condensation between glyceraldehyde acetonide and ethyl acetoacetate in order to produce the corresponding α,β-unsaturated carbonyl compound that is an important intermediate for fine chemicals. The influence of reaction temperature, type of zeolite, and basicity of the sites on the catalytic behavior of the samples was evaluated. All zeolites were active for the studied reaction. The formation of the main condensation product was favored at lower reaction temperatures. Products of further condensations were also observed especially for samples that were only dried before catalytic test.

  10. LASER-INDUCED DECOMPOSITION OF METAL CARBONYLS FOR CHEMICAL VAPOR DEPOSITION OF MICROSTRUCTURES

    OpenAIRE

    Tonneau, D.; Auvert, G.; Pauleau, Y.

    1989-01-01

    Tungsten and nickel carbonyls were used to produce metal microstructures by laser-induced chemical vapor deposition (CVD) on various substrates. The deposition rate of microstructures produced by thermodecomposition of W(CO)6 on Si substrates heated with a cw Ar+ laser beam was relatively low (10 to 30 nm/s) even at high temperatures (above 900°C). Ni microstructures were deposited on quartz substrates irradiated with a CO2 laser beam. Relatively high laser powers were needed to heat the Ni s...

  11. Calculation of High Frequency Complex Permeability of Carbonyl Iron Flakes in a Nomagnetic Matrix

    Institute of Scientific and Technical Information of China (English)

    WEN Fu-Sheng; QIAO Liang; YI Hai-Bo; ZHOU Dong; LI Fa-Shen

    2008-01-01

    The carbonyl iron flakes are fabricated by high-energy ball milling.The effective permeability is measured and calculated for the composite consisting of flakes embedded in a nonmagnetic matrix.The magnetic flakes with a shape anisotropy and random spatial distribution of normal direction are considered to calculate the complex permeability of magnetic flake materials.Its analytical model is derived from the Landau-Lifshitz- Gilbert equation and Bruggeman's effective medium theory.The calculated results agree well with the experiment.

  12. Non-Enzymatic Modification of Aminophospholipids by Carbonyl-Amine Reactions

    Directory of Open Access Journals (Sweden)

    Reinald Pamplona

    2013-02-01

    Full Text Available Non-enzymatic modification of aminophospholipids by lipid peroxidation-derived aldehydes and reducing sugars through carbonyl-amine reactions are thought to contribute to the age-related deterioration of cellular membranes and to the pathogenesis of diabetic complications. Much evidence demonstrates the modification of aminophospholipids by glycation, glycoxidation and lipoxidation reactions. Therefore, a number of early and advanced Maillard reaction-lipid products have been detected and quantified in different biological membranes. These modifications may be accumulated during aging and diabetes, introducing changes in cell membrane physico-chemical and biological properties.

  13. Electromagnetic properties of carbonyl iron and their microwave absorbing characterization as filler in silicone rubber

    Indian Academy of Sciences (India)

    Yuping Duan; Guofang Li; Lidong Liu; Shunhua Liu

    2010-10-01

    The complex permittivity, permeability and microwave-absorbing properties of rubber composites filled with carbonyl iron are measured at frequencies from 2–18 GHz. The results indicate that the reflection loss peak shifts towards low frequency region with increasing layer thickness or increasing weight concentration. The minimum reflection loss value of –23.06 dB was obtained at 3.3 GHz for the composites with 80% wt. These results show that the composites possess good microwave absorbing ability in both low- and highfrequency bands.

  14. An air-tolerant approach to the carbonylative Suzuki-Miyaura coupling: applications in isotope labeling.

    Science.gov (United States)

    Ahlburg, Andreas; Lindhardt, Anders T; Taaning, Rolf H; Modvig, Amalie E; Skrydstrup, Troels

    2013-10-18

    Carbonylative Suzuki-Miyaura coupling conditions have been developed that proceed without the exclusion of oxygen and in the presence of nondegassed and nondried solvents. By adapting the method to a two-chamber setup, the direct handling of carbon monoxide, produced from stable CO precursors, is avoided. The protocol afforded the desired benzophenones with excellent functional group tolerance and in good yields. Substituting the CO precursor, in the CO-producing chamber, with its carbon-13 labeled version generated the corresponding carbon-13 labeled benzophenones. Finally, the developed system was applied in the synthesis and isotope labeling of two pharmaceuticals, nordazepam and Tricor. PMID:24004340

  15. Chemical reactions in organic monomolecular layers. Condensation of hydrazine on carbonyl functions

    International Nuclear Information System (INIS)

    Evidence is given for chemical reactions of hydrazine (NH2-NH2) with different carbonyl functional groups of organic molecules in the solid state, in monomolecular layer structures. The condensation of hydrazine with these molecules leads to conjugated systems by bridging the N-N links, to cyclizations, and also to polycondensations. The reactions investigated were followed up by infrared spectrophotometry, by transmission and metallic reflection. These chemical reactions revealed in the solid phase constitute a polycondensation procedure which is valuable in obtaining organized polymers in monomolecular layers

  16. Multiband microwave absorption films based on defective multiwalled carbon nanotubes added carbonyl iron/acrylic resin

    Science.gov (United States)

    Li, Yong; Chen, Changxin; Pan, Xiaoyan; Ni, Yuwei; Zhang, Song; Huang, Jie; Chen, Da; Zhang, Yafei

    2009-05-01

    Defective multiwalled carbon nanotubes (MWCNTs) were introduced to the carbonyl iron (CI) based composites to improve its microwave absorption by a simple ultrasonic mixing process. The electromagnetic parameters were measured in the 2-18 GHz range. Microwave absorption of CI based composites with 2 mm in thickness was evidently enhanced by adding as little as 1.0 wt% defective MWCNTs with two well separated absorption peaks exceeding -20 dB, as compared with that of pure CI based and defective MWCNTs composites. The enhancement mechanism is thought due to the interaction and better electromagnetic match between defective MWCNTs and ferromagnetic CI particles.

  17. Inactivation of cellular enzymes by carbonyls and protein-bound glycation/glycoxidation products

    DEFF Research Database (Denmark)

    Morgan, Philip E; Dean, Roger T; Davies, Michael Jonathan

    2002-01-01

    glycolaldehyde and hydroxyacetone. Incubation of these enzymes with proteins that had been preglycated with methylglyoxal, but not glucose, also resulted in significant time- and concentration-dependent inhibition with both isolated enzymes and cell lysates. This inhibition was not metal ion, oxygen, superoxide...... detection of cross-linked materials on protein gels. Though direct comparison of the extent of inhibition induced by free versus protein-bound carbonyls was not possible, the significantly higher concentrations of the latter materials over the former in diabetic plasma and cells lead us to suggest that...

  18. Cytoprotective Effects of Hydrophilic and Lipophilic Extracts of Pistacia vera against Oxidative Versus Carbonyl Stress in Rat Hepatocytes.

    Science.gov (United States)

    Shahraki, Jafar; Zareh, Mona; Kamalinejad, Mohammad; Pourahmad, Jalal

    2014-01-01

    This study was conducted to evaluate the cytoprotection of various extracts and bioactive compounds found in Pistacia vera againts cytotoxicity, ROS formation, lipid peroxidation, protein carbonylation, mitochondrial and lysosomal membrane damages in cell toxicity models of diabetes related carbonyl (glyoxal) and oxidative stress (hydroperoxide). Methanol, water and ethyl acetate were used to prepare crude pistachios extracts, which were then used to screen for in-vitro cytoprotection of freshly isolated rat hepatocytes against these toxins. The order of protection by Pistacia vera extracts against both hydroperoxide induced oxidative stress (ROS formation) and glyoxal induced protein carbonylation was: pistachio methanolic extract >pistachio water extract, gallic acid, catechin> α-tochoferol and pistachio ethyl acetate extract. Finally due to higher protection achieved by methanolic extract even compared to sole pretreatment of gallic acid, catechin or α-tochoferol, we suggest that cytoprotection depends on the variety of polar and non-polar compounds found in methanolic extract, it is likely that multiple cytoprotective mechanisms are acting against oxidative and carbonyl induced cytotoxicity. To our knowledge, we are the first to report the cytoprotective activity of Pistacia vera extracts against oxidative and carbonyl stress seen in type 2 diabetes hepatocytes model. PMID:25587316

  19. Engineered Trx2p industrial yeast strain protects glycolysis and fermentation proteins from oxidative carbonylation during biomass propagation

    Directory of Open Access Journals (Sweden)

    Gómez-Pastor Rocío

    2012-01-01

    Full Text Available Abstract Background In the yeast biomass production process, protein carbonylation has severe adverse effects since it diminishes biomass yield and profitability of industrial production plants. However, this significant detriment of yeast performance can be alleviated by increasing thioredoxins levels. Thioredoxins are important antioxidant defenses implicated in many functions in cells, and their primordial functions include scavenging of reactive oxygen species that produce dramatic and irreversible alterations such as protein carbonylation. Results In this work we have found several proteins specifically protected by yeast Thioredoxin 2 (Trx2p. Bidimensional electrophoresis and carbonylated protein identification from TRX-deficient and TRX-overexpressing cells revealed that glycolysis and fermentation-related proteins are specific targets of Trx2p protection. Indeed, the TRX2 overexpressing strain presented increased activity of the central carbon metabolism enzymes. Interestingly, Trx2p specifically preserved alcohol dehydrogenase I (Adh1p from carbonylation, decreased oligomer aggregates and increased its enzymatic activity. Conclusions The identified proteins suggest that the fermentative capacity detriment observed under industrial conditions in T73 wine commercial strain results from the oxidative carbonylation of specific glycolytic and fermentation enzymes. Indeed, increased thioredoxin levels enhance the performance of key fermentation enzymes such as Adh1p, which consequently increases fermentative capacity.

  20. Sulfide intrusion in the tropical seagrasses Thalassia testudinum and Syringodium filiforme

    DEFF Research Database (Denmark)

    Holmer, Marianne; Pedersen, Ole; Krause-Jensen, Dorte;

    2009-01-01

    sediment-derived sulfides. The sulfide intrusion was negatively correlated to the turnover of sulfides in the sediments regulated by both plant parameters and sediment sulfur pools. Sediment iron content played an indirect role by affecting sulfide turnover rates. Leaf production was negatively correlated...

  1. Blood parameters and metabolites in the teleost fish Colossoma macropomum exposed to sulfide or hypoxia.

    Science.gov (United States)

    Affonso, E G; Polez, V L P; Corrêa, C F; Mazon, A F; Araújo, M R R; Moraes, G; Rantin, F T

    2002-11-01

    Juvenile tambaqui, Colossoma macropomum, were exposed to sulfide and hypoxia for 12, 24, 48 and 96 h. Hemoglobin concentrations, red blood cell counts, and mean cell hemoglobin, were higher at 12 h in fish exposed to hypoxia. However, control fish and those exposed to sulfide and hypoxia had lower red blood cell count, hemoglobin concentration and hematocrit at 96 h. Methemoglobin was higher than in the controls, probably due to the hypoxemia induced by these stressors. Sulfhemoglobin was not detected in significant amounts in the blood of fish exposed to sulfide (in vivo), yet hemoglobin converted into sulfhemoglobin at 1-15 mM sulfide in vitro. Anaerobic metabolism seemed to be an important mechanism for adapting to sulfide exposure and blood pH returned to control values after 24 h of sulfide, preventing acidosis. The high sulfide tolerance in tambaqui is associated with its high tolerance to hypoxia. PMID:12379422

  2. Conversion kinetics for smelt anions: cyanate and sulfide

    Energy Technology Data Exchange (ETDEWEB)

    DeMartini, N.

    2004-07-01

    Cyanate and sulfide are two anions found in the molten salts (smelt) from the kraft recovery boiler of the chemical recovery cycle. Their concentrations in smelt are significantly different, as are their origins. The concentration of cyanate in smelt ranges between 0.4 and 2.1 g OCN{sup -}/kg smelt while the concentration of sulfide ranges between 78 and 115 g S{sup 2-}/kg smelt. Cyanate is a by-product of black liquor combustion. It is formed from organic nitrogen compounds in black liquor during the char burning stage. The charge of the cyanate anion is balanced by the alkali metals found in smelt, namely sodium and potassium. It has been found that the nitrogen in cyanate represents about 30% of the nitrogen entering the recovery boiler with the black liquor. This flow is similar in magnitude to the flows of black liquor nitrogen exiting the recovery boiler as the gaseous compounds NO and N{sub 2}. The method for cyanate analysis used in this work is presented in the Methods chapter of this thesis and Paper I. The results from nitrogen balances at three European kraft pulp mills are discussed in this thesis and Papers II and III, with a focus on the fate of cyanate in the recovery boiler and recausticizing process. Cyanate exits the recovery boiler with the smelt and reacts to form ammonia in the recausticizing solutions of the chemical recovery cycle. Papers IV and V of this thesis focus on the rate of ammonia formation from cyanate in model solutions and in kraft green liquors. The experiments were carried out at temperatures of 80 to 95 deg C, which are temperatures similar to those found in the recausticizing process of a kraft pulp mill. The kinetic studies help clarify the catalytic effect of bicarbonate. A rate equation applicable for use in describing ammonia formation from cyanate in highly alkaline solutions such as pulp mill recovery streams is presented. The sulfide anion, on the other hand, is a desired product of black liquor combustion as the

  3. Enhanced microwave absorbing properties and heat resistance of carbonyl iron by electroless plating Co

    International Nuclear Information System (INIS)

    Co coated carbonyl iron particles (Co (CI)) are fabricated through electroless plating method, and the electromagnetic microwave absorbing properties are investigated in the frequencies during 8.2–12.4 GHz. The complex permittivity of CI particles after electroless plating Co is higher than that of raw CI particles due to improvment of the polarization process. Furthermore, according to the XRD and TG results, the Co layer can enhance the heat resistance of CI particles. The bandwidth below −10 dB can reach 3.9 GHz for the Co(CI) absorbent. The results indicate that the electroless plating Co not only enhances the absorbing properties but also improves the heat resistance of CI. - Highlights: • The Co-coated carbonyl iron Co(CI) particles were prepared by electroless plating. • The electromagnetic wave absorbing properties of Co(CI) particles were studied. • The heat treatment on the absorbing property of Co(CI) particles was studied. • The Co(CI) particles have good absorbing property when compared with CI

  4. Impact of silica-coating on the microwave absorption properties of carbonyl iron powder

    International Nuclear Information System (INIS)

    Microwave absorption properties, especially the band width and depth of reflection loss are highlighted as key measurement in studies of microwave absorber. In order to improve the band width and depth of reflection loss of carbonyl iron powder (CIP), we prepared SiO2 layers on the surface of CIP by using tetraethyl orthosilicate (TEOS) as a SiO2 source and 3-aminopropyl triethoxysilane (APTES) as a surface modifier. SiO2 layer was formed by the hydrolysis of TEOS. The results show that after treatment the CIP is covered by a 5–10 nm coating layer. Contrast to uncoated samples, coated samples show improved absorption properties. The minimum of reflection loss is −38.8 dB at 11 GHz and the band width of reflection loss exceeding −10 dB is from 8 GHz to 14 GHz. - Highlights: • Silica coatings were prepared on the surface of carbonyl iron powder. • Coating layers were identified by several ways. • We discussed the absorbing mechanism of coated samples. • Reflection loss was significantly improved, the width of RL exceeding −10 dB is from 8 GHz to 14 GHz

  5. Analysis of the carbonyl group stretching vibrations in some structural fragments of poly-3-hydroxybutyrate

    CERN Document Server

    Pitsevich, George A; Doroshenko, Iryna

    2016-01-01

    The structure and the medium effects exerted on the spectral characteristics of the carbonyl group stretching vibrations in some structural fragments of poly-3-hydroxybutyrate have been analyzed. Calculations of the equilibrium configurations and IR spectra were carried out using the Gaussian program set in the approximation B3LYP/cc-pVDZ. It has been shown that typical bending of the poly-3-hydroxybutyrate chain is observed with an increase in the number of structural units. In order to explain the difference between the calculated and experimental frequencies of the C=O group stretching vibrations, the calculations of the potential energy curve associated with variations in the length of C=O bond and the subsequent numerical solution of a one-dimensional vibrational Schr\\"odinger equation have been performed. The medium effects have been taken into account within the scope of a polarizable continuum model. Owing to the inclusion of the above-mentioned factors, which affect frequencies of the carbonyl groups...

  6. Millimeter-wave spectroscopy of carbonyl diazide, OC(N3)2

    Science.gov (United States)

    Amberger, Brent K.; Esselman, Brian J.; Woods, R. Claude; McMahon, Robert J.

    2014-01-01

    Millimeter-wave absorption spectra for carbonyl diazide (OC(N3)2) are reported in the frequency range of 243-360 GHz, at both 293 K and 213 K. Transitions for two of the three possible conformations, one with both of the azide groups syn to the carbonyl group, or with one syn and the other anti, were observed in the spectra. Theoretical calculations at the CCSD(T)/ANO1 level do an excellent job of predicting the ground state rotational constants and 4th order centrifugal distortion terms for both conformers. Relative line intensities, along with theoretically predicted dipole moments, were used to estimate the energy difference of the two observed forms, yielding a result in good agreement with the ab initio potential energy surface. The spectra of the ν12, ν7, ν9 and 2ν12 excited vibrational states for the more abundant syn-syn conformer have been assigned, and a great many transitions for each of them have been fit using partial 6th and 8th order centrifugal distortion Hamiltonians. Anharmonic vibration-rotation interaction constants from the CCSD(T)/ANO1 calculations are in excellent agreement with the experimentally determined constants in the case of ν7 and ν9, but not for ν12.

  7. Impact of silica-coating on the microwave absorption properties of carbonyl iron powder

    Energy Technology Data Exchange (ETDEWEB)

    Li, J. [School of Science, Lanzhou University of Technology, Lanzhou, Gansu 730050 (China); Feng, W.J., E-mail: wjfeng@lut.cn [State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metal, Lanzhou University of Technology, Lanzhou 730050 (China); School of Science, Lanzhou University of Technology, Lanzhou, Gansu 730050 (China); Wang, J.S.; Zhao, X.; Zheng, W.Q. [School of Science, Lanzhou University of Technology, Lanzhou, Gansu 730050 (China); Yang, H. [State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metal, Lanzhou University of Technology, Lanzhou 730050 (China); School of Science, Lanzhou University of Technology, Lanzhou, Gansu 730050 (China)

    2015-11-01

    Microwave absorption properties, especially the band width and depth of reflection loss are highlighted as key measurement in studies of microwave absorber. In order to improve the band width and depth of reflection loss of carbonyl iron powder (CIP), we prepared SiO{sub 2} layers on the surface of CIP by using tetraethyl orthosilicate (TEOS) as a SiO{sub 2} source and 3-aminopropyl triethoxysilane (APTES) as a surface modifier. SiO{sub 2} layer was formed by the hydrolysis of TEOS. The results show that after treatment the CIP is covered by a 5–10 nm coating layer. Contrast to uncoated samples, coated samples show improved absorption properties. The minimum of reflection loss is −38.8 dB at 11 GHz and the band width of reflection loss exceeding −10 dB is from 8 GHz to 14 GHz. - Highlights: • Silica coatings were prepared on the surface of carbonyl iron powder. • Coating layers were identified by several ways. • We discussed the absorbing mechanism of coated samples. • Reflection loss was significantly improved, the width of RL exceeding −10 dB is from 8 GHz to 14 GHz.

  8. Enhanced microwave absorbing properties and heat resistance of carbonyl iron by electroless plating Co

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hongyu, E-mail: wanghongyu07010310@163.com; Zhu, Dongmei; Zhou, Wancheng; Luo, Fa

    2015-11-01

    Co coated carbonyl iron particles (Co (CI)) are fabricated through electroless plating method, and the electromagnetic microwave absorbing properties are investigated in the frequencies during 8.2–12.4 GHz. The complex permittivity of CI particles after electroless plating Co is higher than that of raw CI particles due to improvment of the polarization process. Furthermore, according to the XRD and TG results, the Co layer can enhance the heat resistance of CI particles. The bandwidth below −10 dB can reach 3.9 GHz for the Co(CI) absorbent. The results indicate that the electroless plating Co not only enhances the absorbing properties but also improves the heat resistance of CI. - Highlights: • The Co-coated carbonyl iron Co(CI) particles were prepared by electroless plating. • The electromagnetic wave absorbing properties of Co(CI) particles were studied. • The heat treatment on the absorbing property of Co(CI) particles was studied. • The Co(CI) particles have good absorbing property when compared with CI.

  9. Infrared Photodissociation Spectra of Mass-Selected Homoleptic Dinuclear Palladium Carbonyl Cluster Cations in the Gas Phase

    Institute of Scientific and Technical Information of China (English)

    崔洁铭; 邢小鹏; 池超贤; 王冠军; 刘智攀; 周鸣飞

    2012-01-01

    Infrared spectra of mass-selected homoleptic dinuclear palladium carbonyl cluster cations Pd2(CO)n (n=5 8) are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The structures are established by comparison of the experimental spectra with simulated spectra derived from density functional calculations. The Pd2(CO)+ cation is characterized to have two weakly semibridging CO groups with C2 symmetry. The Pd2(CO)6+ and Pd2(CO)7+ cations are determined to involve one weakly semibridging CO group. The Pd2(CO)8+ cation is a CO coordination saturated cluster, which is determined to have a D2d structure with all of the carbonyl groups terminally bonded. Bonding analysis indicates that these cluster cations each has a Pd--Pd half bond. The Pd--Pd distance increases with the number of CO ligands.

  10. Complex Permittivity and Permeability Measurements and Numerical Simulation of carbonyl iron rubber in X-Band frequency

    Directory of Open Access Journals (Sweden)

    Adriano Luiz de Paula

    2014-06-01

    Full Text Available Recognizing the importance of an adequate characterization of radar absorbing materials (RAM, and consequently their development, the present study aims to contribute for the establishment and validation of experimental determination and numerical simulation of complex permittivity and permeability of electromagnetic materials, using for this a carbonyl iron was seventy percent of the mass concentration. The present work branches out into two related topics. The first one is concerned with the implementation of a computational modeling to predict the behavior of electromagnetic materials in confined environment by using electromagnetic three-dimensional simulation. The second topic re-examines the Nicolson-Ross-Weir mathematical model to retrieve the constitutive parameters (complex permittivity and permeability of a homogeneous sample (carbonyl iron from scattering coefficient measurements. The measured and calculated results show a good convergence that guarantees the application of the used methodologies for the characterization of carbonyl iron rubber in x-band frequency.

  11. Complex permeability and permittivity variation of carbonyl iron rubber in the frequency range of 2 to 18 GHz

    Directory of Open Access Journals (Sweden)

    Adriana Medeiros Gama

    2010-04-01

    Full Text Available The complex dielectric permittivity (e and magnetic permeability (m of Radar Absorbing Materials (RAM based on metallic magnetic particles (carbonyl iron particles embedded in a dielectric matrix (silicon rubber have been studied in the frequency range of 2 to 18 GHz. The relative permeability and permittivity of carbonyl iron-silicon composites for various mass fractions are measured by the transmission/reflection method using a vector network analyzer. The concentration dependence of permittivity and permeability on the frequency is analyzed. In a general way, the results show that e´ parameter shows a more significant variation among the evaluated parameters (e”, m”, m’. The comparison of dielectric and magnetic loss tangents (e”/e” and m”/m’, respectively shows more clearly the variation of both parameters (e and m according to the frequency. It is also observed that higher carbonyl iron content fractions favor both dielectric and magnetic loss tangents.

  12. Preparation and biological behaviour of some neutral [sup 99m]Tc-carbonyl dithiocarbamates showing rapid hepatobiliary excretion

    Energy Technology Data Exchange (ETDEWEB)

    Baldas, John; Bonnyman, John (Australian Radiation Lab., Yallambie (Australia))

    1992-10-01

    A simple procedure for the preparation of [sup 99m]Tc-carbonyl complexes of dithiocarbamates in high yield and radiochemical purity has been developed and used for the preparation of [sup 99m]Tc-carbonyl complexes of bis(2-hydroxyethyl)dithiocarbamate and bis(2-hydroxypropyl)dithiocarbamate. These complexes were found to be extremely stable and their biological behaviour was studied in mice and compared to that of the [sup 99m]TcN- and the [sup 99m]Tc-complexes [prepared by dithionite (dit) reduction] of the same ligands. The carbonyl complexes were found to be efficient hepatobiliary agents and cleared more rapidly than the corresponding [sup 99m]TcN- and [sup 99m]Tc(dit)-complexes. (Author).

  13. Preparation of Tc-carbonyl complexes of tryptophan and histidine and biodistribution in mice bearing S180 tumor

    International Nuclear Information System (INIS)

    The Tc-carbonyl complexes of tryptophan and histidine were synthesized by two-step method. The yielded complexes were found by paper electrophoresis to be electrically neutral in three buffer solutions (pH = 4.7, 7.4, 9.2). Their possible structures were postulated based on ab initio MO calculations. The biodistribution in mice bearing S180 tumor demonstrated that the Tc-carbonyl complex of histidine showed good stability in vivo and quick clearance, selectively accumulated in tumor. The tumor/muscle ratio attained 3 to 4. However, the complex of tryptophan showed poor stability in vivo and slow clearance, and retained for a long time in organs and tissues. It also accumulated in tumor to some extent. The tumor.muscle ratio attained 2 to 3. The labelling of proteins and polypeptides with the Tc(I)-carbonyl complex was also discussed

  14. Preparation and biological behaviour of some neutral 99mTc-carbonyl dithiocarbamates showing rapid hepatobiliary excretion

    International Nuclear Information System (INIS)

    A simple procedure for the preparation of 99mTc-carbonyl complexes of dithiocarbamates in high yield and radiochemical purity has been developed and used for the preparation of 99mTc-carbonyl complexes of bis(2-hydroxyethyl)dithiocarbamate and bis(2-hydroxypropyl)dithiocarbamate. These complexes were found to be extremely stable and their biological behaviour was studied in mice and compared to that of the 99mTcN- and the 99mTc-complexes [prepared by dithionite (dit) reduction] of the same ligands. The carbonyl complexes were found to be efficient hepatobiliary agents and cleared more rapidly than the corresponding 99mTcN- and 99mTc(dit)-complexes. (Author)

  15. Gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene

    Directory of Open Access Journals (Sweden)

    R. M. Healy

    2008-06-01

    Full Text Available A new denuder-filter sampling technique has been used to investigate the gas/particle partitioning behaviour of the carbonyl products from the photooxidation of isoprene and 1,3,5-trimethylbenzene. A series of experiments was performed in two atmospheric simulation chambers at atmospheric pressure and ambient temperature in the presence of NOx and at a relative humidity of approximately 50%. The denuder and filter were both coated with the derivatizing agent O-(2,3,4,5,6-pentafluorobenzyl-hydroxylamine (PFBHA to enable the efficient collection of gas- and particle-phase carbonyls respectively. The tubes and filters were extracted and carbonyls identified as their oxime derivatives by GC-MS. The carbonyl products identified in the experiments accounted for around 5% and 10% of the mass of secondary organic aerosol formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene respectively.

    Experimental gas/particle partitioning coefficients were determined for a wide range of carbonyl products formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene and compared with the theoretical values based on standard absorptive partitioning theory. Photooxidation products with a single carbonyl moiety were not observed in the particle phase, but dicarbonyls, and in particular, glyoxal and methylglyoxal, exhibited gas/particle partitioning coefficients several orders of magnitude higher than expected theoretically. These findings support the importance of heterogeneous and particle-phase chemical reactions for SOA formation and growth during the atmospheric degradation of anthropogenic and biogenic hydrocarbons.

  16. Kinetics and Mechanism of the Gas-Phase Reaction of Selected Carbonyls with Cl Atoms between 250 and 340 K

    Science.gov (United States)

    Hasson, A. S.; Algrim, L.; Abdelhamid, A.; Tyndall, G. S.; Orlando, J. J.

    2013-12-01

    Carbonyls are important products from the gas phase degradation of most volatile organic compounds. Their atmospheric reactions therefore have a significant impact on atmospheric composition, particularly in aged air masses. While the reactions of short-chain linear carbonyls are well understood, the chemistry of larger (> C6) and branched carbonyl is more uncertain. To provide insight into these reactions, the reactions of three carbonyls (methyl isopropyl ketone, MIK; di-isopropyl ketone, DIK; and diethyl ketone, DEK) with chlorine atoms were investigated between 250 and 340 K and 1 atm in the presence and absence of NOx and an HO2 source (methanol). Experiments were performed in a photochemical reactor using a combination of long-path Fourier transform infra-red spectroscopy, proton transfer reaction mass spectrometry and gas chromatography with flame ionization detection. The kinetics were studied using the relative rate technique with butanone and isopropanol as the reference compounds. The Arrhenius expression for the three rate coefficients was determined to be k(DEK+Cl) = 3.87 x 10-11e(2 × 7 kJ/mol)/RT cm3 molecules-1 s-1 , k(MIPK+Cl) = 7.20 x 10-11e(0.2× 8 kJ/mol)/RT cm3 molecules-1 s-1 , and k(DIPK+Cl) = 3.33 x 10-10e(-3× 8 kJ/mol)/RT cm3 molecules-1 s-1 . Measured reaction products accounted for 38-72 % of the reacted carbon and were consistent with strong deactivation of the carbon atom adjacent to the carbonyl group with respect to H-atom abstraction by Cl atoms. The product distributions also provide insight into radical recycling from the organic peroxy + HO2 reaction, and the relative rates of isomerization, fragmentation and reaction with O2 for carbonyl-containing alkoxy radicals. Implications of these results will be discussed.

  17. Gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene

    Directory of Open Access Journals (Sweden)

    R. M. Healy

    2008-03-01

    Full Text Available A new denuder-filter sampling technique has been used to investigate the gas/particle partitioning behaviour of the carbonyl products from the photooxidation of isoprene and 1,3,5-trimethylbenzene. A series of experiments was performed in two atmospheric simulation chambers at atmospheric pressure and ambient temperature in the presence of NOx and at a relative humidity of approximately 50%. The denuder and filter were both coated with the derivatizing agent O-(2,3,4,5,6-pentafluorobenzyl-hydroxylamine (PFBHA to enable the efficient collection of gas- and particle-phase carbonyls respectively. The tubes and filters were extracted and carbonyls identified as their oxime derivatives by GC-MS. The carbonyl products identified in the experiments accounted for around 5% and 10% of the mass of secondary organic aerosol formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene respectively.

    Experimental gas/particle partitioning coefficients were determined for a wide range of carbonyl products formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene and compared with the theoretical values based on standard absorptive partitioning theory. Photooxidation products with a single carbonyl moiety were not observed in the particle phase, but dicarbonyls, and in particular, glyoxal and methylglyoxal, exhibited gas/particle partitioning coefficients several orders of magnitude higher than expected theoretically. These findings support the importance of heterogeneous chemistry as a pathway for SOA formation and growth during the atmospheric degradation of anthropogenic and biogenic hydrocarbons.

  18. Electromagnetic and microwave absorbing properties of carbonyl iron/BaTiO3 composite absorber for matched load of isolator

    International Nuclear Information System (INIS)

    Composite absorbers made from carbonyl iron powder and BaTiO3 were prepared by blending technique with the matrix of epoxy resin. The structure and microtopography of the carbonyl iron and BaTiO3 particles were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The microstructure and electromagnetic properties of the as-prepared composites were investigated by SEM and vector network analyzer (VNA). The effect of the mass ratio of BaTiO3/carbonyl iron on the electromagnetic properties of the composites is investigated. The bandwidth with an absorption loss exceeding 30 dB is obtained in the whole measured frequency range for all composites, and an optimal reflection loss drop below 1.5 dB with 24 wt% BaTiO3. It is found that the carbonyl iron/BaTiO3 composite absorber can be a promising candidate as a matched load for the isolator. - Highlights: • Composite absorbers made from carbonyl iron powder and BaTiO3 were prepared by blending technique with the matrix of epoxy resin. • The microwave absorption properties of composites were measured by stripline method. • The bandwidth with an absorption loss exceeding 30 dB is obtained in the whole measured frequency range for all composites, and an optimal reflection loss drop below 1.5 dB with 24 wt% BaTiO3. • It is found that the carbonyl iron/BaTiO3 composite absorber can be a promising candidate as a matched load for the isolator

  19. Methane to acetic acid over Cu-exchanged zeolites: mechanistic insights from a site-specific carbonylation reaction.

    Science.gov (United States)

    Narsimhan, Karthik; Michaelis, Vladimir K; Mathies, Guinevere; Gunther, William R; Griffin, Robert G; Román-Leshkov, Yuriy

    2015-02-11

    The selective low temperature oxidation of methane is an attractive yet challenging pathway to convert abundant natural gas into value added chemicals. Copper-exchanged ZSM-5 and mordenite (MOR) zeolites have received attention due to their ability to oxidize methane into methanol using molecular oxygen. In this work, the conversion of methane into acetic acid is demonstrated using Cu-MOR by coupling oxidation with carbonylation reactions. The carbonylation reaction, known to occur predominantly in the 8-membered ring (8MR) pockets of MOR, is used as a site-specific probe to gain insight into important mechanistic differences existing between Cu-MOR and Cu-ZSM-5 during methane oxidation. For the tandem reaction sequence, Cu-MOR generated drastically higher amounts of acetic acid when compared to Cu-ZSM-5 (22 vs 4 μmol/g). Preferential titration with sodium showed a direct correlation between the number of acid sites in the 8MR pockets in MOR and acetic acid yield, indicating that methoxy species present in the MOR side pockets undergo carbonylation. Coupled spectroscopic and reactivity measurements were used to identify the genesis of the oxidation sites and to validate the migration of methoxy species from the oxidation site to the carbonylation site. Our results indicate that the Cu(II)-O-Cu(II) sites previously associated with methane oxidation in both Cu-MOR and Cu-ZSM-5 are oxidation active but carbonylation inactive. In turn, combined UV-vis and EPR spectroscopic studies showed that a novel Cu(2+) site is formed at Cu/Al <0.2 in MOR. These sites oxidize methane and promote the migration of the product to a Brønsted acid site in the 8MR to undergo carbonylation. PMID:25562431

  20. Protein hydroperoxides and carbonyl groups generated by porphyrin-induced photo-oxidation of bovine serum albumin

    DEFF Research Database (Denmark)

    Silvester, J A; Timmins, G S; Davies, Michael Jonathan

    1998-01-01

    Porphyrin-sensitized photo-oxidation of bovine serum albumin results in oxidation at specific sites to produce protein radical species: at the Cys-34 residue (to give a thiyl radical) and at one or both tryptophan residues (Trp-134 and Trp-214) to give tertiary carbon-centered radicals and cause...... disruption of the indole ring system. This study shows that these photo-oxidation processes also consume oxygen and give rise to hydrogen peroxide, protein hydroperoxides, and carbonyl functions. The yield of hydrogen peroxide, protein hydroperoxides, and carbonyl functions is shown to be dependent on...

  1. Pyrrolidine catalyzed reactions of cyclopentadiene with α,β-unsaturated carbonyl compounds: 1,2- versus 1,4-additions

    OpenAIRE

    Coskun, Necdet; Çetin, Meliha; Gronert, Scott; Ma, Jingxiang; Erden, Ihsan

    2015-01-01

    A systematic study of the reactions of cyclopentadiene with α,β-unsaturated carbonyl compounds in the presence of catalytic pyrrolidine-H2O revealed that the reactions can either proceed with a Michael attack at the β-carbon of enone, or 1,2-addition to the carbonyl, leadingeither to 4-cyclopentadienyl-2-butanones or 6-vinylfulvenes. The former can be isolated and/or converted to the corresponding 1,2-dihydropentalenes with base (or in one-pot at longer reaction times). Substitution pattern o...

  2. Determination of gaseous and particulate carbonyls (glycolaldehyde, hydroxyacetone, glyoxal, methylglyoxal, nonanal and decanal) in the atmosphere at Mt. Tai

    Science.gov (United States)

    Kawamura, K.; Okuzawa, K.; Aggarwal, S. G.; Irie, H.; Kanaya, Y.; Wang, Z.

    2013-05-01

    Gaseous and particulate semi-volatile carbonyl compounds were determined every three hours in the atmosphere of Mount Tai (elevation, 1534 m) in the North China Plain during 2-5, 23-24 and 25 June 2006 under clear sky conditions. Using a two-step filter cartridge in a series, particulate carbonyls were first collected on a quartz filter and then gaseous carbonyls were collected on a quartz filter impregnated with O-benzylhydroxylamine (BHA). After the two-step derivatization with BHA and N,O-Bis(trimethylsilyl)trifluoroacetamide (BSTFA), carbonyl derivatives were measured using a gas chromatography. The gaseous concentrations were obtained as follow: glycolaldehyde (range 0-826 ng m-3, average 303 ng m-3), hydroxyacetone (0-579 ng m-3, 126 ng m-3), glyoxal (46-1200 ng m-3, 487 ng m-3), methylglyoxal (88-2690 ng m-3, 967 ng m-3), n-nonanal (0-500 ng m-3, 89 ng m-3), and n-decanal (0-230 ng m-3, 39 ng m-3). These concentrations are among the highest ever reported in the urban and forest atmosphere. We found that gaseous α-dicarbonyls (glyoxal and methylglyoxal) are more than 20 times more abundant than particulate carbonyls and that glycolaldehyde is one order of magnitude more abundant than in aerosol phase. In contrast, hydroxyacetone and normal aldehydes (nonanal and decanal) are equally present in both phases. Time-resolved variations of carbonyls did not show any a clear diurnal pattern, except for hydroxyacetone. We found that glyoxal, methylglyoxal and glycolaldehyde positively correlated with levoglucosan (a tracer of biomass burning), suggesting that a contribution from field burning of agricultural wastes (wheat crops) is significant for the bifunctional carbonyls in the atmosphere of Mt. Tai. Upward transport of the pollutants to the mountaintop from the low lands in the North China Plain is a major process to control the distributions of carbonyls in the upper atmosphere over Mt. Tai.

  3. Cadmium sulfide and lead sulfide quantum dots in glass: Processing, growth, and optical absorption

    Science.gov (United States)

    Rao, Pratima Gattu Naga

    Glasses containing cadmium sulfide and lead sulfide particles were prepared, and their properties were studied. These particles exhibit quantum confinement behavior when they are smaller than their Bohr exciton radii. Quantum confinement leads to size dependence in the optical absorption of particles. This size dependence can tune the optical absorption of the material to a particular wavelength or energy and possibly enhances the nonlinear optical absorption of the particles. These properties have potential applications in photonic devices. To control the growth of these semiconductor particles in glass, the glass processing conditions were studied. CdS-doped glasses were initially prepared with CdO and ZnS. The sublimation temperature for ZnS is at 1185°C; whereas, CdO sublimes at 1559°C, and CdS at 980°C. Loss of both cadmium and sulfur was observed in open crucible melts, even when CdO and ZnS were used. Improvements in glass processing were made by use of preheat and a cover during the glass melting, resulting in better retention of both dopants. Direct CdS addition to the glasses was possible with these improvements, thus eliminating complications of zinc incorporation during the growth of the semiconductor particles. These methods were successfully applied to the synthesis of PbS-doped glasses. CdS and PbS particles were grown in alkali borosilicate glasses, and their optical absorption spectra were measured as a function of heat treatment temperature and time. The position of the absorption peak and edge shifted to longer wave-lengths, or lower energies, with longer heat treatments at a constant temperature. Both CdS and PbS particles exhibited quantum confinement. These measurements were used to calculate particle sizes from quantum confinement models. Comparisons with transmission electron microscopy (TEM) demonstrated that the 1-term effective-mass approximation was appropriate for estimating CdS particle sizes. A sophisticated four-band envelope

  4. The removal of hydrogen sulfide from gas streams using an aqueous metal sulfate absorbent : Part II. the regeneration of copper sulfide to copper oxide - An experimental study

    NARCIS (Netherlands)

    Ter Maat, H.; Hogendoorn, J. A.; Versteeg, G. F.

    2005-01-01

    Aim of this study was to investigate the possibilities for a selective and efficient method to convert copper(II) sulfide (CuS) into copper(II) oxide (CuO). The oxidation of copper sulfide has been studied experimentally using a thermogravimetric analyzer (TGA) at temperatures ranging from 450 to 75

  5. Structure and reactivity of zinc sulfide precipitates formed in the presence of sulfate-reducing bacteria

    International Nuclear Information System (INIS)

    Highlights: → Biogenic zinc sulfides exhibit short-range structural order. → This structural order increases resistance to re-oxidation. → Dissolved Fe and Zn formed distinct sulfide phases. - Abstract: The biologically mediated formation of metal sulfide precipitates in anoxic sediments represents a potentially important mechanism for the sequestration of toxic metals. Current knowledge of the structure and reactivity of these biogenic metal sulfides is scarce, limiting the ability to effectively assess contaminant sequestration in, and remobilization from, these solids. In this study, SO4-reducing bacteria (Desulfovibrio sp.) were grown for 5 days in a high-SO4, minimal metal media amended with Zn at either 30 or 300 micromolar. Zinc speciation in the reactor solids was determined using X-ray absorption spectroscopy, and the results compared to spectra of known metal sulfide mineral phases and freshly formed metal sulfides synthesized through purely chemical processes. Biogenically mediated Zn sulfides showed significantly more short range crystallographic order than the abiotically prepared amorphous precipitates. The presence of dissolved Fe2+ at similar concentrations did not affect the nature of the Zn precipitates formed. The biogenic ZnS solids were also more resistant to re-oxidation than the chemical precipitates but more soluble than sphalerite mineral samples. These results suggest that Zn sulfides formed in anaerobic sediments are likely to be more resistant to re-oxidation than would be expected based on dissolution of Fe sulfides and/or sediment acid volatile sulfides.

  6. Oxygen-free atomic layer deposition of indium sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Martinson, Alex B.; Hock, Adam S.; McCarthy, Robert; Weimer, Matthew S.

    2016-07-05

    A method for synthesizing an In(III) N,N'-diisopropylacetamidinate precursor including cooling a mixture comprised of diisopropylcarbodiimide and diethyl ether to approximately -30.degree. C., adding methyllithium drop-wise into the mixture, allowing the mixture to warm to room temperature, adding indium(III) chloride as a solid to the mixture to produce a white solid, dissolving the white solid in pentane to form a clear and colorless solution, filtering the mixture over a celite plug, and evaporating the solution under reduced pressure to obtain a solid In(III) N,N'-diisopropylacetamidinate precursor. This precursor has been further used to develop a novel atomic layer deposition technique for indium sulfide by dosing a reactor with the precursor, purging with nitrogen, dosing with dilute hydrogen sulfide, purging again with nitrogen, and repeating these steps to increase growth.

  7. The bioleaching of different sulfide concentrates using thermophilic bacteria

    Science.gov (United States)

    Torres, F.; Blázquez, M. L.; González, F.; Ballester, A.; Mier, J. L.

    1995-05-01

    The bioleaching of different mineral sulfide concentrates with thermophilic bacteria (genus Sulfolobus @#@) was studied. Since the use of this type of bacteria in leaching systems involves stirring and the control of temperature, the influence of the type of stirring and the pulp density on dissolution rates was studied in order to ascertain the optimum conditions for metal recovery. At low pulp densities, the dissolution kinetic was favored by pneumatic stirring, but for higher pulp densities, orbital stirring produced the best results. A comparative study of three differential concentrates, one mixed concentrate, and one global concentrate was made. Copper and iron extraction is directly influenced by bacterial activity, while zinc dissolution is basically due to an indirect mechanism that is activated in the presence of copper ions. Galvanic interactions between the different sulfides favors the selective bioleaching of some phases (sphalerite and chalcopyrite) and leads to high metal recovery rates. However, the formation of galvanic couples depends on the type of concentrate.

  8. 'Low-acid' sulfide oxidation using nitrate-enriched groundwater

    Science.gov (United States)

    Donn, Michael; Boxall, Naomi; Reid, Nathan; Meakin, Rebecca; Gray, David; Kaksonen, Anna; Robson, Thomas; Shiers, Denis

    2016-04-01

    Acid drainage (AMD/ARD) is undoubtedly one of the largest environmental, legislative and economic challenges facing the mining industry. In Australia alone, at least 60m is spent on AMD related issues annually, and the global cost is estimated to be in the order of tens of billions US. Furthermore, the challenge of safely and economically storing or treating sulfidic wastes will likely intensify because of the trend towards larger mines that process increasingly higher volumes of lower grade ores and the associated sulfidic wastes and lower profit margins. While the challenge of managing potentially acid forming (PAF) wastes will likely intensify, the industrial approaches to preventing acid production or ameliorating the effects has stagnated for decades. Conventionally, PAF waste is segregated and encapsulated in non-PAF tips to limit access to atmospheric oxygen. Two key limitations of the 'cap and cover' approach are: 1) the hazard (PAF) is not actually removed; only the pollutant linkage is severed; and, 2) these engineered structures are susceptible to physical failure in short-to-medium term, potentially re-establishing that pollutant linkage. In an effort to address these concerns, CSIRO is investigating a passive, 'low-acid' oxidation mechanism for sulfide treatment, which can potentially produce one quarter as much acidity compared with pyrite oxidation under atmospheric oxygen. This 'low-acid' mechanism relies on nitrate, rather than oxygen, as the primary electron accepter and the activity of specifically cultured chemolithoautotrophic bacteria and archaea communities. This research was prompted by the observation that, in deeply weathered terrains of Australia, shallow (oxic to sub-oxic) groundwater contacting weathering sulfides are commonly inconsistent with the geochemical conditions produced by ARD. One key characteristic of these aquifers is the natural abundance of nitrate on a regional scale, which becomes depleted around the sulfide bodies, and

  9. L-Cysteine-assisted Synthesis of Copper Gallium Sulfide Microspheres

    Institute of Scientific and Technical Information of China (English)

    LIANG Xiao-juan; ZHONG Jia-song; CAI Qian; HUANG Hai-yu; LIU Hai-tao; XIANG Wei-dong; SUN Jun-cai

    2012-01-01

    An effective L-cysteine-assisted synthetic route has been successfully developed to prepare copper gallium sulfide(CuGaS2) microspheres under solvothermal conditions with CuCI2-2H2O,GaCl3 and L-cysteine as source materials,in which L-cysteine was used as the sulfide source and eomplexing molecule.The experiments revealed that the synthesized sample was of a typical CuGaS2 tetragonal structure.Moreover,the prepared CuGaS2 crystals consisting of microspheres made up of nanoflakes,and the diameter of the nanoflakes was about 20 nm.Raman spectrum of the obtained CuGaS2 exhibits a high-intensity peak of the A1 mode at 306 cm-1.Meanwhile,a possible growth mechanism was proposed based on the investigations.

  10. Oxygen-free atomic layer deposition of indium sulfide

    Science.gov (United States)

    Martinson, Alex B.; Hock, Adam S.; McCarthy, Robert; Weimer, Matthew S.

    2016-07-05

    A method for synthesizing an In(III) N,N'-diisopropylacetamidinate precursor including cooling a mixture comprised of diisopropylcarbodiimide and diethyl ether to approximately -30.degree. C., adding methyllithium drop-wise into the mixture, allowing the mixture to warm to room temperature, adding indium(III) chloride as a solid to the mixture to produce a white solid, dissolving the white solid in pentane to form a clear and colorless solution, filtering the mixture over a celite plug, and evaporating the solution under reduced pressure to obtain a solid In(III) N,N'-diisopropylacetamidinate precursor. This precursor has been further used to develop a novel atomic layer deposition technique for indium sulfide by dosing a reactor with the precursor, purging with nitrogen, dosing with dilute hydrogen sulfide, purging again with nitrogen, and repeating these steps to increase growth.

  11. Potential impact of climate change on marine dimethyl sulfide emissions

    OpenAIRE

    Bopp, Laurent; Aumont, Oliver; Belviso, Sauveur; MONFRAY, PATRICK

    2011-01-01

    Dimethyl sulfide (DMS) is a biogenic compound produced in sea-surface water and outgased to the atmosphere. Once in the atmosphere, DMS is a significant source of cloud condensation nuclei in the unpolluted marine atmosphere. It has been postulated that climate may be partly modulated by variations in DMS production through a DMS-cloud condensation nuclei-albedo feedback. We present here a modelled estimation of the response of DMS sea-water concentrations and DMS fluxes to climate change, fo...

  12. Ocean color and atmospheric dimethyl sulfide: On their mesoscale variability

    OpenAIRE

    Matrai, Patricia A.; Balch, William M; Cooper, David J; Saltzman, Eric S.

    1993-01-01

    The mesoscale variability of dimethyl sulfide (DMS) and ocean color is explored to determine the feasibility of a predictive relationship. During NASA's Global Tropospheric Experiment/Chemical Instrumentation Test and Evaluation (GTE/CITE 3), simultaneous shipboard and aircraft studies were carried out in the North Atlantic, followed by aircraft studies in the South Atlantic. Surface concentrations of chlorophyll a were measured with an airborne spectroradiometer, the Ocean Data Acquisition S...

  13. Is Hydrogen Sulfide-Induced Suspended Animation General Anesthesia?

    OpenAIRE

    Li, Rosie Q.; McKinstry, Andrew R.; Moore, Jason T.; Caltagarone, Breanna M.; Eckenhoff, Maryellen F.; Eckenhoff, Roderic G.; Kelz, Max B.

    2012-01-01

    Hydrogen sulfide (H2S) depresses mitochondrial function and thereby metabolic rates in mice, purportedly resulting in a state of “suspended animation.” Volatile anesthetics also depress mitochondrial function, an effect that may contribute to their anesthetic properties. In this study, we ask whether H2S has general anesthetic properties, and by extension, whether mitochondrial effects underlie the state of anesthesia. We compared loss of righting reflex, electroencephalography, and electromy...

  14. Laboratory SIP signatures associated with oxidation of disseminated metal sulfides.

    Science.gov (United States)

    Placencia-Gómez, Edmundo; Slater, Lee; Ntarlagiannis, Dimitrios; Binley, Andrew

    2013-05-01

    Oxidation of metal sulfide minerals is responsible for the generation of acidic waters rich in sulfate and metals. When associated with the oxidation of sulfide ore mine waste deposits the resulting pore water is called acid mine drainage (AMD); AMD is a known environmental problem that affects surface and ground waters. Characterization of oxidation processes in-situ is challenging, particularly at the field scale. Geophysical techniques, spectral induced polarization (SIP) in particular, may provide a means of such investigation. We performed laboratory experiments to assess the sensitivity of the SIP method to the oxidation mechanisms of common sulfide minerals found in mine waste deposits, i.e., pyrite and pyrrhotite, when the primary oxidant agent is dissolved oxygen. We found that SIP parameters, e.g., phase shift, the imaginary component of electrical conductivity and total chargeability, decrease as the time of exposure to oxidation and oxidation degree increase. This observation suggests that dissolution-depletion of the mineral surface reduces the capacitive properties and polarizability of the sulfide minerals. However, small increases in the phase shift and imaginary conductivity do occur during oxidation. These transient increases appear to correlate with increases of soluble oxidizing products, e.g., Fe(2+) and Fe(3+) in solution; precipitation of secondary minerals and the formation of a passivating layer to oxidation coating the mineral surface may also contribute to these increases. In contrast, the real component of electrical conductivity associated with electrolytic, electronic and interfacial conductance is sensitive to changes in the pore fluid chemistry as a result of the soluble oxidation products released (Fe(2+) and Fe(3+)), particularly for the case of pyrrhotite minerals. PMID:23531431

  15. Structural, electronic and optical properties of cadmium sulfide nanoparticles

    OpenAIRE

    Frenzel, Johannes

    2007-01-01

    In this work, the structural, electronic, and optical properties of CdS nanoparticles with sizes up to 4nm have been calculated using density-functional theory (DFT). Inaccuracies in the description of the unoccupied states of the applied density-functional based tight-binding method (DFTB) are overcome by a new SCF-DFTB method. Density-functional-based calculations employing linear-response theory have been performed on cadmium sulfide nanoparticles considering different stoichiometries, und...

  16. Evaluation of methods for monitoring air concentrations of hydrogen sulfide

    OpenAIRE

    Katarzyna Janoszka; Agata Wziątek; Gromiec, Jan P.

    2013-01-01

    The development of different branches of industry and a growing fossil fuels mining results in a considerable emission of by-products. Major air pollutants are: CO, CO₂, SO₂, SO₃, H₂S, nitrogen oxides, as well as compounds of an organic origin. The main aspects of this paper is to review and evaluate methods used for monitoring of hydrogen sulfide in the air. Different instrumental techniques were discussed, electrochemical, chromatographic and spectrophotometric (wet and dry), to select the ...

  17. Endogenous Hydrogen Sulfide Production Is Essential for Dietary Restriction Benefits

    OpenAIRE

    Hine, Christopher; Harputlugil, Eylul; Zhang, Yue; Ruckenstuhl, Christoph; Lee, Byung Cheon; Brace, Lear; Longchamp, Alban; Trevino-Villarreal, Jose H.; Mejia, Pedro; Ozaki, C. Keith; Wang, Rui; Gladyshev, Vadim N.; Madeo, Frank; Mair, William B.; Mitchell, James R.

    2014-01-01

    Dietary restriction (DR) without malnutrition encompasses numerous regimens with overlapping benefits including longevity and stress resistance, but unifying nutritional and molecular mechanisms remain elusive. In a mouse model of DR-mediated stress resistance, we found that sulfur amino acid (SAA) restriction increased expression of the transsulfuration pathway (TSP) enzyme cystathionine γ-lyase (CGL), resulting in increased hydrogen sulfide (H2S) production and protection from hepatic ische...

  18. Method of purifying oil and bed water from hydrogen sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Dyadechko, V.N.; Kuzovatkin, R.I.; Nesterov, I.N.; Stavitskiy, B.P.

    1982-01-01

    A method is proposed for purifying oil and bed water of hydrogen sulfide by treatment with a chemical reagent. It is distinguished by the fact that in order to prevent the formation of corrosion-aggressive side products and sulfate-reducing bacteria, in the bed water the chemical reagent complex compounds of copper-hexaamine copper (II) hydroxide or tetraamine copper (II) hydroxide are used in the form of 0.05% aqueous solution.

  19. Brassica juncea Produces a Phytochelatin-Cadmium-Sulfide Complex.

    Science.gov (United States)

    Speiser, D M; Abrahamson, S L; Banuelos, G; Ow, D W

    1992-07-01

    Phytochelatins (PCs) are enzymically synthesized peptides produced in higher plants and some fungi upon exposure to heavy metals. We have examined PC production in the Se-tolerant wild mustard Brassica juncea and found that it produces two types of PC-Cd complexes with the same characteristics as those from fission yeast Schizosaccharomyces pombe, including a high molecular weight PC-Cd-sulfide form. PMID:16669006

  20. Brassica juncea Produces a Phytochelatin-Cadmium-Sulfide Complex 1

    Science.gov (United States)

    Speiser, David M.; Abrahamson, Susan L.; Banuelos, Gary; Ow, David W.

    1992-01-01

    Phytochelatins (PCs) are enzymically synthesized peptides produced in higher plants and some fungi upon exposure to heavy metals. We have examined PC production in the Se-tolerant wild mustard Brassica juncea and found that it produces two types of PC-Cd complexes with the same characteristics as those from fission yeast Schizosaccharomyces pombe, including a high molecular weight PC-Cd-sulfide form. PMID:16669006

  1. Formation of iron sulfide nodules during anaerobic oxidation

    OpenAIRE

    van Dongen, B. E.; Organic Geochemistry Unit, Bristol Biogeochemistry Research Centre, School of Chemistry, Cantock’s Close, Bristol University, Bristol BS8 1TS, United Kingdom; Roberts, A. P.; National Oceanography Centre, University of Southampton, Southampton, UK.; Schouten, S.; Department of Marine Biogeochemistry, Royal Netherlands Institute for Sea Research, P.O. Box 59, 1790 AB Den Burg, Texel, The Netherlands; Jiang, W-T; Department of Earth Sciences, National Cheng Kung University, Tainan 70101, Taiwan, PR China; Florindo, F.; Istituto Nazionale di Geofisica e Vulcanologia, Sezione Roma2, Roma, Italia; Pancost, R. D.; Organic Geochemistry Unit, Bristol Biogeochemistry Research Centre, School of Chemistry, Cantock’s Close, Bristol University, Bristol BS8 1TS, United Kingdom

    2007-01-01

    The biomarker compositions of iron sulfide nodules (ISNs; upper Pliocene Valle Ricca section near Rome, Italy) that contain the ferrimagnetic mineral greigite (Fe3S4) were examined. In addition to the presence of specific terrestrial and marine biomarkers, consistent with formation in coastal marine sediments, these ISNs contain compounds thought to originate from sulfate reducing bacteria (SRB). These compounds include a variety of low-molecular-weight and branched alkanols and seve...

  2. Discrimination among iron sulfide species formed in microbial cultures.

    Science.gov (United States)

    Popa, R; Kinkle, B K

    2000-10-01

    A quantitative method for the study of iron sulfides precipitated in liquid cultures of bacteria is described. This method can be used to quantify and discriminate among amorphous iron sulfide (FeS(amorph)), iron monosulfide minerals such as mackinawite or greigite (FeS(min)), and iron disulfide minerals such as pyrite or marcasite (FeS(2min)) formed in liquid cultures. Degradation of iron sulfides is performed using a modified Cr(2+) reduction method with reflux distillation. The basic steps of the method are: first, separation of FeS(amorph); second, elimination of interfering species of S such as colloidal sulfur (S(c) degrees ), thiosulphate (S(2)O(3)(2-)) and polysulfides (S(x)(2-)); third, separation of FeS(min); and fourth, separation of FeS(2min). The final product is H(2)S which is determined after trapping. The efficiency of recovery is 96-99% for FeS(amorph), 76-88% for FeS(min), and >97% for FeS(2min). This method has a high reproducibility if the experimental conditions are rigorously applied and only glass conduits are used. A well ventilated fume hood must be used because of the toxicity and volatility of several reagents and products. The advantage relative to previously described methods are better resolution for iron sulfide species and use of the same bottles for both incubation of cultures and acid degradation. The method can also be used for Fe/S stoichiometry with sub-sampling and Fe analysis. PMID:11018273

  3. Fabrication and applications of copper sulfide (CuS) nanostructures

    Science.gov (United States)

    Shamraiz, Umair; Hussain, Raja Azadar; Badshah, Amin

    2016-06-01

    This review article presents different fabrication procedures (under the headlines of solvothermal routes, aerosol methods, solution methods and thermolysis), and applications (photocatalytic degradation, ablation of cancer cells, electrode material in lithium ion batteries and in gas sensing, organic solar cells, field emission properties, super capacitor applications, photoelectrochemical performance of QDSCs, photocatalytic reduction of organic pollutants, electrochemical bio sensing, enhanced PEC characteristics of pre-annealed CuS film electrodes) of copper sulfide (Covellite).

  4. Spurious hydrogen sulfide production by Providencia and Escherichia coli species.

    OpenAIRE

    Treleaven, B E; Diallo, A. A.; Renshaw, E C

    1980-01-01

    Hydrogen sulfide production was noted in two Escherichia coli strands and one Provaidenica alcalifaciens (Proteus inconstans A) strain isolated from clinical stool specimens durin the summer of 1979. An investigation into this phenomenon revealed the predence of Eubacterium lentum, an anaerobe, growing in synergism with the Enterobacteriaceae and producing H2s. The implications of this association are discssed with reference to clinical microbiology laboratory practice.

  5. Support Effect in Hydrodesulfurization of Thiophene over Rhodium Sulfide

    Czech Academy of Sciences Publication Activity Database

    Kaluža, Luděk; Vít, Zdeněk; Zdražil, Miroslav

    Prague: J. Heyrovský Institute of Physical Chemistry of the ASCR, v.v.i, 2009, s. 74-75. ISBN 978-80-87351-04-8. [Symposium on Catalysis /41./. Prague (CZ), 02.11.2009-03.11.2009] R&D Projects: GA ČR GA104/09/0751 Institutional research plan: CEZ:AV0Z40720504 Keywords : hydrodesulfurization * rhodium sulfide * support effect Subject RIV: CF - Physical ; Theoretical Chemistry

  6. Productivity-Diversity Relationships from Chemolithoautotrophically Based Sulfidic Karst Systems

    OpenAIRE

    Porter Megan L.; Summers Engel Annette; Kane Thomas C.; Kinkle Brian K.

    2009-01-01

    Although ecosystems thriving in the absence of photosynthetic processes are no longer considered unique phenomena, we haveyet to understand how these ecosystems are energetically sustained via chemosynthesis. Ecosystem energetics were measuredin microbial mats from active sulfidic caves (Movile Cave, Romania; Frasassi Caves, Italy; Lower Kane Cave, Wyoming, USA; andCesspool Cave, Virginia, USA) using radiotracer techniques. We also estimated bacterial diversity using 16S rRNA sequences torela...

  7. Study of crystallization behavior of poly(phenylene sulfide)

    OpenAIRE

    Liliana B. Nohara; Evandro L. Nohara; Andreza Moura; Joseane M. R. P. Gonçalves; Michelle L. Costa; Mirabel C. Rezende

    2006-01-01

    Poly(phenylene sulfide) (PPS) is an engineering thermoplastic polymer that presents high temperature resistance (glass transition temperature around 85 ºC and melting point at 285 ºC). These properties combined with its mechanical properties and its high chemical resistance allows its use in technological applications such as molding resins and as matrix for structural thermoplastic composites. During the manufacture of thermoplastic composites, the polymer is exposed to repeated melting, que...

  8. Spectrophotometric determination of carbonyl compounds as γ-radiation degradation products in the extraction system of TBP-kerosene-HNO3-UO2(NO3)2

    International Nuclear Information System (INIS)

    A method for determinating trace quantities of carbonyl compounds using spectrophotometry in the extraction system of TBP-kerosens-HNO3-UO2(NO3)2 is reported. The effects of radiation dose, acidity of nitric acid and the concentration of uranium in the aqueous phase, and radiation temperature on the production of carbonyl compounds are investigated

  9. Syntheses of fused tetrahydro--carboline analogues through imide carbonyl activation using BBr3: Evidence for the involvement of fused cyclic -acyliminium ion intermediate

    Indian Academy of Sciences (India)

    Selvaraj Mangalaraj; Jayaraman Selvakumar; Chinnasamy Ramaraj Ramanathan

    2015-05-01

    The fused cyclic -acyliminium ion generated during the imide carbonyl activation reaction of phenethylphthalimide was confirmed by single crystal X-ray diffraction. The Lewis acid assisted imide carbonyl activation methodology was successfully extended to synthesize fused tetrahydro--carboline units from the corresponding -indolylethylimides.

  10. Evaluation of methods for monitoring air concentrations of hydrogen sulfide

    Directory of Open Access Journals (Sweden)

    Katarzyna Janoszka

    2013-06-01

    Full Text Available The development of different branches of industry and a growing fossil fuels mining results in a considerable emission of by-products. Major air pollutants are: CO, CO₂, SO₂, SO₃, H₂S, nitrogen oxides, as well as compounds of an organic origin. The main aspects of this paper is to review and evaluate methods used for monitoring of hydrogen sulfide in the air. Different instrumental techniques were discussed, electrochemical, chromatographic and spectrophotometric (wet and dry, to select the method most suitable for monitoring low levels of hydrogen sulfide, close to its odor threshold. Based on the literature review the method for H₂S determination in the air, involving absorption in aqueous zinc acetate and reaction with N,N-dimethylo-p-phenylodiamine and FeCl₃, has been selected and preliminary verified. The adopted method allows for routine measurements of low concentration of hydrogen sulfide, close to its odor threshold in workplaces and ambient air. Med Pr 2013;64(3:449–454

  11. Benzothiazole sulfide compatibilized polypropylene/halloysite nanotubes composites

    Science.gov (United States)

    Liu, Mingxian; Guo, Baochun; Lei, Yanda; Du, Mingliang; Jia, Demin

    2009-02-01

    Clay-philic benzothiazole sulfide, capable of donating electrons, is grafted onto polypropylene (PP) backbones when N-cyclohexyl-2-benzothiazole sulfonamide (CBS), a commonly used accelerator in the tire industry, is included in the processing of PP/halloysite nanotubes (HNTs) composites. CBS decomposes at elevated temperature and yields benzothiazole sulfide radicals, which react with the PP polymeric free radicals generated during the processing of the composites. On the other hand, the benzothiazole group of CBS is reactive to HNTs via electron transferring. The compatibilization between HNTs and PP is thus realized via interfacial grafting and electron transferring mechanism. The interfacial interactions in the compatibilized systems were fully characterized. Compared with the control sample, the dispersion of HNTs and the interfacial bonding are enhanced substantially in the compatibilized composites. The significantly improved mechanical properties and thermal properties of benzothiazole sulfide compatibilized PP/HNTs composites are correlated to the enhanced interfacial property. The present work demonstrates a novel interfacial design via interfacial grafting/electron transferring for the compatibilization of PP/clay composites.

  12. Benzothiazole sulfide compatibilized polypropylene/halloysite nanotubes composites

    International Nuclear Information System (INIS)

    Clay-philic benzothiazole sulfide, capable of donating electrons, is grafted onto polypropylene (PP) backbones when N-cyclohexyl-2-benzothiazole sulfonamide (CBS), a commonly used accelerator in the tire industry, is included in the processing of PP/halloysite nanotubes (HNTs) composites. CBS decomposes at elevated temperature and yields benzothiazole sulfide radicals, which react with the PP polymeric free radicals generated during the processing of the composites. On the other hand, the benzothiazole group of CBS is reactive to HNTs via electron transferring. The compatibilization between HNTs and PP is thus realized via interfacial grafting and electron transferring mechanism. The interfacial interactions in the compatibilized systems were fully characterized. Compared with the control sample, the dispersion of HNTs and the interfacial bonding are enhanced substantially in the compatibilized composites. The significantly improved mechanical properties and thermal properties of benzothiazole sulfide compatibilized PP/HNTs composites are correlated to the enhanced interfacial property. The present work demonstrates a novel interfacial design via interfacial grafting/electron transferring for the compatibilization of PP/clay composites.

  13. Benzothiazole sulfide compatibilized polypropylene/halloysite nanotubes composites

    Energy Technology Data Exchange (ETDEWEB)

    Liu Mingxian [Department of Polymer Materials and Engineering, South China University of Technology, Guangzhou 510640 (China); Guo Baochun, E-mail: psbcguo@scut.edu.cn [Department of Polymer Materials and Engineering, South China University of Technology, Guangzhou 510640 (China); Lei Yanda; Du Mingliang; Jia Demin [Department of Polymer Materials and Engineering, South China University of Technology, Guangzhou 510640 (China)

    2009-02-15

    Clay-philic benzothiazole sulfide, capable of donating electrons, is grafted onto polypropylene (PP) backbones when N-cyclohexyl-2-benzothiazole sulfonamide (CBS), a commonly used accelerator in the tire industry, is included in the processing of PP/halloysite nanotubes (HNTs) composites. CBS decomposes at elevated temperature and yields benzothiazole sulfide radicals, which react with the PP polymeric free radicals generated during the processing of the composites. On the other hand, the benzothiazole group of CBS is reactive to HNTs via electron transferring. The compatibilization between HNTs and PP is thus realized via interfacial grafting and electron transferring mechanism. The interfacial interactions in the compatibilized systems were fully characterized. Compared with the control sample, the dispersion of HNTs and the interfacial bonding are enhanced substantially in the compatibilized composites. The significantly improved mechanical properties and thermal properties of benzothiazole sulfide compatibilized PP/HNTs composites are correlated to the enhanced interfacial property. The present work demonstrates a novel interfacial design via interfacial grafting/electron transferring for the compatibilization of PP/clay composites.

  14. A kit for preparation of 188Re sulfide suspension

    International Nuclear Information System (INIS)

    The 188Re sulfide suspension could be prepared quickly by a kit. The kit consists of three 10 mL vials. All the procedures were carried out in sterility circumstance. Vial A consisted of 1 mL KReO4 and Na2S2O3 (mole ratio 1:70) solution with excipient. Vial B was 5 mol/L HCl solution. Vial C consisted of 1.5 mL PVP and NaOH solution (mole ratio 1000:1). Vial B was sealed, Vial A and C were freeze-dried. Bacterium check, endotoxin check and security check were qualified. Kits were kept at ambient temperature and the Labelling efficiency of 188Re sulfide suspension was more than 98% with 2 months. The particle sizes were 1-5 μm (60.1 +- 12.7)%; 5-10 μm (30.9 +- 8.1)%; > 10 μm (9.0 +- 4.7)%. The radiochemical purity of 188Re sulfide suspension made by the kit was higher than 98% in 5 days with particle sizes 1-5 μm (49.9 +- 14.4%); 5-10 μm (41.1 +- 5.4)%; > 10μm (9.0 +- 3.3)%

  15. Magnetite-sulfide-metal complexes in the Allende meteorite

    Science.gov (United States)

    Haggerty, S. E.; Mcmahon, B. M.

    1979-01-01

    A model of liquid immiscibility is presented that seemingly accounts for the sulfide-oxide-metal complexes that are present in olivine-rich chondrules in the Allende meteorite. The four major assemblages that are identified are: (1) magnetite + Ni-Fe metal; (2) magnetite + troilite + Ni-Fe metal; (3) magnetite + troilite + pentlandite + Ni-Fe metal; and (4) troilite + or - pentlandite. Specific attention is focused on oxide-metal associations and experimental data confirm earlier suggestions that magnetite results from the oxidation of an initially high-Fe-content metal alloy. Oxidation decreases the modal abundance of the Fe metal and this is accompanied by substantial increases in Ni contents which reach a maximum of approximately 70 wt % Ni. The proposed oxidation mechanism is entirely consistent with condensation of Fe-metal + olivine (Fa5) that subsequently reequilibrated at lower temperatures. Although the sulfide constituents could also have formed by the reaction of Fe-Ni metal + gaseous H2S, sulfide immiscibility under increased conditions of partial O2 pressure is the preferred process.

  16. A recovery installation for sodium sulfates, thiosulfates and sulfides from waste water resulting from hydrogen sulfide fabrication

    International Nuclear Information System (INIS)

    An installation for recovery of sodium sulfate and sulfur suspensions from waste water was conceived. It consists from a preheater, vacuum evaporator and a refrigerating system with drum and scraper. This equipment concentration the solution by eliminating in the first stage the water in the vacuum evaporator. The water resulting at this stage is chemically pure and can be discharged in the sewage sludge system. The concentrated solution is then directed to the refrigerating system with drum and scrapper. Here the sodium sulfates, thiosulfates and sulfides get crystallized onto the drum surface. The resulting aqueous solution to be discharged in the sewage sludge system is previously analyzed as in case of the absent of the recovery installation, but the amount of pollutants will be much lower because sulfates, thiosulfates and sulfides were already recovered as scales from the drum. These solid scales can be used in detergent industry

  17. Regulation of bacterial sulfate reduction and hydrogen sulfide fluxes in the central Namibian coastal upwelling zone

    DEFF Research Database (Denmark)

    Bruchert, V.; Jørgensen, BB; Neumann, K.;

    2003-01-01

    low capacity to oxidize and trap sulfide. The inner shelf break marks the seaward border of sulfidic bottom waters, and separates two different regimes of bacterial sulfate reduction. In the sulfidic bottom waters on the shelf, up to 55% of sulfide oxidation is mediated by the large nitrate......The coastal upwelling system off central Namibia is one of the most productive regions of the oceans and is characterized by frequently occurring shelf anoxia with severe effects for the benthic life and fisheries. We present data on water column dissolved oxygen, sulfide, nitrate and nitrite, pore...... water profiles for dissolved,sulfide and sulfate, S-35-sulfate reduction rates, as well as bacterial counts of large sulfur bacteria from 20 stations across the continental shelf and slope. The stations covered two transects and included the inner shelf with its anoxic and extremely oxygen...

  18. Microbial control of the production of hydrogen sulfide by sulfate-reducing bacteria.

    Science.gov (United States)

    Montgomery, A D; McLnerney, M J; Sublette, K L

    1990-03-01

    A sulfide-resistant ctrain of Thiobacillus denitrificans, strain F, prevented the accumulation of sulfide by Desulfovibrio desulfuricans when both organisms were grown in liquid medium or in Berea sandstone cores. The wild-type strain of T. denitrificans did not prevent the accumulation of sulfide produced by D. desulfuricans. Strain F also prevented the accumulation of sulfide by a mixed population of sulfate-reducing bacteria enriched from an oil field brine. Fermentation balances showed that strain F stoichiometrically oxidized the sulfide produced by D. desulfuricans and the oil field brine enrichment to sulfate. These data suggest that strain F would be effective in controlling sulfide production in oil reservoirs and other environments. PMID:18592547

  19. When can Electrochemical Techniques give Reliable Corrosion Rates on Carbon Steel in Sulfide Media?

    DEFF Research Database (Denmark)

    Hilbert, Lisbeth Rischel; Hemmingsen, Tor; Nielsen, Lars Vendelbo;

    2005-01-01

    of film formation in sulfide solutions was followed by video. It can be shown that capacitative and diffusional effects due to porous reactive deposits tend to dominate the data resulting in unreliable corrosion rates measured by electrochemical techniques. The effect is strongly increased if biofilm......Effects of film formation on carbon steel in hydrogen sulfide media may corrupt corrosion rate monitoring by electrochemical techniques. Electrochemical data from hydrogen sulfide solutions, biological sulfide media and natural sulfide containing geothermal water have been collected and the process...... in combination with ferrous sulfide corrosion products cover the steel surface. Corrosion rates can be overestimated by a factor of 10 to 100 with electrochemical techniques - both by linear polarization resistance (LPR) and electrochemical impedance spectroscopy (EIS). Oxygen entering the system...

  20. Inhibition of Sulfide Mineral Oxidation by Surface Coating Agents: Batch

    Science.gov (United States)

    Choi, J.; Ji, M. K.; Yun, H. S.; Park, Y. T.; Gee, E. D.; Lee, W. R.; Jeon, B.-H.

    2012-04-01

    Mining activities and mineral industries have impacted on rapid oxidation of sulfide minerals such as pyrite (FeS2) which leads to Acid Mine Drainage (AMD) formation. Some of the abandoned mines discharge polluted water without proper environmental remediation treatments, largely because of financial constraints in treating AMD. Magnitude of the problem is considerable, especially in countries with a long history of mining. As metal sulfides become oxidized during mining activities, the aqueous environment becomes acid and rich in many metals, including iron, lead, mercury, arsenic and many others. The toxic heavy metals are responsible for the environmental deterioration of stream, groundwater and soils. Several strategies to remediate AMD contaminated sites have been proposed. Among the source inhibition and prevention technologies, microencapsulation (coating) has been considered as a promising technology. The encapsulation is based on inhibition of O2 diffusion by surface coating agent and is expected to control the oxidation of pyrite for a long time. Potential of several surface coating agents for preventing oxidation of metal sulfide minerals from both Young-Dong coal mine and Il-Gwang gold mine were examined by conducting batch experiments and field tests. Powdered pyrite as a standard sulfide mineral and rock samples from two mine outcrops were mixed with six coating agents (KH2PO4, MgO and KMnO4 as chemical agents, and apatite, cement and manganite as mineral agents) and incubated with oxidizing agents (H2O2 or NaClO). Batch experiments with Young-Dong coal mine samples showed least SO42- production in presence of KMnO4 (16% sulfate production compared to no surface coating agents) or cement (4%) within 8 days. In the case of Il-Gwang mine samples, least SO42- production was observed in presence of KH2PO4 (8%) or cement (2%) within 8 days. Field-scale pilot tests at Il-Gwang site also showed that addition of KH2PO4 decreased sulfate production from 200 to