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Sample records for allyl sulfides studies

  1. 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

  2. Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters

    Directory of Open Access Journals (Sweden)

    Malcolm J. D'Souza

    2013-04-01

    Full Text Available At 25.0 °C the specific rates of solvolysis for allyl and vinyl chloroformates have been determined in a wide mix of pure and aqueous organic mixtures. In all the solvents studied, vinyl chloroformate was found to react significantly faster than allyl chloroformate. Multiple correlation analyses of these rates are completed using the extended (two-term Grunwald-Winstein equation with incorporation of literature values for solvent nucleophilicity (NT and solvent ionizing power (YCl. Both substrates were found to solvolyze by similar dual bimolecular carbonyl-addition and unimolecular ionization channels, each heavily dependent upon the solvents nucleophilicity and ionizing ability.

  3. Isolation determination of garlic allyl sulfides and their antioxidant activity%大蒜烯丙基硫化物的分离鉴定及抗氧化性

    Institute of Scientific and Technical Information of China (English)

    刘玲; 陈琭璐; 张瑶; 白冰; 纪淑娟

    2015-01-01

    为了研究大蒜烯丙基硫化物的抗氧化活性,该文利用离子交换层析与制备液相技术从大蒜中分离得到 S-烯丙基-L-半胱氨酸(S-allyl-L-cysteine,SAC)、S-烯丙基-L-半胱氨酸亚砜(S-allyl-L-cysteine sulfoxide,ACSO)和γ-谷氨酰-S-烯丙基-L-半胱氨酸(γ-L-glutamyl-S-allyl-L-cysteine,GSAC)3种水溶性烯丙基硫化物。分离产物利用高效液相色谱-电喷雾离子化串联质谱联用(high performance liquid chromatography-electrospray ionization-mass/mass spectrometry, HPLC-ESI-MS/MS)、核磁共振氢谱(proton nuclear magnetic resonance,1H NMR)和核磁共振碳谱(carbon-13 nuclear magnetic resonance,13C NMR)技术及比旋光度检测方法鉴定,并与合成标准品比对分析确定。同时,该文以具有半胱氨酸结构的还原型谷胱甘肽(glutathione,GSH)为参照测定了 SAC、ACSO、GSAC 的1,1-二苯基-2-三硝基苯肼(1,1-diphenyl-2-picrylhydrazyl,DPPH)自由基清除能力及铁离子螯合能力。结果表明,SAC和GSAC对DPPH自由基的清除率较高(73.55%,72.68%)且与 GSH(71.14%)无显著性差异(P<0.05);SAC 和 ACSO 对铁离子的螯合率较高(81.21%,79.18%)且与GSH(78.13%)无显著性差异(P<0.05),尤其是GSAC对铁离子螯合率(92.76%)显著性高于GSH(P<0.05),证实了3种硫化物均具有很好的抗氧化性能。研究结果进一步解释和阐述大蒜硫化物的螯合能力,进而为大蒜硫化物以抗氧化为基础的其他功能活性研究提供参考。%The allyl-substituted cysteine derivatives were major components of sulfur compounds in garlic. This study separated and identified 3 allyl-substituted cysteine derivatives, i.e.S-allyl-L-cysteine (SAC),S-allyl-L-cysteine sulfoxide (ACSO) andγ-L-glutamyl-S-allyl-L-cysteine (GSAC). Furthermore, scavenging ability of 1,1-Diphenyl-2-picrylhydrazyl (DPPH) free radical and iron chelating ability were tested

  4. Electrochemical studies and self diffusion coefficients in cyclic ammonium based ionic liquids with allyl substituents

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Tzi-Yi [Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan (China); Department of Polymer Materials, Kun Shan University, Tainan 71003, Taiwan (China); Su, Shyh-Gang [Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan (China); Wang, H. Paul [Department of Environmental Engineering, National Cheng Kung University, Tainan, Taiwan (China); Lin, Yuan-Chung [Institute of Environmental Engineering, National Sun Yat-Sen University, Kaohsiung 804, Taiwan (China); Gung, Shr-Tusen; Lin, Ming-Wei [Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan (China); Sun, I.-Wen, E-mail: iwsun@mail.ncku.edu.t [Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan (China)

    2011-03-30

    Research highlights: Cyclic ammonium-based ionic liquids with allyl substituent have high conductivity. Ionic liquids with allyl substituent have wide electrochemical window. Electrochemical and self diffusion coefficients are available for comparison. The Stokes-Einstein plots of DT{sup -1} vs. {eta}{sup -1} for redox couples in ILs are evaluated. Stokes-Einstein product of ferrocene is larger than that of cobaltocenium in ILs. - Abstract: Several cyclic ammonium-based ionic liquids (ILs) with allyl substituent are synthesized, these allyl substituent ILs have high ionic conductivity (up to 4.72 mS cm{sup -1} at 30 {sup o}C) and wide electrochemical window of 5 V. The electrochemical behaviors of two organometallic redox couples Fc/Fc{sup +} (ferrocene/ferrocenium) and Cc/Cc{sup +} (cobaltocene/cobaltocenium) have been studied in these ILs, the calculated Stokes-Einstein product (D{eta} T{sup -1}) of ferrocene in ILs is larger than that of cobaltocenium in ILs. The self-diffusion coefficients of cation and anion in these ILs are studied using pulsed gradient spin-echo NMR technique. There are very few reports where electrochemically derived diffusion coefficients and self diffusion coefficients are available for comparison, so a new key concept in electrochemistry could be developed in this paper.

  5. The allylic chalcogen effect in olefin metathesis

    Directory of Open Access Journals (Sweden)

    Yuya A. Lin

    2010-12-01

    Full Text Available Olefin metathesis has emerged as a powerful tool in organic synthesis. The activating effect of an allylic hydroxy group in metathesis has been known for more than 10 years, and many organic chemists have taken advantage of this positive influence for efficient synthesis of natural products. Recently, the discovery of the rate enhancement by allyl sulfides in aqueous cross-metathesis has allowed the first examples of such a reaction on proteins. This led to a new benchmark in substrate complexity for cross-metathesis and expanded the potential of olefin metathesis for other applications in chemical biology. The enhanced reactivity of allyl sulfide, along with earlier reports of a similar effect by allylic hydroxy groups, suggests that allyl chalcogens generally play an important role in modulating the rate of olefin metathesis. In this review, we discuss the effect of allylic chalcogens in olefin metathesis and highlight its most recent applications in synthetic chemistry and protein modifications.

  6. The allylic chalcogen effect in olefin metathesis

    Science.gov (United States)

    Lin, Yuya A

    2010-01-01

    Summary Olefin metathesis has emerged as a powerful tool in organic synthesis. The activating effect of an allylic hydroxy group in metathesis has been known for more than 10 years, and many organic chemists have taken advantage of this positive influence for efficient synthesis of natural products. Recently, the discovery of the rate enhancement by allyl sulfides in aqueous cross-metathesis has allowed the first examples of such a reaction on proteins. This led to a new benchmark in substrate complexity for cross-metathesis and expanded the potential of olefin metathesis for other applications in chemical biology. The enhanced reactivity of allyl sulfide, along with earlier reports of a similar effect by allylic hydroxy groups, suggests that allyl chalcogens generally play an important role in modulating the rate of olefin metathesis. In this review, we discuss the effect of allylic chalcogens in olefin metathesis and highlight its most recent applications in synthetic chemistry and protein modifications. PMID:21283554

  7. 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.

  8. Iridium-catalyzed allylic substitutions with cyclometalated phosphoramidite complexes bearing a dibenzocyclooctatetraene ligand: preparation of (π-allyl)Ir complexes and computational and NMR spectroscopic studies.

    Science.gov (United States)

    Raskatov, Jevgenij A; Jäkel, Mascha; Straub, Bernd F; Rominger, Frank; Helmchen, Günter

    2012-11-01

    (π-Allyl)Ir complexes derived from dibenzocyclooctatetraene and phosphoramidites by cyclometalation are effective catalysts for allylic substitution reactions of linear monosubstituted allylic carbonates. These catalysts provide exceptionally high degrees of regioselectivity and allow the reactions to be run under aerobic conditions. A series of (π-allyl)Ir complexes were prepared and characterized by X-ray crystal structure analyses. An allylic amination with aniline displayed different resting states depending on the presence of a strong base. DFT calculations were carried out on the mechanistic aspects of these reactions. The results suggest that for the (π-allyl)Ir complexes, the formation and reactions with nucleophiles proceed with comparable rates. PMID:23018807

  9. Experimental and Kinetic Modeling Study of 2-Methyl-2-Butene: Allylic Hydrocarbon Kinetics.

    Science.gov (United States)

    Westbrook, Charles K; Pitz, William J; Mehl, Marco; Glaude, Pierre-Alexandre; Herbinet, Olivier; Bax, Sarah; Battin-Leclerc, Frederique; Mathieu, Olivier; Petersen, Eric L; Bugler, John; Curran, Henry J

    2015-07-16

    Two experimental studies have been carried out on the oxidation of 2-methyl-2-butene, one measuring ignition delay times behind reflected shock waves in a stainless steel shock tube, and the other measuring fuel, intermediate, and product species mole fractions in a jet-stirred reactor (JSR). The shock tube ignition experiments were carried out at three different pressures, approximately 1.7, 11.2, and 31 atm, and at each pressure, fuel-lean (ϕ = 0.5), stoichiometric (ϕ = 1.0), and fuel-rich (ϕ = 2.0) mixtures were examined, with each fuel/oxygen mixture diluted in 99% Ar, for initial postshock temperatures between 1330 and 1730 K. The JSR experiments were performed at nearly atmospheric pressure (800 Torr), with stoichiometric fuel/oxygen mixtures with 0.01 mole fraction of 2M2B fuel, a residence time in the reactor of 1.5 s, and mole fractions of 36 different chemical species were measured over a temperature range from 600 to 1150 K. These JSR experiments represent the first such study reporting detailed species measurements for an unsaturated, branched hydrocarbon fuel larger than iso-butene. A detailed chemical kinetic reaction mechanism was developed to study the important reaction pathways in these experiments, with particular attention on the role played by allylic C-H bonds and allylic pentenyl radicals. The results show that, at high temperatures, this olefinic fuel reacts rapidly, similar to related alkane fuels, but the pronounced thermal stability of the allylic pentenyl species inhibits low temperature reactivity, so 2M2B does not produce "cool flames" or negative temperature coefficient behavior. The connections between olefin hydrocarbon fuels, resulting allylic fuel radicals, the resulting lack of low-temperature reactivity, and the gasoline engine concept of octane sensitivity are discussed. PMID:25822578

  10. Neutron response study using poly allyl diglycol carbonate

    Indian Academy of Sciences (India)

    Basma A El-Badry; M F Zaki; Tarek M Hegazy; A Ahmed Morsy

    2007-10-01

    The results of an experimental work aimed at improving the performance of the CR-39 nuclear track detector for neutron dosimetry applications are reported. A set of CR-39 plastic detectors was exposed to 252Cf neutron source, which has the emission rate of 0.68 × 108 s-1, and neutron dose equivalent rate 1 m apart from the source is equal to 3.8 mrem/h. The detection of fast neutrons performed with CR-39 detector foils, subsequent chemical etching and evaluation of the etched tracks by an automatic track counting system was studied. It is found that the track density increases with the increase of neutron dose and etching time. The track density in the detector is directly proportional to the neutron fluence producing the recoil tracks, provided the track density is in the countable range. This fact plays an important role in determining the equivalent dose in the field of neutron dosimetry. These results are compared with previous work. It is found that our results are in good agreement with their investigations.

  11. Interplay of metal-allyl and metal-metal bonding in dimolybdenum allyl complexes.

    Energy Technology Data Exchange (ETDEWEB)

    Trovitch, R. J.; John, K. D.; Martin, R. L.; Obrey, S. J.; Sattelberger, A. P.; Scott, B. L.; Baker, R. T.; LANL; Univ. of Ottawa

    2009-01-01

    Addition of PMe{sub 3} to Mo{sub 2}(allyl){sub 4} afforded Mo{sub 2}(allyl){sub 4}(PMe{sub 3}){sub 2}, in which two of the allyl groups adopt an unprecedented {mu}{sub 2}-{eta}{sup 1}, {eta}{sup 3} bonding mode; theoretical studies elucidate the roles of the {sigma}- and {pi}-donor ligands in the interplay of metal-allyl and metal-metal bonding.

  12. Studies on the Synthesis of Morphinan Alkaloid: Preparation of the Key Allylic Silyl Ether Precursor

    Institute of Scientific and Technical Information of China (English)

    Zhen Lei SONG; Yong Qiang TU; Shuan Hu GAO; Yi Jun JIANG; Shu Yu ZHANG

    2005-01-01

    A convergent strategy to the key allylic silyl ether precursor 4 in our synthetic efforts toward morphinan alkaloid is presented. The vital step is the selective 1,2-addition of the organocerium agent of 6 to ketene 5.

  13. Synthetic Studies on Tricyclic Diterpenoids: Direct Allylic Amination Reaction of Isopimaric Acid Derivatives.

    Science.gov (United States)

    Timoshenko, Mariya A; Kharitonov, Yurii V; Shakirov, Makhmut M; Bagryanskaya, Irina Yu; Shults, Elvira E

    2016-02-01

    A selective synthesis of 7- or 14-nitrogen containing tricyclic diterpenoids was completed according to a strategy in which the key step was the catalyzed direct allylic amination of methyl 14α-hydroxy-15,16-dihydroisopimarate with a wide variety of nitrogenated nucleophiles. It was revealed that the selectivity of the reaction depends on the nature of nucleophile. The catalyzed reaction of the mentioned diterpenoid allylic alcohol with 3-nitroaniline, 3-(trifluoromethyl)aniline, and 4-(trifluoromethyl)aniline yield the subsequent 7α-, 7β- and 14αnitrogen-containing diterpenoids. The reaction with 2-nitroaniline, 4-nitro-2-chloroaniline, 4-methoxy-2-nitroaniline, phenylsulfamide, or tert-butyl carbamate proceeds with the formation of 7α-nitrogen-substituted diterpenoids as the main products. PMID:27308214

  14. Theoretical study on the gas phase reaction of allyl chloride with hydroxyl radical.

    Science.gov (United States)

    Zhang, Yunju; Chao, Kai; Sun, Jingyu; Zhang, Wanqiao; Shi, Haijie; Yao, Cen; Su, Zhongmin; Pan, Xiumei; Zhang, Jingping; Wang, Rongshun

    2014-02-28

    The reaction of allyl chloride with the hydroxyl radical has been investigated on a sound theoretical basis. This is the first time to gain a conclusive insight into the reaction mechanism and kinetics for important pathways in detail. The reaction mechanism confirms that OH addition to the C=C double bond forms the chemically activated adducts, IM1 (CH2CHOHCH2Cl) and IM2 (CH2OHCHCH2Cl) via low barriers, and direct H-abstraction paths may also occur. Variational transition state model and multichannel RRKM theory are employed to calculate the temperature-, pressure-dependent rate constants. The calculated rate constants are in good agreement with the experimental data. At 100 Torr with He as bath gas, IM6 formed by collisional stabilization is the major products in the temperature range 200-600 K; the production of CH2CHCHCl via hydrogen abstractions becomes dominant at high temperatures (600-3000 K). PMID:24588171

  15. Theoretical study on the gas phase reaction of allyl chloride with hydroxyl radical

    Science.gov (United States)

    Zhang, Yunju; Chao, Kai; Sun, Jingyu; Zhang, Wanqiao; Shi, Haijie; Yao, Cen; Su, Zhongmin; Pan, Xiumei; Zhang, Jingping; Wang, Rongshun

    2014-02-01

    The reaction of allyl chloride with the hydroxyl radical has been investigated on a sound theoretical basis. This is the first time to gain a conclusive insight into the reaction mechanism and kinetics for important pathways in detail. The reaction mechanism confirms that OH addition to the C=C double bond forms the chemically activated adducts, IM1 (CH2CHOHCH2Cl) and IM2 (CH2OHCHCH2Cl) via low barriers, and direct H-abstraction paths may also occur. Variational transition state model and multichannel RRKM theory are employed to calculate the temperature-, pressure-dependent rate constants. The calculated rate constants are in good agreement with the experimental data. At 100 Torr with He as bath gas, IM6 formed by collisional stabilization is the major products in the temperature range 200-600 K; the production of CH2CHCHCl via hydrogen abstractions becomes dominant at high temperatures (600-3000 K).

  16. Computational study of dissociative electron attachment to π-allyl ruthenium (II) tricarbonyl bromide

    Science.gov (United States)

    Thorman, Rachel M.; Bjornsson, Ragnar; Ingólfsson, Oddur

    2016-08-01

    Motivated by the current interest in low energy electron induced fragmentation of organometallic complexes in focused electron beam induced deposition (FEBID) we have evaluated different theoretical protocols for the calculation of thermochemical threshold energies for DEA to the organometallic complex π-allyl ruthenium (II) tricarbonyl bromide. Several different computational methods including density functional theory (DFT), hybrid-DFT and coupled cluster were evaluated for their ability to predict these threshold energies and compared with the respective experimental values. Density functional theory and hybrid DFT methods were surprisingly found to have poor reliability in the modelling of several DEA reactions; however, the coupled cluster method LPNO-pCCSD/2a was found to produce much more accurate results. Using the local correlation pair natural orbital (LPNO) methodology, high level coupled cluster calculations for open-shell systems of this size are now affordable, paving the way for reliable theoretical DEA predictions of such compounds. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.

  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. Resonance Raman spectrum of the allyl-d5 radical and the force field analysis of the allyl radical

    Science.gov (United States)

    Liu, Xianming; Getty, James D.; Kelly, Peter B.

    1993-08-01

    Resonance Raman spectra of the allyl-d5 radical have been obtained with excitation between 247 and 223 nm. Analysis of the spectra yields the first observation of fundamental frequencies, nu4, nu5, and nu7 and overtone frequencies 2nu9, 2nu10, and 2nu12. The new vibrational data are combined with previously observed frequencies of allyl-h5 and allyl-d5 radical to produce the force field analysis for the allyl radical. This study suggests reassignment of several previously observed infrared (IR) bands. Experimental frequencies and assignments for allyl-h5 and allyl-d5 are compared with results from ab initio calculations. Force constants obtained in the present work are compared with the force constants of other sp2 hybridization molecules such as benzene, allene, and ethylene.

  19. 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.

  20. Study on the Preparation of Allyl-modified Starch in Isopropyl/Water Medium for Warp Sizing

    Institute of Scientific and Technical Information of China (English)

    LI Man-li; ZHU Zhi-feng; ZHANG Long-qiu

    2008-01-01

    A new method for the pretreatment of starch by etherification was developed to eliminate the problems of lower grafting efficiency associated with the preparation of starch graft copolymers as warp sizing agents.The etherification of starch with allyl chloride was investigated in order to effectively enhance the reaction efficiency.The technological variables of the reaction considered for evaluating the etherification included sodium hydroxide amount,water content in water-isopropyi alcohol medium,allyl cldoride concentration,reaction temperature and reaction time.The experimental result demonstrated that the variables considered showed evident effect on the reaction efficiency.For the etherification,a condition of 20% for the water content,1.5:1 for the molar ratio of sodium hydroxide to allyl chloride.and at 30℃ under 24h reaction is Sufficient to retain the reaction efficiency above 50%.Furthermore,a contrast test demonstrated that the graft efficiency can be increased with the etherification pretreatment.

  1. Allyl 4-hydroxyphenyl carbonate

    Directory of Open Access Journals (Sweden)

    Víctor Hugo Flores Ahuactzin

    2009-07-01

    Full Text Available The title molecule, C10H10O4, is a functionalized carbonate used in the synthetic route to organic glasses. The central CH fragment of the allyl group is disordered over two positions, with occupancies in a 0.758 (10:0.242 (10ratio. This disorder reflects the torsional flexibility of the oxygen–allyl group, although both disordered parts present the expected anticlinal conformation, with O—CH2—CH=CH2 torsion angles of −111 (2 and 119.1 (4°. The crystal structure is based on chains parallel to [010], formed by O...H—O hydrogen bonds involving hydroxyl and carbonyl groups as donors and acceptors, respectively. The molecular packing is further stabilized by two weak C—H...π contacts from the benzene ring of the asymmetric unit with two benzene rings of neighboring molecules.

  2. XAFS characterization of industrial catalysts: in situ study of phase transformation of nickel sulfide

    Science.gov (United States)

    Wang, J.; Jia, Z.; Wang, Q.; Zhao, S.; Xu, Z.; Yang, W.; Frenkel, A. I.

    2016-05-01

    The online sulfiding process for nickel-contained catalyst often ends up with a nickel sulfide mixture in refinery plant. To elucidate the local environment of nickel and its corresponding sulfur species, a model catalyst (nickel sulfide) and model thermal process were employed to explore the possibilities for characterization of real catalysts in industrial conditions. The present investigation shows effectiveness of in situ XANES and EXAFS measurements for studying the phase stability and phase composition in these systems, which could be used to simulate real sulfiding process in industrial reactions, such as hydrodesulfurizations of oil.

  3. 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

  4. Velocity Map Imaging Study of Ion-Radical Chemistry: Charge Transfer and Carbon-Carbon Bond Formation in the Reactions of Allyl Radicals with C(.).

    Science.gov (United States)

    Pei, Linsen; Farrar, James M

    2016-08-11

    We present an experimental and computational study of the dynamics of collisions of ground state carbon cations with allyl radicals, C3H5, at a collision energy of 2.2 eV. Charge transfer to produce the allyl cation, C3H5(+), is exoergic by 3.08 eV and proceeds via energy resonance such that the electron transfer occurs without a significant change in nuclear velocities. The products have sufficient energy to undergo the dissociation process C3H5(+) → C3H4(+) + H. Approximately 80% of the reaction products are ascribed to charge transfer, with ∼40% of those products decaying via loss of a hydrogen atom. We also observe products arising from the formation of new carbon-carbon bonds. The experimental velocity space flux distributions for the four-carbon products are symmetric about the centroid of the reactants, providing direct evidence that the products are mediated by formation of a C4H5(+) complex living at least a few rotational periods. The primary four-carbon reaction products are formed by elimination of molecular hydrogen from the C4H5(+) complex. More than 75% of the nascent C4H3(+) products decay by C-H bond cleavage to yield a C4H2(+) species. Quantum chemical calculations at the MP2/6-311+g(d,p) level of theory support the formation of a nonplanar cyclic C4H5(+) adduct that is produced when the p-orbital containing the unpaired electron on C(+) overlaps with the unpaired spin density on the terminal carbon atoms in allyl. Product formation then occurs by 1,2-elimination of molecular hydrogen from the cyclic intermediate to form a planar cyclic C4H3(+) product. The large rearrangement in geometry as the C4H3(+) products are formed is consistent with high vibrational excitation in that product and supports the observation that the majority of those products decay to form the C4H2(+) species. PMID:27434380

  5. Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device

    OpenAIRE

    Peter Fremerey; Andreas Jess; Ralf Moos

    2015-01-01

    In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H2S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nicke...

  6. Molecular Simulation Study on Interaction of Thiophene Sulfides with Transition Metals

    Institute of Scientific and Technical Information of China (English)

    Liu Yujian; Long Jun; Zhou Han; Zhu Yuxia; Da Zhijian

    2003-01-01

    The computer molecular simulation technique was applied to study the chemisorption of thiophene and tetramethylthiophene as the model sulfides on the simple oxides and complex oxides of some transition metals as the catalytic materials. The study disclosed that the thiophene sulfides could enter into chemisorption with metal oxides such as VO, ZnO, NiO and Zn-Al-spinel. This interaction could lead to thiophene molecular structure deformation to be in an activated adsorption state, which could help to promote the conversion of thiophene sulfides in the course of catalytic cracking. The VO with a valence of 2 could provide relatively strong selective adsorption sites for the conversion of thiophene sulfides to apparently transform the molecular structures and electron cloud states of such heterocyclic sulfur compounds such as thiophene and tetramethylthiophene into an activated adsorption state. The effect of this interaction was more pronounced with respect to tetramethylthiophene.

  7. Allylation of Aromatic Aldehyde under Microwave Irradiation

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Yu-Mei; JIA,Xue-Feng; WANG,Jin-Xian

    2004-01-01

    @@ Allylation of carbonyl compounds is one of the most interesting processes for the preparation of homoallylic alcohols. Over the past few decades, many reagents have been developed for such reactions[1~3]. In this paper, we first report allylic zinc reagent 1, which can be prepared from zinc dust and allyl bromide conveniently in THF, and reacted with aromatic aldehyde to give homo-allylic alcohols under microwave irradiation.

  8. Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device

    Directory of Open Access Journals (Sweden)

    Peter Fremerey

    2015-10-01

    Full Text Available In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H2S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nickel sulfide occurred. This conductivity increase by decades during sulfidation had not been expected since both nickel and nickel sulfides behave metallic. Only by assuming a percolation phenomenon that originates from a volume increase of the nickel contacts when reacting to nickel sulfides, this effect can be explained. This assumption was supported by sulfidation tests with differently nickel loaded catalysts and it was quantitatively estimated by a general effective media theory. The single pellet sensor device for in operando investigation of sulfidation can be considered as a valuable tool to get further insights into catalysts under reaction conditions.

  9. Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device.

    Science.gov (United States)

    Fremerey, Peter; Jess, Andreas; Moos, Ralf

    2015-01-01

    In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H₂S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nickel sulfide occurred. This conductivity increase by decades during sulfidation had not been expected since both nickel and nickel sulfides behave metallic. Only by assuming a percolation phenomenon that originates from a volume increase of the nickel contacts when reacting to nickel sulfides, this effect can be explained. This assumption was supported by sulfidation tests with differently nickel loaded catalysts and it was quantitatively estimated by a general effective media theory. The single pellet sensor device for in operando investigation of sulfidation can be considered as a valuable tool to get further insights into catalysts under reaction conditions. PMID:26512669

  10. 烯丙基苯并恶嗪改性BT树脂的研究%Study on Bismaleimide-Triazine Resin Modiifed by Allyl Benzoxazine

    Institute of Scientific and Technical Information of China (English)

    陈虹; 寇开昌; 王益群; 张宇; 卓龙海

    2014-01-01

    采用熔融缩聚法合成了烯丙基苯并恶嗪(Boz-allyl),并利用傅立叶变换红外光谱,磁共振氢谱对其表征。用动态扫描量热与热重分析研究了其固化过程及热性能,随后用其对双马来酰亚胺-三嗪树脂(BT树脂)改性,并分析了改性树脂的力学性能。结果表明,Boz-allyl存在两种固化机理,固化物5%和10%热失重温度分别为325,385℃,在800℃时质量保持率仍可达34%,说明其具有优良的热稳定性和耐烧蚀性,用其改性后BT树脂韧性明显提高,当Boz-allyl质量分数为8%时冲击和弯曲强度达到最大值,分别为11.32 kJ/m2和127.11 MPa。%An allyl benzoxazine(Boz-allyl) was synthesized by melt polycondensation method and the structures of Boz-allyl was confirmed by Fourier transform infrared spectroscopy and nuclear magnetic resonance. Using differential scanning calorimetery and thermal gravimetric analysis,the curing behavior and thermal property of it were probed. Then the bismaleimide-triazine resin modified by Boz-allyl was prepared and its mechanical properties was investigated. The results show a dual cure pattern of Boz-allyl ,while the 5%and 10%weight loss temperatures of polybenzoxazine is 325℃and 385℃respectively,with quality retention rate up to 34%at 800℃,which reveals good heat resistance and ablation resistance. The addition of Boz-allyl into BT resin significantly improves toughness and strength,its impact strength and flexural strength is up to their maximums of 11.32 kJ/m2 and 127.11 MPa when the mass fraction of Boz-allyl is 8%.

  11. Characteristics of the interaction of azulene with water and hydrogen sulfide: A computational study.

    Science.gov (United States)

    Cabaleiro-Lago, Enrique M; Rodríguez-Otero, Jesús; Peña-Gallego, Angeles

    2008-08-28

    A computational study was carried out for studying the characteristics of the interaction between azulene and water or hydrogen sulfide. In azulene...water complex the water molecule is located with both hydrogen atoms pointing toward the aromatic cloud but displaced to the five-membered ring. Hydrogen sulfide adopts a similar arrangement but located roughly over the central C-C bond of azulene. Calculations show that hydrogen sulfide interacts with azulene more strongly (-4.19 kcal/mol) than water (-3.76 kcal/mol), although this is only revealed at the highest levels of calculation. The nature of the interaction is electrostatic and dispersive in the same percentage for water cluster, whereas for hydrogen sulfide dispersion is the dominant contribution. Clusters containing two water molecules are controlled by the possibility of establishing an O-H...O hydrogen bond. As a consequence, the most stable structure corresponds to the interaction between a water dimer and azulene, with an interaction energy amounting to -11.77 kcal/mol. Hydrogen sulfide interaction is stronger with azulene than with itself, so structures with S-H...S contact and others, where H(2)S only interacts with azulene, present similar interaction energies (-8.02 kcal/mol for the most stable one).

  12. Antifoaming materials studies in G.S. (Girlder sulfide) heavy water plants. Chemical and thermical stability. Pt. 3

    International Nuclear Information System (INIS)

    In Girlder sulfide (G.S.) heavy water plants hydrogen sulfide-water systems are inherentely foaming, so the adding of antifoaming materials is of great importance. These may be of high volatility, pyrolizable or chemically unstable in plant operation conditions (water and hydrogen sulfide at 2 MPa, up to 230 deg C). Five commercial surfactants were studied from the point of view of their chemical and thermical stability in order to select the most suitable. (Author)

  13. Studies on silicone based antifoaming agents to be used in G.S. (Girlder sulfide) heavy water plants

    International Nuclear Information System (INIS)

    In Girlder sulfide (G.S.) heavy water plants hydrogen sulfide-water systems are inherentely foaming, so the adding of antifoaming materials is of great importance. These may be of high volatility, pyrolizable or chemically unstable in plant operation conditions (water and hydrogen sulfide at 2MPa, up to 230 deg C). Six commercial silicone based antifoaming agents were studied from the point of view of their chemical and thermical stability in order to select the most suitable. (Author)

  14. Spectroscopic study of Se(IV) removal from water by reductive precipitation using sulfide.

    Science.gov (United States)

    Jung, Bahngmi; Safan, Aya; Batchelor, Bill; Abdel-Wahab, Ahmed

    2016-11-01

    This study investigates the removal of selenium (IV) from water by reductive precipitation using sodium sulfide at neutral pH. Also, it examines the application of UV light as an activating method to enhance reductive precipitation. Furthermore, this work evaluates the effects of sulfide dose and solution pH on behavior of Se(IV) reduction. Selenium was effectively removed in sulfide solution at both neutral and acidic pH. UV irradiation did not enhance removal efficiency of Se(IV) at conditions tested, but it affected solids morphology and composition. SEM/EDS and XPS results showed that selenite was reduced to elemental Se or Se-S precipitates (e.g. SenS8-n) in sulfide solution. High resolution S 2p XPS spectra suggested the presence of sulfur-containing anions (e.g. S2O3(2-), HSO3(-), etc.) or elemental S (S(0)), monosulfide (S(2-)), and polysulfides (Sn(2-)), which could be produced from sulfide photolysis or reaction with Se. In addition, large aggregates of irregular shape, which suggest Se-S precipitates or elemental sulfur, were found more prominently at pH 4 than at pH 7, and they were more noticeable in the presence of UV with longer reaction times. In addition, XRD patterns showed that gray elemental Se solids were dominant in experiments without UV, whereas Se-S precipitates (Se3S5) with an orange color were found in those with UV. PMID:27552695

  15. Selenium Sulfide

    Science.gov (United States)

    Selenium sulfide, an anti-infective agent, relieves itching and flaking of the scalp and removes the dry, scaly particles ... Selenium sulfide comes in a lotion and is usually applied as a shampoo. As a shampoo, selenium sulfide usually ...

  16. Thiol addition to protected allyl glycosides: an improved method for the preparation of spacer-arm glycosides

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Seeventer, P.B. van; Dorst, J.A.L.M. van; Siemerink, J.F.; Kamerling, J.P.

    1997-01-01

    A useful method for the preparation of differently functionalized sulfide spacer-arm glycosides is presented. Several protected allyl glycosides were variously elongated via a radical addition reaction with pentanethiol, methyl 3-mercaptopropionate, or 2-mercaptoethanol. The hydroxyl function of pro

  17. Computational study of the interaction of indole-like molecules with water and hydrogen sulfide.

    Science.gov (United States)

    Cabaleiro-Lago, Enrique M; Rodríguez-Otero, Jesús; Peña-Gallego, Ángeles

    2011-10-01

    The characteristics of the interaction between water and hydrogen sulfide with indole and a series of analogs obtained by substituting the NH group of indole by different heteroatoms have been studied by means of ab initio calculations. In all cases, minima were found corresponding to structures where water and hydrogen sulfide interact by means of X-H···π contacts. The interaction energies for all these π complexes are quite similar, spanning from -13.5 to -18.8 kJ/mol, and exhibiting the stability sequence NH > CH(2) ≈ PH > Se ≈ S > O, for both water and hydrogen sulfide. Though interaction energies are similar, hydrogen sulfide complexes are slightly favored over their water counterparts when interacting with the π cloud. σ-Type complexes were also considered for the systems studied, but only in the case of water complexes this kind of complexes is relevant. Only for complexes formed by water and indole, a significantly more stable σ-type complex was found with an interaction energy amounting to -23.6 kJ/mol. Oxygen and phosphorous derivatives also form σ-type complexes of similar stability as that observed for π ones. Despite the similar interaction energies exhibited by complexes with water and hydrogen sulfide, the nature of the interaction is very different. For π complexes with water the main contributions to the interaction energy are electrostatic and dispersive contributing with similar amounts, though slightly more from electrostatics. On the contrary, in hydrogen sulfide complexes dispersion is by far the main stabilizing contribution. For the σ-type complexes, the interaction is clearly dominated by the electrostatic contribution, especially in the indole-water complex.

  18. High-temperature study of superconducting hydrogen and deuterium sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Durajski, A.P. [Institute of Physics, Czestochowa University of Technology, Ave. Armii Krajowej 19, 42-200 Czestochowa (Poland); Szczesniak, R. [Institute of Physics, Czestochowa University of Technology, Ave. Armii Krajowej 19, 42-200 Czestochowa (Poland); Institute of Physics, Jan Dlugosz University, Ave. Armii Krajowej 13/15, 42-200 Czestochowa (Poland); Pietronero, L. [Sapienza, Universita di Roma, Dip. Fisica, P. le A. Moro 2, 00185 Roma (Italy); Institute of Complex Systems, CNR, Via dei Taurini 19 Roma (Italy); London Institute for Mathematical Sciences, South Street 22, Mayfair London (United Kingdom)

    2016-05-15

    Hydrogen-rich compounds are extensively explored as candidates for a high-temperature superconductors. Currently, the measured critical temperature of 203 K in hydrogen sulfide (H{sub 3}S) is among the highest over all-known superconductors. In present paper, using the strong-coupling Eliashberg theory of superconductivity, we compared in detail the thermodynamic properties of two samples containing different hydrogen isotopes H{sub 3}S and D{sub 3}S at 150 GPa. Our research indicates that it is possible to reproduce the measured values of critical temperature 203 K and 147 K for H{sub 3}S and D{sub 3}S by using a Coulomb pseudopotential of 0.123 and 0.131, respectively. However, we also discuss a scenario in which the isotope effect is independent of pressure and the Coulomb pseudopotential for D{sub 3}S is smaller than for H{sub 3}S. For both scenarios, the energy gap, specific heat, thermodynamic critical field and related dimensionless ratios are calculated and compared with other conventional superconductors. We shown that the existence of the strong-coupling and retardation effects in the systems analysed result in significant differences between values obtained within the framework of the Eliashberg formalism and the prediction of the Bardeen-Cooper-Schrieffer theory. (copyright 2015 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. A computational study of adhesion between rubber and metal sulfides at rubber–brass interface

    International Nuclear Information System (INIS)

    Highlights: • An atomic level model for brass–rubber interactions has been presented. • The main adhesion force has been tracked to the rubber sulfur–brass zinc or brass copper interaction. • The model gives new understanding of the adhesion and can be used for further developments of the system. - Abstract: Computational study at level of density functional theory has been carried out in order to investigate the adhesion between rubber and brass plated steel cord, which has high importance in tire manufacturing. Adsorption of natural rubber based adsorbate models has been studied on zinc sulfide, ZnS(1 1 0), and copper sulfide, Cu2S(1 1 1) and CuS(0 0 1), surfaces as the corresponding phases are formed in adhesive interlayer during rubber vulcanization. Saturated hydrocarbons exhibited weak interactions, whereas unsaturated hydrocarbons and sulfur-containing adsorbates interacted with the metal atoms of sulfide surfaces more strongly. Sulfur-containing adsorbates interacted with ZnS(1 1 0) surface stronger than unsaturated hydrocarbons, whereras both Cu2S(1 1 1) and CuS(0 0 1) surfaces showed opposite adsorption preference as unsaturated hydrocarbons adsorbed stronger than sulfur-containing adsorbates. The different interaction strength order can play role in rubber–brass adhesion with different relative sulfide concentrations. Moreover, Cu2S(1 1 1) surface exhibits higher adsorption energies than CuS(0 0 1) surface, possibly indicating dominant role of Cu2S in the adhesion between rubber and brass

  20. Studies on ternary silver sulfides; Fukugo gin ryukabutsu ni kansuru kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-10-31

    Some sulfides containing silver show high ion mobility based on movability of silver, whose application is expected. Studies have been carried out centrally on synthesis of new compounds of ternary silver sulfides by elucidating the relationship among their compositions, structures and properties by means of crystal chemical studies mainly on their phase relationship. A few new compounds have been synthesized, such as the ones having the argyrodite family compound structure including transition metals. The synthesizing process takes a kind of turbulent liquid state structure at elevated temperatures because of movability of silver, but silver is fixed at low temperatures in different sites between skeleton structures made by other atoms. These studies on phase transfer, structures, and silver movability have been based on X-ray diffraction, infrared and Raman spectroscopic measurements, NMR, measurements of electric and thermal characteristics. For the studies related to compositions and structures of ternary metal sulfides which take compound crystalline structure, a structure analyzing method based on multi-dimensional hyperspatial groups was used. This paper reports the summary of the studies in seven chapters, and dwells on the remaining problems and future prospects. 158 refs., 114 figs., 65 tabs.

  1. Preparation and study of thickness dependent electrical characteristics of zinc sulfide thin films

    Indian Academy of Sciences (India)

    A U Ubale; D K Kulkarni

    2005-02-01

    Zinc sulfide thin films have been deposited onto glass substrates by chemical bath deposition. The various deposition parameters such as volume of sulfide ion source, pH of bath, deposition time, temperature etc are optimized. Thin films of ZnS with different thicknesses of 76–332 nm were prepared by changing the deposition time from 6–20 h at 30°C temperature. The effect of film thickness on structural and electrical properties was studied. The electrical resistivity was decreased from 1.83 × 105 -cm to 0.363 × 105 -cm as film thickness decreased from 332 nm to 76 nm. The structural and activation energy studies support this decrease in the resistivity due to improvement in crystallinity of the films which would increase the charge carrier mobility and decrease in defect levels with increase in the thickness.

  2. Study of the interaction between water and hydrogen sulfide with polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Cabaleiro-Lago, Enrique M; Carrazana-García, Jorge A; Rodríguez-Otero, Jesús

    2009-06-21

    A computational study has been carried out for determining the characteristics of the interaction between one water and hydrogen sulfide molecule with a series of polycyclic aromatic hydrocarbons of increasing size, namely, benzene, anthracene, triphenylene, coronene, circumcoronene, and dicircumcoronene. Potential energy curves were calculated for structures where H(2)X (X=O,S) molecule is located over the central six-membered ring with its hydrogen atoms pointing toward to (mode A) or away from (mode B) the hydrocarbon. The accuracy of different methods has been tested against the results of coupled cluster calculations extrapolated to basis set limit for the smaller hydrocarbons. The spin component scaled MP2 (SCS-MP2) method and a density functional theory method empirically corrected for dispersion (DFT-D) reproduce fairly well the results of high level calculations and therefore were employed for studying the larger systems, though DFT-D seems to underestimate the interaction in hydrogen sulfide clusters. Water complexes in mode A have interaction energies that hardly change with the size of the hydrocarbon due to compensation between the increase in the correlation contribution to the interaction energy and the increase in the repulsive character of the Hartree-Fock energy. For all the other clusters studied, there is a continuous increase in the intensity of the interaction as the size of the hydrocarbon increases, suggesting already converged values for circumcoronene. The interaction energy for water clusters extrapolated to an infinite number of carbon atoms amounts to -13.0 and -15.8 kJ/mol with SCS-MP2 and DFT-D, respectively. Hydrogen sulfide interacts more strongly than water with the hydrocarbons studied, leading to a limiting value of -21.7 kJ/mol with the SCS-MP2 method. Also, complexes in mode B are less stable than the corresponding A structures, with interaction energies amounting to -8.2 and -18.2 kJ/mol for water and hydrogen sulfide

  3. Highly enantio- and diastereoselective allylic alkylation of Morita-Baylis-Hillman carbonates with allyl ketones

    KAUST Repository

    Tong, Guanghu

    2013-05-17

    The asymmetric allylic alkylation of Morita-Baylis-Hillman (MBH) carbonates with allyl ketones has been developed. The α-regioselective alkylation adducts, containing a hexa-1,5-diene framework with important synthetic value, were achieved in up to 83% yield, >99% ee, and 50:1 dr by using a commercially available Cinchona alkaloid as the catalyst. From the allylic alkylation adduct, a cyclohexene bearing two adjacent chiral centers was readily prepared. © 2013 American Chemical Society.

  4. Synthesis of acrylic and allylic bifunctional cross-linking monomers derived from PET waste

    Science.gov (United States)

    Cruz-Aguilar, A.; Herrera-González, A. M.; Vázquez-García, R. A.; Navarro-Rodríguez, D.; Coreño, J.

    2013-06-01

    An acrylic and two novel allylic monomers synthesized from bis (hydroxyethyl) terephthalate, BHET, are reported. This was obtained by glycolysis of post-consumer PET with boiling ethylene glycol. The bifunctional monomer bis(2-(acryloyloxy)ethyl) terephthalate was obtained from acryloyl chloride, while the allylic monomers 2-(((allyloxi)carbonyl)oxy) ethyl (2-hydroxyethyl) terephthalate and bis(2-(((allyloxi)carbonyl)oxy)ethyl) terephthalate, from allyl chloroformate. Cross-linking was studied in bulk polymerization using two different thermal initiators. Monomers were analyzed by means of 1H NMR and the cross-linked polymers by infrared spectroscopy. Gel content higher than 90% was obtained for the acrylic monomer. In the case of the mixture of the allylic monomers, the cross-linked polymer was 80 % using BPO initiator, being this mixture 24 times less reactive than the acrylic monomer.

  5. Molecular Beam Optical Study of Gold Sulfide and Gold Oxide

    Science.gov (United States)

    Zhang, Ruohan; Yu, Yuanqin; Steimle, Timothy

    2016-06-01

    Gold-sulfur and gold-oxygen bonds are key components to numerous established and emerging technologies that have applications as far ranging as medical imaging, catalysis, electronics, and material science. A major theoretical challenge for describing this bonding is correctly accounting for the large relativistic and electron correlation effects. Such effects are best studied in diatomic, AuX, molecules. Recently, the observed AuS electronic state energy ordering was measured and compared to a simple molecular orbital diagram prediction. Here we more thoroughly investigate the nature of the electronic states of both AuS and AuO from the analysis of high-resolution (FWHM\\cong35MHz) optical Zeeman spectroscopy of the (0,0){B}2Σ--{X}2Π3/2 bands. The determined fine and hyperfine parameters for the {B}2Σ- state of AuO differ from those extracted from the analysis of a hot, Doppler-limited, spectrum. It is demonstrated that the nature of the {B}2Σ- states of AuO and AuS are radically different. The magnetic tuning of AuO and AuS indicates that the {B}2Σ- states are heavily contaminated. Supported by the National Science Foundation under Grant No.1265885. D. L. Kokkin, R. Zhang, T. C. Steimle, I. A. Wyse, B. W. Pearlman and T. D. Varberg, J. Phys. Chem. A., 119(48), 4412, 2015. L. C. O'Brien, B. A. Borchert, A. Farquhar, S. Shaji, J. J. O'Brien and R. W. Field, J. Mol. Spectrosc., 252(2), 136, 2008

  6. Cationic ruthenium-cyclopentadienyl-diphosphine complexes as catalysts for the allylation of phenols with allyl alcohol: relation between structure and catalytic performance in O- vs. C-allylation

    NARCIS (Netherlands)

    van Rijn, J.A.; Lutz, M.; von Chrzanowski, L.S.; Spek, A.L.; Bouwman, E.; Drent, E.

    2009-01-01

    A new catalytic method has been investigated to obtain either O- or C-allylated phenolic products using allyl alcohol or diallyl ether as the allyl donor. With the use of new cationic ruthenium(II) complexes as catalyst, both reactions can be performed with good selectivity. Active cationic Ru(II) c

  7. N-Allylation of amines with allyl acetates using chitosan-immobilized palladium

    Science.gov (United States)

    A simple procedure for N-Allylation of allyl Acetates has been developed using a biodegradable and easily recyclable heterogeneous chitosan-supported palladium catalyst. The general methodology, applicable to wide range of substrates, has sustainable features that include a ligan...

  8. Compound list: allyl alcohol [Open TG-GATEs

    Lifescience Database Archive (English)

    Full Text Available allyl alcohol AA 00010 ftp://ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Human/in_vitro/allyl_alcohol....Human.in_vitro.Liver.zip ftp://ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Rat/in_vitro/allyl_alcohol...dbc.jp/archive/open-tggates/LATEST/Rat/in_vivo/Liver/Repeat/allyl_alcohol.Rat.in_vivo.Liver.Repeat.zip ftp:/.../ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Rat/in_vivo/Kidney/Single/allyl_alcohol.Rat.in_vivo.Kidney....Single.zip ftp://ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Rat/in_vivo/Kidney/Repeat/allyl_alcohol.Rat.in_vivo.Kidney.Repeat.zip ...

  9. Experimental Study of Gas Explosions in Hydrogen Sulfide-Natural Gas-Air Mixtures

    Directory of Open Access Journals (Sweden)

    André Vagner Gaathaug

    2014-01-01

    Full Text Available An experimental study of turbulent combustion of hydrogen sulfide (H2S and natural gas was performed to provide reference data for verification of CFD codes and direct comparison. Hydrogen sulfide is present in most crude oil sources, and the explosion behaviour of pure H2S and mixtures with natural gas is important to address. The explosion behaviour was studied in a four-meter-long square pipe. The first two meters of the pipe had obstacles while the rest was smooth. Pressure transducers were used to measure the combustion in the pipe. The pure H2S gave slightly lower explosion pressure than pure natural gas for lean-to-stoichiometric mixtures. The rich H2S gave higher pressure than natural gas. Mixtures of H2S and natural gas were also studied and pressure spikes were observed when 5% and 10% H2S were added to natural gas and also when 5% and 10% natural gas were added to H2S. The addition of 5% H2S to natural gas resulted in higher pressure than pure H2S and pure natural gas. The 5% mixture gave much faster combustion than pure natural gas under fuel rich conditions.

  10. Bacterial leaching of a sulfide ore by Thiobacillus ferrooxidans and Thiobacillus thiooxidans: I. Shake flask studies.

    Science.gov (United States)

    Lizama, H M; Suzuki, I

    1988-06-20

    Bacterial leaching of a sulfide ore containing pyrite, chalcopyrite, and sphalerite was studied in shake flask experiments using Thiobacillus ferrooxidans and Thiobacillus thiooxidans strains isolated from mine sites. The Fe(2+)grown T. ferrooxidans isolates solubilized sphalerite preferentially over chalcopyrite leaching 7-10% Cu, 68-76% Zn, and 10-22% Fe from the ore in 18 days. The sulfur grown T. thiooxidans isolates leached Zn much more slowly and very little Fe, with a Cu-Zn extraction ratio twice the value obtained with T. ferrooxidans. The ore adapted T. ferrooxidans started solubilizing Cu and Zn without a lag period. The ore-adapted T. thiooxidans extracted Cu as well as T. ferrooxidans, but the extraction of Zn or Fe was still much slower in the low-phosphate medium, while in the high-phosphate medium it approached the value obtained with T. ferrooxidans. A high Cu-Zn extraction ratio of 0.34 was obtained with T. thiooxidans in the low phosphate medium. In the mixed-culture experiments with T. ferrooxidans and T. thiooxidans, the culture behaved as T. thiooxidans in the low-phosphate medium with a higher Cu-Zn extraction ratio and as T. ferrooxidans in the high-phosphate medium with a lower Cu-Zn extraction ratio. It is concluded that T. ferrooxidans and T. thiooxidans solubilize sulfide minerals by different mechanisms.

  11. In-situ STM study of sulfide adsorption on Au(100) in alkaline solution

    Science.gov (United States)

    Schlaup, Christian; Wandelt, Klaus

    2015-01-01

    The adsorption of sulfide on a Au(100) electrode from a 0.01 M NaOH + 0.5 mM Na2S electrolyte was studied by in situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV). Starting with a sulfur free electrode surface at low potentials the subsequent formation of a p(2 × 2)-S, a c(2 × 6)-S and a c(2 × 2)-S phase was observed during potential increase. Only the p(2 × 2)-S (ΘS = 0.25 ML) phase appears as a single species phase; the c(2 × 6)-S (ΘS = 0.33 ML) and the c(2 × 2)-S (ΘS = 0. 5 ML) phase are accompanied by the simultaneous appearance of additional "dimer" particles. Concomitant changes of the step morphology and the results of the electrochemical characterization strongly suggest that these additional particles contain both, sulfur and gold atoms. Upon further potential increase the formation of a phase consisting of ring-like units was found, which is well known for Au(111) surfaces in the presence of sulfur. This phase is, by analogy, interpreted as a gold sulfide compound formed under electrochemical conditions.

  12. Enantioselective synthesis of fluorinated branched allylic compounds via Ir-catalyzed allylations of functionalized fluorinated methylene derivatives.

    Science.gov (United States)

    Zhang, Hongbo; Chen, Jiteng; Zhao, Xiao-Ming

    2016-08-14

    Enantioselective introduction of the functionalized monofluorinated methylenes into the allylic fragment under Ir catalysis has been realized, which gave the fluorinated branched allyl products in good to high yields with excellent regio- and enantioselectivities. PMID:27383920

  13. Kinetic Resolution of Racemic and Branched Monosubstituted Allylic Acetates by a Ruthenium-Catalyzed Regioselective Allylic Etherification.

    Science.gov (United States)

    Shinozawa, Toru; Terasaki, Shou; Mizuno, Shota; Kawatsura, Motoi

    2016-07-01

    We demonstrated the kinetic resolution of racemic and branched monosubstituted allylic acetates by a ruthenium-catalyzed regioselective allylic etherification. The reaction was effectively catalyzed by the chiral ruthenium catalyst, which was generated by [RuCl2(p-cymene)]2 and (S,S)-iPr-pybox and a catalytic amount of TFA, and both the allylic etherification product and recovered allylic acetate were obtained as an enantiomerically enriched form with up to a 103 s value. PMID:27276556

  14. Allylic Nitro Compounds as Nitrite Donors

    OpenAIRE

    Chakrapani, Harinath; Gorczynski, Michael J.; King, S Bruce

    2006-01-01

    Allylic nitro compounds were synthesized and evaluated as organic sources of nitrite and nitric oxide. Unactivated allylic nitro compounds do not spontaneously release nitrite and nucleophile promoted nitrite release is slow. However, 2-(nitromethyl)-cyclohex-1-ene-3-one spontaneously dissociates in buffer (pH = 7.4) to release nitrite with a kobs = 1.6 × 10−5 s−1. In the presence of L-cysteine, this compound rapidly yields nitrite and reacts with hemoglobin similarly to sodium nitrite. Struc...

  15. Elementary reaction allyl radical with oxygen

    Institute of Scientific and Technical Information of China (English)

    DONG Feng; KONG Fanao

    2003-01-01

    The elementary reaction between allyl radical with oxygen molecule wasexperimentally investigated. The allyl radical was produced via laser photolysis of C3H5Br in gaseous phase. Nascent vibrational excited products HCO, CO2, CH3CHO and HCOOH were recorded by the time- resolved Fourier transform infrared spectroscopy. The product channels of C2H5+CO2, CH3CHO+HCO, and HCOOH + C2H3 have been identified. The vibrational populations of product CO2 are obtained by spectral simulation. A mechanism forming a series of three-membered ring-struc- ture intermediates is suggested.

  16. A novel method for improving cerussite sulfidization

    Institute of Scientific and Technical Information of China (English)

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

    2016-01-01

    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 sul-fide 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.

  17. Sulfide intrusion and detoxification in Zostera marina

    DEFF Research Database (Denmark)

    Hasler-Sheetal, Harald; Holmer, Marianne

    2014-01-01

    Sulfide intrusion in seagrasses represents a global threat to seagrasses. In contrast seegrasses grow in hostile sediments, where they are constantly exposed to sulfide intrusion. Little is known about the strategies to survive sulfide intrusion, if there are 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...... to trace sulfur compounds and as well as metabolomics upon sulfide and anoxia exposure we identified different strategies to cope with sulfidic sediments. 1) Avoidance, by reoxidation of gaseous sulfide in the arenchyma to elemental sulfur and sulfate; where precipitation of sulfide occurred as non...

  18. A STUDY TO EVALUATE CARBON MONOXIDE AND HYDROGEN SULFIDE CONTINUOUS EMISSION MONITORS AT AN OIL REFINERY

    Science.gov (United States)

    An eleven month field evaluation was done on five hydrogen sulfide and four carbon monoxide monitors located at an oil refinery. The hydrogen sulfide monitors sampled a fuel gas feed line and the carbon monoxide monitors sampled the emissions from a fluid cat cracker (FCC). Two o...

  19. Experimental Studies on the Sulfide Capacities of CaO-SiO2-CrOx Slags

    Science.gov (United States)

    Wang, Lijun; Seetharaman, Seshadri

    2010-04-01

    To understand the desulfurization process during the refining of Cr-containing steel grades, this work was initiated to study the reactions between Cr-sulfur and chromium-containing slags. The sulfide capacities of CaO-SiO2-CrOx pseudo-ternary slags were measured using the traditional gas-slag equilibration technique between 1823 K and 1923 K. Sixteen different slag compositions were examined, and two different equilibrium oxygen partial pressures were used to understand the impact of the varying valence of Cr on the sulfide capacities. The results showed that log10 Cs varied linearly with the reciprocal T, and the slope was higher than the corresponding value reported for the binary CaO-SiO2 of corresponding composition. It was difficult to isolate the relative effects of the bi- and trivalent Cr in the slags because the Cr2+/Cr3+ ratio was influenced by the basicity of the slag. By using the equation developed by these authors earlier that related Cr2+/Cr3+ with basicity, oxygen partial pressure, and temperature, it was possible to obtain an approximate trend of the CrO effect on the sulfide capacities; viz. the sulfide shows a decreasing trend as Cr2+ replaces Ca2+ in the slag. With a continued increase of Cr2+ content, indications of the occurrence of a minimum point were observed; beyond which the sulfide capacities showed a slight increasing trend. The latter was attributed, based on slag-structure analysis by Gaskell et al., to the increasing extent of the polymerization reaction releasing oxygen ions for sulfide reactions.

  20. In-situ STM study of sulfide adsorption on Au(100) in alkaline solution

    DEFF Research Database (Denmark)

    Schlaup, Christian Georg; Wandelt, Klaus

    2015-01-01

    The adsorption of sulfide on a Au(100) electrode from a 0.01 M NaOH + 0.5 mM Na2S electrolyte was studied by in situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV). Starting with a sulfur free electrode surface at low potentials the subsequent formation of a p(2 × 2)-S, a c(2 × 6......)-S and a c(2 × 2)-S phase was observed during potential increase. Only the p(2 × 2)-S (ΘS = 0.25 ML) phase appears as a single species phase; the c(2 × 6)-S (ΘS = 0.33 ML) and the c(2 × 2)-S (ΘS = 0. 5 ML) phase are accompanied by the simultaneous appearance of additional "dimer" particles...

  1. Evaluation of thiosulfate as a substitute for hydrogen sulfide in sour corrosion fatigue studies

    Science.gov (United States)

    Kappes, Mariano Alberto

    This work evaluates the possibility of replacing hydrogen sulfide (H 2S) with thiosulfate anion (S2O32- ) in sour corrosion fatigue studies. H2S increases the corrosion fatigue crack growth rate (FCGR) and can be present in carbon steel risers and flowlines used in off-shore oil production. Corrosion tests with gaseous H2S require special facilities with safety features, because H2S is a toxic and flammable gas. The possibility of replacing H2S with S2O32-, a non-toxic anion, for studying stress corrosion cracking of stainless and carbon steels in H2S solutions was first proposed by Tsujikawa et al. ( Tsujikawa et al., Corrosion, 1993. 49(5): p. 409-419). In this dissertation, Tsujikawa work will be extended to sour corrosion fatigue of carbon steels. H2S testing is often conducted in deareated condition to avoid oxygen reaction with sulfide that yields sulfur and to mimic oil production conditions. Nitrogen deareation was also adopted in S2O3 2- testing, and gas exiting the cell was forced through a sodium hydroxide trap. Measurements of the sulfide content of this trap were used to estimate the partial pressure of H2S in nitrogen, and Henry's law was used to estimate the content of H2S in the solution in the cell. H2S was produced by a redox reaction of S2O 32-, which required electrons from carbon steel corrosion. This reaction is spontaneous at the open circuit potential of steel. Therefore, H2S concentration was expected to be maximum at the steel surface, and this concentration was estimated by a mass balance analysis. Carbon steel specimens exposed to S2O32- containing solutions developed a film on their surface, composed by iron sulfide and cementite. The film was not passivating and a good conductor of electrons. Hydrogen permeation experiments proved that this film controls the rate of hydrogen absorption of steels exposed to thiosulfate containing solutions. The absorption of hydrogen in S2O3 2- solutions was compared with the absorption of hydrogen in

  2. Palladium Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Fristrup, Peter

    2011-01-01

    The atom-efficiency of one of the most widely used catalytic reactions for forging C-C bonds, the Tsuji-Trost reaction, is limited by the need of preoxidized reagents. This limitation can be overcome by utilization of the recently discovered palladium-catalyzed C-H activation, the allylic C...

  3. First principles study of transition metal (TM=Pb, Cu) oxides/sulfides

    Science.gov (United States)

    Caudle, Sean; Tao, Meng; Peng, Xihong

    2012-10-01

    Earth-abundant transition meal oxides/sulfides have inspired special research attention recently due to their potential applications in solar cells. A clear understanding of the fundamental properties of these materials, especially the electronic properties and their tunability via chemical doping, are critically important towards the applications. In this presentation, we report first principles density-functional theory (DFT) study on the electronic structures of Pb and Cu oxides/sulfides and their oxysulfides compositions. The band structure and bandgap can be systematically tuned by increasing S component in the metal oxides. For example, the DFT predicted bandgap for PbO is 1.72 eV. While the bandgaps for PbO0.937 S0.063, PbO0.875S0.125, and PbO0.75S0.25 are 1.64 eV, 1.43 eV, and 0.79 eV, respectively. For Cu2O, the standard DFT seriously underestimates the bandgap to be 0.49 eV, compared to the experimental value of 2.17 eV. Two methods, DFT+U and hybrid functional (HSE06), were implemented to overcome this problem. Our results showed that DFT+U method fails and the bandgap doesn't further open up by providing a U potential. The hybrid functional predicts the bandgap to be 2.00 eV, which is in a good agreement with the experimental value.

  4. A study on the mechanism of stress corrosion cracking of duplex stainless steels in hot alkaline-sulfide solution

    Science.gov (United States)

    Chasse, Kevin Robert

    Duplex stainless steels (DSS) generally have superior strength and corrosion resistance as compared to most standard austenitic and ferritic stainless grades owing to a balanced microstructure of austenite and ferrite. As a result of having favorable properties, DSS have been selected for the construction of equipment in pulp and paper, chemical processing, nuclear, oil and gas as well as other industries. The use of DSS has been restricted in some cases because of stress corrosion cracking (SCC), which can initiate and grow in either the ferrite or austenite phase depending on the environment. Thorough understanding of SCC mechanisms of DSS in chloride- and hydrogen sulfide-containing solutions has been useful for material selection in many environments. However, understanding of SCC mechanisms of DSS in sulfide-containing caustic solutions is limited, which has restricted the capacity to optimize process and equipment design in pulp and paper environments. Process environments may contain different concentrations of hydroxide, sulfide, and chloride, altering corrosion and SCC susceptibility of each phase. Crack initiation and growth behavior will also change depending on the relative phase distribution and properties of austenite and ferrite. The role of microstructure and environment on the SCC of standard grade UNS S32205 and lean grade UNS S32101 in hot alkaline-sulfide solution were evaluated in this work using electrochemical, film characterization, mechanical testing, X-ray diffraction, and microscopy techniques. Microstructural aspects, which included residual stress state, phase distribution, phase ratio, and microhardness, were related to the propensity for SCC crack initiation in different simulated alkaline pulping liquors at 170 °C. Other grades of DSS and reference austenitic and superferritic grades of stainless steel were studied using exposure coupons for comparison to understand compositional effects and individual phase susceptibility

  5. Interfacial tension studies between Fe-Cu-Ni sulfide and halo-norilsk basalt slag system

    Institute of Scientific and Technical Information of China (English)

    SU; Shangguo

    2005-01-01

    The interfacial tension of the matte/halo-Norilsk basalt slag systems of FeS-Cu2S-Ni3S2 and FeO-FeS were investigated using the sessile drop technique. The results indicate that interfacial tension decreases with increasing copper and nickel contents in the matte of FeS-Cu2S-Ni3S2 system while it increases with increasing oxygen content in the matte of FeO-FeS system. It is inferred from these results that two conditions are critical for the formation of giant Cu-Ni sulfide deposits. One is that mafic-ultramafic parent magma of sulfide deposits should be rich in copper and nickel where due to the low interfacial tension, it is difficult to form sulfide droplet in the early stage of magma evolution. In other words, sulfide liquid conglomeration occurs more difficultly. The other condition is that the magma emplacement should be shallow; and a lot of faults occur in the magma emplacement field. Since oxygen content is high in the environment, interfacial tension is high, which helps sulfide liquid conglomeration and consequently Cu-Ni sulfide deposits form.

  6. Synthesis of (-)-Piperitylmagnolol Featuring ortho-Selective Deiodination and Pd-Catalyzed Allylation.

    Science.gov (United States)

    Ikoma, Atsushi; Ogawa, Narihito; Kondo, Daiki; Kawada, Hiroki; Kobayashi, Yuichi

    2016-05-01

    A 1,4-addition strategy using an enone and a copper reagent was studied for the synthesis of (-)-piperitylmagnolol. A MOM-protected biphenol copper reagent was added to BF3·OEt2-activated 4-isopropylcyclohexenone, whereas 1,4-addition of protected monophenol reagents possessing an allyl group was found to be unsuccessful. The allyl group was later attached to the p-,p'-diiodo-biphenol ring by Pd-catalyzed coupling with allylborate. The aforementioned iodide was synthesized using a new method for ortho-selective deiodination of o-,p-diiodophenols. PMID:27109890

  7. Pressure Dependent Product Formation in the Photochemically Initiated Allyl + Allyl Reaction

    Directory of Open Access Journals (Sweden)

    Thomas Zeuch

    2013-11-01

    Full Text Available Photochemically driven reactions involving unsaturated radicals produce a thick global layer of organic haze on Titan, Saturn’s largest moon. The allyl radical self-reaction is an example for this type of chemistry and was examined at room temperature from an experimental and kinetic modelling perspective. The experiments were performed in a static reactor with a volume of 5 L under wall free conditions. The allyl radicals were produced from laser flash photolysis of three different precursors allyl bromide (C3H5Br, allyl chloride (C3H5Cl, and 1,5-hexadiene (CH2CH(CH22CHCH2 at 193 nm. Stable products were identified by their characteristic vibrational modes and quantified using FTIR spectroscopy. In addition to the (re- combination pathway C3H5+C3H5 → C6H10 we found at low pressures around 1 mbar the highest final product yields for allene and propene for the precursor C3H5Br. A kinetic analysis indicates that the end product formation is influenced by specific reaction kinetics of photochemically activated allyl radicals. Above 10 mbar the (re- combination pathway becomes dominant. These findings exemplify the specificities of reaction kinetics involving chemically activated species, which for certain conditions cannot be simply deduced from combustion kinetics or atmospheric chemistry on Earth.

  8. Electrochemical Studies of Microwave Synthesised Bimetallic Sulfides Nanostructures As Faradaic Electrodes

    International Nuclear Information System (INIS)

    Highlights: • Use of microwave technology for production of nanostructured materials. • Hydrothermal microwave irradiation of NixCoyS4 with different stoichiometry. • Materials produced exhibited good Faradaic behaviour. - Abstract: A microwave irradiation method has been used to prepare mixed nickel cobalt sulfide (NixCoyS4) nanosheets with different stoichiometric composition as electrodes for electrochemical capacitors. This study has been undertaken to determine the effect of synthesis time and concentration of nickel on the morphology and pseudocapacitance behavior of the NixCoyS4. It was observed that the time had an effect on the morphology of NixCoyS4, producing sheet-like (leaf-like) morphology which curls in flower-like shapes with increase in growth (synthesis) time. The effect of morphology on the electrochemical behavior was studied by cyclic voltammetry (CV), chronopotentiometry (CP) and electrochemical impedance spectroscopy (EIS) techniques in aqueous solutions. The sample with a concentration ratio of 2:1 of nickel and cobalt (NixCoyS4-3) shows higher faradaic performance when compared to other samples grown under similar conditions but with different ratios. The maximum specific capacitance values obtained for was 1110 F g−1 at a scan rate of 5 mV s−1 for this sample. The Coulombic efficiency of the sample was ∼80% after 2000 galvanostatic charge-discharge cycles at a current density of 5 A g−1

  9. SYNTHESIS OF ALLYL PHENYL ETHER AND CLAISEN REARRANGEMENT

    Directory of Open Access Journals (Sweden)

    Gagik Torosyan

    2011-12-01

    Full Text Available It has been established the possibility for phenol allylation on natural zeolites and them analogs. Here is demonstrated the synthesis of allyl phenol, which has wide industrial applications. The offered method in comparison with the traditional methods has more advantages – higher selectivity, smaller material and power resources consumption. It has been obtained the mixture of allylating phenols (30% in general with allyl phenyl ether (1 with 80% yields. At 600 K is obtained allylphenyl ether, at 700 K beginning the formation of allyl phenols, which is the result of direct C-allylation of the aromatic ring. It has been investigated the possibility of Claisen rearrangement in the same conditions. All of that are established by gas-liquid chromatography and liquid chromatography data.

  10. A comprehensive study on atomic layer deposition of molybdenum sulfide for electrochemical hydrogen evolution.

    Science.gov (United States)

    Kwon, Do Hyun; Jin, Zhenyu; Shin, Seokhee; Lee, Wook-Seong; Min, Yo-Sep

    2016-04-01

    Atomic layer deposition (ALD) has emerged as an efficient method to design and prepare catalysts with atomic precision. Here, we report a comprehensive study on ALD of molybdenum sulfide (MoSx) for an electrocatalytic hydrogen evolution reaction. By using molybdenum hexacarbonyl and dimethyldisulfide as the precursors of Mo and S, respectively, the MoSx catalysts are grown at 100 °C on porous carbon fiber papers (CFPs). The ALD process results in the growth of particle-like MoSx on the CFP due to the lack of adsorption sites, and its crystallographic structure is a mixture of amorphous and nano-crystalline phases. In order to unveil the intrinsic activity of the ALD-MoSx, the exchange current densities, Tafel slopes, and turnover frequencies of the catalysts grown under various ALD conditions have been investigated by considering the fractional surface coverage of MoSx on the CFP and catalytically-active surface area. In addition, the ALD-MoSx/CFP catalysts exhibit excellent catalytic stability due to the strong adhesion of MoSx on the CFP and the mixed phase. PMID:26973254

  11. Cp*Co(III)-Catalyzed Dehydrative C-H Allylation of 6-Arylpurines and Aromatic Amides Using Allyl Alcohols in Fluorinated Alcohols.

    Science.gov (United States)

    Bunno, Youka; Murakami, Nanami; Suzuki, Yudai; Kanai, Motomu; Yoshino, Tatsuhiko; Matsunaga, Shigeki

    2016-05-01

    Cp*Co(III)-catalyzed C-H allylation of various aromatic C-H bonds using allyl alcohols as allylating reagents is described. Improved reaction conditions using fluorinated alcohol solvents afforded efficient directed C-H allylation of 6-arylpurines, benzamides, and a synthetically useful Weinreb amide with good functional group compatibility.

  12. Sulfur isotope values in the sulfidic Frasassi cave system, central Italy: A case study of a chemolithotrophic S-based ecosystem

    Science.gov (United States)

    Zerkle, Aubrey L.; Jones, Daniel S.; Farquhar, James; Macalady, Jennifer L.

    2016-01-01

    Sulfide oxidation forms a critical step in the global sulfur cycle, although this process is notoriously difficult to constrain due to the multiple pathways and highly reactive intermediates involved. Multiple sulfur isotopes (δ34S and Δ33S) can provide a powerful tool for unravelling sulfur cycling processes in modern (and ancient) environments, although they have had limited application to systems with well-resolved oxidative S cycling. In this study, we report the major (δ34S) and minor (Δ33S) isotope values of sulfur compounds in streams and sediments from the sulfidic Frasassi cave system, Marche Region, Italy. These microaerophilic cave streams host prominent white biofilms dominated by chemolithotrophic organisms that oxidize sulfide to S0, allowing us to estimate S isotope fractionations associated with in situ sulfide oxidation and to evaluate any resulting isotope biosignatures. Our results demonstrate that chemolithotrophic sulfide oxidation produces 34S enrichments in the S0 products that are larger than those previously measured in laboratory experiments, with 34εS0-H2S of up to 8‰ calculated. These small reverse isotope effects are similar to those produced during phototrophic sulfide oxidation (⩽7‰), but distinct from the small normal isotope effects previously calculated for abiotic oxidation of sulfide with O2 (∼-5‰). An inverse correlation between the magnitude of 34εS0-H2S effects and sulfide availability, along with substantial differences in Δ33S, both support complex sulfide oxidation pathways and intracellular recycling of S intermediates by organisms inhabiting the biofilms. At the ecosystem level, we calculate fractionations of less than 40‰ between sulfide and sulfate in the water column and in the sediments. These fractionations are smaller than those typically calculated for systems dominated by sulfate reduction (>50‰), and contrast with the commonly held assumption that oxidative recycling of sulfide generally

  13. Studies of the possibility of hydrogen sulfide absorption by limestones during the gasification of liquid and solid fuels

    Energy Technology Data Exchange (ETDEWEB)

    Hrncir, J.; Biba, V.

    1980-01-01

    When solid or liquid fuels such as coal or oil are gasified with air, the fuel gases produced can contain substantial amounts of sulfur. One possible way to remove this sulfur and thus purify the gas is to use limestone in a fluidized bed to absorb the sulfur as hydrogen sulfide. A study of the feasibility of such a process examined the kinetics of the CaO-H/sub 2/S reaction in a differential kinetic reactor in the 1290/sup 0/-1650/sup 0/F temperature range. The investigation (1) tested the reactivity of four natural limestones, (2) evaluated the experimental data via the M. Pell model, (3) examined the effects of the structural parameters of the limestones and the limestone calcinates upon the reaction with hydrogen sulfide, and (4) for one type of limestone, determined the dependence of its reactivity on a specific surface and described this dependence by a mathematical model.

  14. Temperature-controlled redox-neutral ruthenium(ii)-catalyzed regioselective allylation of benzamides with allylic acetates.

    Science.gov (United States)

    Manikandan, Rajendran; Jeganmohan, Masilamani

    2016-08-10

    Substituted aromatic amides reacted efficiently with allylic acetates in the presence of a cationic ruthenium complex in ClCH2CH2Cl at room temperature providing ortho allylated benzamides in a highly regioselective manner without any oxidant and base. The whole catalytic reaction occurred in a Ru(ii) oxidation state and thus the oxidation step is avoided. By tuning the reaction temperature, ortho allyl and vinyl benzamides were prepared exclusively. Later, ortho allyl and vinylated benzamides were converted into biologically useful six- and five-membered benzolactones in the presence of HCl. PMID:27456467

  15. Studying inhibition of calcium oxalate stone formation: an in vitro approach for screening hydrogen sulfide and its metabolites

    Directory of Open Access Journals (Sweden)

    S. Vaitheeswari

    2015-06-01

    Full Text Available ABSTRACTPurpose:Calcium oxalate urolithiasis is one of the most common urinary tract diseases and is of high prevalence. The present study proposes to evaluate the antilithiatic property of hydrogen sulfide and its metabolites like thiosulfate & sulfate in an in vitro model.Materials and Methods:The antilithiatic activity of sodium hydrogen sulfide (NaSH, sodium thiosulfate (Na2S2O3 and sodium sulfate (Na2SO4 on the kinetics of calcium oxalate crystal formation was investigated both in physiological buffer and in urine from normal and recurrent stone forming volunteers. The stones were characterized by optical and spectroscopic techniques.Results:The stones were characterized to be monoclinic, prismatic and bipyramidal habit which is of calcium monohydrate and dihydrate nature. The FTIR displayed fingerprint corresponding to calcium oxalate in the control while in NaSH treated, S=O vibrations were visible in the spectrum. The order of percentage inhibition was NaSH>Na2S2O3>Na2SO4.Conclusion:Our study indicates that sodium hydrogen sulfide and its metabolite thiosulfate are inhibitors of calcium oxalate stone agglomeration which makes them unstable both in physiological buffer and in urine. This effect is attributed to pH changes and complexing of calcium by S2O32-and SO42- moiety produced by the test compounds.

  16. Influence of arsenic on iron sulfide transformations

    NARCIS (Netherlands)

    Wolthers, M.; Butler, I.B.; Rickard, D.

    2007-01-01

    The association of arsenate, As(V), and arsenite, As(III), with disordered mackinawite, FeS, was studied in sulfide-limited (Fe:S = 1:1) and excess-sulfide (Fe:S = 1:2) batch experiments. In the absence of arsenic, the sulfide-limited experiments produce disordered mackinawite while the excess-sulfi

  17. Studies of the surface reactivity of metal oxyhydroxides and sulfides with relevance to environmental chemistry

    Science.gov (United States)

    Pierre-Louis, Andro-Marc

    With the benefits of an ever increasing advance of industrialization around the globe come formidable environmental problems. Three environmental problems that have relevance to the research described in this thesis are the 1) buildup of atmospheric CO2 gas through the burning of fossil fuels, 2) eutrophication of aquatic systems, and 3) the acidification of environments from acid mine drainage (AMD) resulting from coal-mining activities. In particular research is presented in this thesis that investigated the surface chemistry of CO2 and phosphate (PO43-) on a suite of environmentally relevant iron oxyhydroxide materials and the chemistry of phospholipid molecules on environmentally relevant iron sulfide surfaces to suppress AMD. To develop a microscopic understanding of the surface chemistry of the different systems, an array of experimental and computational techniques were used in the research. Techniques included X-ray photoelectron spectroscopy, atomic adsorption, X-ray diffraction, scanning transmission microscopy with electron dispersive X-ray spectroscopy (STEM/EDS), ion chromatography (IC), and attenuated total reflectance Fourier transform Infrared (ATR-FTIR). Results from the latter technique were interpreted with the aid of density function theory (DFT) calculations. Iron oxyhydroxides, which consisted of ferrihydrite (FeOOH), goethite (α-FeOOH), ferrimagnetic ferrihydrite (FerriFh), and aluminum-doped iron oxyhydroxide (content from 0-100 mol%) were synthesized and studied before and after exposure to gaseous CO2, CO32-, and PO43- species. FeOOH and mixed Al/Fe oxyhydroxide surfaces showed high affinities for the formation of carbonate and bicarbonate species upon exposure to gaseous CO2. Within the Al/Fe oxyhydroxide circumstance, a low Al level of incorporation in the iron oxyhydroxide structure caused a slight increase in surface area and increase in the amount of oxyanion (e.g., CO32- or PO43-) adsorption up to an Al level of 30 mol%. Significant

  18. Experimental study on liquid immiscibility of lamprophyre-sulfide melt at high temperature and high pressure and its geological significance

    Institute of Scientific and Technical Information of China (English)

    LI Bo; HUANG Zhilong; ZHU Chengming

    2009-01-01

    With lamprophyre and pyrite from the Laowangzhai gold deposit, Yunnan Province, China, as starting materials, and at pressures from 1.5 to 3.0 GPa and temperatures from 1160 to 1560℃, an experimental study was carried out on the liquid immiscibility of lamprophyre-sulfide melt at high temperature and ultra-high pressure in the DS-29A cubic 3600T/6-type high pressure apparatus. Results showed that the liquid immiscibility of lampropyre-sulfide melt in the magmatic system would happen during the early magmatic evolution (high temperature and high pressure conditions) and was controlled by temperature and pressure. The sulfide melt which was separated from the lamprophyric melt would make directional movement in the temperature and pressure field and assemble in the low-temperature and low-pressure region. Because the density of SM is higher than that of the lamprophyric melt, the former would gather together at the bottom of the magma chamber and there would exist a striking boundary between the two melts. On the other hand, the results also suggested that there would be little possibility for lamprophyric magma to carry massive gold, and lamprophyres can't provide many of ore-forming materials (Au) in the processes of gold mineralization.

  19. Spectroscopic study on sorption of hydrogen sulfide by means of red soil.

    Science.gov (United States)

    Ko, T H; Chu, H

    2005-07-01

    This paper reports the results of the characterization of red soils in relation to the sorption of H2S from coal gas at 500 degrees C by spectroscopic techniques in order to provide more information on red soils' structural change both before and after reaction. In addition, by-products analysis has also been studied using Fourier transform infrared (FTIR) spectroscopy. Before and after the experiments the red soils were characterized with X-ray powder diffraction (XRPD), energy dispersion spectrum (EDS), X-ray photoelectron spectroscopy (XPS) and FTIR spectroscopy. XRPD results indicate that iron oxide species disappear from the original to reacted red soil. EDS analysis shows that a significant amount of sulfur is present in the reacted red soil, which is in agreement with the results of the elemental analysis and the calculated value based on breakthrough curve. XPS regression fitting results further indicate that sulfur retention may be associated with the iron oxides. S 2p XPS fittings point out that the major sulfur species present in the reacted red soil are composed of S(-2), elemental sulfur, polysulfide, sulfite and sulfate. Additionally, the binding energy of iron shifts to a lower position for the reacted red soil, which indicates that iron oxides in the original red soil have been converted into iron sulfide. Appreciable amounts of the by-products CO2, SO2 and COS are detected by on-line FTIR spectroscopy during the initial and later stages of the sorption process. The formation of CO2 is related to the water-shift reaction, and SO2 is probably attributable to the reaction of organic matters and H2S. The concentration of COS is quantified by GC/FPD and found it to be about 350 ppm, which is close to the equilibrium concentration of the reaction of inlet CO and H2S at a temperature of 500 degrees C.

  20. Toward Efficient Palladium-Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Jensen, Thomas; Fristrup, Peter

    2009-01-01

    Recent breakthroughs have proved that direct palladium (II)-catalyzed allylic C-H alkylation can be achieved. This new procedure shows that the inherent requirement for a leaving group in the Tsuji-Trost palladium-catalyzed allylic alkylation can be lifted. These initial reports hold great promise...

  1. Zinc Oxide Hydrogen Sulfide Removal Catalyst/ Preparation, Activity Test and Kinetic Study

    Directory of Open Access Journals (Sweden)

    Ameel. M. Rahman

    2008-01-01

    Full Text Available Hydrogen sulfide removal catalyst was prepared chemically by precipitation of zinc bicarbonate at a controlled pH. The physical and chemical catalyst characterization properties were investigated. The catalyst was tested for its activity in adsorption of H2S using a plant that generates the H2S from naphtha hydrodesulphurization and a unit for the adsorption of H2S. The results comparison between the prepared and commercial catalysts revealed that the chemical method can be used to prepare the catalyst with a very good activity.It has observed that the hydrogen sulfide removal over zinc oxide catalyst follows first order reaction kinetics with activation energy of 19.26 kJ/mole and enthalpy and entropy of activation of 14.49 kJ/mole and -220.41 J/mole respectively.

  2. STUDY ON EVOLUTION REGULARITIES AND ABSORPTION CHARACTERISTICS OF SULFIDE DURING BITUMINOUS BRIQUETTE HORIZONTAL COMBUSTION

    Institute of Scientific and Technical Information of China (English)

    路春美; 王永征

    1999-01-01

    This paper discusses the evolution regularity and the absorption characters of sulfide for bituminous briquette burned in a horizontal burning furnace. The evolution rate of sulphur is affected by some factors, such as the sulphur content in the burning coal, burning time and the meane excess air coefficient in the furnace. With processing the experimental result, the calculation related expression has been obtained to predict the evolution rate of sulfide. The sulphur absorption efficiency of briquette is affected by the factors such as the character of the sulphur sorbent, the type of the coal and the operating parameters. "By means of appropriately adjusting the calciumsulphur mole ratio, the mean excess air coefficient and the time-interval between pushing two layer briquettes, a high sulphur absorption efficiency (>74%) can be obtained.

  3. Zinc Oxide Hydrogen Sulfide Removal Catalyst/ Preparation, Activity Test and Kinetic Study

    OpenAIRE

    Ameel. M. Rahman; Zuhair A-A Khammas; Karim H. Hassan

    2008-01-01

    Hydrogen sulfide removal catalyst was prepared chemically by precipitation of zinc bicarbonate at a controlled pH. The physical and chemical catalyst characterization properties were investigated. The catalyst was tested for its activity in adsorption of H2S using a plant that generates the H2S from naphtha hydrodesulphurization and a unit for the adsorption of H2S. The results comparison between the prepared and commercial catalysts revealed that the chemical method can be used to prepare th...

  4. Inhibition of sulfide mineral oxidation by surface coating agents: batch and field studies.

    Science.gov (United States)

    Ji, Min-Kyu; Gee, Eun-Do; Yun, Hyun-Shik; Lee, Woo-Ram; Park, Young-Tae; Khan, Moonis Ali; Jeon, Byong-Hun; Choi, Jaeyoung

    2012-08-30

    The potential of several surface coating agents to inhibit the oxidation of metal sulfide minerals from Young-Dong coal mine and the Il-Gwang gold mine was examined by conducting laboratory scale 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 (KH(2)PO(4), MgO and KMnO(4) as chemical agents, and apatite, cement and manganite as mineral agents) and incubated with oxidizing agents (H(2)O(2) or NaClO). For the observed time period (8 days), Young-Dong coal mine samples exhibited the least sulfate (SO(4)(2-)) production in the presence of KMnO(4) (16%) or cement (4%) while, for Il-Gwang mine samples, the least SO(4)(2-) production was observed in presence of KH(2)PO(4) (8%) or cement (2%) compared to control. Field-scale pilot tests at the Il-Gwang site also showed that addition of KH(2)PO(4) decreased SO(4)(2-) production from 200 to 13 mg L(-1) and it also reduced Cu and Mn from 8 and 3 mg L(-1), respectively to detection limits). The experimental results suggested that the use of surface coating agents is a promising alternative for sulfide oxidation inhibition at acid mine drainage sites. PMID:22727481

  5. 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...

  6. Genome wide association mapping in Arabidopsis thaliana identifies novel genes involved in linking allyl glucosinolate to altered biomass and defense

    Directory of Open Access Journals (Sweden)

    Marta Francisco

    2016-07-01

    Full Text Available A key limitation in modern biology is the ability to rapidly identify genes underlying newly identified complex phenotypes. Genome wide association studies (GWAS have become an increasingly important approach for dissecting natural variation by associating phenotypes with genotypes at a genome wide level. Recent work is showing that the Arabidopsis thaliana defense metabolite, allyl glucosinolate (GSL, may provide direct feedback regulation, linking defense metabolism outputs to the growth and defense responses of the plant. However, there is still a need to identify genes that underlie this process. To start developing a deeper understanding of the mechanism(s that modulate the ability of exogenous allyl GSL to alter growth and defense, we measured changes in plant biomass and defense metabolites in a collection of natural 96 A. thaliana accessions fed with 50 µM of allyl GSL. Exogenous allyl GSL was introduced exclusively to the roots and the compound transported to the leaf leading to a wide range of heritable effects upon plant biomass and endogenous GSL accumulation. Using natural variation we conducted GWAS to identify a number of new genes which potentially control allyl responses in various plant processes. This is one of the first instances in which this approach has been successfully utilized to begin dissecting a novel phenotype to the underlying molecular/polygenic basis.

  7. Study on application of biological iron sulfide composites in treating vanadium-extraction wastewater containing chromium (VI) and chromium reclamation.

    Science.gov (United States)

    Xie, Yi-Fei; Li, Xu-Dong; Li, Fu-De

    2013-04-01

    In this study, the Cr(VI)-resistant properties and regeneration characteristics of biological iron sulfide composites were investigated, which consist of sulfate reducing bacteria (SRB) and its in situ synthesized nanosized iron sulfides. Then the application of the composites in treating vanadium-extraction wastewater containing high concentration Cr(VI) and reclaiming Cr were performed. It was found that SRB in composites still survived after being used to treat vanadium-extraction wastewater, which could reduce reaction products Fe3+ and sulphur into Fe2+ and S2 by using them as the electron accepters and thus regenerating biological iron sulfide composites. The SRB also could be resistant to 600 mgl(-1) Cr(VI) and reduce it gradually. Based on the Cr(VI)-resistant properties and regeneration characteristics of the composites, a reduction-regeneration recirculation process for treating vanadium-extraction wastewater and reclamation of Cr was developed. The results indicated that the contaminants in effluent reached the Chinese discharge standard of pollutants for vanadium industry (GB 26452-2011), i.e. the concentration of total Cr(TCr) was less than 0.912 mgl(-1), Cr(VI) was less than 0.017 mgl(-1) and V was less than 0.260 mgl(-1). After 10 cycles of treatment, the Cr2O3 content in sludge reached 41.03%, and the ratio of Cr2O3/FeO was 7.35. The sludge reached the chemical and metallurgical (hydrometallurgy) grade of chromite ore and could be reclaimed. PMID:24620597

  8. Glutathione-Garlic Sulfur Conjugates: Slow Hydrogen Sulfide Releasing Agents for Therapeutic Applications

    Directory of Open Access Journals (Sweden)

    Ashif Iqbal Bhuiyan

    2015-01-01

    Full Text Available Natural organosulfur compounds (OSCs from Allium sativum L. display antioxidant and chemo-sensitization properties, including the in vitro inhibition of tumor cell proliferation through the induction of apoptosis. Garlic water- and oil-soluble allyl sulfur compounds show distinct properties and the capability to inhibit the proliferation of tumor cells. In the present study, we optimized a new protocol for the extraction of water-soluble compounds from garlic at low temperatures and the production of glutathionyl-OSC conjugates during the extraction. Spontaneously, Cys/GSH-mixed-disulfide conjugates are produced by in vivo metabolism of OSCs and represent active molecules able to affect cellular metabolism. Water-soluble extracts, with (GSGaWS or without (GaWS glutathione conjugates, were here produced and tested for their ability to release hydrogen sulfide (H2S, also in the presence of reductants and of thiosulfate:cyanide sulfurtransferase (TST enzyme. Thus, the TST catalysis of the H2S-release from garlic OSCs and their conjugates has been investigated by molecular in vitro experiments. The antiproliferative properties of these extracts on the human T-cell lymphoma cell line, HuT 78, were observed and related to histone hyperacetylation and downregulation of GAPDH expression. Altogether, the results presented here pave the way for the production of a GSGaWS as new, slowly-releasing hydrogen sulfide extract for potential therapeutic applications.

  9. Glutathione-garlic sulfur conjugates: slow hydrogen sulfide releasing agents for therapeutic applications.

    Science.gov (United States)

    Bhuiyan, Ashif Iqbal; Papajani, Vilma Toska; Paci, Maurizio; Melino, Sonia

    2015-01-01

    Natural organosulfur compounds (OSCs) from Allium sativum L. display antioxidant and chemo-sensitization properties, including the in vitro inhibition of tumor cell proliferation through the induction of apoptosis. Garlic water- and oil-soluble allyl sulfur compounds show distinct properties and the capability to inhibit the proliferation of tumor cells. In the present study, we optimized a new protocol for the extraction of water-soluble compounds from garlic at low temperatures and the production of glutathionyl-OSC conjugates during the extraction. Spontaneously, Cys/GSH-mixed-disulfide conjugates are produced by in vivo metabolism of OSCs and represent active molecules able to affect cellular metabolism. Water-soluble extracts, with (GSGaWS) or without (GaWS) glutathione conjugates, were here produced and tested for their ability to release hydrogen sulfide (H2S), also in the presence of reductants and of thiosulfate:cyanide sulfurtransferase (TST) enzyme. Thus, the TST catalysis of the H2S-release from garlic OSCs and their conjugates has been investigated by molecular in vitro experiments. The antiproliferative properties of these extracts on the human T-cell lymphoma cell line, HuT 78, were observed and related to histone hyperacetylation and downregulation of GAPDH expression. Altogether, the results presented here pave the way for the production of a GSGaWS as new, slowly-releasing hydrogen sulfide extract for potential therapeutic applications. PMID:25608858

  10. Zinc Mediated Tandem Fragmentation-Allylation of Methyl 5-Iodopentofuranosides

    DEFF Research Database (Denmark)

    Hyldtoft, Lene; Madsen, Robert

    1999-01-01

    In the presence of zinc and allyl bromide methyl 5-iodopentofuranosides undergo a tandem fragmentation alkylation to give functionalized dienes. These can undergo ring-closing olefin metathesis to produce cyclohexenes which on dihydroxylation give quercitols.......In the presence of zinc and allyl bromide methyl 5-iodopentofuranosides undergo a tandem fragmentation alkylation to give functionalized dienes. These can undergo ring-closing olefin metathesis to produce cyclohexenes which on dihydroxylation give quercitols....

  11. STUDY ON GREY FORECASTING MODEL OF COPPER EXTRACTION RATE WITH BIOLEACHING OF PRIMARY SULFIDE ORE

    Institute of Scientific and Technical Information of China (English)

    A.X. Wu; Y. Xi; B.H. Yang; X.S. Chen; H.C. Jiang

    2007-01-01

    A model GM (grey model) (1,1) for forecasting the rate of copper extraction during the bioleaching of primary sulphide ore was established on the basis of the mathematical theory and the modeling process of grey system theory. It was used for forecasting the rate of copper extraction from the primary sulfide ore during a laboratory microbial column leaching experiment. The precision of the forecasted results were examined and modified via "posterior variance examination". The results show that the forecasted values coincide with the experimental values. GM (1,1) model has high forecast accuracy; and it is suitable for simulation control and prediction analysis of the original data series of the processes that have grey characteristics, such as mining, metallurgical and mineral processing, etc. The leaching rate of such copper sulphide ore is low. The grey forecasting result indicates that the rate of copper extraction is approximately 20% even after leaching for six months.

  12. Hydrogen Sulfide Oxidation by Myoglobin.

    Science.gov (United States)

    Bostelaar, Trever; Vitvitsky, Victor; Kumutima, Jacques; Lewis, Brianne E; Yadav, Pramod K; Brunold, Thomas C; Filipovic, Milos; Lehnert, Nicolai; Stemmler, Timothy L; Banerjee, Ruma

    2016-07-13

    Enzymes in the sulfur network generate the signaling molecule, hydrogen sulfide (H2S), from the amino acids cysteine and homocysteine. Since it is toxic at elevated concentrations, cells are equipped to clear H2S. A canonical sulfide oxidation pathway operates in mitochondria, converting H2S to thiosulfate and sulfate. We have recently discovered the ability of ferric hemoglobin to oxidize sulfide to thiosulfate and iron-bound hydropolysulfides. In this study, we report that myoglobin exhibits a similar capacity for sulfide oxidation. We have trapped and characterized iron-bound sulfur intermediates using cryo-mass spectrometry and X-ray absorption spectroscopy. Further support for the postulated intermediates in the chemically challenging conversion of H2S to thiosulfate and iron-bound catenated sulfur products is provided by EPR and resonance Raman spectroscopy in addition to density functional theory computational results. We speculate that the unusual sensitivity of skeletal muscle cytochrome c oxidase to sulfide poisoning in ethylmalonic encephalopathy, resulting from the deficiency in a mitochondrial sulfide oxidation enzyme, might be due to the concentration of H2S by myoglobin in this tissue. PMID:27310035

  13. Allylation of Intraerythrocytic Hemoglobin by Raw Garlic Extracts

    OpenAIRE

    Bonaventura, Joseph; Rodriguez, Eva N.; Beyley, Veronica; Vega, Irving E.

    2010-01-01

    Recent studies have shown that deoxygenated human red blood cells (RBCs) converted garlic-derived polysulfides into hydrogen sulfide, which in turn produced vasorelaxation in aortic ring preparations. The vasoactivity was proposed to occur via glucose- and thiol-dependent acellular reactions. In the present study, we investigated the interaction of garlic extracts with human deoxygenated RBCs and its effect on intracellular hemoglobin molecules. The results showed that garlic extract covalent...

  14. A randomized, double-blind study comparing the efficacy of selenium sulfide shampoo 1% and ciclopirox shampoo 1% as adjunctive treatments for tinea capitis in children.

    Science.gov (United States)

    Chen, Catherine; Koch, Laine H; Dice, James E; Dempsey, Kimberly K; Moskowitz, Alan B; Barnes-Eley, Myra L; Hubbard, Thomas W; Williams, Judith V

    2010-01-01

    Our objective was to compare the efficacy of selenium sulfide shampoo 1% and ciclopirox shampoo 1% as adjunctive treatments for tinea capitis in children. Forty children aged 1-11 years with clinically diagnosed tinea capitis were randomized to receive selenium sulfide shampoo 1% or ciclopirox shampoo 1% twice a week as adjuncts to an 8-week course of ultramicronized griseofulvin dosed at 10-12 mg/kg/day. At weeks 2, 4, and 8, subjects returned to the clinic for evaluation and scalp cultures. Subjects then returned for follow-up visits 4 weeks after completing treatment. Overall, by 8 weeks, 30 of 33 (90.9%) treated children demonstrated mycological cure. Selenium sulfide shampoo 1% and ciclopirox shampoo 1% were equally effective as adjunctive treatments for tinea capitis in children in our study.

  15. A chemical assessment of the suitability of allyl- iso-propyltelluride as a Te precursor for metal organic vapour phase epitaxy

    Science.gov (United States)

    Hails, Janet E.; Cole-Hamilton, David J.; Stevenson, John; Bell, William; Foster, Douglas F.; Ellis, David

    2001-04-01

    The chemical studies, which led to the testing of allyl- iso-propyltelluride (allylTePr i) as a Te precursor in metal organic vapour phase epitaxy are presented. The pyrolysis in hydrogen of allylTePr i gave products including 1,5-hexadiene, propane and propene. Co-pyrolysis of dimethylcadmium (Me 2Cd) and allylTePr i gave the hydrocarbons expected from the pyrolysis of the individual precursors plus additional hydrocarbons including 2-methylpropane and 1-butene. Plots of percentage decomposition versus temperature, which proved extremely useful in determining the likely growth temperatures for both CdTe and HgTe, showed that allylTePr i is less stable than both Pr 2iTe (di- iso-propyltelluride) and Me 2Cd. The possible role of Hg in the growth of CdTe is also discussed. The chemistry of allylTePr i is well suited for use as an efficient precursor for epitaxial growth of tellurium containing semiconductors since there is very little formation of other organotellurium compounds on pyrolysis.

  16. On the key role of water in the allylic activation catalysed by Pd (II) bisphosphinite complexes

    Indian Academy of Sciences (India)

    Rakesh Kumar Sharma; Ashoka G Samuelson

    2006-11-01

    Palladium and platinum complexes of bisphosphinites and bisphosphines derived from mandelic acid have been prepared and characterized. Their ability to catalyze allylation of imines with allyltributylstannane has been studied. Bisphophinite complexes of Pd (II) are shown to be ideal and they work best in the presence of one equivalent of water. The near neutral conditions employed make the catalysts suitable for a wide variety of substrates.

  17. Biotechnological reduction of sulfide in an industrial primary wastewater treatment system: A sustainable and successful case study

    Energy Technology Data Exchange (ETDEWEB)

    Rajamani, S. [Central Leather Research Institute, Madras (India)

    1996-12-31

    The leather industry is an important export-oriented industry in India, with more than 3,000 tanneries located in different clusters. Sodium sulfide, a toxic chemical, is used in large quantities to remove hair and excess flesh from hides and skins. Most of the sodium sulfide used in the process is discharged as waste in the effluent, which causes serious environmental problems. Reduction of sulfide in the effluent is generally achieved by means of chemicals in the pretreatment system, which involves aerobic mixing using large amounts of chemicals and high energy, and generating large volumes of sludge. A simple biotechnological system that uses the residual biosludge from the secondary settling tank was developed, and the commercial-scale application established that more than 90% of the sulfide could be reduced in the primary treatment system. In addition to the reduction of sulfide, foul smells, BOD and COD are reduced to a considerable level. 3 refs., 2 figs., 1 tab.

  18. Study on the Size-Dependent Oxidation Reaction Kinetics of Nanosized Zinc Sulfide

    Directory of Open Access Journals (Sweden)

    Qing-Shan Fu

    2014-01-01

    Full Text Available Numerous oxidation problems of nanoparticles are often involved during the preparation and application of nanomaterials. The oxidation rate of nanomaterials is much faster than bulk materials due to nanoeffect. Nanosized zinc sulfide (nano-ZnS and oxygen were chosen as a reaction system. The influence regularities were discussed and the influence essence was elucidated theoretically. The results indicate that the particle size can remarkably influence the oxidation reaction kinetics. The rate constant and the reaction order increase, while the apparent activation energy and the preexponential factor decrease with the decreasing particle size. Furthermore, the logarithm of rate constant, the apparent activation energy and the logarithm of preexponential factor are linearly related to the reciprocal of particle diameter, respectively. The essence is that the rate constant is influenced by the combined effect of molar surface energy and molar surface entropy, the reaction order by the molar surface area, the apparent activation energy, by the molar surface energy, and the preexponential factor by the molar surface entropy. The influence regularities and essence can provide theoretical guidance to solve the oxidation problems involved in the process of preparation and application of nanomaterials.

  19. Study on hydrogen sulfide removal based on bench-scale experiment by bio-trickling filter

    Institute of Scientific and Technical Information of China (English)

    TIAN Shu-lei; ZHANG Lan-he; WANG Qun-hui; WANG Xu-ming; XIE Wei-min

    2007-01-01

    A bench-scale experiment for control of hydrogen sulfide (H2S) emissions was carried out continuously for nearly four months by using bio-trickling filter packed with ZX01 stuffing. The results suggested that the bio-trickling filter had proven excellent performance over substantial operational periods. Removal efficiency of H2S was nearly 100% when volumetric loading of the bio-trickling filter varied from 0.64 g/(m3·h)to 38.20 g/(m3·h) and metabolism products of H2S were mainly composed of SO42-. When inlet concentration of H2S was 250 mg/m3, the optimum gas retention time was 30 s and the optimum spray water not blocked during experiments for nearly four months during which resistance was maintained at relatively lower value, so that the bio-trickling filter need not carry out back washing frequently and can be operated steadily for long-term.

  20. Aqueous studies of hydrogen sulfide releases from a heavy water extraction facility

    Energy Technology Data Exchange (ETDEWEB)

    Kiser, D.L.

    1979-03-01

    Upsets in the operation of the wastewater strippers in the 400 Area of the Savannah River Plant have released hydrogen sulfide in quantities as large as 1800 kg to the effluent stream. Fish kills in the swamp area of Beaver Dam Creek have occurred following the large releases. A literature survey revealed volatilization and oxidation as the major loss mechanisms of H/sub 2/S. Laboratory investigations supported the literature survey. The computer code for pollutant transport in a stream, LODIPS, has an option to account for sink-source effects in a stream. Volatilization and oxidation rate constants were developed for the sink option from two H/sub 2/S releases (18 kg and 118 kg) and results were predicted with LODIPS. Based on the predicted concentration-time profiles for various hypothetical cases, releases as small as 568 kg if discharged over a 30-minute period or releases as large as 1818 kg if discharged over a 360-minute period or less are lethal to swamp fish.

  1. Tether-directed synthesis of highly substituted oxasilacycles via an intramolecular allylation employing allylsilanes

    Directory of Open Access Journals (Sweden)

    Cox Liam R

    2007-02-01

    Full Text Available Abstract Background Using a silyl tether to unite an aldehyde electrophile and allylsilane nucleophile into a single molecule allows a subsequent Lewis-acid-mediated allylation to proceed in an intramolecular sense and therefore receive all the benefits associated with such processes. However, with the ability to cleave the tether post allylation, a product that is the result of a net intermolecular reaction can be obtained. In the present study, four diastereoisomeric β-silyloxy-α-methyl aldehydes, which contain an allylsilane tethered through the β-carbinol centre, have been prepared, in order to probe how the relative configuration of the two stereogenic centres affects the efficiency and selectivity of the intramolecular allylation. Results Syn-aldehydes, syn-4a and syn-4b, both react poorly, affording all four possible diastereoisomeric oxasilacycle products. In contrast, the anti aldehydes anti-4a and anti-4b react analogously to substrates that lack substitution at the α-site, affording only two of the four possible allylation products. Conclusion The outcome of the reaction with anti-aldehydes is in accord with reaction proceeding through a chair-like transition state (T.S.. In these systems, the sense of 1,3-stereoinduction can be rationalised by the aldehyde electrophile adopting a pseudoaxial orientation, which will minimise dipole-dipole interactions in the T.S. The 1,4-stereoinduction in these substrates is modest and seems to be modulated by the R substituent in the starting material. In the case of the syn-substrates, cyclisation through a chair T.S. is unlikely as this would require the methyl substituent α to the reacting carbonyl group to adopt an unfavourable pseudoaxial position. It is therefore proposed that these substrates react through poorly-defined T.S.s and consequently exhibit essentially no stereoselectivity.

  2. The soft X-ray absorption spectrum of the allyl free radical.

    Science.gov (United States)

    Alagia, M; Bodo, E; Decleva, P; Falcinelli, S; Ponzi, A; Richter, R; Stranges, S

    2013-01-28

    The first experimental study of the X-ray absorption spectrum (XAS) of the allyl free radical, CH(2)CHCH(2), is reported. A supersonic He seeded beam of hyperthermal allyl radicals was crossed by a high resolution synchrotron radiation (SR) in the focus of a 3D ion momentum imaging time-of-flight (TOF) spectrometer to investigate the soft X-ray absorption and fragmentation processes. The XAS, recorded as Total-Ion-Yield (TIY), is dominated by C1s electron excitations from either the central carbon atom, C(C), or the two terminal carbon atoms, C(T), to the frontier orbitals, the semi-occupied-molecular-orbital (SOMO) and the lowest-unoccupied-molecular-orbital (LUMO). All of the intense features in the XAS could only be assigned with the aid of ab initio spectral simulation at the Multi-Configuration Self-Consistent-Field (MCSCF) level of theory, this level being required because of the multi-reference nature of the core-excited state wavefunctions of the open shell molecule. The ionization energies (IEs) of the singlet and triplet states of the C1s ionized allyl radical (XPS) were also calculated at the MCSCF level. PMID:23232557

  3. Molecular cytotoxicity mechanisms of allyl alcohol (acrolein) in budding yeast.

    Science.gov (United States)

    Golla, Upendarrao; Bandi, Goutham; Tomar, Raghuvir S

    2015-06-15

    Allyl alcohol (AA) is one of the environmental pollutants used as a herbicide and industrial chemical. AA undergoes enzymatic oxidation in vivo to form Acrolein (Acr), a highly reactive and ubiquitous environmental toxicant. The exposure to AA/Acr has detrimental effects on cells and is highly fatal. In corroboration to the current literature describing AA/Acr toxicity, this study aimed to investigate the molecular cytotoxicity mechanisms of AA/Acr using budding yeast as a eukaryotic model organism. Genome-wide transcriptome analysis of cells treated with a sublethal dose of AA (0.4 mM) showed differential regulation of approximately 30% of the yeast genome. Functional enrichment analysis of the AA transcriptome revealed that genes belong to diverse cellular processes including the cell cycle, DNA damage repair, metal homeostasis, stress response genes, ribosomal biogenesis, metabolism, meiosis, ubiquitination, cell morphogenesis, and transport. Moreover, we have identified novel molecular targets of AA/Acr through genetic screening, which belongs to oxidative stress, DNA damage repair, iron homeostasis, and cell wall integrity. This study also demonstrated the epigenetic basis of AA/Acr toxicity mediated through histone tails and chromatin modifiers. Interestingly, our study disclosed the use of pyrazole and ethanol as probable antidotes for AA intoxication. For the first time, this study also demonstrated the reproductive toxicity of AA/Acr using the yeast gametogenesis (spermatogenesis) model. Altogether, this study unravels the molecular mechanisms of AA/Acr cytotoxicity and facilitates the prediction of biomarkers for toxicity assessment and therapeutic approaches. PMID:25919230

  4. Scalable and sustainable electrochemical allylic C-H oxidation

    Science.gov (United States)

    Horn, Evan J.; Rosen, Brandon R.; Chen, Yong; Tang, Jiaze; Chen, Ke; Eastgate, Martin D.; Baran, Phil S.

    2016-05-01

    New methods and strategies for the direct functionalization of C-H bonds are beginning to reshape the field of retrosynthetic analysis, affecting the synthesis of natural products, medicines and materials. The oxidation of allylic systems has played a prominent role in this context as possibly the most widely applied C-H functionalization, owing to the utility of enones and allylic alcohols as versatile intermediates, and their prevalence in natural and unnatural materials. Allylic oxidations have featured in hundreds of syntheses, including some natural product syntheses regarded as “classics”. Despite many attempts to improve the efficiency and practicality of this transformation, the majority of conditions still use highly toxic reagents (based around toxic elements such as chromium or selenium) or expensive catalysts (such as palladium or rhodium). These requirements are problematic in industrial settings; currently, no scalable and sustainable solution to allylic oxidation exists. This oxidation strategy is therefore rarely used for large-scale synthetic applications, limiting the adoption of this retrosynthetic strategy by industrial scientists. Here we describe an electrochemical C-H oxidation strategy that exhibits broad substrate scope, operational simplicity and high chemoselectivity. It uses inexpensive and readily available materials, and represents a scalable allylic C-H oxidation (demonstrated on 100 grams), enabling the adoption of this C-H oxidation strategy in large-scale industrial settings without substantial environmental impact.

  5. Transition metal catalysed Grignard-like allylic activation across tetragonal tin(II) oxide

    Indian Academy of Sciences (India)

    Pradipta Sinha; Moloy Banerjee; Abhijit Kundu; Sujit Roy

    2002-08-01

    The reaction of allyl halide and a carbonyl compound under the aegis of tetragonal tin(II) oxide and catalytic 8, 10 metal complexes provides the corresponding homoallylic alcohol, via a novel allyl tin intermediate.

  6. Structurally defined allyl compounds of main group metals: coordination and reactivity.

    Science.gov (United States)

    Lichtenberg, Crispin; Okuda, Jun

    2013-05-10

    Organometallic allyl compounds are important as allylation reagents in organic synthesis, as polymerization catalysts, and as volatile metal precursors in material science. Whereas the allyl chemistry of synthetically relevant transition metals such as palladium and of the lanthanoids is well-established, that of main group metals has been lagging behind. Recent progress on allyl complexes of Groups 1, 2, and 12-16 now provides a more complete picture. This is based on a fundamental understanding of metal-allyl bonding interactions in solution and in the solid state. Furthermore, reactivity trends have been rationalized and new types of allyl-specific reactivity patterns have been uncovered. Key features include 1) the exploitation of the different types of metal-allyl bonding (highly ionic to predominantly covalent), 2) the use of synergistic effects in heterobimetallic compounds, and 3) the adjustment of Lewis acidity by variation of the charge of allyl compounds.

  7. A convenient procedure for the synthesis of allyl and benzyl ethers from alcohols and phenols

    Indian Academy of Sciences (India)

    H Surya Prakash Rao; S P Senthilkumar

    2001-06-01

    Allyl and benzyl ethers of alcohols can be prepared conveniently and in high yield with allyl and benzyl bromide in the presence of solid potassium hydroxide without use of any solvent. Phenols can be converted to allyl ethers but are inert to benzylation under above conditions.

  8. 40 CFR 721.7000 - Polymer of disodium maleate, allyl ether, and ethylene oxide.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polymer of disodium maleate, allyl... New Uses for Specific Chemical Substances § 721.7000 Polymer of disodium maleate, allyl ether, and... substance identified generically as a polymer of disodium maleate, allyl ether, and ethylene oxide...

  9. 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

  10. Study on Influencing Factors of Ferrous Sulfide Formation%影响硫化亚铁产生的因素实验研究

    Institute of Scientific and Technical Information of China (English)

    修丽群; 穆超; 刘丽丽; 刘帅

    2015-01-01

    随着以蒸汽吞吐为主要手段的热力开采技术的应用,油井套管气中开始出现硫化氢,伴随着热采时间的增加和 SAGD 技术的应用,含硫化氢油井数目不断增加,硫化氢浓度不断升高,产生腐蚀产物——硫化亚铁。硫化亚铁具有自燃性,在常温下与空气中的氧气接触能迅速反应放热而引起自燃。为了避免设备发生硫化亚铁自燃事故,必须对硫化亚铁自燃机理开展深入研究。通过室内试验研究本文发现:常温下,干燥的环境中干燥的 H2S 气体能与铁的氧化物比较容易发生硫化反应。温度、H2S 的湿度、不同的铁氧化物,均对硫化亚铁的生成有重要影响。铁氧化物的含水量不同,其硫化产物 FeS 的量也不同。%During application of the steam stimulation as the thermal mining technology, hydrogen sulphide appears in oil well casing gas. Along with the increase of thermal recovery time and application of SAGD technology, the number of hydrogen sulfide-bearing wells increases, the concentration of hydrogen sulfide is also rising, and ferrous sulfide as corrosion products forms. Ferrous sulfide has the feature of spontaneous combustion, if it contacts with oxygen in air at room temperature, they can quickly react to cause spontaneous combustion. In order to avoid the occurrence of ferrous sulfide self-ignition accident, it is necessary to conduct in-depth research on ferrous sulfide self-ignition mechanism. Laboratory studies show that, under normal temperature, dry H2S gas and iron oxide can react easily in the dry environment. Temperature, H2S humidity and iron oxide have important influence on the formation of ferrous sulfide. If the water content of iron oxide is different, then the quantity of FeS is also different..

  11. Iridium-Catalyzed Selective Isomerization of Primary Allylic Alcohols.

    Science.gov (United States)

    Li, Houhua; Mazet, Clément

    2016-06-21

    This Account presents the development of the iridium-catalyzed isomerization of primary allylic alcohols in our laboratory over the past 8 years. Our initial interest was driven by the long-standing challenge associated with the development of a general catalyst even for the nonasymmetric version of this seemingly simple chemical transformation. The added value of the aldehyde products and the possibility to rapidly generate molecular complexity from readily accessible allylic alcohols upon a redox-economical isomerization reaction were additional sources of motivation. Certainly influenced by the success story of the related isomerization of allylic amines, most catalysts developed for the selective isomerization of allylic alcohols were focused on rhodium as a transition metal of choice. Our approach has been based on the commonly accepted precept that hydrogenation and isomerization are often competing processes, with the latter being usually suppressed in favor of the former. The cationic iridium complexes [(Cy3P)(pyridine)Ir(cod)]X developed by Crabtree (X = PF6) and Pfaltz (X = BArF) are usually considered as the most versatile catalysts for the hydrogenation of allylic alcohols. Using molecular hydrogen to generate controlled amounts of the active form of these complexes but performing the reaction in the absence of molecular hydrogen enabled deviation from the typical hydrogenation manifold and favored exclusively the isomerization of allylic alcohols into aldehydes. Isotopic labeling and crossover experiments revealed the intermolecular nature of the process. Systematic variation of the ligand on the iridium center allowed us to identify the structural features beneficial for catalytic activity. Subsequently, three generations of chiral catalysts have been investigated and enabled us to reach excellent levels of enantioselectivity for a wide range of 3,3-disubstituted aryl/alkyl and alkyl/alkyl primary allylic alcohols leading to β-chiral aldehydes. The

  12. A physiologically based kinetic model for bacterial sulfide oxidation

    NARCIS (Netherlands)

    Klok, J.B.; Graaff, M. de; Bosch, P.L. van den; Boelee, N.C.; Keesman, K.J.; Janssen, A.J.W.M.

    2013-01-01

    In the biotechnological process for hydrogen sulfide removal from gas streams, a variety of oxidation products can be formed. Under natron-alkaline conditions, sulfide is oxidized by haloalkaliphilic sulfide oxidizing bacteria via flavocytochrome c oxidoreductase. From previous studies, it was concl

  13. Highly Enantioselective Formation of α-Allyl-α-Arylcyclopentanones via Pd-Catalysed Decarboxylative Asymmetric Allylic Alkylation.

    Science.gov (United States)

    Akula, Ramulu; Doran, Robert; Guiry, Patrick J

    2016-07-11

    A highly enantioselective Pd-catalysed decarboxylative asymmetric allylic alkylation of cyclopentanone derived α-aryl-β-keto esters employing the (R,R)-ANDEN-phenyl Trost ligand has been developed. The product (S)-α-allyl-α-arylcyclopentanones were obtained in excellent yields and enantioselectivities (up to >99.9 % ee). This represents one of the most highly enantioselective formations of an all-carbon quaternary stereogenic center reported to date. This reaction was demonstrated on a 4.0 mmol scale without any deterioration of enantioselectivity and was exploited as the key enantioselective transformation in an asymmetric formal synthesis of the natural product (+)-tanikolide. PMID:27191198

  14. Study of benzotriazole as corrosion inhibitors of carbon steel in chloride solution containing hydrogen sulfide using electrochemical impedance spectroscopy (EIS)

    International Nuclear Information System (INIS)

    Corrosion and inhibition studies on API 5LX65 carbon steel in chloride solution containing various concentrations of benzotriazole has been conducted at temperature of 70°C using Electrochemical Impedance Spectroscopy (EIS). Corroded carbon steel surface with and without inhibitor have been observed using X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), and Energy Dispersive Spectroscopy (EDS). The objectives of this research are to study the performance of benzotriazole as corrosion inhibitors. The experimental results of carbon steel corrosion in 3.5% NaCl solution containing 500 mg/l H2S at different BTAH concentrations showed that corrosion rate of carbon steel decreases with increasing of BTAH concentrations from 0 to 10 mmol/l. The inhibition efficiency of BTAH was found to be affected by its concentration. The optimum efficiency obtained of BTAH is 93% at concentration of 5 mmol/l. The result of XRD and EDS analysis reveal the iron sulfide (FeS) formation on corroded carbon steel surface without inhibitor. The EDS spectrum show the Nitrogen (N) bond on carbon steel surface inhibited by BTAH

  15. Study of benzotriazole as corrosion inhibitors of carbon steel in chloride solution containing hydrogen sulfide using electrochemical impedance spectroscopy (EIS)

    Energy Technology Data Exchange (ETDEWEB)

    Solehudin, Agus, E-mail: asolehudin@upi.edu [Department of Mechanical Engineering Education, Indonesia University of Education (UPI), Bandung, West Java (Indonesia); Nurdin, Isdiriayani [Department of Chemical Engineering, Bandung Institute of Technology, Bandung, West Java (Indonesia)

    2014-03-24

    Corrosion and inhibition studies on API 5LX65 carbon steel in chloride solution containing various concentrations of benzotriazole has been conducted at temperature of 70°C using Electrochemical Impedance Spectroscopy (EIS). Corroded carbon steel surface with and without inhibitor have been observed using X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), and Energy Dispersive Spectroscopy (EDS). The objectives of this research are to study the performance of benzotriazole as corrosion inhibitors. The experimental results of carbon steel corrosion in 3.5% NaCl solution containing 500 mg/l H{sub 2}S at different BTAH concentrations showed that corrosion rate of carbon steel decreases with increasing of BTAH concentrations from 0 to 10 mmol/l. The inhibition efficiency of BTAH was found to be affected by its concentration. The optimum efficiency obtained of BTAH is 93% at concentration of 5 mmol/l. The result of XRD and EDS analysis reveal the iron sulfide (FeS) formation on corroded carbon steel surface without inhibitor. The EDS spectrum show the Nitrogen (N) bond on carbon steel surface inhibited by BTAH.

  16. Study of benzotriazole as corrosion inhibitors of carbon steel in chloride solution containing hydrogen sulfide using electrochemical impedance spectroscopy (EIS)

    Science.gov (United States)

    Solehudin, Agus; Nurdin, Isdiriayani

    2014-03-01

    Corrosion and inhibition studies on API 5LX65 carbon steel in chloride solution containing various concentrations of benzotriazole has been conducted at temperature of 70°C using Electrochemical Impedance Spectroscopy (EIS). Corroded carbon steel surface with and without inhibitor have been observed using X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), and Energy Dispersive Spectroscopy (EDS). The objectives of this research are to study the performance of benzotriazole as corrosion inhibitors. The experimental results of carbon steel corrosion in 3.5% NaCl solution containing 500 mg/l H2S at different BTAH concentrations showed that corrosion rate of carbon steel decreases with increasing of BTAH concentrations from 0 to 10 mmol/l. The inhibition efficiency of BTAH was found to be affected by its concentration. The optimum efficiency obtained of BTAH is 93% at concentration of 5 mmol/l. The result of XRD and EDS analysis reveal the iron sulfide (FeS) formation on corroded carbon steel surface without inhibitor. The EDS spectrum show the Nitrogen (N) bond on carbon steel surface inhibited by BTAH.

  17. Sulfonium-based Ionic Liquids Incorporating the Allyl Functionality

    Directory of Open Access Journals (Sweden)

    Paul J. Dyson

    2007-04-01

    Full Text Available A series of sulfonium halides bearing allyl groups have been prepared andcharacterized. Anion metathesis with Li[Tf2N] and Ag[N(CN2] resulted in sulfonium-basedionic liquids which exhibit low viscosities at room temperature. The solid state structure ofone of the halide salts was determined by single crystal X-ray diffraction.

  18. Electrochemical Allylic Oxidation of Olefins: Sustainable and Safe.

    Science.gov (United States)

    Waldvogel, Siegfried R; Selt, Maximilian

    2016-10-01

    The power you're supplying: With the application of an optimized electrochemical approach, the allylic oxidation of olefins, which is an important C-H activation process that provides access to enones, becomes a sustainable, versatile, and potent key reaction for organic synthesis.

  19. Study and modeling of the evolution of gas-liquid partitioning of hydrogen sulfide in model solutions simulating winemaking fermentations.

    Science.gov (United States)

    Mouret, Jean-Roch; Sablayrolles, Jean-Marie; Farines, Vincent

    2015-04-01

    The knowledge of gas-liquid partitioning of aroma compounds during winemaking fermentation could allow optimization of fermentation management, maximizing concentrations of positive markers of aroma and minimizing formation of molecules, such as hydrogen sulfide (H2S), responsible for defects. In this study, the effect of the main fermentation parameters on the gas-liquid partition coefficients (Ki) of H2S was assessed. The Ki for this highly volatile sulfur compound was measured in water by an original semistatic method developed in this work for the determination of gas-liquid partitioning. This novel method was validated and then used to determine the Ki of H2S in synthetic media simulating must, fermenting musts at various steps of the fermentation process, and wine. Ki values were found to be mainly dependent on the temperature but also varied with the composition of the medium, especially with the glucose concentration. Finally, a model was developed to quantify the gas-liquid partitioning of H2S in synthetic media simulating must to wine. This model allowed a very accurate prediction of the partition coefficient of H2S: the difference between observed and predicted values never exceeded 4%.

  20. Study of structural, optical and photoluminescence properties of indium-doped zinc sulfide thin films for optoelectronic applications

    Science.gov (United States)

    Jrad, Abdelhak; Ben Nasr, Tarek; Turki-Kamoun, Najoua

    2015-12-01

    In the present work, we have deposited indium-doped zinc sulfide (ZnS:In) thin films by chemical bath deposition technique (CBD). The structural properties studied by X-ray diffraction indicate that ZnS:In has a cubic structure with an average crystallite size 4.7-11.0 nm. Transmission and reflection spectra reveal the presence of interference fringes indicating thickness uniformity and surface homogeneity of deposited material. All the films were transparent in the visible and infrared regions (⩾60%), which allows us to use this material as an optical window or a buffer layer in solar cells. The obtained band gap energy Eg is in the range of 3.70-3.76 eV. The refractive index and thickness of ZnS:In thin films was calculated using envelope method. The variation of the refractive index along the Cauchy distribution was observed in all ZnS:In thin films. The analysis of the refractive index data through the Wemple-DiDomenico model leads to the single oscillator energy (E0) and the dispersion energy (Ed).

  1. Study and modeling of the evolution of gas-liquid partitioning of hydrogen sulfide in model solutions simulating winemaking fermentations.

    Science.gov (United States)

    Mouret, Jean-Roch; Sablayrolles, Jean-Marie; Farines, Vincent

    2015-04-01

    The knowledge of gas-liquid partitioning of aroma compounds during winemaking fermentation could allow optimization of fermentation management, maximizing concentrations of positive markers of aroma and minimizing formation of molecules, such as hydrogen sulfide (H2S), responsible for defects. In this study, the effect of the main fermentation parameters on the gas-liquid partition coefficients (Ki) of H2S was assessed. The Ki for this highly volatile sulfur compound was measured in water by an original semistatic method developed in this work for the determination of gas-liquid partitioning. This novel method was validated and then used to determine the Ki of H2S in synthetic media simulating must, fermenting musts at various steps of the fermentation process, and wine. Ki values were found to be mainly dependent on the temperature but also varied with the composition of the medium, especially with the glucose concentration. Finally, a model was developed to quantify the gas-liquid partitioning of H2S in synthetic media simulating must to wine. This model allowed a very accurate prediction of the partition coefficient of H2S: the difference between observed and predicted values never exceeded 4%. PMID:25763810

  2. Allyl/propenyl phenol synthases from the creosote bush and engineering production of specialty/commodity chemicals, eugenol/isoeugenol, in Escherichia coli.

    Science.gov (United States)

    Kim, Sung-Jin; Vassão, Daniel G; Moinuddin, Syed G A; Bedgar, Diana L; Davin, Laurence B; Lewis, Norman G

    2014-01-01

    The creosote bush (Larrea tridentata) harbors members of the monolignol acyltransferase, allylphenol synthase, and propenylphenol synthase gene families, whose products together are able to catalyze distinct regiospecific conversions of various monolignols into their corresponding allyl- and propenyl-phenols, respectively. In this study, co-expression of a monolignol acyltransferase with either substrate versatile allylphenol or propenylphenol synthases in Escherichia coli established that various monolignol substrates were efficiently converted into their corresponding allyl/propenyl phenols, as well as providing proof of concept for efficacious conversion in a bacterial platform. This capability thus potentially provides an alternate source to these important plant phytochemicals, whether for flavor/fragrance and fine chemicals, or ultimately as commodities, e.g., for renewable energy or other intermediate chemical purposes. Previous reports had indicated that specific and highly conserved amino acid residues 84 (Phe or Val) and 87 (Ile or Tyr) of two highly homologous allyl/propenyl phenol synthases (circa 96% identity) from a Clarkia species mainly dictate their distinct regiospecific catalyzed conversions to afford either allyl- or propenyl-phenols, respectively. However, several other allyl/propenyl phenol synthase homologs isolated by us have established that the two corresponding amino acid 84 and 87 residues are not, in fact, conserved.

  3. Fluorinated alcohols as promoters for the metal-free direct substitution reaction of allylic alcohols with nitrogenated, silylated, and carbon nucleophiles.

    Science.gov (United States)

    Trillo, Paz; Baeza, Alejandro; Nájera, Carmen

    2012-09-01

    The direct allylic substitution reaction using allylic alcohols in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and 2,2,2-trifluoroethanol (TFE) as reaction media is described. The developed procedure is simple, works under mild conditions (rt, 50 and 70 °C), and proves to be very general, since different nitrogenated nucleophiles and carbon nucleophiles can be used achieving high yields, especially when HFIP is employed as solvent and aromatic allylic alcohols are the substrates. Thus, sulfonamides, carbamates, carboxamides, and amines can be successfully employed as nitrogen-based nucleophiles. Likewise, silylated nucleophiles such as trimethylsilylazide, allyltrimethylsilane, trimethylsilane, and trimethylsilylphenylacetylene give the corresponding allylic substitution products in high yields. Good results for the Friedel-Crafts adducts are also achieved with aromatic compounds (phenol, anisole, indole, and anilines) as nucleophiles. Particularly interesting are the results obtained with electron-rich anilines, which can behave as nitrogenated or carbon nucleophiles depending on their electronic properties and the solvent employed. In addition, 1,3-dicarbonyl compounds (acetylacetone and Meldrum's acid) are also successfully employed as soft carbon nucleophiles. Studies for mechanism elucidation are also reported, pointing toward the existence of carbocationic intermediates and two working reaction pathways for the obtention of the allylic substitution product.

  4. Textural, mineralogical and stable isotope studies of hydrothermal alteration in the main sulfide zone of the Great Dyke, Zimbabwe and the precious metals zone of the Sonju Lake Intrusion, Minnesota, USA

    Science.gov (United States)

    Li, C.; Ripley, E.M.; Oberthur, T.; Miller, J.D., Jr.; Joslin, G.D.

    2008-01-01

    Stratigraphic offsets in the peak concentrations of platinum-group elements (PGE) and base-metal sulfides in the main sulfide zone of the Great Dyke and the precious metals zone of the Sonju Lake Intrusion have, in part, been attributed to the interaction between magmatic PGE-bearing base-metal sulfide assemblages and hydrothermal fluids. In this paper, we provide mineralogical and textural evidence that indicates alteration of base-metal sulfides and mobilization of metals and S during hydrothermal alteration in both mineralized intrusions. Stable isotopic data suggest that the fluids involved in the alteration were of magmatic origin in the Great Dyke but that a meteoric water component was involved in the alteration of the Sonju Lake Intrusion. The strong spatial association of platinum-group minerals, principally Pt and Pd sulfides, arsenides, and tellurides, with base-metal sulfide assemblages in the main sulfide zone of the Great Dyke is consistent with residual enrichment of Pt and Pd during hydrothermal alteration. However, such an interpretation is more tenuous for the precious metals zone of the Sonju Lake Intrusion where important Pt and Pd arsenides and antimonides occur as inclusions within individual plagioclase crystals and within alteration assemblages that are free of base-metal sulfides. Our observations suggest that Pt and Pd tellurides, antimonides, and arsenides may form during both magmatic crystallization and subsolidus hydrothermal alteration. Experimental studies of magmatic crystallization and hydrothermal transport/deposition in systems involving arsenides, tellurides, antimonides, and base metal sulfides are needed to better understand the relative importance of magmatic and hydrothermal processes in controlling the distribution of PGE in mineralized layered intrusions of this type. ?? Springer-Verlag 2007.

  5. Thermophysical properties and reaction kinetics of γ-irradiated poly allyl diglycol carbonates nuclear track detector

    Science.gov (United States)

    Elmaghraby, Elsayed K.; Seddik, Usama

    2015-07-01

    Kinetic thermogravimetric technique was used to study the effect of gamma irradiation on the poly allyl diglycol carbonates (PADC) within the dose range from 50 to ? Gy. The approach of Coats-Redfern was used to analyze the data. Results showed that low doses around 50 Gy make the polymer slightly more resistive to heat treatment. Higher radiation doses cause severe effects in the samples accompanied by the formation of lower molecular mass species and consequent crosslinking. Results support the domination of re-polymerization and crosslinking for the γ radiation interaction PADC at dose below about ? Gy, while the situation is inverted above ? Gy in which chain secession dominates.

  6. Mechanistic Investigation of Palladium–Catalyzed Allylic C–H Activation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Jensen, Thomas; Rodríguez-Rodríguez, Sergio;

    2013-01-01

    The mechanism for the palladium–catalyzed allylic C–H activation was investigated using a combination of experimental and theoretical methods. A Hammett study revealed a buildup of a partial negative charge in the rate-determining step, while determination of the kinetic isotope effect (KIE...... acetate acts as a base in an intramolecular fashion during the C–H activation step. The re-oxidation of palladium was found to reach a similar energy level as that of the C–H activation. Calculations of turnover frequencies (TOF) for the entire catalytic cycle for the C–H alkylation were used to acquire a...

  7. Allyl Isothiocyanate Increases MRP1 Function and Expression in a Human Bronchial Epithelial Cell Line

    OpenAIRE

    Dian-lei Wang; Chen-yin Wang; Yin Cao; Xian Zhang; Xiu-hua Tao; Li-li Yang; Jin-pei Chen; Shan-shan Wang; Ze-geng Li

    2014-01-01

    Multidrug resistance-associated protein 1 (MRP1), a member of the ATP-binding cassette (ABC) superfamily of transporters, plays an important role in normal lung physiology by protecting cells against oxidative stress and toxic xenobiotics. The present study investigates the effects of allyl isothiocyanate (AITC) on MRP1 mRNA and MRP1 protein expression and transporter activity in the immortalised human bronchial epithelial cell line 16HBE14o-. MRP1 mRNA and MRP1 protein expression in 16HBE14o...

  8. Branching Out: Rhodium-Catalyzed Allylation with Alkynes and Allenes.

    Science.gov (United States)

    Koschker, Philipp; Breit, Bernhard

    2016-08-16

    We present a new and efficient strategy for the atom-economic transformation of both alkynes and allenes to allylic functionalized structures via a Rh-catalyzed isomerization/addition reaction which has been developed in our working group. Our methodology thus grants access to an important structural class valued in modern organic chemistry for both its versatility for further functionalization and the potential for asymmetric synthesis with the construction of a new stereogenic center. This new methodology, inspired by mechanistic investigations by Werner in the late 1980s and based on preliminary work by Yamamoto and Trost, offers an attractive alternative to other established methods for allylic functionalization such as allylic substitution or allylic oxidation. The main advantage of our methodology consists of the inherent atom economy in comparison to allylic oxidation or substitution, which both produce stoichiometric amounts of waste and, in case of the substitution reaction, require prefunctionalization of the starting material. Starting out with the discovery of a highly branched-selective coupling reaction of carboxylic acids with terminal alkynes using a Rh(I)/DPEphos complex as the catalyst system, over the past 5 years we were able to continuously expand upon this chemistry, introducing various (pro)nucleophiles for the selective C-O, C-S, C-N, and C-C functionalization of both alkynes and the double-bond isomeric allenes by choosing the appropriate rhodium/bidentate phosphine catalyst. Thus, valuable compounds such as branched allylic ethers, sulfones, amines, or γ,δ-unsaturated ketones were successfully synthesized in high yields and with a broad substrate scope. Beyond the branched selectivity inherent to rhodium, many of the presented methodologies display additional degrees of selectivity in regard to regio-, diastereo-, and enantioselective transformations, with one example even proceeding via a dynamic kinetic resolution. Many advances

  9. Impact history of the Chelyabinsk meteorite: Electron microprobe and LA-ICP-MS study of sulfides and metals

    Science.gov (United States)

    Andronikov, A. V.; Andronikova, I. E.; Hill, D. H.

    2015-12-01

    Electron microprobe and LA-ICP-MS study of sulfides and metals from two fragments of the LL5 Chelyabinsk meteorite were conducted. The fragments are impact breccias, one fragment contains both chondritic and shock vein lithologies, and the other contains shock-darkened chondritic clasts and vesicular impact melts. The chondritic lithology and shock veins display very similar opaque mineral compositions. The mineral compositions in the impact-melt breccias are distinctly different. The brecciated state of the Chelyabinsk meteorite suggests strong involvement of shock-related processes during the evolution of the parent body. Multiple heavy impact events occurred on the parent asteroid and on the Chelyabinsk meteoroid itself over the time period from ca. 4.5 Ga until ca. 1.2 Ma. The shock veins were produced in situ on the parent body. The impact-melt breccias could have formed because of the dramatic impact to the parent LL-chondrite body that could be partly disintegrated. The fragment containing shock-darkened chondritic clasts and vesicular impact melt lithologies preserves a record of melting, volatilization, partial degassing, and quenching of the molten material. The abundance and size (up to 1 mm) of the vesicles suggest that the impact melt must have been buried at some depth after formation. After impact and subsequent melting occurred, the impact-induced pressure on the shallow asteroid interior was released that caused "boiling" of volatiles and generation of S-rich bubbles. Such an impact excavated down to depths of the body generating multiple fragments with complicated histories. These fragments reaccumulated into a gravitational aggregate and formed the parental meteoroid for the Chelyabinsk meteorite.

  10. 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...

  11. Studies on the Tolerating Mechanism for Sulfide in Urechis unicinctus ( Echiura : Urechidae) ——Cytological Observation on Urechis unicinctus in Different Hydrogen Sulfide Environment

    Institute of Scientific and Technical Information of China (English)

    张志峰; 邵明瑜; 康庆浩; 金在敏

    2003-01-01

    This study on the cytological changes of the body wall, aspiratory intestine and crissalbursa in Urechis unicinctus by light microscope (LM) and transmission electron microscope (TEM)showed that the difference between the body wall and the natural environment rich in H2 S was notobvious; that the wall color of the aspiratory intestine in H2 S rich environment changed from normalsemitransparency to dark brown; that its epithelia were disassembled and the electron density of itscytoplasm matrix was lower; and that in H2 S rich enviromnent many basophilic granules occurred inthe epithelia of the crissal bursa. Granules with single membrane and myelinefingure were foundwith TEM.

  12. ION EXCHANGE SUBSTANCES BY SAPONIFICATION OF ALLYL PHOSPHATE POLYMERS

    Science.gov (United States)

    Kennedy, J.

    1959-04-14

    An ion exchange resin having a relatively high adsorption capacity tor uranyl ion as compared with many common cations is reported. The resin comprises an alphyl-allyl hydrogen phosphate polymer, the alphyl group being either allyl or a lower alkyl group having up to 5 carbon atoins. The resin is prepared by polymerizing compounds such as alkyl-diallyl phosphate and triallyl phosphate in the presence of a free radical generating substance and then partially hydrolyzing the resulting polymer to cause partial replacement of organic radicals by cations. A preferred free radical gencrating agent is dibenzoyl peroxide. The partial hydrolysis is brought about by refluxing the polymer with concentrated aqueous NaOH for three or four hours.

  13. Radiation initiated copolymerization of allyl alcohol with acrylonitrile

    Energy Technology Data Exchange (ETDEWEB)

    Solpan, Dilek; Guven, Olgun [Hacettepe Univ., Ankara (Turkey). Dept. of Chemistry

    1996-07-01

    Copolymerization of allyl alcohol (AA) with acrylonitrile (AN) initiated by {gamma}-rays has been investigated to determine the respective reactivity ratios. Three different experimental techniques, namely Fourier Transform Infrared (FTIR), Ultraviolet (UV/vis) and elemental analysis (EA) have been used for the determination of copolymer compositions. Fineman-Ross (FR), Kelen-Tudos (KT), Non-Linear Least Square (NLLS) Analysis and Q-e methods have been applied to the three sets of experimental data. It has been concluded that data obtained from elemental analysis as applied to the Non-Linear Least Square approach gave the most reliable reactivity ratios as 2.09 and 0.40 for acrylonitrile and allyl alcohol, respectively. (Author).

  14. Radiation initiated copolymerization of allyl alcohol with acrylonitrile

    Science.gov (United States)

    Şolpan, Dilek; Güven, Olgun

    1996-07-01

    Copolymerization of allyl alcohol (AA) with acrylonitrile (AN) initiated by γ-rays has been investigated to determine the respective reactivity ratios. Three different experimental techniques, namely Fourier Transform Infrared (FTIR), Ultraviolet (UV/vis) and elemental analysis (EA) have been used for the determination of copolymer compositions. Fineman-Ross (FR), Kelen-Tüdös (KT), Non-Linear Least Square (NLLS) Analysis and Q-e methods have been applied to the three sets of experimental data. It has been concluded that data obtained from elemental analysis as applied to the Non-Linear Least Square approach gave the most reliable reactivity ratios as 2.09 and 0.40 for acrylonitrile and allyl alcohol, respectively.

  15. The utilization of the mesoporous Ti-SBA-15 catalyst in the epoxidation of allyl alcohol to glycidol and diglycidyl ether in the water medium

    Directory of Open Access Journals (Sweden)

    Wróblewska Agnieszka

    2015-12-01

    Full Text Available This work presents the studies on the optimization the process of allyl alcohol epoxidation over the Ti-SBA-15 catalyst. The optimization was carried out in an aqueous medium, wherein water was introduced into the reaction medium with an oxidizing agent (30 wt% aqueous solution of hydrogen peroxide and it was formed in the reaction medium during the processes. The main investigated technological parameters were: the temperature, the molar ratio of allyl alcohol/hydrogen peroxide, the catalyst content and the reaction time. The main functions the process were: the selectivity of transformation to glycidol in relation to allyl alcohol consumed, the selectivity of transformation to diglycidyl ether in relation to allyl alcohol consumed, the conversion of allyl alcohol and the selectivity of transformation to organic compounds in relation to hydrogen peroxide consumed. The analysis of the layer drawings showed that in water solution it is best to conduct allyl alcohol epoxidation in direction of glycidol (selectivity of glycidol 54 mol% at: the temperature of 10–17°C, the molar ratio of reactants 0.5–1.9, the catalyst content 2.9–4.0 wt%, the reaction time 2.7–3.0 h and in direction of diglycidyl ether (selectivity of diglycidyl ether 16 mol% at: the temperature of 18–33°C, the molar ratio of reactants 0.9–1.65, the catalyst content 2.0–3.4 wt%, the reaction time 1.7–2.6 h. The presented method allows to obtain two very valuable intermediates for the organic industry.

  16. First-principles study of structures and electronic properties of cadmium sulfide clusters

    Institute of Scientific and Technical Information of China (English)

    Chu He-Ying; Liu Zhao-Xia; Qiu Guo-Li; Kong De-Guo; Wu Si-Xin; Li Yun-Cai; Du Zu-Liang

    2008-01-01

    The lowest-energy structures and the electronic properties of CdnSn(n=1-8) clusters have been studied by using density-functional theory simulating package DMol3 in the generalized gradient approximation (GGA). The ring-like structures are the lowest-energy configurations for n=2,3 and the three-dimensional spheroid configurations for n=4-8. The three-dimensional structures may be considered as being built from the Cd2S2 and Cd3S3 rings. Compared to the previous reports, we have found the more stable structures for CdnSn(n=7,8). Calculations show that the magic numbers of CdnSn(n=1-8) clusters are n=3 and 6. As cluster size increases, the properties of CdnSn clusters tend to bulk-like ones in binding energy per CdS unit and Mulliken atomic charge, obtained by comparing with the calculated results of the wurtzite and zinc blende CdS for the same simulating parameters.

  17. Enantioconvergent synthesis by sequential asymmetric Horner-Wadsworth-Emmons and palladium-catalyzed allylic substitution reactions

    DEFF Research Database (Denmark)

    Pedersen, Torben Møller; Hansen, E. Louise; Kane, John;

    2001-01-01

    A new method for enantioconvergent synthesis has been developed. The strategy relies on the combination of an asymmetric Horner-Wadsworth-Emmons (HWE) reaction and a palladium-catalyzed allylic substitution. Different $alpha@-oxygen-substituted, racemic aldehydes were initially transformed by...... asymmetric HWE reactions into mixtures of two major $alpha@,$beta@-unsaturated esters, possessing opposite configurations at their allylic stereocenters as well as opposite alkene geometry. Subsequently, these isomeric mixtures of alkenes could be subjected to palladium-catalyzed allylic substitution...

  18. Gold(I)-Assisted α-Allylation of Enals and Enones with Alcohols.

    Science.gov (United States)

    Mastandrea, Marco Michele; Mellonie, Niall; Giacinto, Pietro; Collado, Alba; Nolan, Steven P; Miscione, Gian Pietro; Bottoni, Andrea; Bandini, Marco

    2015-12-01

    The intermolecular α-allylation of enals and enones occurs by the condensation of variously substituted allenamides with allylic alcohols. Cooperative catalysis by [Au(ItBu)NTf2] and AgNTf2 enables the synthesis of a range of densely functionalized α-allylated enals, enones, and acyl silanes in good yield under mild reaction conditions. DFT calculations support the role of an α-gold(I) enal/enone as the active nucleophilic species.

  19. The pure rotational spectrum of a Claisen rearrangement precursor Allyl Phenyl Ether using CP-FTMW spectroscopy

    Science.gov (United States)

    Grubbs, G. S.; Frank, Derek S.; Obenchain, Daniel A.; Cooke, S. A.; Novick, Stewart E.

    2016-06-01

    The pure rotational spectrum of a Claisen rearrangement precursor, Allyl Phenyl Ether (APE), has been measured on a chirped pulse Fourier transform microwave (CP-FTMW) spectrometer in the 8-14 GHz region. Rotational and centrifugal distortion constants for multiple conformations have been determined and are reported for the first time. This is the first study of a phenyl-containing ether where multiple conformers were experimentally observed all within their ground vibrational states. Quantum chemical calculations have been performed to isolate low energy geometries of APE and are implemented to aid in spectral assignment. Other structural parameters such as planar moments and inertial defects for the Allyl Phenyl Ether conformers are presented and compared to similar molecules.

  20. REDUCING NONSELECTIVE PROTEIN ADSORPTION AND CELL ADHESION ON POLYACRYLONITRILE FILMS BY COPOLYMERIZATION OF ACRYLONITRILE WITH α-ALLYL GLUCOSIDE

    Institute of Scientific and Technical Information of China (English)

    Rui-qiang Kou; Chao Qu; Zhi-kang Xu; You-yi Xu; Ke Yao

    2003-01-01

    In this work, the surface properties of novel sugar-containing polymers, α-allyl glucoside (AG)/acrylonitrile (AN)copolymers, were studied by contact angle, protein adsorption and cell adhesion measurements. It was found that the contact angle of the copolymer films decreased from 68° to 30° with the increase of AG content in the copolymer. The adsorption amount of bovine serum albumin (BSA) and the adhesive macrophage onto the film surface also decreased significantly with increasing α-allyl glucoside content from 0 to 42 wt% in the copolymer. These preliminary results reveal that both the hydrophilicity and the biocompatibility of polyacrylonitrile-based membranes could be improved by copolymerizing acrylonitrile with vinyl carbohydrates.

  1. Corrosion Study of Super Ferritic Stainless Steel UNS S44660 (26Cr-3Ni-3Mo) and Several Other Stainless Steel Grades (UNS S31603, S32101, and S32205) in Caustic Solution Containing Sodium Sulfide

    Science.gov (United States)

    Chasse, Kevin R.; Singh, Preet M.

    2013-11-01

    Electrochemical techniques, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) were used in this study to show how the corrosion mechanism of several commercial grades of stainless steel in hot caustic solution is strongly influenced by the presence of sodium sulfide. Experimental results from super ferritic stainless steel UNS S44660 (26Cr-3Ni-3Mo) were compared to austenitic stainless steel UNS S31603, lean duplex stainless steel (DSS) UNS S32101, and standard DSS UNS S32205 in caustic solution, with and without sodium sulfide, at 443 K (170 °C). Weight loss measurements indicated that corrosion rates of UNS44660 were much lower than the other grades of stainless steel in the presence of the sodium sulfide. Potentiodynamic polarization and linear polarization resistance measurements showed that the electrochemical behavior was altered by the adhesion of sulfur species, which reduced the polarization resistances and increased the anodic current densities. SEM and XPS results imply that the surface films that formed in caustic solution containing sodium sulfide were defective due to the adsorption of sulfide, which destabilized the passive film and led to the formation of insoluble metal sulfide compounds.

  2. Os and S isotope studies of ultramafic rocks in the Duke Island Complex, Alaska: variable degrees of crustal contamination of magmas in an arc setting and implications for Ni-Cu-PGE sulfide mineralization

    Science.gov (United States)

    Stifter, Eric C.; Ripley, Edward M.; Li, Chusi

    2016-10-01

    The Duke Island Complex is one of the several "Ural-Alaskan" intrusions of Cretaceous age that occur along the coast of SE Alaska. Significant quantities of magmatic Ni-Cu-PGE sulfide mineralization are locally found in the complex, primarily within olivine clinopyroxenites. Sulfide mineralization is Ni-poor, consistent with petrologic evidence which indicates that sulfide saturation was reached after extensive olivine crystallization. Olivine clinopyroxenites were intruded by magmas that produced sulfide-poor, adcumulate dunites. As part of a study to investigate the potential for Ni-rich sulfide mineralization in association with the dunites, a Re-Os and S isotope study of the dunites, as well as sulfide mineralization in the olivine clinopyroxenites, was initiated. Importantly, recent drilling in the complex identified the presence of sulfidic and carbonaceous country rocks that may have been involved in the contamination of magmas and generation of sulfide mineralization. γOs (110 Ma) values of two sulfidic country rocks are 1022 and 2011. δ34S values of the country rocks range from -2.6 to -16.1 ‰. 187Os/188Os ratios of sulfide minerals in the mineralization hosted by olivine clinopyroxenites are variable and high, with γOs (110 Ma) values between 151 and 2059. Extensive interaction with Re-rich sedimentary country rocks is indicated. In contrast, γOs (110 Ma) values of the dunites are significantly lower, ranging between 2 and 16. 187Os/188Os ratios increase with decreasing Os concentration. This inverse relation is similar to that shown by ultramafic rocks from several arc settings, as well as altered abyssal dunites and peridotites. The relation may be indicative of magma derivation from a sub-arc mantle that had experienced metasomatism via slab-derived fluids. Alternatively, the relation may be indicative of minor contamination of magma by crustal rocks with low Os concentrations but high 187Os/188Os ratios. A third alternative is that the low Os

  3. Iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso–ene mechanism

    Directory of Open Access Journals (Sweden)

    David Porter

    2015-12-01

    Full Text Available Iron(II complexes of the tetradentate amines tris(2-pyridylmethylamine (TPA and N,N′-bis(2-pyridylmethyl-N,N′-dimethylethane-1,2-diamine (BPMEN are established catalysts of C–O bond formation, oxidising hydrocarbon substrates via hydroxylation, epoxidation and dihydroxylation pathways. Herein we report the capacity of these catalysts to promote C–N bond formation, via allylic amination of alkenes. The combination of N-Boc-hydroxylamine with either FeTPA (1 mol % or FeBPMEN (10 mol % converts cyclohexene to the allylic hydroxylamine (tert-butyl cyclohex-2-en-1-yl(hydroxycarbamate in moderate yields. Spectroscopic studies and trapping experiments suggest the reaction proceeds via a nitroso–ene mechanism, with involvement of a free N-Boc-nitroso intermediate. Asymmetric induction is not observed using the chiral tetramine ligand (+-(2R,2′R-1,1′-bis(2-pyridylmethyl-2,2′-bipyrrolidine ((R,R′-PDP.

  4. 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...

  5. Synchrotron Photoionization Mass Spectrometry Measurements of Kinetics and Product Formation in the Allyl Radical (H2CCHCH2)Self Reaction

    Science.gov (United States)

    Selby, Talitha M.; Melini, giovanni; Goulay, Fabien; Leone, Stephen R.; Fahr, Askar; Taatjes, Craig A.; Osborn, David L.

    2008-01-01

    Product channels for the self-reaction of the resonance-stabilized allyl radical, C3H5 + C3H5, have been studied with isomeric specificity at temperatures from 300-600 K and pressures from 1-6 Torr using time-resolved multiplexed photoionization mass spectrometry. Under these conditions 1,5-hexadiene was the only C6H10 product isomer detected. The lack of isomerization of the C6H10 product is in marked contrast to the C6H6 product in the related C3H3 + C3H3 reaction, and is due to the more saturated electronic structure of the C6H10 system. The disproportionation product channel, yielding allene + propene, was also detected, with an upper limit on the branching fraction relative to recombination of 0.03. Analysis of the allyl radical decay at 298 K yielded a total rate coefficient of (2.7 +/- 0.8) x 10(exp -11) cu cm/molecule/s, in good agreement with pre.vious experimental measurements using ultraviolet kinetic absorption spectroscopy and a recent theoretical determination using variable reaction coordinate transition state theory. This result provides independent indirect support for the literature value of the allyl radical ultraviolet absorption cross-section near 223 nm.

  6. γ‐ and δ-Lactams through Palladium-Catalyzed Intramolecular Allylic Alkylation: Enantioselective Synthesis, NMR Investigation, and DFT Rationalization

    DEFF Research Database (Denmark)

    Bantreil, Xavier; Prestat, Guillaume; Moreno, Aitor;

    2011-01-01

    The Pd-catalyzed intramolecular allylic alkylation of unsaturated amides to give gamma- and delta-lactams has been studied in the presence of chiral ligands. Ligand (R)-3,5-tBu-MeOBIPHEP (MeOBIPHEP=6,6'-dimethoxybiphenyl-2,2-diyl)bis(diphenylphosphine)) afforded the best results and allowed the c...

  7. 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...

  8. Oxidation and Precipitation of Sulfide in Sewer Networks

    DEFF Research Database (Denmark)

    Nielsen, A. H.

    for the accumulation of metal sulfides in the biofilms. This was the case even when the iron concentration in the wastewater was increased approximately ten times compared to the in situ concentration. In aerobic biofilms, iron precipitation was apparently controlled by phosphate. Based on the experimental studies...... were studied in both wastewater and biofilms. Particular emphasis was on the importance of iron in the sulfur cycle. Iron is typically among the dominant metals in wastewater. The experiments showed that, ferric iron (Fe(III)) that was added to anaerobic wastewater was rapidly reduced to ferrous iron...... (Fe(II)) and precipitated subsequently with dissolved sulfide as ferrous sulfide (FeS). The ferrous sulfide precipitation was relatively fast, but not immediate. Despite the very low solubility of ferrous sulfide, initially present iron did not react completely with sulfide. This observation...

  9. A comprehensive study on photocatalytic activity of supported Ni/Pb sulfide and oxide systems onto natural zeolite nanoparticles.

    Science.gov (United States)

    Babaahamdi-Milani, Majid; Nezamzadeh-Ejhieh, Alireza

    2016-11-15

    The Ni(II)-Pb(II) exchanged clinoptilolite nanoparticles (NCP) were transformed to corresponding oxides and sulfides via calcination and sulfiding processes, respectively. The obtained catalysts were characterized by XRD, FT-IR, TEM and DRS and used in photodegradation of p-nitrophenol (4-NP) aqueous solution under Hg-lamp irradiation. Results showed considerable increase in activity of the coupled semiconductors with respect to monocomponent one. In NiO-PbO-NCP system, conduction band (CB) of NiO is enough negative for easily migration of photogenerated electrons to CB-PbO level, while such phenomena take place from more negative CB-PbS level to CB-NiS level in NiS-PbS-NCP. These phenomena significantly prevented from electron-hole recombination which increased photocatalytic activity of the coupled semiconductors. Best photodegradation activities obtained by NiO1.3%-PbO14.7%-NCP and NiS2.1%-PbS10.0%-NCP, confirming semiconductors' mass-ratio dependence of the photocatalytic process. The supported coupled semiconductors showed blue shifts in band gap energies with respect to the bulk semiconductors which confirm formation of semiconductors nanoparticles inside the zeolite framework. The highest degradation percentage of 4-NP was obtained at: 0.5gL(-1) photocatalysts, 15mgL(-1) 4-NP at pH 7.5.

  10. Magnetic silica supported palladium catalyst: synthesis of allyl aryl ethers in water

    Science.gov (United States)

    A simple and benign procedure for the synthesis of aryl allyl ethers has been developed using phenols, allyl acetates and magnetically recyclable silica supported palladium catalyst in water; performance of reaction in air and easy separation of the catalyst using an external mag...

  11. Palladium(0)-Catalyzed Intermolecular Allylic Dearomatization of Indoles by a Formal [4+2] Cycloaddition Reaction.

    Science.gov (United States)

    Gao, Run-Duo; Xu, Qing-Long; Zhang, Bo; Gu, Yiting; Dai, Li-Xin; You, Shu-Li

    2016-08-01

    Bridged indoline derivatives were synthesized by an intermolecular Pd-catalyzed allylic dearomatization reaction of substituted indoles. The reaction between indoles and allyl carbonates bearing a nucleophilic alcohol side-chain proceeds in a cascade fashion, providing bridged indolines in excellent enantioselectivity. PMID:27321285

  12. Allyl sulphides in olefin metathesis: catalyst considerations and traceless promotion of ring-closing metathesis.

    Science.gov (United States)

    Edwards, Grant A; Culp, Phillip A; Chalker, Justin M

    2015-01-11

    Allyl sulphides are reactive substrates in ruthenium-catalysed olefin metathesis reactions, provided each substrate is matched with a suitable catalyst. A profile of catalyst activity is described, along with the first demonstration of allyl sulphides as traceless promoters in relayed ring-closing metathesis reactions.

  13. Memory effects in palladium-catalyzed allylic Alkylations of 2-cyclohexen-1-yl acetate

    DEFF Research Database (Denmark)

    Svensen, Nina; Fristrup, Peter; Tanner, David Ackland;

    2007-01-01

    The objective of this work was to characterize the enantiospecificity of the allylic alkylation of enantioenriched 2-cyclohexen-1-yl acetate with the enolate ion of dimethyl malonate catalyzed by unsymmetrical palladium catalysts. The precatalysts employed were (eta(3)-allyl)PdLCl, where L...

  14. Pd-catalyzed cascade allylic alkylation and dearomatization reactions of indoles with vinyloxirane.

    Science.gov (United States)

    Gao, Run-Duo; Xu, Qing-Long; Dai, Li-Xin; You, Shu-Li

    2016-09-14

    We have developed Pd-catalyzed intermolecular Friedel-Crafts-type allylic alkylation and allylic dearomatization reactions of substituted indoles bearing a nucleophilic group with vinyloxirane, providing an efficient method to synthesize structurally diverse tetrahydrocarboline and spiroindolenine derivatives under mild conditions. PMID:27511802

  15. Allyl sulphides in olefin metathesis: catalyst considerations and traceless promotion of ring-closing metathesis.

    Science.gov (United States)

    Edwards, Grant A; Culp, Phillip A; Chalker, Justin M

    2015-01-11

    Allyl sulphides are reactive substrates in ruthenium-catalysed olefin metathesis reactions, provided each substrate is matched with a suitable catalyst. A profile of catalyst activity is described, along with the first demonstration of allyl sulphides as traceless promoters in relayed ring-closing metathesis reactions. PMID:25410944

  16. 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

  17. Sulfide scaling in low enthalpy geothermal environments; A survey

    Energy Technology Data Exchange (ETDEWEB)

    Criaud, A.; Fouillac, C. (Bureau de Recherches Geologiques et Minieres (BRGM), 45 - Orleans (France))

    1989-01-01

    A review of the sulfide scaling phenomena in low-temperature environments is presented. While high-temperature fluids tend to deposit metal sulfides because of their high concentrations of dissolved metals and variations of temperature, pressure and fluid chemistry, low temperature media are characterized by very low metal content but much higher dissolved sulfide. In the case of the goethermal wells of the Paris Basin, detailed studies demonstrate that the relatively large concentrations of chloride and dissolved sulfide are responsible for corrosion and consequent formation of iron sulfide scale composed of mackinawite, pyrite and pyrrhotite. The effects of the exploitation schemes are far less important than the corrosion of the casings. The low-enthalpy fluids that do not originate from sedimentary aquifers (such as in Iceland and Bulgaria), have a limited corrosion potential, and the thin sulfide film that appears may prevent the progress of corrosion.

  18. 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.

  19. Highly efficient redox isomerization of allylic alcohols at ambient temperature catalyzed by novel ruthenium-cyclopentadienyl complexes--new insight into the mechanism.

    Science.gov (United States)

    Martín-Matute, Belén; Bogár, Krisztián; Edin, Michaela; Kaynak, F Betül; Bäckvall, Jan-E

    2005-10-01

    A range of ruthenium cyclopentadienyl (Cp) complexes have been prepared and used for isomerization of allylic alcohols to the corresponding saturated carbonyl compounds. Complexes bearing CO ligands show higher activity than those with PPh3 ligands. The isomerization rate is highly affected by the substituents on the Cp ring. Tetra(phenyl)methyl-substituted catalysts rapidly isomerize allylic alcohols under very mild reaction conditions (ambient temperature) with short reaction times. Substituted allylic alcohols have been isomerized by employing Ru-Cp complexes. A study of the isomerization catalyzed by [Ru(Ph5Cp)(CO)2H] (14) indicates that the isomerization catalyzed by ruthenium hydrides partly follows a different mechanism than that of ruthenium halides activated by KOtBu. Furthermore, the lack of ketone exchange when the isomerization was performed in the presence of an unsaturated ketone (1 equiv), different from that obtained by dehydrogenation of the starting allylic alcohol, supports a mechanism in which the isomerization takes place within the coordination sphere of the ruthenium catalyst. PMID:16028298

  20. Construction of an Asymmetric Quaternary Carbon Center via Allylation of Hydrazones

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jin Bum; Satyender, Apuri; Jang, Doo Ok [Yonsei Univ., Wonju (Korea, Republic of)

    2013-11-15

    Asymmetric indium-mediated allylation of imine derivatives bearing a chiral auxiliary is a reliable strategy for the synthesis of chiral homoallylic amines. Various techniques for indium-mediated stereoselective allylation of imines bearing a chiral auxiliary have been reported. In 1997 Loh and co-workers reported indium-mediated allylation with imines derived from L-valine methyl ester. Since then, many forms of indium-mediated allylation bearing a chiral auxiliary have been reported, including imines derived from (S)-valinol, (R)-phenylglycinol, uracil, (R)-phenylglycinol methyl ester, N-tert-butanesufinamide, and (1R,2S)-1-amino-2-indanol. However, the synthesis of chiral auxiliaries often involves a laborious multi-step synthesis with expensive reagents. Therefore, the development of readily accessible chiral auxiliaries for asymmetric indium-mediated all-ylation is in high demand.

  1. 烯丙基酚醛树脂的固化动力学%Curing Kinetics of Allyl Phenolic Resin

    Institute of Scientific and Technical Information of China (English)

    刘洋; 刘诗薇; 李志强; 于景坤

    2012-01-01

    The curing behavior of allyl phenolic resin was analyzed at different heating rates using differential scanning calorimetry.The obtained kinetic data were treated by Kissinger and KAS(Kissinger-Akahira-Sunose) methods to obtain the curing reaction kinetic parameters.A curing kinetics model was established for allyl phenolic resin.Compared with phenolic resin,the curing temperature of allyl phenolic resin is higher,the reaction order is closer to 1,and the average activation energy of the curing reaction is lower,111.45 kJ/mol.The activation energy of allyl phenolic resin is almost constant and changes little with temperature in the curing process.The curing kinetics model of allyl phenolic resin provides a theoretical basis for the study of curing process parameters.%利用差示扫描量热法分析了烯丙基酚醛树脂在不同升温速率下的固化行为,用Kissinger法和KAS(Kissinger-Akahira-Sunose)法对获得的动力学数据进行处理,得到了固化反应动力学参数,并建立了烯丙基酚醛树脂的固化动力学模型.结果表明:与纯酚醛树脂相比,烯丙基酚醛树脂固化温度较高,反应级数更接近于1,固化反应所需的平均表观活化能较低,为111.45kJ/mol;在整个固化过程中,烯丙基酚醛树脂的活化能较为恒定,随温度变化不大;烯丙基酚醛树脂固化动力学模型为研究该体系固化工艺参数提供了理论依据.

  2. Cutting thin sheets of allyl diglycol carbonate (CR-39) with a CW CO2, laser

    International Nuclear Information System (INIS)

    Recent studies have shown that Allyl Diglycol Carbonate, commercially known as CR-39 (the most sensitive among etch track detectors) can detect relativistic oxygen and other heavier nuclei. We are using large sheets of special grade CR-39 (DOP) in our experiment in Space Shuttle-Spacelab-3. As CR-39 is a highly brittle substance, special care is required to cut CR-39 shetts, especially in case of large sheets and circular cuts. A study of cutting of CR-39 sheets using laser light is described in this paper. It has been found that this method is sufficiently fast to handle large number of sheets and also equally safe for big sheets. A maximum speed up to 200 cm/min with a 5 x 104 W/cm2 laser is obtained during the present study. This study also shows that laser cutting does not affect the track properties of CR-39. (orig.)

  3. Activity studies of sesquiterpene oxides and sulfides from the plant Hyptis suaveolens (Lamiaceae) and its repellency on Ixodes ricinus (Acari: Ixodidae).

    Science.gov (United States)

    Ashitani, T; Garboui, S S; Schubert, F; Vongsombath, C; Liblikas, I; Pålsson, K; Borg-Karlson, A-K

    2015-12-01

    Hyptis suaveolens (Lamiaceae), a plant traditionally used as a mosquito repellent, has been investigated for repellent properties against nymphs of the tick Ixodes ricinus. Essential oils and volatile compounds of fresh and dried leaves, from plants originating from Laos and Guinea-Bissau, were identified by GC-MS and tested in a tick repellency bioassay. All the essential oils were strongly repellent against the ticks, even though the main volatile constituents differed in their proportions of potentially tick repellent chemicals. (+)/(-)-sabinene were present in high amounts in all preparations, and dominated the emission from dry and fresh leaves together with 1,8-cineol and α-phellandrene. 1,8-Cineol and sabinene were major compounds in the essential oils from H. suaveolens from Laos. Main compounds in H. suaveolens from Guinea-Bissau were (-)-sabinene, limonene and terpinolene. Among the sesquiterpene hydrocarbons identified, α-humulene exhibited strong tick repellency (96.8 %). Structure activity studies of oxidation or sulfidation products of germacrene D, α-humulene and β-caryophyllene, showed increased tick repellent activity: of mint sulfide (59.4 %), humulene-6,7-oxide (94.5 %) and caryophyllene-6,7-oxide (96.9 %). The substitution of oxygen with sulfur slightly lowered the repellency. The effects of the constituents in the oils can then be regarded as a trade off between the subsequently lower volatility of the sesquiterpene derivatives compared to the monoterpenes and may thus increase their potential usefulness as tick repellents. PMID:26385208

  4. 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.

  5. 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.

  6. Sulfide oxidation in a biofilter

    DEFF Research Database (Denmark)

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

    2012-01-01

    Observed hydrogen sulfide uptake rates in a biofilter treating waste air from a pig farm were too high to be explained within conventional limits of sulfide solubility, diffusion in a biofilm and bacterial metabolism. Clone libraries of 16S and 18S rRNA genes from the biofilter found no sulfide...

  7. Sulfide oxidation in a biofilter

    DEFF Research Database (Denmark)

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

    Observed hydrogen sulfide uptake rates in a biofilter treating waste air from a pig farm were too high to be explained within conventional limits of sulfide solubility, diffusion in a biofilm and bacterial metabolism. Clone libraries of 16S and 18S rRNA genes from the biofilter found no sulfide...

  8. Radiation polymerization of allyl derivatives of glycerin

    International Nuclear Information System (INIS)

    Radiation polymerization of 1 allyloxi-3-(chlorine)-alkoxipropanol-2, 1-cro otoxy-3=ethyloxypropanol-2, 1-allylamino-3-amyloxypropanol-2, 1-butoxy-2-allyloxi-3-chlorpropane has been carried out. Some kinetic character ristics of the polymerization process have been obtained. A dependence of the polymerization rate on exposure doze rate, on the persence of modifier (orthopho osphoric acid) and its ratio to the manometer has been studied

  9. Fault locator of an allyl chloride plant

    Directory of Open Access Journals (Sweden)

    Savković-Stevanović Jelenka B.

    2004-01-01

    Full Text Available Process safety analysis, which includes qualitative fault event identification, the relative frequency and event probability functions, as well as consequence analysis, was performed on an allye chloride plant. An event tree for fault diagnosis and cognitive reliability analysis, as well as a troubleshooting system, were developed. Fuzzy inductive reasoning illustrated the advantages compared to crisp inductive reasoning. A qualitative model forecast the future behavior of the system in the case of accident detection and then compared it with the actual measured data. A cognitive model including qualitative and quantitative information by fuzzy logic of the incident scenario was derived as a fault locator for an ally! chloride plant. The obtained results showed the successful application of cognitive dispersion modeling to process safety analysis. A fuzzy inductive reasoner illustrated good performance to discriminate between different types of malfunctions. This fault locator allowed risk analysis and the construction of a fault tolerant system. This study is the first report in the literature showing the cognitive reliability analysis method.

  10. Enantioselective functionalization of allylic C-H bonds following a strategy of functionalization and diversification.

    Science.gov (United States)

    Sharma, Ankit; Hartwig, John F

    2013-11-27

    We report the enantioselective functionalization of allylic C-H bonds in terminal alkenes by a strategy involving the installation of a temporary functional group at the terminal carbon atom by C-H bond functionalization, followed by the catalytic diversification of this intermediate with a broad scope of reagents. The method consists of a one-pot sequence of palladium-catalyzed allylic C-H bond oxidation under neutral conditions to form linear allyl benzoates, followed by iridium-catalyzed allylic substitution. This overall transformation forms a variety of chiral products containing a new C-N, C-O, C-S, or C-C bond at the allylic position in good yield with a high branched-to-linear selectivity and excellent enantioselectivity (ee ≤97%). The broad scope of the overall process results from separating the oxidation and functionalization steps; by doing so, the scope of nucleophile encompasses those sensitive to direct oxidative functionalization. The high enantioselectivity of the overall process is achieved by developing an allylic oxidation that occurs without acid to form the linear isomer with high selectivity. These allylic functionalization processes are amenable to an iterative sequence leading to (1,n)-functionalized products with catalyst-controlled diastereo- and enantioselectivity. The utility of the method in the synthesis of biologically active molecules has been demonstrated.

  11. Low-temperature Electrodeposition of Aluminium from Lewis Acidic 1-Allyl-3-methylimidazolium Chloroaluminate Ionic Liquids

    Institute of Scientific and Technical Information of China (English)

    郑勇; 张锁江; 吕兴梅; 王倩; 左勇; 刘恋

    2012-01-01

    Lewis acidic 1-allyl-3-methylimidazolium chloroaluminate ionic liquids were used as promising electrolytes in the low-temperature electrodeposition of aluminium. Systematic studies on deposition process have been performed by cYClic voltammetry and chronoamperometry. The surface morphology and X-ray diffraction (XRD) patterns of deposits prepared at different experimental conditions were also investigated. It was shown that the nucleation density and growth rate of crystallites had a great effect on the structure of aluminium deposited. The crys- tallographic orientation of deposits was mainly influenced by temperature and current density. Smooth, dense and well adherent aluminium coatings were obtained on copper substrates at 10-25 mA.cm^-2 and 313.2-353.2 K. More- over, the current efficiency of deposition and purity of aluminium have been significantly improved, demonstrating that the ionic liquids tested have a prospectful potential in electroplating and electrorefining of aluminium.

  12. Sulfide capacities of fayalite-base slags

    Science.gov (United States)

    Simeonov, S. R.; Sridhar, R.; Toguri, J. M.

    1995-04-01

    The sulfide capacities of fayalite-base slags were measured by a gas-slag equilibration technique under controlled oxygen and sulfur potentials similar to those encountered in the pyrometallurgical processing of nonferrous metals. The oxygen pressure range was from 10-9.5 to 10-11 MPa and the sulfur pressure range from 10-3 to 10-4.5 MPa, over a temperature range of 1473 to 1623 K. The slags studied were FeO-SiO2 at silica saturation and those with addition of CaO, MgO, and Al2O3 to determine their effect on sulfide capacities. For these slags, the sulfide capacities were found to vary from 10-3.3 to 10-5. The sulfide capacities increased with increasing temperature from 1473 to 1623 K. A comparison of the reported plant data on sulfur content of industrial slags shows good agreement with the present experimental results. The present data will be useful in estimating metal losses in slag due to metal sulfide entrainment in nonferrous smelters.

  13. Studies of high temperature ternary phases in mixed-metal-rich early transition metal sulfide and phosphide systems

    Energy Technology Data Exchange (ETDEWEB)

    Marking, G.A.

    1994-01-04

    Investigations of ternary mixed early transition metal-rich sulfide and phosphide systems resulted in the discovery of new structures and new phases. A new series of Zr and Hf - group V transition metal - sulfur K-phases was synthesized and crystallographically characterized. When the group V transition metal was Nb or Ta, the unit cell volume was larger than any previously reported K-phase. The presence of adventitious oxygen was determined in two K-phases through a combination of neutron scattering and X-ray diffraction experiments. A compound Hf{sub 10}Ta{sub 3}S{sub 3} was found to crystallize in a new-structure type similar to the known gamma brasses. This structure is unique in that it is the only reported {open_quotes}stuffed{close_quotes} gamma-brass type structure. The metal components, Hf and Ta, are larger in size and more electropositive than the metals found in normal gamma brasses (e.g. Cu and Zn) and because of the larger metallic radii, sulfur can be incorporated into the structure where it plays an integral role in stabilizing this phase relative to others. X-ray single-crystal, X-ray powder and neutron powder refinements were performed on this structure. A new structure was found in the ternary Nb-Zr-P system which has characteristics in common with many known early transition metal-rich sulfides, selenides, and phosphides. This structure has the simplest known interconnection of the basic building blocks known for this structural class. Anomalous scattering was a powerful tool for differentiating between Zr and Nb when using Mo K{alpha} X-radiation. The compounds ZrNbP and HfNbP formed in the space group Prima with the simple Co{sub 2}Si structure which is among the most common structures found for crystalline solid materials. Solid solution compounds in the Ta-Nb-P, Ta-Zr-P, Nb-Zr-P, Hf-Nb-P, and Hf-Zr-S systems were crystallographically characterized. The structural information corroborated ideas about bonding in metal-rich compounds.

  14. 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.

  15. 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

    2016-08-01

    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.

  16. A Facile and Mild Synthesis of Trisubstituted Allylic Sulfones from Morita-Baylis-Hillman Carbonates

    Directory of Open Access Journals (Sweden)

    Lin Jiang

    2015-05-01

    Full Text Available An efficient and catalyst-free synthesis of trisubstituted allylic sulfones through an allylic sulfonylation reaction of Morita-Baylis-Hillman (MBH carbonates with sodium sulfinates has been developed. Under the optimized reaction conditions, a series of trisubstituted allylic sulfones were rapidly prepared in good to excellent yields (71%–99% with good to high selectivity (Z/E from 79:21 to >99:1. Compared with known synthetic methods, the current protocol features mild reaction temperature, high efficiency and easily available reagents.

  17. Scanning electrochemical microscopy studies of micropatterned copper sulfide (CuxS) thin films fabricated by a wet chemistry method

    Science.gov (United States)

    Chen, Miao; Zhao, Jing; Zhao, Xiaocui

    2011-01-01

    Patterned copper sulfide (CuxS) microstructures on Si (1 1 1) wafers were successfully fabricated by a relatively simple solution growth method using copper sulfate, ethylenediaminetetraacetate and sodium thiosulfate aqueous solutions as precursors. The CuxS particles were selectively deposited on a patterned self-assembled monolayer of 3-aminopropyltriethoxysilane regions created by photolithography. To obtain high quality CuxS films, preparative conditions such as concentration, proportion, pH and temperature of the precursor solutions were optimized. Various techniques such as optical microscopy, atomic force microscopy (AFM), X-ray diffraction, optical absorption and scanning electrochemical microscopy (SECM) were employed to examine the topography and properties of the micro-patterned CuxS films. Optical microscopy and AFM results indicated that the CuxS micro-pattern possessed high selectivity and clear edge resolution. From combined X-ray diffraction analysis and optical band gap calculations we conclude that Cu9S5 (digenite) was the main phase within the resultant CuxS film. Both SECM image and cyclic voltammograms confirmed that the CuxS film had good electrical conductivity. Moreover, from SECM approach curve analysis, the apparent electron-transfer rate constant (k) in the micro-pattern of CuxS dominated surface was estimated as 0.04 cm/s. The SECM current map showed high edge acuity of the micro-patterned CuxS. PMID:21785491

  18. Scanning electrochemical microscopy studies of micropatterned copper sulfide (Cu(x)S) thin films fabricated by a wet chemistry method.

    Science.gov (United States)

    Chen, Miao; Zhao, Jing; Zhao, Xiaocui

    2011-05-30

    Patterned copper sulfide (Cu(x)S) microstructures on Si (1 1 1) wafers were successfully fabricated by a relatively simple solution growth method using copper sulfate, ethylenediaminetetraacetate and sodium thiosulfate aqueous solutions as precursors. The Cu(x)S particles were selectively deposited on a patterned self-assembled monolayer of 3-aminopropyltriethoxysilane regions created by photolithography. To obtain high quality Cu(x)S films, preparative conditions such as concentration, proportion, pH and temperature of the precursor solutions were optimized. Various techniques such as optical microscopy, atomic force microscopy (AFM), X-ray diffraction, optical absorption and scanning electrochemical microscopy (SECM) were employed to examine the topography and properties of the micro-patterned Cu(x)S films. Optical microscopy and AFM results indicated that the Cu(x)S micro-pattern possessed high selectivity and clear edge resolution. From combined X-ray diffraction analysis and optical band gap calculations we conclude that Cu(9)S(5) (digenite) was the main phase within the resultant Cu(x)S film. Both SECM image and cyclic voltammograms confirmed that the Cu(x)S film had good electrical conductivity. Moreover, from SECM approach curve analysis, the apparent electron-transfer rate constant (k) in the micro-pattern of Cu(x)S dominated surface was estimated as 0.04 cm/s. The SECM current map showed high edge acuity of the micro-patterned Cu(x)S.

  19. 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

  20. 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.

  1. Sulfide detoxification in plant mitochondria.

    Science.gov (United States)

    Birke, Hannah; Hildebrandt, Tatjana M; Wirtz, Markus; Hell, Rüdiger

    2015-01-01

    In contrast to animals, which release the signal molecule sulfide in small amounts from cysteine and its derivates, phototrophic eukaryotes generate sulfide as an essential intermediate of the sulfur assimilation pathway. Additionally, iron-sulfur cluster turnover and cyanide detoxification might contribute to the release of sulfide in mitochondria. However, sulfide is a potent inhibitor of cytochrome c oxidase in mitochondria. Thus, efficient sulfide detoxification mechanisms are required in mitochondria to ensure adequate energy production and consequently survival of the plant cell. Two enzymes have been recently described to catalyze sulfide detoxification in mitochondria of Arabidopsis thaliana, O-acetylserine(thiol)lyase C (OAS-TL C), and the sulfur dioxygenase (SDO) ethylmalonic encephalopathy protein 1 (ETHE1). Biochemical characterization of sulfide producing and consuming enzymes in mitochondria of plants is fundamental to understand the regulatory network that enables mitochondrial sulfide homeostasis under nonstressed and stressed conditions. In this chapter, we provide established protocols to determine the activity of the sulfide releasing enzyme β-cyanoalanine synthase as well as sulfide-consuming enzymes OAS-TL and SDO. Additionally, we describe a reliable and efficient method to purify OAS-TL proteins from plant material.

  2. 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.

  3. Ultrafine particles derived from mineral processing: A case study of the Pb-Zn sulfide ore with emphasis on lead-bearing colloids.

    Science.gov (United States)

    Mikhlin, Yuri; Vorobyev, Sergey; Romanchenko, Alexander; Karasev, Sergey; Karacharov, Anton; Zharkov, Sergey

    2016-03-01

    Although mining and mineral processing industry is a vast source of heavy metal pollutants, the formation and behavior of micrometer- and nanometer-sized particles and their aqueous colloids entered the environment from the technological media has received insufficient attention to date. Here, the yield and characteristics of ultrafine mineral entities produced by routine grinding of the Pb-Zn sulfide ore (Gorevskoe ore deposit, Russia) were studied using laser diffraction analysis (LDA), dynamic light scattering (DLS) and zeta potential measurement, microscopy, X-ray photoelectron spectroscopy, with most attention given to toxic lead species. It was revealed, in particular, that the fraction of particles less that 1 μm in the ground ore typical reaches 0.4 vol. %. The aquatic particles in supernatants were micrometer size aggregates with increased content of zinc, sulfur, calcium as compared with the bulk ore concentrations. The hydrodynamic diameter of the colloidal species decreased with time, with their zeta potentials remaining about -12 mV. The colloids produced from galena were composed of 20-50 nm PbS nanoparticles associated with lead sulfate and thiosulfate, while the surface oxidation products at precipitated galena were largely lead oxyhydroxides. The size and zeta potential of the lead-bearing colloids decreased with time down to about 100 nm and from -15 mV to -30 mV, respectively. And, conversely, lead sulfide nanoparticles were mobilized before the aggregates during redispersion of the precipitates in fresh portions of water. The potential environmental impact of the metal-bearing colloids, which is due to the large-scale production and relative stability, is discussed. PMID:26761598

  4. 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).

  5. Sulfide and methane production in sewer sediments.

    Science.gov (United States)

    Liu, Yiwen; Ni, Bing-Jie; Ganigué, Ramon; Werner, Ursula; Sharma, Keshab R; Yuan, Zhiguo

    2015-03-01

    Recent studies have demonstrated significant sulfide and methane production by sewer biofilms, particularly in rising mains. Sewer sediments in gravity sewers are also biologically active; however, their contribution to biological transformations in sewers is poorly understood at present. In this study, sediments collected from a gravity sewer were cultivated in a laboratory reactor fed with real wastewater for more than one year to obtain intact sediments. Batch test results show significant sulfide production with an average rate of 9.20 ± 0.39 g S/m(2)·d from the sediments, which is significantly higher than the areal rate of sewer biofilms. In contrast, the average methane production rate is 1.56 ± 0.14 g CH4/m(2)·d at 20 °C, which is comparable to the areal rate of sewer biofilms. These results clearly show that the contributions of sewer sediments to sulfide and methane production cannot be ignored when evaluating sewer emissions. Microsensor and pore water measurements of sulfide, sulfate and methane in the sediments, microbial profiling along the depth of the sediments and mathematical modelling reveal that sulfide production takes place near the sediment surface due to the limited penetration of sulfate. In comparison, methane production occurs in a much deeper zone below the surface likely due to the better penetration of soluble organic carbon. Modelling results illustrate the dependency of sulfide and methane productions on the bulk sulfate and soluble organic carbon concentrations can be well described with half-order kinetics.

  6. Oxidation study of the synthetic sulfides molybdenite (MoS2) and covellite (CuS) by acidithiobacillus ferrooxidants using respirometric experiments

    International Nuclear Information System (INIS)

    This paper analyses the oxidation of covellite and molybdenite by Acidithiobacillus ferrooxidans strain LR using respirometric experiments. The results showed that both sulfides were oxidized by A. ferrooxidans, however, the covellite oxidation was much higher than molybdenite. Regarding the kinetic oxidation, the findings revealed that just molybdenite oxidation followed the classical Michaelis-Menten kinetic. It is probably associated with the pathway which these sulfides react to chemistry-bacterial attack, what is influenced by its electronic structures. Besides, experiments conducted in the presence of Fe3+ did not indicate alterations in molybdenite oxidation. Thus, ferric ions seem not to be essential to the sulfide oxidations. (author)

  7. 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.

  8. Facile synthesis of allyl resinate monomer in an aqueous solution under microwave irradiation

    Indian Academy of Sciences (India)

    Yanju Lu; Mixia Wang; Zhendong Zhao; Yuxiang Chen; Shichao Xu; Jing Wang; Liangwu Bi

    2015-07-01

    We have developed a facile method for production of allyl resinate monomer (allyl rosin ester) via a phase transfer reaction under microwave irradiation. The synthesis of allyl resinate was conducted using allyl chloride and sodium resinate as starting materials in aqueous solution at 50°C for 30 min with a yield of 94.7%, which is 20% higher than conventional heating method. The products precipitated spontaneously from the aqueous phase after reaction, which significantly facilitated the subsequent separation of monomer products. The synthesized monomer product appeared as a viscous liquid, with a viscosity of 460 mPa·s at 25°C and a density of 1.0469 g/cm3. The physical and chemical properties suggested that the synthesized monomer has great potential for free radical polymerization.

  9. Total Synthesis of Clavosolide A via Tandem Allylic Oxidation/Oxa-Conjugate Addition Reaction

    Science.gov (United States)

    Baker, Joseph B.; Kim, Hyoungsu; Hong, Jiyong

    2015-01-01

    The tandem allylic oxidation/oxa-conjugate addition reaction promoted by the gem-disubstituent effect in conjunction with the NHC-mediated oxidative esterification was explored for the facile synthesis of clavosolide A. PMID:26236051

  10. Effect of palladium on sulfide tarnishing of noble metal alloys.

    Science.gov (United States)

    Suoninen, E; Herø, H; Minni, E

    1985-10-01

    Electron spectroscopic studies of Au-Ag-Cu alloys of the type used for dental castings show that small additions (less than or equal to 3 wt%) of palladium reduce essentially the thickness of the sulfide layer formed on surfaces of samples treated in aqueous Na2S solutions. Relative to silver, palladium does not enrich in the sulfide, but statistically significant enrichment is found immediately below the sulfide layer. This enrichment probably takes place during the exposure of the substrate surface to atmosphere before the sulfiding treatment. The mechanism of the impeding effect of palladium on sulfiding is assumed to be a decrease in diffusion from the bulk alloy to the surface due to the enriched layer. The effect cannot be explained by changes in the electronic structure of the alloy due to palladium alloying.

  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. Highly selective palladium–benzothiazole carbene-catalyzed allylation of active methylene compounds under neutral conditions

    OpenAIRE

    Antonio Monopoli; Pietro Cotugno; Zambonin, Carlo G.; Francesco Ciminale; Angelo Nacci

    2015-01-01

    The Pd–benzothiazol-2-ylidene complex I was found to be a chemoselective catalyst for the Tsuji–Trost allylation of active methylene compounds carried out under neutral conditions and using carbonates as allylating agents. The proposed protocol consists in a simplified procedure adopting an in situ prepared catalyst from Pd2dba3 and 3-methylbenzothiazolium salt V as precursors. A comparison of the performance of benzothiazole carbene with phosphanes and an analogous imidazolium carbene ligand...

  13. Selective epoxidation of allylic alcohols with a titania-silica aerogel

    Energy Technology Data Exchange (ETDEWEB)

    Dusi, M.; Mallat, T.; Baiker, A. [Lab. of Technical Chemistry, Swiss Federal Inst. of Technology, ETH-Zentrum, Zuerich (Switzerland)

    1998-12-31

    An amorphous mesoporous titania-silica aerogel (20 wt%TiO{sub 2} - 80 wt% SiO{sub 2}) and tert.-butylhydroperoxide (TBHP) have been used for the epoxidation of various allylic alcohols. Allylic alcohols possessing an internal double bond were more reactive than those with a terminal C=C bond. Epoxide selectivities could be improved by addition of (basic) zeolite 4 A and NaHCO{sub 3} to the reaction mixture. (orig.)

  14. Anti-inflammatory potential of allyl-isothiocyanate – role of Nrf2, NF-κB and microRNA-155

    OpenAIRE

    Wagner, Anika Eva; Boesch-Saadatmandi, Christine; Dose, Janina; Schultheiss, Gerhard; Rimbach, Gerald

    2012-01-01

    Abstract In this study, the underlying mechanisms of the potential anti-inflammatory properties of allyl-isothiocyanate (AITC) were analysed in vitro and in vivo. Murine RAW264.7 macrophages stimulated with lipopolysaccharide (LPS) were supplemented with increasing concentrations of AITC. In addition, C57BL/6 mice (n= 10 per group) were fed a pro-inflammatory high-fat diet and AITC was administered orally via gavage for 7 days. Biomarkers of inflammation were determined both in cultured cells...

  15. 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.

  16. Palladium-Catalyzed Dearomative Allylic Alkylation of Indoles with Alkynes To Synthesize Indolenines with C3-Quarternary Centers.

    Science.gov (United States)

    Gao, Shang; Wu, Zijun; Fang, Xinxin; Lin, Aijun; Yao, Hequan

    2016-08-01

    A palladium-catalyzed dearomative allylic alkylation of indoles with alkynes to construct indolenines with C3-quarternary centers was reported. The in situ formed arylallene intermediate omitted the need to install leaving groups on the allylic compounds and employ extra oxidants to oxidize the allylic C-H bonds. The reaction exhibited good functional group tolerance and high atom economy. Moreover, the reaction was further expanded to synthesize pyrroloindolines and furanoindolines. PMID:27442021

  17. A Review on Mutagenicity Testing for Hazard Classification of Chemicals at Work: Focusing on in vivo Micronucleus Test for Allyl Chloride.

    Science.gov (United States)

    Rim, Kyung-Taek; Kim, Soo-Jin

    2015-09-01

    Chemical mutagenicity is a major hazard that is important to workers' health. Despite the use of large amounts of allyl chloride, the available mutagenicity data for this chemical remains controversial. To clarify the mutagenicity of allyl chloride and because a micronucleus (MN) test had not yet been conducted, we screened for MN induction by using male ICR mice bone marrow cells. The test results indicated that this chemical is not mutagenic under the test conditions. In this paper, the regulatory test battery and several assay combinations used to determine the genotoxic potential of chemicals in the workplace have been described. Further application of these assays may prove useful in future development strategies of hazard evaluations of industrial chemicals. This study also should help to improve the testing of this chemical by commonly used mutagenicity testing methods and investigations on the underlying mechanisms and could be applicable for workers' health. PMID:26929826

  18. Allyl thiourea as a corrosion inhibitor for cold rolled steel in H{sub 3}PO{sub 4} solution

    Energy Technology Data Exchange (ETDEWEB)

    Li Xianghong, E-mail: xianghong-li@163.com [Faculty of Science, Southwest Forestry University, Kunming 650224 (China) and Key Laboratory for Forest Resources Conservation and Use in the Southwest Mountains of China Ministry of Education, Southwest Forestry University, Kunming 650224 (China); Deng Shuduan [Faculty of Materials Engineering, Southwest Forestry University, Kunming 650224 (China); Fu Hui [Faculty of Science, Southwest Forestry University, Kunming 650224 (China)

    2012-02-15

    Highlights: Black-Right-Pointing-Pointer Allyl thiourea (ATU) acts as a good inhibitor for steel in 1.0 M H{sub 3}PO{sub 4}. Black-Right-Pointing-Pointer Inhibition efficiency increases slightly with the temperature at 0.2-0.5 mM. Black-Right-Pointing-Pointer The adsorption of ATU on steel surface obeys Langmuir adsorption isotherm. Black-Right-Pointing-Pointer ATU behaves as a mixed-type inhibitor. - Abstract: The inhibition effect of allyl thiourea (ATU) on the corrosion of cold rolled steel (CRS) in 1.0 M H{sub 3}PO{sub 4} solution at 20-50 Degree-Sign C was studied by weight loss, potentiodynamic polarisation, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) methods. The results show that ATU is a good inhibitor, and the maximum inhibition efficiency of 0.5 mM inhibitor is higher than 95% at all studied temperatures. The adsorption of ATU obeys Langmuir adsorption isotherm. Polarisation curves show that ATU behaves as a mixed-type inhibitor. EIS spectra exhibit one capacitive loop. The inhibition action is also evidenced by SEM.

  19. UV RADIATION INDUCED GRAFT COPOLYMERIZATION OF ALLYL ACETATE ONTO POLY(ETHYLENE TEREPHTHALATE) (PET) FILMS FOR FUEL CELL MEMBRANES

    Institute of Scientific and Technical Information of China (English)

    Mostak Ahmed; Mubarak A. Khan; Nazia Rahman; M. Anwar H. Khan

    2012-01-01

    Ultraviolet (UV)-induced graft copolymerization of allyl acetate (AA) monomer onto poly(ethylene terephthalate) (PET) films and the subsequent sulfonation on the monomer units in the grafting chain using chlorosulfonic acid (C1SO3H) were carried out to prepare proton exchange membranes (PEMs) for fuel cells.A maximum grafting value of 12.8% was found for 35 vol% allyl acetate after 3 h radiation time.Optimum concentration of ClSO3H was selected for the sulfonation reaction to be 0.05 mol/L based on the degree of sulfonation and the tensile strength studies of the membrane.The degree of sulfonation increased as the sulfonation reaction temperature and sulfonation time were increasing.The radiation grafting and the sulfonation have been confirmed by titrimetric and gravimetric analyses as well as FTIR spectroscopy.The maximum ion exchange capacity (IEC) of 0.04125 mmol g-1 was found at 12.1% degree of sulfonation and the maximum proton conductivity was found to be 0.035 S cm-1 at 30℃ and a relative humidity of 60%.The various physical and chemical properties of the PEMs such as water uptake,mechanical strength,thermal durability and oxidative stability were also studied.To investigate the suitability of the prepared membrane for fuel cell applications,its properties were compared with those of Nation 117.

  20. 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.

  1. Study on effect of the scavenger for eliminating hydrogen sulfide%硫化氢捕消剂清除硫化氢效果研究

    Institute of Scientific and Technical Information of China (English)

    邹兵; 朱胜杰; 石昕

    2012-01-01

    硫化氢气体是高毒性气体,当其发生泄漏事故时将产生严重危害.目前,应对硫化氢泄漏事故的方法较少,主要为消防水喷淋和人员疏散,不能完全消除硫化氢的危害.针对硫化氢气体的特点,研制了在泄漏事故中用于清除硫化氢气体的捕消剂.硫化氢捕消剂为干粉状的,由吸附载体、反应组分和疏水组分组成.当发生硫化氢泄漏时,将捕消剂喷洒在泄漏源周围的空气中,使捕消剂与硫化氢充分接触反应以降低危害程度和范围.清除硫化氢实验结果表明,硫化氢捕消剂能够有效地清除泄漏在空气中的硫化氢气体.%Hydrogen sulfide is a kind of gas with high toxic, and it will cause serious harm in the event of a leakage. At present, the response to hydrogen sulfide leakage is mainly water spray and personnel evacuation, which can not completely eliminate the hazards of hydrogen sulfide. Hydrogen sulfide scavenger was developed to remove hydrogen sulfide in gas leak. The scavenger was made up of adsorption carrier, reaction components and hydropho-bic friction. When hydrogen sulfide leak, the scavenger will be sprayed into the air. At the same time, the scavenger will react with the hydrogen sulfide in the air to reduce the extent and scope of damage. Experimental results showed that hydrogen sulfide scavenger could effectively eliminate hydrogen sulfide gas in the air.

  2. 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

  3. 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.

  4. 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

  5. Effect of radiation on wettability and floatability of sulfide minerals

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The feasibility for modifying the wettability and floatability of sulfide minerals by electron beam irradiation has been studied experimentally. The wettability of crystalline pyrite and floatability of some sulfide as pyrite, arsenopyrite, chalcopyrite and marmatite after irradiation were examined by flotation in a modified Hallimond tube. Experimental results show that the hydrophobicity of crystalline pyrite enhances with the increase of irradiation dose in a low dose range. And the flotation responses of sulfide minerals on irradiation dosevary with the mineral species and particle size. The floatability of minerals can be regulated by altering irradiation dose. An explanationfor the mechanism has been suggested based on the principle of radiation chemistry.

  6. 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

  7. Rice: Sulfide-induced Barriers to Root Radial Oxygen Loss, Fe2+ and Water Uptake, and Lateral Root Emergence

    OpenAIRE

    ARMSTRONG, JEAN; Armstrong, William (Canadian painter, civil engineer, photographer, 1822-1914)

    2005-01-01

    • Background and Aims Akagare and Akiochi are diseases of rice associated with sulfide toxicity. This study investigates the possibility that rice reacts to sulfide by producing impermeable barriers in roots.

  8. Effect of three 2-allyl-p-mentha-6,8-dien-2-ols on inhibition of mild steel corrosion in 1 M HCl

    Directory of Open Access Journals (Sweden)

    S. Kharchouf

    2014-11-01

    Full Text Available 2-Allyl-p-mentha-6,8-dien-2-ols P1−P3 synthesized from carvone P are tested as corrosion inhibitors of steel in 1 M HCl using weight loss measurements, potentiodynamic polarisation and impedance spectroscopy (EIS methods. The addition of 2-allyl-p-mentha-6,8-dien-2-ols reduced the corrosion rate. Potentiodynamic polarisation studies clearly reveal that the presence of inhibitors does not change the mechanism of hydrogen evolution and that they act essentially as cathodic inhibitors. 2-Allyl-p-mentha-6,8-dien-2-ols tested adsorb on the steel surface according to Langmuir isotherm. From the adsorption isotherm some thermodynamic data for the adsorption process are calculated and discussed. EIS measurements show the increase of the charge-transfer resistance with the inhibitor concentration. The highest inhibition efficiency (92% is obtained for P1 at 3 g/L. The corrosion rate decreases with the rise of temperature. The corresponding activation energies are determined.

  9. XAFS study on the sulfidation mechanisms of Co-Mo catalysts supported on activated carbon and alumina: effect of complexing agent.

    Science.gov (United States)

    Tsuji, K; Umeki, T; Yokoyama, Y; Kitada, T; Iwanami, Y; Nonaka, O; Shimada, H; Matsubayashi, N; Nishijima, A; Nomura, M

    2001-03-01

    The effect of nitrilotriacetic acid (NTA) as a complexing agent on the sulfidation mechanisms of Co-Mo catalysts supported on activated carbon and alumina was examined by the XAFS technique. The XAFS results revealed that NTA interacted with Co atoms and formed the Co-NTA interaction, while it showed almost no influence on the local structures around Mo atoms. The Co-NTA interaction suppressed the aggregation of cobalt atoms and the interaction between cobalt and alumina during sulfiding, and consequently promoted the formation of the Co-Mo-S phase.

  10. Micro-aeration for hydrogen sulfide removal from biogas

    Science.gov (United States)

    Duangmanee, Thanapong

    The presence of sulfur compounds (e.g. protein, sulfate, thiosulfate, sulfite, etc.) in the feed stream generates highly corrosive and odorous hydrogen sulfide during anaerobic digestion. The high sulfide level in the biogas stream is not only poisonous to many novel metal catalysts employed in thermo-catalytic processes but also reduces the quality of methane to produce renewable energy. This study used an innovative, low-maintenance, low-cost biological sulfide removal technology to remove sulfides simultaneously from both gas and liquid phase. ORP (Oxidation-Reduction-Potential) was used as the controlling parameter to precisely regulate air injection to the sulfide oxidizing unit (SOU). The microaeration technique provided just enough oxygen to partially oxidize sulfides to elemental sulfur without inhibiting methanogenesis. The SOU was equipped with a diffuser at the bottom for the dispersion of sulfide-laden biogas and injected air throughout the column. The SOU can be operated as a standalone unit or coupled with an anaerobic digester to simultaneously remove sulfide from the biogas and effluent. The integrated system was capable of reducing hydrogen sulfide in biogas from 2,450 to less than 2 ppmV with minimal sulfate production at the highest available sulfide loading rate of 0.24 kg/m3-day. More than 98% of sulfide removed was recovered as elemental sulfur. However, the standalone SOU was able to operate at high hydrogen sulfide loading of 1.46 kg/m 3-day at inlet sulfide concentration of 3000 ppmV and reduce the off-gas hydrogen sulfide concentrations to less than 10 ppmV. The experiment also revealed that the ORP controlled aeration was sensitive enough to prevent oxygen overdosing (dampening effect) during unexpected surges of aeration. Using generalized linear regression, a model predicting output H2S concentration based on input H2S concentrations, SOU medium heights, and biogas flow rates, was derived. With 95% confidence, output H2S concentration

  11. Prevention of sulfide oxidation in sulfide-rich waste rock

    Science.gov (United States)

    Nyström, Elsa; Alakangas, Lena

    2015-04-01

    The ability to reduce sulfide oxidation in waste rock after mine closure is a widely researched area, but to reduce and/or inhibit the oxidation during operation is less common. Sulfide-rich (ca 30 % sulfur) waste rock, partially oxidized, was leached during unsaturated laboratory condition. Trace elements such as As and Sb were relatively high in the waste rock while other sulfide-associated elements such as Cu, Pb and Zn were low compared to common sulfide-rich waste rock. Leaching of unsaturated waste rock lowered the pH, from around six down to two, resulting in continuously increasing element concentrations during the leaching period of 272 days. The concentrations of As (65 mg/L), Cu (6.9 mg/L), Sb (1.2 mg/L), Zn (149 mg/L) and S (43 g/L) were strongly elevated at the end of the leaching period. Different alkaline industrial residues such as slag, lime kiln dust and cement kiln dust were added as solid or as liquid to the waste rock in an attempt to inhibit sulfide oxidation through neo-formed phases on sulfide surfaces in order to decrease the mobility of metals and metalloids over longer time scale. This will result in a lower cost and efforts of measures after mine closure. Results from the experiments will be presented.

  12. Rapid formation of β-allyl substituted isotetronic acid derivatives via Claisen rearrangement using a microfludic device

    Institute of Scientific and Technical Information of China (English)

    Xia Ping Ma; Zhi Ming Li; Quan Rui Wang

    2011-01-01

    The thermal Claisen rearrangement of O-allyl substituted isotetronic acids 1 was successfully carried out within a glass microreactor operated with temperature at 150 ℃ and a flow rate of 1 mL/h. The strategy provides an efficient alternative way to β-allyl substituted isotetronic acid derivatives 2 in high yields with much accelerated reaction speed.

  13. Dicyano-Functionalized MCM-41-Supported Palladium Complex as An Efficient Catalyst for Allylation of Aldehydes and Ketones

    Institute of Scientific and Technical Information of China (English)

    ZHAO Hong; CAI Ming-Zhong

    2006-01-01

    Dicyano-functionalized MCM-41-supported palladium complex was prepared from dicyano-functionalized MCM-41 and palladium chloride. This complex exhibited high catalytic activity in the allylation of aldehydes and ketones with allylic chlorides in the presence of SnCl2. This polymeric palladium complex can be recovered and reused without noticeable loss of activity.

  14. How phenyl makes a difference: mechanistic insights into the ruthenium( ii )-catalysed isomerisation of allylic alcohols

    KAUST Repository

    Manzini, Simone

    2013-10-16

    [RuCl(η5-3-phenylindenyl)(PPh3)2] (1) has been shown to be a highly active catalyst for the isomerisation of allylic alcohols to the corresponding ketones. A variety of substrates undergo the transformation, typically with 0.25-0.5 mol% of catalyst at room temperature, outperforming commonly-used complexes such as [RuCl(Cp)(PPh3) 2] and [RuCl(η5-indenyl)(PPh3) 2]. Mechanistic experiments and density functional theory have been employed to investigate the mechanism and understand the effect of catalyst structure on reactivity. These investigations suggest a oxo-π-allyl mechanism is in operation, avoiding intermediate ruthenium hydride complexes and leading to a characteristic 1,3-deuterium shift. Important mechanistic insights from DFT and experiments also allowed for the design of a protocol that expands the scope of the transformation to include primary allylic alcohols. © 2013 The Royal Society of Chemistry.

  15. Allyl Isothiocyanate Induces Cell Toxicity by Multiple Pathways in Human Breast Cancer Cells.

    Science.gov (United States)

    Bo, Peng; Lien, Jin-Cherng; Chen, Ya-Yin; Yu, Fu-Shun; Lu, Hsu-Feng; Yu, Chun-Shu; Chou, Yu-Cheng; Yu, Chien-Chih; Chung, Jing-Gung

    2016-01-01

    Isothiocyanates (ITCs) occur in many cruciferous vegetables. These compounds, which have significant anticancer actions, can induce apoptosis in different human cancer cell lines. In the present study, we investigated if allyl isothiocyanate (AITC) would induce toxicity in human breast cancer MCF-7 (estrogen receptor positive) and MDA-MB-231 (estrogen receptor negative) cells. We found that AITC stimulated reactive oxygen species and Ca[Formula: see text] production, and decreased the mitochondrial membrane potential. Activity of caspase-8, -9 and -3 was increased by AITC in both cell lines. AITC also induced mitochondrial-mediated apoptosis, as shown by cytochrome c, AIF and Endo G release from mitochondria, activation of caspase-9 and caspase-3, and formation of DAPI-positive cells. There was a significant reduction in the levels of the anti-apoptotic protein Bcl-2 along with a marked increase in the pro-apoptotic protein Bax in both cell lines. AITC induced apoptosis in human breast cancer MCF-7 cells via AIF and Endo G signaling pathways, but in MDA-MB-231 cells apoptosis occurred via the GADD153 pathway. This study has revealed novel anti-cancer mechanisms of AITC, a compound that is ordinarily present in human diets and may have potential therapeutic effects in various cancers. PMID:27080949

  16. Allyl isothiocyanates and cinnamaldehyde potentiate miniature excitatory postsynaptic inputs in the supraoptic nucleus in rats.

    Science.gov (United States)

    Yokoyama, Toru; Ohbuchi, Toyoaki; Saito, Takeshi; Sudo, Yuka; Fujihara, Hiroaki; Minami, Kouichiro; Nagatomo, Toshihisa; Uezono, Yasuhito; Ueta, Yoichi

    2011-03-25

    Allyl isothiocyanates (AITC) and cinnamaldehyde are pungent compounds present in mustard oil and cinnamon oil, respectively. These compounds are well known as transient receptor potential ankyrin 1 (TRPA1) agonists. TRPA1 is activated by low temperature stimuli, mechanosensation and pungent irritants such as AITC and cinnamaldehyde. TRPA1 is often co-expressed in TRPV1. Recent study showed that hypertonic solution activated TRPA1 as well as TRPV1. TRPV1 is involved in excitatory synaptic inputs to the magnocellular neurosecretory cells (MNCs) that produce vasopressin in the supraoptic nucleus (SON). However, it remains unclear whether TRPA1 may be involved in this activation. In the present study, we examined the role of TRPA1 on the synaptic inputs to the MNCs in in vitro rat brain slice preparations, using whole-cell patch-clamp recordings. In the presence of tetrodotoxin, AITC (50μM) and cinnamaldehyde (30μM) increased the frequency of miniature excitatory postsynaptic currents without affecting the amplitude. This effect was significantly attenuated by previous exposure to ruthenium red (10μM), non-specific TRP channels blocker, high concentration of menthol (300μM) and HC-030031 (10μM), which are known to antagonize the effects of TRPA1 agonists. These results suggest that TRPA1 may exist at presynaptic terminals to the MNCs and enhance glutamate release in the SON. PMID:21266172

  17. Mechanochemical reduction of copper sulfide

    DEFF Research Database (Denmark)

    Balaz, P.; Takacs, L.; Jiang, Jianzhong;

    2002-01-01

    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....

  18. 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.

  19. Limitations in the use of archived vent mussel samples to assess genetic connectivity among seafloor massive sulfide deposits: a case study with implications for environmental management

    Directory of Open Access Journals (Sweden)

    Rachel Elizabeth Boschen

    2015-12-01

    Full Text Available Genetic connectivity studies can inform the design of mitigation strategies used in environmental management. However, the expense of developing species-specific molecular markers and collecting samples at appropriate spatial and temporal scales can be prohibitive. Using archived material and existing molecular markers may provide a cost-effective way to assess population connectivity. Genetic connectivity studies are increasingly in demand in the deep sea in response to mounting anthropogenic pressures, including seafloor massive sulfide (SMS mining. The feasibility of using archived material was assessed using the New Zealand-endemic vent mussel Gigantidas gladius, which inhabits areas licensed for the prospecting phase of SMS mining. Four molecular markers were tested, but only one (mitochondrial COI provided suitable sequences. Of 942 specimens, only 150 individuals were informative, largely due to poor tissue quality of archived samples. Seven populations spanning the distributional range of G. gladius were assessed. The results indicate that G. gladius has high levels of gene flow among sites 10s to 100s km apart and limited genetic structure. Haplotypic diversity was not equally distributed among populations, with lower diversity for the Macauley Volcano population at the northern extent of the species distribution and greater diversity within central populations. Migrant exchange was also greatest between central populations, with one population at Rumble V Seamount appearing important in terms of maintaining genetic diversity within the Kermadec Volcanic Arc region. However, interpretation of the results should be viewed with caution as small sample sizes may have limited the ability to detect genetic structure. Despite these limitations, mitigation strategies that protect areas of seabed from mining activities should consider the genetic vulnerability of the population at the northern edge of the species’ distribution and the

  20. Study of atomic layer deposition of indium oxy-sulfide films for Cu(In,Ga)Se{sub 2} solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Bugot, Cathy, E-mail: cathy-externe.bugot@edf.fr [Institut de Recherche et Développement sur l' Energie Photovoltaïque (IRDEP, UMR 7174 CNRS-EDF-Chimie Paristech), Chatou (France); Schneider, Nathanaelle [Institut de Recherche et Développement sur l' Energie Photovoltaïque (IRDEP, UMR 7174 CNRS-EDF-Chimie Paristech), Chatou (France); Bouttemy, Muriel; Etcheberry, Arnaud [Institut Lavoisier de Versailles, UMR 8180 (CNRS-UVSQ), Versailles (France); Lincot, Daniel; Donsanti, Frédérique [Institut de Recherche et Développement sur l' Energie Photovoltaïque (IRDEP, UMR 7174 CNRS-EDF-Chimie Paristech), Chatou (France)

    2015-05-01

    This paper explores the growth mechanism of plasma enhanced atomic layer deposition of In{sub 2}(S,O){sub 3} films. The films were deposited using indium acetylacetonate (In(acac){sub 3}), hydrogen sulfide (H{sub 2}S) and Ar/O{sub 2} plasma as oxygen precursor. The films were characterized using X-ray reflectometry, spectrophotometry, energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. To understand the growth mechanism and especially the interactions between Ar/O{sub 2} plasma and In{sub 2}(S,O){sub 3} growing film, in-situ analyses were performed using quadrupole mass spectrometry. In-situ qualitative analysis revealed good correlation between the species detected in vapor phase and thin film properties. High concentrations of atomic and molecular oxygen were measured in the vapor phase during O{sub 2} plasma pulses. Significant decrease of these species could be observed by varying the plasma power from 2600 to 300 W, while the optical band gap remained at high values (> 2.6 eV). The analysis of the O{sub 2}-free/Ar plasma process showed that some of these oxygen species originate either from the indium precursor or from the substrate surface. This study explains the high oxygen content of the films, and allows us to reduce and control it. Generally, this report provides keys to understand the effect of plasma reactivity for the elaboration of oxide based materials. - Highlights: • In{sub 2}(S,O){sub 3} films were synthesized by plasma enhanced atomic layer deposition. • Growth mechanism was studied via gas phase analysis by Quadrupole Mass Spectrometry. • Good correlation between the vapor phase species and thin films properties was observed. • The film compositions and band gaps can be controlled by varying the plasma power.

  1. Optimization of biological sulfide removal in a CSTR bioreactor.

    Science.gov (United States)

    Roosta, Aliakbar; Jahanmiri, Abdolhossein; Mowla, Dariush; Niazi, Ali; Sotoodeh, Hamidreza

    2012-08-01

    In this study, biological sulfide removal from natural gas in a continuous bioreactor is investigated for estimation of the optimal operational parameters. According to the carried out reactions, sulfide can be converted to elemental sulfur, sulfate, thiosulfate, and polysulfide, of which elemental sulfur is the desired product. A mathematical model is developed and was used for investigation of the effect of various parameters on elemental sulfur selectivity. The results of the simulation show that elemental sulfur selectivity is a function of dissolved oxygen, sulfide load, pH, and concentration of bacteria. Optimal parameter values are calculated for maximum elemental sulfur selectivity by using genetic algorithm as an adaptive heuristic search. In the optimal conditions, 87.76% of sulfide loaded to the bioreactor is converted to elemental sulfur.

  2. 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.

  3. Selective adsorption of bacteria on sulfide minerals surface

    Institute of Scientific and Technical Information of China (English)

    JIA Chun-yun; WEI De-zhou; LIU Wen-gang; HAN Cong; GAO Shu-ling; WANG Yu-juan

    2008-01-01

    The adsorption of bacteria on sulfide minerals surface was studied, and the selective adsorption mechanism of cells on the sulfide minerals was investigated by means of FTIR, UVS and XPS. The results show that the three strains of bacteria adsorbed more preferentially on pyrite than on other two sulfide minerals surface at neutral and alkaline pH conditions. FTIR and UVS of three strains of bacteria indicate that there are more functional groups on their surface, such as O-H, C=O, N-H, C-O, and the content of saccharide is more than that of protein. The state of every element on sulfide minerals surface was analyzed by XPS. The empty orbital number of electronic shell of metal ions on minerals surface is important in selective adsorption process, and some stable constants of metal coordinates can be used to explain the contribution of some groups in saccharide of cell wall to the selective adsorption.

  4. Highly selective palladium–benzothiazole carbene-catalyzed allylation of active methylene compounds under neutral conditions

    Directory of Open Access Journals (Sweden)

    Antonio Monopoli

    2015-06-01

    Full Text Available The Pd–benzothiazol-2-ylidene complex I was found to be a chemoselective catalyst for the Tsuji–Trost allylation of active methylene compounds carried out under neutral conditions and using carbonates as allylating agents. The proposed protocol consists in a simplified procedure adopting an in situ prepared catalyst from Pd2dba3 and 3-methylbenzothiazolium salt V as precursors. A comparison of the performance of benzothiazole carbene with phosphanes and an analogous imidazolium carbene ligand is also proposed.

  5. Chemoselective and stereoselective lithium carbenoid mediated cyclopropanation of acyclic allylic alcohols.

    Science.gov (United States)

    Durán-Peña, M J; Flores-Giubi, M E; Botubol-Ares, J M; Harwood, L M; Collado, I G; Macías-Sánchez, A J; Hernández-Galán, R

    2016-03-01

    The reaction of geraniol with different lithium carbenoids generated from n-BuLi and the corresponding dihaloalkane has been evaluated. The reaction occurs in a chemo and stereoselective manner, which is consistent with a directing effect from the oxygen of the allylic moiety. Furthermore, a set of polyenes containing allylic hydroxyl or ether groups were chemoselectively and stereoselectively converted into the corresponding gem-dimethylcyclopropanes in one single step in moderate to good yields mediated by a lithium carbenoid generated in situ by the reaction of n-BuLi and 2,2-dibromopropane.

  6. One-pot synthesis and characterization of a new, branched polycarbosilane bearing allyl groups

    Institute of Scientific and Technical Information of China (English)

    Tian Hua Huang; Zhao Ju Yu; Xu Min He; Mu He Huang; Li Fu Chen; Hai Ping Xia; Li Tong Zhang

    2007-01-01

    A highly branched polycarbosilane bearing allyl groups has been prepared by a one-pot synthesis with chloromethyltrichlorosilane, chloromethylmethyldichlorosilane and allyl chloride as the starting materials.The resultant polymer, with the approximate formula [SiH1.2(CH)30.71(CH2CH=CH2)0.09CH2]n,has been characterized by 1H, 13C, and 29Si NMR, GPC, TG and elemental analysis.It could be cross-linked thermally at 170℃ in the absence of oxygen.Pyrolysis of the polymer gave a ceramic with a yield of about 70%.

  7. Ultraviolet Photodissociation Dynamics of the Allyl Radical via the B̃(2)A1(3s), C̃(2)B2(3py), and Ẽ(2)B1(3px) Electronic Excited States.

    Science.gov (United States)

    Song, Yu; Lucas, Michael; Alcaraz, Maria; Zhang, Jingsong; Brazier, Christopher

    2015-12-17

    Ultraviolet (UV) photodissociation dynamics of jet-cooled allyl radical via the B̃(2)A1(3s), C̃(2)B2(3py), and Ẽ(2)B1(3px) electronically excited states are studied at the photolysis wavelengths from 249 to 216 nm using high-n Rydberg atom time-of-flight (HRTOF) and resonance-enhanced multiphoton ionization (REMPI) techniques. The photofragment yield (PFY) spectra of the H atom products are measured using both allyl chloride and 1,5-hexadiene as precursors of the allyl radical and show a broad peak centered near 228 nm, whereas the previous UV absorption spectra of the allyl radical peak around 222 nm. This difference suggests that, in addition to the H + C3H4 product channel, another dissociation channel (likely CH3 + C2H2) becomes significant with increasing excitation energy. The product translational energy release of the H + C3H4 products is modest, with the P(ET) distributions peaking near 8.5 kcal/mol and the fraction of the average translational energy in the total excess energy, ⟨fT⟩, in the range 0.22-0.18 from 249 to 216 nm. The P(ET)'s are consistent with production of H + allene and H + propyne, as suggested by previous experimental and theoretical studies. The angular distributions of the H atom products are isotropic, with the anisotropy parameter β ≈ 0. The H atom dissociation rate constant from the pump-probe study gives a lower limit of 1 × 10(8)/s. The dissociation mechanism is consistent with unimolecular decomposition of the hot allyl radical on the ground electronic state after internal conversion of the electronically excited state. PMID:26334360

  8. Allylic amination reactivity of Ni, Pd, and Pt heterobimetallic and monometallic complexes.

    Science.gov (United States)

    Carlsen, Ryan W; Ess, Daniel H

    2016-06-14

    Transition metal heterobimetallic complexes with dative metal-metal interactions have the potential for novel fast reactivity. There are few studies that both compare the reactivity of different metal centers in heterobimetallic complexes and compare bimetallic reactivity to monometallic reactivity. Here we report density-functional calculations that show the reactivity of [Cl2Ti(N(t)BuPPh2)2M(II)(η(3)-methallyl)] heterobimetallic complexes for allylic amination follows M = Ni > Pd > Pt. This reactivity trend was not anticipated since the amine addition transition state involves M(II) to M(0) reduction and this could disadvantage Ni. Comparison of heterobimetallic complexes to the corresponding monometallic (CH2)2(N(t)BuPPh2)2M(II)(η(3)-methallyl) complexes reveals that this reactivity trend is due to the bimetallic interaction and that the bimetallic interaction significantly lowers the barrier height for amine addition by >10 kcal mol(-1). The impact of the early transition metal center on the amination addition barrier height depends on the late transition metal center. The lowest barrier heights for this reaction occur when late and early transition metal centers are from the same periodic table row. PMID:26893287

  9. Allyl Isothiocyanate Inhibits Actin-Dependent Intracellular Transport in Arabidopsis thaliana

    Directory of Open Access Journals (Sweden)

    Bjørnar Sporsheim

    2015-12-01

    Full Text Available Volatile allyl isothiocyanate (AITC derives from the biodegradation of the glucosinolate sinigrin and has been associated with growth inhibition in several plants, including the model plant Arabidopsis thaliana. However, the underlying cellular mechanisms of this feature remain scarcely investigated in plants. In this study, we present evidence of an AITC-induced inhibition of actin-dependent intracellular transport in A. thaliana. A transgenic line of A. thaliana expressing yellow fluorescent protein (YFP-tagged actin filaments was used to show attenuation of actin filament movement by AITC. This appeared gradually in a time- and dose-dependent manner and resulted in actin filaments appearing close to static. Further, we employed four transgenic lines with YFP-fusion proteins labeling the Golgi apparatus, endoplasmic reticulum (ER, vacuoles and peroxisomes to demonstrate an AITC-induced inhibition of actin-dependent intracellular transport of or, in these structures, consistent with the decline in actin filament movement. Furthermore, the morphologies of actin filaments, ER and vacuoles appeared aberrant following AITC-exposure. However, AITC-treated seedlings of all transgenic lines tested displayed morphologies and intracellular movements similar to that of the corresponding untreated and control-treated plants, following overnight incubation in an AITC-absent environment, indicating that AITC-induced decline in actin-related movements is a reversible process. These findings provide novel insights into the cellular events in plant cells following exposure to AITC, which may further expose clues to the physiological significance of the glucosinolate-myrosinase system.

  10. Sulfide capacity of high alumina blast furnace slags

    Science.gov (United States)

    Shankar, Amitabh; Görnerup, Märten; Seetharaman, S.; Lahiri, A. K.

    2006-12-01

    Sulfide capacities of high alumina blast furnace slags were experimentally determined using the gas-slag equilibration technique. Two different slag systems were considered for the current study, namely, CaO-SiO2-MgO-Al2O3 quaternary and CaO-SiO2-MgO-Al2O3-TiO2 quinary system. The liquid slag was equilibrated with the Ar-CO-CO2-SO2 gas mixture. Experiments were conducted in the temperature range of 1773 to 1873 K. The effects of temperature, basicity, and the MgO and TiO2 contents of slags on sulfide capacity were studied. As expected, sulfide capacity was found to increase with the increase in temperature and basicity. At the higher experimental temperature, titania decreases the sulfide capacity of slag. However, at the lower temperature, there was no significant effect of titania on the sulfide capacity of slag. Sulfide capacity increases with the increase in MgO content of slag if the MgO content is more than 5 pct.

  11. Solvent-Controlled, Tunable β-OAc and β-H Elimination in Rh(III)-Catalyzed Allyl Acetate and Aryl Amide Coupling via C-H Activation.

    Science.gov (United States)

    Dai, Huimin; Yu, Chao; Wang, Zihao; Yan, Hong; Lu, Changsheng

    2016-07-15

    The Heck reaction between arenes and allyl acetate has led to cinnamyl derivatives and allyl products depending on the regioselectivity of β-elimination. The regioselectivity can be controlled by the solvent in the Rh(III)-catalyzed arene-allyl acetate coupling via C-H activation: (1) in THF, cinnamyl derivatives via β-H elimination were generated; (2) in MeOH, allyl products via β-OAc elimination were produced. Both routes have advantages such as excellent γ-selectivity toward allyl acetate, good to excellent yields, and broad substrate scope. PMID:27351917

  12. The development of a potassium-sulfide glass fiber cell and studies on impurities in alkali metal-sulfur cells

    Science.gov (United States)

    Tsang, F. Y.

    1977-01-01

    Potassium sulfur rechargeable cells, having as the electrolyte the thin walls of hollow glass fibers made from permeable glass, were developed. The cells had short lives, probably due to the construction materials and impurities in the potassium. The effect of the impurities in the analogous NA-S system was studied. Calcium, potassium, and NaOH/oxide impurities caused increased resistance or corrosion of the glass fibers. For long lived cell operation, the Na must contain less than 1 ppm Ca and less than a few ppm of hydroxide/oxide. Up to 150 ppm K can be tolerated. After purification of the Na anolyte, cell lifetimes in excess of 1000 deep charge-discharge cycles or over 8 months on continuous cycling at 10-30 percent depth of discharge were obtained.

  13. Study of caffeine as corrosion inhibitors of carbon steel in chloride solution containing hydrogen sulfide using electrochemical impedance spectroscopy (EIS)

    Science.gov (United States)

    Solehudin, Agus; Berman, Ega Taqwali; Nurdin, Isdiriayani

    2015-09-01

    The corrosion behaviour of steel surface in the absence and presence of caffeine in 3.5% NaCl solution containing dissolved H2S gas is studied using electrochemical impedance spectroscopy (EIS). The experimental results of carbon steel corrosion in 3.5% NaCl solution containing 500 mg/l H2S at different caffeine concentrations showed that corrosion rate of carbon steel decreases with increasing of caffeine concentrations from 0 to 0,1 mmol/l. Whereas, the corrosion rate increase with increasing of caffeine concentrations from 1 to 10 mmol/l. It is clear that no inhibition efficiency increases with increasing inhibitor concentration. The optimum value of inhibition efficiency was 90% at a caffeine concentration of 0.1 mmol/l. This suggests that caffeine's performance as a corrosion inhibitor is more effective at a concentration of 0.1 mmol/l.

  14. Sulfide oxidation in fluidized bed bioreactor using nylon support material

    Institute of Scientific and Technical Information of China (English)

    Varsha Midha; M K Jha; Apurba Dey

    2012-01-01

    A continuous fluidized bed bioreactor(FBBR)with nylon support particles was used to treat synthetic sulfide wastewater at different hydraulic retention time of 25,50 and 75 min and upflow velocity of 14,17 and 20 m/hr.The effects of upflow velocity,hydraulic retention time and reactor operation time on sulfide oxidation rate were studied using statistical model.Mixed culture obtained from the activated sludge,taken from tannery effluent treatment plant,was used as a source for microorganisms.The diameter and density of the nylon particles were 2-3 mm and 1140 kg/m3,respectively.Experiments were carried out in the reactor at a temperature of(30± 2)℃,at a fixed bed height of 16 cm after the formation of biofilm on the surface of support particles.Biofilm thickness reached(42±3)μm after 15 days from reactor start-up.The sulfide oxidation,sulfate and sulfur formation is examined at all hydraulic retention times and upflow velocities.The results indicated that almost 90%-92% sulfide oxidation was achieved at all hydraulic retention times.Statistical model could explain 94% of the variability and analysis of variance showed that upflow velocity and hydraulic retention time slightly affected the sulfide oxidation rate.The highest sulfide oxidation of 92% with 70% sulfur was obtained at hydraulic retention time of 75 min and upflow velocity of 14 m/hr.

  15. Study on the Toxic Sulfide of Oilfield Drilling Fluids and Handled Method%钻井液有毒硫化物分析及处理方法研究

    Institute of Scientific and Technical Information of China (English)

    奚宏军

    2013-01-01

    油田钻井过程中往往随着地层特性产生硫化氢等有毒气体,浸入钻井液后形成有毒硫化物,容易对钻具和人身造成重大影响.通过分析钻井液中有毒硫化物的物质成分、特性及其对钻井工作的危害和影响,指出有效的钻井液硫化氢处理方法.在对钻井液选择、钻井液pH值调节、添加H2S处理剂等三种方法的对比分析基础上,针对这些方法除硫的优缺点,结合钻井液氧化除硫方法,提出基于金属盐的钻井液氧化除硫方法.通过实验表明,金属离子可以促进钻井液氧化除硫效率的提升;同时高阶氧化性金属盐具有很高的除硫效率,可以作为钻井液中处理硫化氢的有效添加物使用.研究结果对于油田用钻井液中有毒硫化物的处理具有一定的实际意义.%The oilfield drilling processes often produce toxic gases such as hydrogen sulfide with the formation properties, and the contaminated drilling fluid is easy taking a significant impact to drill and person to have. By analyzing the material ingredients, the properties, the drilling work hazards and impact of the toxic sulfide drilling fluid, the effective treatment method for drilling fluid hydrogen sulfide is pointed out. Based on the three methods' comparative analysis of drilling fluid selection, drilling fluid pH value adjustment, adding H2S treatment agent, a metal salt-based drilling fluid oxide sulfur removal method is proposed with the advantages and disadvantages of the above three methods. The experiments show that, the metal ions can promote drilling fluid oxidation enhance sulfur removal efficiency, order oxidizing metal salt can be used as effective additives for drilling fluid handling hydrogen sulfide with its high sulfur removal efficiency. The study results take a practical significance for the treatment of oilfield drilling fluid toxic sulfide.

  16. Study and properties of materials. Dry corrosion of materials. Industrial cases: sulfidation, nitridation; Etude et proprietes des metaux. Corrosion seche des metaux. Cas industriels: sulfuration, nitruration

    Energy Technology Data Exchange (ETDEWEB)

    Antoni, L. [Ecole Nationale Superieure d' Electrochimie et d' Electrometallurgie, 38 - Grenoble (France)

    2002-12-01

    This paper presents the corrosion mechanisms of materials for the sulfidation and the nitridation. The sulfur is one of the most corrosive pollutants existing in the high temperature industrial processes. The nitridation is a surface hardening processing but also a corrosion mode. The nitridation becomes a problem at high temperature, if the oxygen content in the atmosphere is insufficient or when the nitrogen exists at the atomique state. (A.L.B.)

  17. In(OTf)3 catalyzed allylation reaction of imines with tetraallyltin

    Institute of Scientific and Technical Information of China (English)

    Xiao Ning Wei; Ling Yan Liu; Bing Wang; Wei Xing Chang; Jing Li

    2009-01-01

    In the presence of catalytic amount of In(OTf)3 (10 mol%), a series of aldimines reacted with tetraallyltin in a 2:1 molar ratio to afford the corresponding homoallylic amines in good yields. The good atom efficiency was achieved under mild reaction conditions and a new protocol (allyl)4Sn/In(OTf)3 for simple imines was developed.

  18. Enantioselective copper catalyzed allylic alkylation using Grignard reagents; Applications in synthesis

    NARCIS (Netherlands)

    Zijl, Anthoni Wouter van

    2009-01-01

    Enantioselective copper catalyzed allylic alkylation is a powerful carbon-carbon bond forming reaction. In this thesis the development of a new catalyst for the use of Grignard reagents in this reaction is described. This catalyst is based on copper and the ligand Taniaphos. The high regio- and enan

  19. 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

  20. Reactions of unsaturated compounds. CXXIV. Claisen rearrangement of allyl and propargyloxydienyl phosphonates

    Energy Technology Data Exchange (ETDEWEB)

    Dangyan, Yu.M.; Tirakyan, M.R.; Panosyan, G.A.; Badanyan, Sh.O.

    1986-12-20

    O,O-Dialkyl-1-ethylidene-2-allyl(propargyl)oxy-2-butenyl phosphonates have been obtained from vinylallenyl phosphonates and undergo thermal Claisen rearrangement to form highly unsaturated ketophosphonates. Comprehensive coupling constant and chemical shift figures from an NMR analysis are given.

  1. Organocatalytic asymmetric allylic amination of Morita–Baylis–Hillman carbonates of isatins

    Directory of Open Access Journals (Sweden)

    Hang Zhang

    2012-08-01

    Full Text Available The investigation of a Lewis base catalyzed asymmetric allylic amination of Morita–Baylis–Hillman carbonates derived from isatins afforded an electrophilic pathway to access multifunctional oxindoles bearing a C3-quaternary stereocenter, provided with good to excellent enantioselectivity (up to 94% ee and in high yields (up to 97%.

  2. Zirconium-allyl complexes as resting states in zirconocene-catalyzed α-olefin polymerization.

    Science.gov (United States)

    Panchenko, Valentina N; Babushkin, Dmitrii E; Brintzinger, Hans H

    2015-01-01

    UV-vis spectroscopic data indicate that zirconocene cations with Zr-bound allylic chain ends are generally formed during olefin polymerization with zirconocene catalysts. The rates and extent of their formation and of their re-conversion to the initial pre-catalyst cations depend on the types of zirconocene complexes and activators used.

  3. Synthesis of telechelic vinyl/allyl functional siloxane copolymers with structural control

    DEFF Research Database (Denmark)

    Madsen, Frederikke Bahrt; Javakhishvili, Irakli; Jensen, Rasmus Egekjær;

    2014-01-01

    Multifunctional siloxane copolymers with terminal vinyl or allyl functional groups are synthesised through the borane-catalysed polycondensation of hydrosilanes and alkoxysilanes. Copolymers of varying mole- cular weights ( M ̄ w =13200 – 70 300 g mol − 1 ), spatially well-distributed functional...

  4. Allylic and benzylic sp3 C-H oxidation in water.

    Science.gov (United States)

    Ang, Wei Jie; Lam, Yulin

    2015-01-28

    A copper-catalyzed method for the oxidation of allylic and benzylic sp(3) C-H by aqueous tert-butyl hydroperoxide (T-Hydro) in water using a recyclable fluorous ligand has been developed. The reaction procedure is tolerant to additional functional groups and the fluorous ligand could be reused with little loss of catalytic activity. PMID:25412371

  5. Polystyrene-supported Selenides and Selenoxide:Versatile Routes to Synthesize Allylic Alcohols

    Institute of Scientific and Technical Information of China (English)

    Wei Ming XU; You Chu ZHANG; Xian HUANG

    2003-01-01

    Several polystyrene-supported selenides and selenoxide have been prepared firstly. These novel reagents were treated with LDA to produce selenium stabilized carbanions, which reacted with aldehydes and alkyl halides, followed by selenoxide syn-elimination and [2,3] sigmatropic rearrangement respectively to give Z-allylic alcohols stereoselectively.

  6. Silylene-mediated ring contraction of homoallylic ethers to form allylic silanes.

    Science.gov (United States)

    Bourque, Laura E; Haile, Pamela A; Woerpel, K A

    2009-09-18

    (-)-Isopulegol derivatives undergo a ring contraction under silylene-mediated conditions to provide cyclopentane products. Silylene transfer to other homoallylic ethers did not provide the ring contraction products. Allylic silane products were elaborated to determine the stereochemical course of the ring contraction reaction. A mechanism for the transformation is proposed. PMID:19681592

  7. Antifoaming materials in G.S. (Girlder sulfide) heavy water plants. Thermical stability. Pt. 2

    International Nuclear Information System (INIS)

    In Girlder sulfide (G.S.) heavy water plants hydrogen sulfide-water systems are inherentely foaming, so the adding of antifoaming materials is of great importance. These may be of high volatility, pyrolizable or chemically unstable in plant operation conditions (water and hydrogen sulfide at 2 MPa, up to 230 deg C). About twenty commercial surfactants were studied from the point of view of their thermical stability. (Author)

  8. Research of the Plasma Sulfide Layer Formed on the Nitrocarburizing Layer

    Institute of Scientific and Technical Information of China (English)

    LI Xin; MA Shi-ning; HU Chun-hua; QIU Ji; HUANG Yuan-lin

    2004-01-01

    Low-temperature sulfurizing after nitrocarburizing are compared with only low-temperature sulfurizing on the surface of CrMoCu alloyed cast iron, the surface morphologies and microstructures are investigated by SEM and EDS.Results show that under proper treatment parameters, there are sulfide layer on both of the surfaces, and can more easily obtain sulfide layers on the surface of nitrocarburizing. Forming mechanism of sulfides were also studied elementarily.

  9. High Temperature Corrosion of Fe-C-S Cast Irons in Oxidizing and Sulfidizing Atmospheres

    Institute of Scientific and Technical Information of China (English)

    Thuan-Dinh NGUYEN; Dong-Bok LEE

    2008-01-01

    The corrosion behavior of spheroidal graphite and flake graphite cast irons was studied in oxidizing and sulfidizing atmospheres between 600 and 800℃ for 50 h. The corrosion rate in the sulfidizing atmosphere was faster than that in air above 700℃, due to the formation of the Feo.975S sulfide. The corrosion rate of the spheroidal graphite cast iron was similar to that of the flake graphite cast iron.

  10. Influence of sulfide concentration on the corrosion behavior of pure copper in synthetic seawater

    Science.gov (United States)

    Taniguchi, Naoki; Kawasaki, Manabu

    2008-09-01

    Corrosion rate and stress corrosion cracking (SCC) behavior of pure copper under anaerobic conditions were studied by immersion tests and slow strain rate tests (SSRT) in synthetic seawater containing Na 2S. The corrosion rate was increased with sulfide concentration both in simple saline solution and in bentnite-sand mixture. The results of SSRT showed that copper was susceptible to intergranular attack; selective dissolution at lower sulfide concentration (less than 0.005 M) and SCC at higher sulfide concentration (0.01 M). It was expected that if the sulfide concentration in groundwater is less than 0.001 M, pure copper is possible to exhibit superior corrosion resistance under anaerobic condition evident by very low corrosion rates and immunity to SCC. In such a low sulfide environment, copper overpack has the potential to achieve super-long lifetimes exceeding several tens of thousands years according to long-term simulations of corrosion based on diffusion of sulfide in buffer material.

  11. Modeling of hydrogen sulfide oxidation in concrete corrosion products from sewer pipes.

    Science.gov (United States)

    Jensen, Henriette Stokbro; Nielsen, Asbjørn Haaning; Hvitved-Jacobsen, Thorkild; Vollertsen, Jes

    2009-04-01

    Abiotic and biotic oxidation of hydrogen sulfide related to concrete corrosion was studied in corrosion products originating from a sewer manhole. The concrete corrosion products were suspended in an acidic solution, mimicking the conditions in the pore water of corroded concrete. The removal of hydrogen sulfide and dissolved oxygen was measured in parallel in the suspension, upon which the suspension was sterilized and the measurement repeated. The results revealed the biotic oxidation to be fast compared with the abiotic oxidation. The stoichiometry of the hydrogen sulfide oxidation was evaluated using the ratio between oxygen and hydrogen sulfide uptake. The ratio for the biotic oxidation pointed in the direction of elemental sulfur being formed as an intermediate in the oxidation of hydrogen sulfide to sulfuric acid. The experimental results were applied to suggest a hypothesis and a mathematical model describing the hydrogen sulfide oxidation pathway in a matrix of corroded concrete.

  12. N-allyl epiderpride: An extremely potent SPECT radioligand for the dopamine D2 receptor

    Energy Technology Data Exchange (ETDEWEB)

    Kessler, R.M.; Mason, N.S.; Ansari, M.S. [Vanderbilt Univ., Nashville, TN (United States)] [and others

    1994-05-01

    We have previously reported that epidepride is a potent (K{sub D} 24pM) and specific SPECT radioligand for the dopamine D2 receptor which can be used to study striatal and extrastriatal dopamine D2 receptors in man. We have synthesized and evaluated the N-allyl analogue of epiderpride (APID) as a potential SPECT radioligand for the dopamine D2 receptor. In comparison to epidepride it is even more potent at the dopamine D2 receptor, the K{sub D} for APID being 11 frontal cortical homogenate. The lipophilicity, evaluated using the log kw pH 7.5, was 2.9 versus 2.05 for epidepride. Competitive binding studies using rat striatal, hippocampal and frontal cortical homogenates showed high affinity for only dopamine D2 like cerebellar ratio of 275:1 at 320 minutes post injection-similar to that seen with epidepride, but with nearly four times higher brain uptake. Of interest was the off-rate from the dopamine D2 receptor; it was 0.0046 min{sup -1} in vitro at 25{degrees}C-corresponding to an t 1/2 of 150 minutes. Studies in rhesus monkeys show an in vivo off rate (following 2.5 mg/kg raclopride IV) of about 0.0082 min{sup -1} seen that with epidepride. SPECT studies in rhesus monkeys reveal APID is a promising SPECT radioligand that appears to be similar to epidepride, but with higher brain uptake due to its more optimal lipophilicity for entry into brain.

  13. The Wacker oxidation of allyl alcohol along cyclic-intermediate routes: An ab initio molecular dynamics investigation

    Science.gov (United States)

    Imandi, Venkataramana; Nair, Nisanth N.

    2016-09-01

    The absence of isotope scrambling observed by Henry and coworkers in the Wacker oxidation of deuterated allylic alcohol was used by them as support for the inner-sphere mechanism hydroxypalladation mechanism. One of the assumptions used to interpret their experimental data was that allyl alcohol oxidation takes place through non-cyclic intermediate routes as in the case of ethene. Here we verify this assumption through ab initio metadynamics simulations of the Wacker oxidation of allyl alcohol in explicit solvent. Importance of our results in interpreting the isotope scrambling experiments is discussed.

  14. Gold(I)-Catalyzed Intramolecular Hydroamination of N-Allylic,N′-Aryl Ureas to form Imidazolidin-2-ones

    OpenAIRE

    Li, Hao; Song, Feijie; Widenhoefer, Ross A.

    2011-01-01

    Treatment of N-allylic,N′-aryl ureas with a catalytic 1:1 mixture of di-tert-butyl-o-biphenylphoshphine gold(I) chloride and silver hexafluorophosphate (1 mol %) in chloroform at room temperature led to 5-exo hydroamination to form the corresponding imidazolidin-2-ones in excellent yield. In the case of N-allylic ureas that possessed an allylic alkyl, benzyloxymethyl, or acetoxymethyl substituent, gold(I)-catalyzed 5-exo hydroamination leads to formation of the corresponding trans-3,4-disubst...

  15. Gold(I)-Catalyzed Intramolecular Hydroamination of N-Allylic,N'-Aryl Ureas to form Imidazolidin-2-ones.

    Science.gov (United States)

    Li, Hao; Song, Feijie; Widenhoefer, Ross A

    2011-04-18

    Treatment of N-allylic,N'-aryl ureas with a catalytic 1:1 mixture of di-tert-butyl-o-biphenylphoshphine gold(I) chloride and silver hexafluorophosphate (1 mol %) in chloroform at room temperature led to 5-exo hydroamination to form the corresponding imidazolidin-2-ones in excellent yield. In the case of N-allylic ureas that possessed an allylic alkyl, benzyloxymethyl, or acetoxymethyl substituent, gold(I)-catalyzed 5-exo hydroamination leads to formation of the corresponding trans-3,4-disubstituted imidazolidin-2-ones in excellent yield with ≥50:1 diastereoselectivity. PMID:21709731

  16. Enhanced performance of denitrifying sulfide removal process under micro-aerobic condition

    International Nuclear Information System (INIS)

    The denitrifying sulfide removal (DSR) process with bio-granules comprising both heterotrophic and autotrophic denitrifiers can simultaneously convert nitrate, sulfide and acetate into di-nitrogen gas, elementary sulfur and carbon dioxide, respectively, at high loading rates. This study determines the reaction rate of sulfide oxidized into sulfur, as well as the reduction of nitrate to nitrite, would be enhanced under a micro-aerobic condition. The presence of limited oxygen mitigated the inhibition effects of sulfide on denitrifier activities, and enhanced the performance of DSR granules. The advantages and disadvantages of applying the micro-aerobic condition to the DSR process are discussed.

  17. Does 1-Allyl-3-methylimidazolium chloride Act as a Biocompatible Solvent for Stem Bromelain?

    Science.gov (United States)

    Jha, Indrani; Bisht, Meena; Venkatesu, Pannuru

    2016-06-30

    The broader scope of ILs in chemical sciences particularly in pharmaceutical, bioanalytical and many more applications is increasing day by day. Hitherto, a very less amount of research is available in the depiction of conformational stability, activity, and thermal stability of enzymes in the presence of ILs. In the present study, the perturbation in the structure, stability, and activity of stem bromelain (BM) has been observed in the presence of 1-allyl-3-methylimidazolium chloride ([Amim][Cl]) using various techniques. This is the first report in which the influence of [Amim][Cl] has been studied on the enzyme BM. Fluorescence spectroscopy has been utilized to map out the changes in the environment around tryptophan (Trp) residues of BM and also to discuss the variations in the thermal stability of BM as an outcome of its interaction with the IL at different concentrations. Further, the work delineates the denaturing effect of high concentration of IL on enzyme structure and activity. It dictates the fact that low concentrations (0.01-0.10 M) of [Amim][Cl] are only changing the structural arrangement of the protein without having harsh consequences on its activity and stability. However, high concentrations of IL proved to be totally devastating for both activity and stability of BM. The observed decrease in the stability of BM at high concentration may be due to the combined effect of cation and anion interactions with the protein residues. The present work is successful in dictating the probable mechanism of interaction between BM and [Amim][Cl]. These results can prove to be fruitful in the studies of enzymes in aqueous IL systems since the used IL is thermally stable and nonvolatile in nature thereby providing a pathway of alteration in the activity of enzymes in potentially green systems. PMID:27268069

  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. Sulfur speciation and sulfide oxidation in the water column of the Black Sea

    Science.gov (United States)

    Luther, George W., III; Church, Thomas M.; Powell, David

    We have applied sulfur speciation techniques to understand the chemistry and cycling of sulfur in Black Sea waters. The only reduced dissolved inorganic sulfur species detected (above the low minimum detection limits of the voltammetric methods employed) in the water column was hydrogen sulfide. The maximum concentration of sulfide (423 μM) is similar to previous reports. Using a cathodic stripping square wave voltammetry (CSSWV) method for nanomolar levels of sulfide, we determined the precise boundary between the "free" hydrogen sulfide (sulfidic) zone and the upper (oxic/suboxic) water column at the two stations studied. This boundary has apparently moved up by about 50 m in the past 20 years. Our results help demonstrate three chemically distinct zones of water in the central basin of the Black Sea: (1) the oxic [0-65 m], (2) the anoxic/nonsulfidic [65-100 m] and (3) the sulfidic [>100 m]. Sulfide bound to metals ("complexed" sulfide) is observed in both the oxic and anoxic/nonsulfidic zones of the water column. This supports previous studies on metal sulfide forms. From the electrochemical data, it is possible to estimate the strength of the complexation of sulfide to metals (log K = 10 to 11). Thiosulfate and sulfite were below our minimum detectable limit (MDL) of 50 nM using CSSWV. Elemental sulfur (MDL 5 nM) was detected below the onset of the hydrogen sulfide zone (90-100 m) with a maximum of 30-60 nM near 120 m. The sulfur speciation results for the Black Sea are lower by one order of magnitude or more than other marine systems such as the Cariaco Trench and salt marshes. New HPLC techniques were applied to detect thiols at submicromolar levels. The presence of thiols (2-mercaptoethylamine, 2-mercaptoethanol, N-acetylcysteine and glutathione) is correlated with the remineralization of organic matter at the oxic and anoxic/nonsulfidic interface. Water samples collected from the upper 50 m of the sulfidic zone showed significant sulfide oxidation on

  1. 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...

  2. 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...

  3. 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....

  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. Contrastive study on the removal of sulfide from carbide slag slurry for desulfurization%脱硫用电石渣浆液中硫化物去除工艺的对比研究

    Institute of Scientific and Technical Information of China (English)

    郭国良; 姚微源; 莫建松; 王海强; 吴忠标

    2012-01-01

    分别研究了空气催化氧化法、双氧水氧化法和漂白粉氧化法对脱硫用电石渣浆液中硫化物的去除效果.实验结果表明,在适当条件下,空气氧化法可在240 min内使硫化物的去除率达到80%,适量的双氧水和漂白粉能够使硫化物降至0.5 mg/L以下,去除率达到99%以上.在此基础上对比了3种工艺的经济成本:空气催化氧化法<漂白粉氧化法<双氧水氧化法.%The removal effect of sulfide from carbide slag slurry for desulfurization by three processes, including catalytic air oxidation, H2O2 oxidation and chlorinated lime oxidation, has been studied. The results show that under appropriate conditions the removing rate of sulfide reaches 80% within 240 min by air oxidation process. The sulfide removing rate can be higher than 99% ,by using appropriate amount of H2O2 and chlorinated lime. Based on these studies, the economic costs of the three processes are contrasted. It is found that the economic cost of catalytic air oxidant process is less than that of chlorinated lime oxidation process and the cost of chlorinated lime oxidation process is less than that of H2O2 oxidation process.

  6. Sulfide Oxidation in the Anoxic Black-Sea Chemocline

    DEFF Research Database (Denmark)

    JØRGENSEN, BB; FOSSING, H.; WIRSEN, CO;

    1991-01-01

    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 sulfide zone.......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......-99 m. Oxygen in the water column immediately overlying the sulfide zone was depleted to undetectable levels resulting in a 20-30-m deep intermediate layer of O2- and H2S-free water. Radiotracer studies with S-35-labelled H2S showed that high rates of sulfide oxidation, up to a few micromoles per liter...

  7. Substrate and stereocontrolled iodocycloetherification of highly functionalized enantiomerically pure allylic alcohols: application to synthesis of cytotoxic 2-epi jaspine B and its biological evaluation.

    Science.gov (United States)

    Kundooru, Somireddy; Das, Pintu; Meena, Sanjeev; Kumar, Vikash; Siddiqi, Mohammad Imran; Datta, Dipak; Shaw, Arun K

    2015-08-14

    Stereoselectivities of electrophilic additions of molecular iodine to enantiomerically pure highly functionalized allylic alcohols with internal nucleophiles have been investigated. The intramolecular nucleophilic attack on the I2-π complex by an oxygen nucleophile to obtain tri- and tetrasubstituted THFs is highly regio-, stereoselective and substrate controlled. The application of this study has been shown by utilizing one of the THFs 4a as a key intermediate to complete the total synthesis of marine anti-cancer natural product 2-epi jaspine B. PMID:26133669

  8. Pyritization processes and greigite formation in the advancing sulfidization front in the Upper Pleistocene sediments of the Black Sea

    DEFF Research Database (Denmark)

    Neretin, LN; Bottcher, ME; Jørgensen, BB;

    2004-01-01

    showed that the process started at the Pleistocene/Holocene transition between 6360 and 11600 yr BP. Our study highlights the importance of anaerobic methane oxidation in generating and maintaining S-enriched layers in marine sediments and has paleoenvironmental implications. Copyright (C) 2004 Elsevier......Pyritization in late Pleistocene sediments of the Black Sea is driven by sulfide formed during anaerobic methane oxidation. A sulfidization front is formed by the opposing gradients of sulfide and dissolved iron. The sulfidization processes are controlled by the diffusion flux of sulfide from above...... and polysulfides, formed from H,S by a reductive dissolution of Fe(Ill)-containing minerals, serve as intermediates to convert iron sulfides into pyrite. In the second process, a "direct" pyrite precipitation occurs through prolonged exposure of iron-containing minerals to dissolved sulfide. Methane-driven sulfate...

  9. Formation and evolution stages of gold rich Barika massive sulfide deposit, east of Sardasht, northern Sanandaj-Sirjan zone: based on structural, textural and fluid inclusion studies

    Directory of Open Access Journals (Sweden)

    Hossein Ali Tajeddin

    2010-05-01

    Full Text Available Barika gold (and silver rich massive sulfide deposit is located 18 km east of Sardasht, north western part of Sanandaj-Sirjan metamorphic zone. Rock units outcropped in this area are Cretaceous metamorphosed volcano-sedimentary rocks in green schist facies, and include association of meta-andesite, meta-tuffite, phyllite and slate rocks, where the meta-andesitic unit (Kmv1 is host rock to the deposit. Barika deposit is composed of stratiform ore and stringer zone. Stratiform part contains massive and banded sulfide and barite associated with subordinary silica bands underlain by stringer silicic zone. The massive and banded ore is surrounded by an extensive zone of silicic stringer veins and disseminated mineralization within strongly altered and deformed andesitic volcanic rocks. Ore mineral assemblages in stratiform part of the deposit are quite variable and consist of pyrite, sphalerite, galena, stibnite, a variety of sulfosalt minerals and gold (electrum. Ore mineral assemblages in silicic veins in the stringer zone are simpler and consist of pyrite, galena, sphalerite, tetrahedrrite and trace chalcopyrite. Average gold and silver grades in stratiform ore are 8.3 and 420 g/t respectively and in silicic stringer veins are 0.7 and 30 g/t. Base metal content in both parts of the deposit are less than 1%. Based on our research, Barika is an immature Kuroko type massive sulfide deposit, which contains only black ore. The Barika deposit underwent low-grade metamorphism and high grade deformation after the ore deposition event. Geologic processes appear to control the mode of occurrence of gold in the deposit. In synvolcanism stage, deposition of a gold–bearing low temperature (140-200°C and low salinity (1-9.6 wt% NaCl hydrothermal fluid formed a Kuroko black ore type deposit. In the stage of mineralization, invisible gold was concentrated in framboidal pyrite and other sulfide minerals. The main effect of progressive metamorphism (D1 on gold

  10. Stereoselective coordination: a six-membered P,N-chelate tailored for asymmetric allylic alkylation.

    Science.gov (United States)

    Császár, Z; Farkas, G; Bényei, A; Lendvay, G; Tóth, I; Bakos, J

    2015-10-01

    Six-membered chelate complexes [Pd(1a-b)Cl2], (2a-b) and [Pd(1a-b)(η(3)-PhCHCHCHPh)]BF4, (3a-b) of P,N-type ligands 1a, ((2S,4S)-2-diphenyl-phosphino-4-isopropylamino-pentane) and 1b, ((2S,4S)-2-diphenyl-phosphino-4-methylamino-pentane) have been prepared. The Pd-complexes have been characterized in solution by 1D and 2D NMR spectroscopy. The observed structures were confirmed by DFT calculations and in the case of 2a also by X-ray crystallography. Unexpectedly, the coordination of the all-carbon-backbone aminophosphine 1a resulted in not only a stereospecific locking of the donor nitrogen atom into one of the two possible configurations but also the conformation of the six-membered chelate rings containing three alkyl substituents was forced into the same single chair structure showing the axially placed isopropyl group on the coordinated N-atom. The stereodiscriminative complexation of 1a led to the formation of a palladium catalyst with a conformationally rigid chelate having a configurationally fixed nitrogen and electronically different coordination sites due to the presence of P and N donors. The stereochemically fixed catalyst provided excellent ee's (up to 96%) and activities in asymmetric allylic alkylation reactions. In contrast, the chelate rings formed by 1b exist in two different chair conformations, both containing axial methyl groups, but with the opposite configurations of the coordinated N-atom. Pd-complexes of 1b provided low enantioselectivities in similar alkylations, therefore emphasizing the importance of the stereoselective coordination of N-atoms in analogous P-N chelates. The factors determining the coordination of the ligands were also studied with respect to the chelate ring conformation and the nitrogen configuration.

  11. [Characterization of surface properties of 1-allyl-3-methylimidazolium chloride ionic liquid by inverse gas chromatography].

    Science.gov (United States)

    Chen, Yali; Wang, Qiang; Deng, Lishuang; Zhang, Zhengfang; Tang, Jun

    2013-02-01

    The determination of the dispersive component of surface free energies (gamma(s)d) at different temperatures and Lewis acid-base parameters of 1-allyl-3-methylimidazolium chloride ionic liquid ([AMIM]Cl) were investigated by means of inverse gas chromatography (IGC). Four n-alkanes, including n-hexane (C6), n-heptane (C7), n-octane (C8) and n-nonane (C9), were chosen as the apolar probes to characterize the dispersive component of the surface free energies at 343.15, 353.15, 363.15 and 373.15 K, respectively; and dichloromethane (DCM), trichloromethane (TCM), tetrahydrofuran (THF), ethyl acetate (EtAc), acetone (Acet) as the polar probes to estimate the Lewis acid-base parameters to judge the interactions between [AMIM] Cl and the solvents. The IGC characterizations encompassed the adsorption thermodynamic parameters to acid-base surface interactions, including the standard enthalpy (deltaHa(s)) and the free energy change of adsorption (deltaGa(s)) at different temperatures. The results showed that the Lewis acid parameter Ka of [AMIM] Cl was 0.34, and the base parameter Kb was 1.68, which indicated it was Lewis amphoteric with predominantly basic character. Furthermore, the free energy of adsorption deltaGa(s) was also figured out. It was found that the gamma(s)d of the [AMIM] Cl were 52.26, 50.82, 46.08 and 42.05 mJ/m2 at 343.15, 353.15, 363.15 and 373.15 K, respectively. The results are of great importance to the study of the surface properties and the application of ionic liquid.

  12. S-Allyl-Cysteines Reduce Amelioration of Aluminum Induced Toxicity in Rats

    Directory of Open Access Journals (Sweden)

    Sadhana Shrivastava

    2011-01-01

    Full Text Available Problem statement: Aluminum (Al is a trivalent cation found in its ionic form in most kinds of animal tissues and in natural waters everywhere. Approach: It is a potent neurotoxin and has been associated in the pathogenesis of several clinical disorders including Alzheimer’s disease. Results: The aim of the study was to demonstrate the protective effect of S-Allyl-Cysteines (SAC against Al-induced toxicity in rat model on certain biochemical parameters, lipid peroxidation and oxidative stress enzymes of white albino rats. Six rats per group were divided into various treatment groups. Group one rats were given normal saline and served as control group. Group two animals received Al as aluminum nitrate 32.5 mg (i.p. for the induction of toxicity. Group three to five received different doses of SAC (25, 50 and 100 mg kg-1 for 3 days after 24 h of Al toxicity. Rats were orally administered their respective doses every day for 3 days. Evaluations were made in blood and tissues. The activity of Acetylcholinesterase (AchE was inhibited in all the parts of brain after Al intoxication. Significant rise were observed the Activities of Serum Transaminases (AST and ALT after toxicant exposure. The activity of â-Aminolevulinic acid Dehydratase (ALAD in blood and â-Aminolevulinic Acid Synthetase (ALAS in brain was decreased after Al exposure. Al significant increased cholesterol, triglyceride, creatinine and urea level in serum. TBARS level was significantly higher and GSH content were significantly lower during toxicity. Total and esterified cholesterol in liver, kidney and brain were increased after Al exposure. Histopathological changes in liver, kidney and brain were also recouped with the therapy. Conclusion/Recommendations: Our data proved that SAC which is a bioactive and bioavailable component of garlic has organosulfur compounds which regulates the thiol status of the cell and scavenges free radicals and work as an antioxidant. Thus SAC

  13. Proton conductive membranes based on poly (styrene-co-allyl alcohol semi-IPN

    Directory of Open Access Journals (Sweden)

    Felipe Augusto Moro Loureiro

    2014-01-01

    Full Text Available The optimization of fuel cell materials, particularly polymer membranes, for PEMFC has driven the development of methods and alternatives to achieve systems with more adequate properties to this application. The sulfonation of poly (styrene-co-allyl alcohol (PSAA, using sulfonating agent:styrene ratios of 2:1, 1:1, 1:2, 1:4, 1:6, 1:8 and 1:10, was previously performed to obtain proton conductive polymer membranes. Most of those membranes exhibited solubility in water with increasing temperature and showed conductivity of approximately 10-5 S cm-1. In order to optimize the PSAA properties, especially decreasing its solubility, semi-IPN (SIPN membranes are proposed in the present study. These membranes were obtained from the diglycidyl ether of bisphenol A (DGEBA, curing reactions in presence of DDS (4,4-diaminodiphenyl sulfone and PSAA. Different DGEBA/PSAA weight ratios were employed, varying the PSAA concentration between 9 and 50% and keeping the mass ratio of DGEBA:DDS as 1:1. The samples were characterized by FTIR and by electrochemical impedance spectroscopy. Unperturbed bands of PSAA were observed in the FTIR spectra of membranes, suggesting that chemical integrity of the polymer is maintained during the synthesis. In particular, bands involving C-C stretching (1450 cm-1, C=C (aromatic, ~ 3030 cm-1 and C-H (2818 and 2928 cm-1 were observed, unchanged after the synthesis. The disappearance or reduction of the intensity of the band at 916 cm-1, attributed to the DGEBA epoxy ring, is evidenced for all samples, indicating the epoxy ring opening and the DGEBA crosslinking. Conductivity of H3PO4 doped membranes increases with temperature, reaching 10-4 S cm-1.

  14. Vibronic spectra of the allyl radical at 6-8 eV with resonance-enhanced multiphoton ionization technique

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The allyl radical was produced in molecular beam by pyrolysis of allyl iodide. The vibronic spectra from ground state to six new electronic states of the allyl radical at 6-8 eV, p?3dxz , p?3dxy, and p?ns (n=4, 6, 7, 8) were observed firstly with the aid of time-of-flight mass spectroscopy and resonance-enhanced multiphoton ionization technique. Vibrational progression of n7 (C3 bend) with gross spacing of about 430 cm-1 was observed in ns Rydberg states. The adiabatic ionization potential of the allyl radical was obtained to be (65641 ± 20) cm-1 ((8.138 ± 0.002) eV) by fitting the term values of ns (n=4,6,7,8) Rydberg states with Rydberg formula.

  15. 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.

  16. (2,4-二甲氧基苯基)烯丙基丙二酸二乙酯异构体的GC/MS研究%Study on Diethyl [3-(2,4-Dimethoxyphenyl) Allyl] Malonate Isomers by Gas Chromatography-Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    王敏; 彭奇

    2012-01-01

    A method applying gas chromatography-ion trap mass spectrometry (GC/MS) for the simultaneous analysis of diethyl [3-(2,4-dimethoxyphenyl)allyl]malonate isomers is described. The diethyl [3-(2,4-dimethoxyph-enyl)allyl]malonate mixture of isomers was prepared by the decarboxylative Heck reaction of 2,4-dimethoxybenzoic acid with diethyl 2-al-lylmalonate firstly, and then was analyzed by GC/MS in Electron ionization (El) and Chemical ionization (CD full-scan mode. Two components were isolated by gas chromatography" and identified as isomers from the determination of the molecular ions. Next, the isomers were analyzed by tandem mass spectrometry (MS/MS) mode. Through the analysis of different cleavage fragments of the isomers in MS/MS mode, mass spectrometric fragmentation pathways of the isomers were discussed. The structures of two isomers were determined on the base of different mass characteristic fragmentation pathways. This new meth- od of identifying isomers is a time-saving, economical and effective method, which could provide reference for analysis and identification of this kind of compounds.%为了研究钯催化的2,4-二甲氧基苯甲酸与烯丙基丙二酸二乙酯的脱羧Heck反应的产物结构,建立了(2,4-二甲氧基苯基)烯丙基丙二酸二乙酯同分异构体的分离与鉴定的气相色谱-离子阱质谱方法.首先通过脱羧Heek反应制得(2,4-二甲氧基苯基)烯丙基丙二酸二乙酯异构体混合物,然后利用GC/MS联用技术对混合物进行分析,得到各组分的EI和CI全扫描模式质谱信息.通过对照各组分的分子离子峰确定互为异构体的组分,再对异构体组分采用MS/MS模式获取各自的裂解碎片.通过分析异构体的不同的裂解碎片,讨论质谱裂解方式,从而确定异构体的结构.该方法省时、经济、高效,可为此类化合物的分析与鉴别提供参考.

  17. Structural analysis by reductive cleavage with LiAlH4 of an allyl ether choline-phospholipid, archaetidylcholine, from the hyperthermophilic methanoarchaeon Methanopyrus kandleri

    Directory of Open Access Journals (Sweden)

    Masateru Nishihara

    2002-01-01

    Full Text Available A choline-containing phospholipid (PL-4 in Methanopyrus kandleri cells was identified as archaetidylcholine, which has been described by Sprott et al. (1997. The PL-4 consisted of a variety of molecular species differing in hydrocarbon composition. Most of the PL-4 was acid-labile because of its allyl ether bond. The identity of PL-4 was confirmed by thin-layer chromatography (TLC followed by positive staining with Dragendorff-reagent and fast-atom bombardment–mass spectrometry. A new method of LiAlH4 hydrogenolysis was developed to cleave allyl ether bonds and recover the corresponding hydrocarbons. We confirmed the validity of the LiAlH4 method in a study of the model compound synthetic unsaturated archaetidic acid (2,3-di-O-geranylgeranyl-sn-glycerol-1-phosphate. Saturated ether bonds were not cleaved by the LiAlH4 method. The hydrocarbons formed following LiAlH4 hydrogenolysis of PL-4 were identified by gas–liquid chromatography and mass spectrometry. Four kinds of hydrocarbons with one to four double bonds were detected: 47% of the hydrocarbons had four double bonds; 11% had three double bonds; 14% had two double bonds; 7% had one double bond; and 6% were saturated species. The molecular species composition of PL-4 was also estimated based on acid lability: 77% of the molecular species had two acid-labile hydrocarbons; 11% had one acid-labile and one acid-stable hydrocarbon; and 11% had two acid-stable hydrocarbons. To our knowledge, this is the first report of a specific chemical degradation method for the structural analysis of allyl ether phospholipid in archaea.

  18. Enantioselective Allylic C-H Oxidation of Terminal Olefins to Isochromans by Palladium(II)/Chiral Sulfoxide Catalysis.

    Science.gov (United States)

    Ammann, Stephen E; Liu, Wei; White, M Christina

    2016-08-01

    The enantioselective synthesis of isochroman motifs has been accomplished by palladium(II)-catalyzed allylic C-H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide-oxazoline (ArSOX) ligand. The allylic C-H oxidation reaction proceeds with the broadest scope and highest levels of asymmetric induction reported to date (avg. 92 % ee, 13 examples with greater than 90 % ee). PMID:27376625

  19. 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

  20. 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.

  1. 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.

  2. The impact of electrogenic sulfide oxidation on elemental cycling and solute fluxes in coastal sediment

    NARCIS (Netherlands)

    Rao, A.M.F.; Malkin, S.Y.; Hidalgo-Martinez, S.; Meysman, Filip

    2016-01-01

    Filamentous sulfide oxidizing cable bacteria are capable of linking the oxidation of free sulfide in deep anoxic layers of marine sediments to the reduction of oxygen or nitrate in surface sediments by conducting electrons over centimeter-scale distances. Previous studies have shown that this newly

  3. Microbial control of hydrogen sulfide production in a porous medium

    Energy Technology Data Exchange (ETDEWEB)

    McInerney, M.J.; Wofford, N.Q. [Univ. of Oklahoma, Norman, OK (United States); Sublette, K.L. [Univ. of Tulsa, OK (United States)

    1996-12-31

    The ability of a sulfide- and glutaraldehyde-tolerant strain of Thiobacillus denitrificans (strain F) to control sulfide production in an experimental system of cores and formation water from the Redfield, Iowa natural gas storage facility was investigated. A stable, sulfide-producing biofilm was established in two separate core systems, one of which was inoculated with strain F, and 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 5mM nitrate was injected into both core systems, the effluent sulfide concentrations in the control core system ranged from 200-460 {mu}M. In the test core system inoculated with strain F, the effluent sulfide concentrations were lower, ranging from 70-110 {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 3800 pM, and then decreased to about 1100 {mu}M after 5 wk. However, in the test core system inoculated with strain F, the effluent sulfide concentrations were much lower, 160-330 {mu}M. Nitrate consumption (5 mM) and high concentrations (101-1011 cells/mL) of strain F were detected in the test core system. An accumulation of biomass occurred in the influent lines during 2 mo of continuous operation, but only a small increase in injection pressure was observed. These studies showed that inoculation with strain F was needed for effective control of sulfide production, and that significant plugging or loss of injectivity owing to microbial inoculation did not occur. 7 refs., 3 figs., 1 tab.

  4. Rheology and viscosity scaling of gelatin/1-allyl-3-methylimidazolium chloride solution

    Science.gov (United States)

    Qiao, Congde; Li, Tianduo; Zhang, Ling; Yang, Xiaodeng; Xu, Jing

    2014-05-01

    Gelatin/1-allyl-3-methylimidazolium chloride solutions are prepared by using the ionic liquid 1-allyl-3-methylimidazolium chloride as solvent. The rheological properties of the gelatin solutions have been investigated by steady shear and oscillatory shear measurements. In the steady shear measurements, the gelatin solutions with high concentration show a shear-thinning flow behavior at high shear rates, while another shear thinning region can be found in the dilute gelatin solutions at low shear rates. The overlap concentration of gelatin in [amim]Cl is 1.0 wt% and the entanglement concentration is a factor of 4 larger (4.0 wt%). The high intrinsic viscosity (295 mL/g) indicates that the gelatin chains dispersed freely in the ionic liquid and no aggregation phenomenon occurs in dilute gelatin solution. The frequency dependences of modulus changed obviously with an increase in gelatin concentration. The empirical time-temperature superposition principle holds true at the experimental temperatures.

  5. Highly Regioselective Palladium-Catalyzed Carboxylation of Allylic Alcohols with CO2.

    Science.gov (United States)

    Mita, Tsuyoshi; Higuchi, Yuki; Sato, Yoshihiro

    2015-11-01

    Various allylic alcohols were carboxylated in the presence of a catalytic amount of PdCl2 and PPh3 using ZnEt2 as a stoichiometric transmetalation agent under a CO2 atmosphere (1 atm). This carboxylation proceeded in a highly regioselective manner to afford branched carboxylic acids predominantly. The β,γ-unsaturated carboxylic acid thus obtained was successfully converted into an optically active γ-butyrolactone, a known intermediate of (R)-baclofen.

  6. Iron(III) chloride catalyzed glycosylation of peracylated sugars with allyl/alkynyl alcohols

    Energy Technology Data Exchange (ETDEWEB)

    Narayanaperumal, Senthil; Silva, Rodrigo Cesar da; Monteiro, Julia L.; Correa, Arlene G.; Paixao, Marcio W., E-mail: mwpaixao@ufscar.br [Universidade Federal de Sao Carlos (UFSCAR), SP (Brazil). Dept. de Quimica

    2012-11-15

    In this work, the use of ferric chloride as an efficient catalyst in glycosylation reactions of sugars in the presence of allyl and alkynyl alcohols is described. The corresponding glycosides were obtained with moderate to good yields. This new procedure presented greater selectivity when compared to classic methods found in the literature. Principal features of this simple method include non-hazardous reaction conditions, low-catalyst loading, good yields and high anomeric selectivity (author)

  7. Lewis base catalyzed enantioselective allylic hydroxylation of Morita-Baylis-Hillman carbonates with water

    KAUST Repository

    Zhu, Bo

    2011-08-19

    A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using 18O-labeling experiments. © 2011 American Chemical Society.

  8. Synthesis of alkenyl boronates from allyl-substituted aromatics using an olefin cross-metathesis protocol.

    Science.gov (United States)

    Hemelaere, Rémy; Carreaux, François; Carboni, Bertrand

    2013-07-01

    An efficient synthesis of 3-aryl-1-propenyl boronates from pinacol vinyl boronic ester and allyl-substituted aromatics by cross metathesis is reported. Although the allylbenzene derivatives are prone to isomerization reaction under metathesis conditions, we found that some ruthenium catalysts are effective for this methodology. This strategy thus provides an interesting alternative approach to alkyne hydroboration, leading to the preparation of unknown compounds. Moreover, the boron substituent can be replaced by various functional groups in good yields.

  9. Surprisingly Mild Enolate-Counterion-Free Pd(0)-Catalyzed Intramolecular Allylic Alkylations

    DEFF Research Database (Denmark)

    Madec, David; Prestat, Guillaume; Martini, Elisabetta;

    2005-01-01

    Palladium-catalyzed intramolecular allylic alkylations of unsaturated EWG-activated amides can take place under phase-transfer conditions or in the presence of a crown ether. These new reaction conditions are milder and higher yielding than those previously reported. A rationalization for such an...... for such an unexpected result is put forth and validated by DFT-B3LYP calculations. The results suggest cyclization via a counterion-free (E)-enolate TS....

  10. Allyl isothiocyanate induced stress response in Caenorhabditis elegans

    OpenAIRE

    Saini AkalRachna K; Tyler Robert T; Shim Youn; Reaney Martin JT

    2011-01-01

    Abstract Background Allyl isothiocyanate (AITC) from mustard is cytotoxic; however the mechanism of its toxicity is unknown. We examined the effects of AITC on heat shock protein (HSP) 70 expression in Caenorhabditis elegans. We also examined factors affecting the production of AITC from its precursor, sinigrin, a glucosinolate, in ground Brassica juncea cv. Vulcan seed as mustard has some potential as a biopesticide. Findings An assay to determine the concentration of AITC in ground mustard ...

  11. Rhodium-catalysed asymmetric allylic arylation of racemic halides with arylboronic acids

    Science.gov (United States)

    Sidera, Mireia; Fletcher, Stephen P.

    2015-11-01

    Csp2-Csp2 cross-coupling reactions between arylboronic acid and aryl halides are widely used in both academia and industry and are strategically important in the development of new agrochemicals and pharmaceuticals. Csp2-Csp3 cross-coupling reactions have been developed, but enantioselective variations are rare and simply retaining the stereochemistry is a problem. Here we report a highly enantioselective Csp2-Csp3 bond-forming method that couples arylboronic acids to racemic allyl chlorides. Both enantiomers of a cyclic chloride are converted into a single enantiomer of product via a dynamic kinetic asymmetric transformation. This Rh-catalysed method uses readily available and inexpensive building blocks and is mild and broadly applicable. For electron-deficient, electron-rich or ortho-substituted boronic acids better results are obtained with racemic allyl bromides. Oxygen substitution in the allyl halide is tolerated and the products can be functionalized to provide diverse building blocks. The approach fills a significant gap in the methods for catalytic asymmetric synthesis.

  12. 几种硫醚类香料抑菌活性的研究%Study on antibacterial activity of several sulfide flavors

    Institute of Scientific and Technical Information of China (English)

    张公亮; 丁佳琦; 董伟峰; 刘阳; 王衍; 李冉; 侯红漫

    2012-01-01

    The antibacterial activity of eight sulfide flavors was determined by measuring the diameter of inhibition zone.The effect of structure on their antibacterial activities was further investigated according to a statistical significance test.The results indicated that dimethyl sulfide(DMS),diethyl sulfide(DES),dibutyl sulfide(DBS),but not diallyl sulfide(DAS),showed no antibacterial activities against Escherichia coil,Staphylococcus aureus,Shigella flexneri,Salmonella and Bacillus subtilis.The inhibitory effects of the selected sulfide flavors on these bacteria followed the order diallyl disulfide(DADS)dipropyl disulfide(DPDS)or≈dimethyl disulfide(DMDS),dimethyl trisulfide(DMTS)DMDSDMS and DADSDAS.These results suggested that diallyl was contributed to the antibacterial activity of monosulfide flavors,and the unsaturation of alkenyl groups has influence on the antibacterial activity of disulfide.A larger number of sulfur atoms is more favorable to the antibacterial activity of sulfide flavors with same alk(en)yl groups.%选取八种硫醚类香料,通过测量抑菌圈直径考察其抑菌活性,并根据显著性分析结果探讨结构对其抑菌活性的影响。结果表明:对于大肠杆菌、金黄色葡萄球菌、沙门氏菌、福氏志贺氏菌及枯草芽孢杆菌,二甲基硫醚(DMS)、二乙基硫醚(DES)及二丁基硫醚(DBS)均无抑菌作用,而二烯丙基硫醚(DAS)则具有一定的抑菌作用;以二烯丙基二硫醚(DADS)为阳性对照,选取的硫醚类香料对五种供试细菌抑制作用大小为DADS〉二丙基二硫醚(DPDS)〉或≈二甲基二硫醚(DMDS),二甲基三硫醚(DMTS)〉DMDS〉DMS及DADS〉DAS。这些结果说明二烯丙基对单硫醚类香料的抑菌作用有一定贡献,双键的存在对二硫醚类香料的抑菌作用有重要影响。对于具有相同取代基团的硫醚类香料,硫原子数越多,其抑菌效果越强。

  13. 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.

  14. Nouvelles Réactions d'Allylation Radicalaire : Exploitation de la Rupture homolytique de Liaisons Carbone-Oxygène et Carbone-Carbone

    OpenAIRE

    Debien, Laurent

    2013-01-01

    This PhD thesis is divided in eight chapters. The first three bibliographic chapters present the general principles of radical chemistry, the possibility offered by the xanthate radical chemistry and a review of the radical allylation methods, main focus of this work. The three next chapters are dedicated to the exploitation of the radical allylation of allylic alcohols, recently discovered in our laboratory. The use of such a technology enabled the preparation of functionalized enol ethers, ...

  15. Growth kinetics of hydrogen sulfide oxidizing bacteria in corroded concrete from sewers.

    Science.gov (United States)

    Jensen, Henriette Stokbro; Lens, Piet N L; Nielsen, Jeppe L; Bester, Kai; Nielsen, Asbjørn Haaning; Hvitved-Jacobsen, Thorkild; Vollertsen, Jes

    2011-05-30

    Hydrogen sulfide oxidation by microbes present on concrete surfaces of sewer pipes is a key process in sewer corrosion. The growth of aerobic sulfur oxidizing bacteria from corroded concrete surfaces was studied in a batch reactor. Samples of corrosion products, containing sulfur oxidizing bacteria, were suspended in aqueous solution at pH similar to that of corroded concrete. Hydrogen sulfide was supplied to the reactor to provide the source of reduced sulfur. The removal of hydrogen sulfide and oxygen was monitored. The utilization rates of both hydrogen sulfide and oxygen suggested exponential bacterial growth with median growth rates of 1.25 d(-1) and 1.33 d(-1) as determined from the utilization rates of hydrogen sulfide and oxygen, respectively. Elemental sulfur was found to be the immediate product of the hydrogen sulfide oxidation. When exponential growth had been achieved, the addition of hydrogen sulfide was terminated leading to elemental sulfur oxidation. The ratio of consumed sulfur to consumed oxygen suggested that sulfuric acid was the ultimate oxidation product. To the knowledge of the authors, this is the first study to determine the growth rate of bacteria involved in concrete corrosion with hydrogen sulfide as source of reduced sulfur.

  16. Growth kinetics of hydrogen sulfide oxidizing bacteria in corroded concrete from sewers

    International Nuclear Information System (INIS)

    Hydrogen sulfide oxidation by microbes present on concrete surfaces of sewer pipes is a key process in sewer corrosion. The growth of aerobic sulfur oxidizing bacteria from corroded concrete surfaces was studied in a batch reactor. Samples of corrosion products, containing sulfur oxidizing bacteria, were suspended in aqueous solution at pH similar to that of corroded concrete. Hydrogen sulfide was supplied to the reactor to provide the source of reduced sulfur. The removal of hydrogen sulfide and oxygen was monitored. The utilization rates of both hydrogen sulfide and oxygen suggested exponential bacterial growth with median growth rates of 1.25 d-1 and 1.33 d-1 as determined from the utilization rates of hydrogen sulfide and oxygen, respectively. Elemental sulfur was found to be the immediate product of the hydrogen sulfide oxidation. When exponential growth had been achieved, the addition of hydrogen sulfide was terminated leading to elemental sulfur oxidation. The ratio of consumed sulfur to consumed oxygen suggested that sulfuric acid was the ultimate oxidation product. To the knowledge of the authors, this is the first study to determine the growth rate of bacteria involved in concrete corrosion with hydrogen sulfide as source of reduced sulfur.

  17. What do we really know about the role of microorganisms in iron sulfide mineral formation?

    Science.gov (United States)

    Picard, Aude; Gartman, Amy; Girguis, Peter

    2016-06-01

    Iron sulfide mineralization in low-temperature systems is a result of biotic and abiotic processes, though the delineation between these two modes of formation is not always straightforward. Here we review the role of microorganisms in the precipitation of extracellular iron sulfide minerals. We summarize the evidence that links sulfur-metabolizing microorganisms and sulfide minerals in nature and we present a critical overview of laboratory-based studies of the nucleation and growth of iron sulfide minerals in microbial cultures. We discuss whether biologically derived minerals are distinguishable from abiotic minerals, possessing attributes that are uniquely diagnostic of biomineralization. These inquiries have revealed the need for additional thorough, mechanistic and high-resolution studies to understand microbially mediated formation of a variety of sulfide minerals across a range of natural environments.

  18. 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.

  19. 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...

  20. On the Nature of the Intermediates and the Role of Chloride Ions in Pd-Catalyzed Allylic Alkylations: Added Insight from Density Functional Theory

    DEFF Research Database (Denmark)

    Fristrup, Peter; Ahlquist, Mårten Sten Gösta; Tanner, David Ackland;

    2008-01-01

    The reactivity of intermediates in palladium-catalyzed allylic alkylation was investigated using DFT (B3LYP) calculations including a PB-SCRF solvation model. In the presence of both phosphine and chloride ligands, the allyl intermediate is in equilibrium between a cationic eta(3)-allylPd complex...... with two phosphine ligands, the corresponding neutral complex with one phosphine and one chloride ligand, and a neutral eta(1)-allylPd complex with one chloride and two phosphine ligands. The eta(1)-complex is unreactive toward nucleophiles. The cationic eta(3)-complex is the intermediate most...

  1. 滩涂贝类养殖区底质硫化物的去除及修复%Study on Restoration of Sulfide in Sediment Environment of Shellfish Mudflat Culture Areas

    Institute of Scientific and Technical Information of China (English)

    牛俊翔; 蒋玫; 李磊; 袁骐; 吴庆元; 许高鹏; 沈新强

    2013-01-01

    以滩涂现场实验与室内模拟实验相结合的途径,运用物理修复方法(翻耕、压沙加翻耕)和投放双齿围沙蚕(Perinereis aibuhitensis)的生物修复方法开展滩涂文蛤(Meretrix meretrix)养殖底质中硫化物的去除修复实验.结果表明,现场和室内物理修复实验中,翻耕和压沙加翻耕处理去除硫化物效果均达到显著水平(P<0.05),其中压沙加翻耕修复效果优于翻耕,室内翻耕30 cm修复效果优于翻耕20cm.室内生物修复实验中,各沙蚕处理组较对照组均表现出了较好的硫化物修复效果,且硫化物的去除效果随沙蚕投放密度的适量增加而增强,其中0.14 kg·m-2和0.21 kg·m-2沙蚕组的修复效果达到显著水平(P<0.05),而当增加沙蚕投放密度至0.28 kg·m-2时,硫化物的去除效果反而减弱,表明最佳沙蚕修复效果有一个适宜的密度投放值.%The sulfide in mariculture environments could not only influence directly the seawater environmental qualities,but also induce the pollution of sediment environments and result in impairments of the shellfish cultured.In this study,laboratory experiment and field experiment were used to investigate the restoration of sulfide in sediment environment of shellfish mudflat culture areas.And two methods on restoration of sediment environment were involved,one was bioremediation(the densities of Perinereis aibuhitensis were 0.07 kg· m-2,0.14kg· m-2,0.21 kg· m-2 and 0.28 kg· m-2 respectively),and the other was physical way(only beach ploughing,both covering sand and beach ploughing).The results indicated that two physical ways had achieved significant results in both laboratory experiment and field experiment (P<0.05),and the result of both covering sand and beach ploughing was better than only beach ploughing in both two experiments,and the effect of ploughed 30cm was better than ploughed 20 cm in laboratory experiment.Compared with the control group of bioremediation,all density

  2. 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).

  3. Amperometric inhibitive biosensor based on horseradish peroxidase-nanoporous gold for sulfide determination

    Science.gov (United States)

    Sun, Huihui; Liu, Zhuang; Wu, Chao; Xu, Ping; Wang, Xia

    2016-08-01

    As a well-known toxic pollutant, sulfide is harmful to human health. In this study, a simple and sensitive amperometric inhibitive biosensor was developed for the determination of sulfide in the environment. By immobilizing nanoporous gold (NPG) on glassy carbon electrode (GCE), and encapsulating horseradish peroxidase (HRP) onto NPG, a HRP/NPG/GCE bioelectrode for sulfide detection was successfully constructed based on the inhibition of sulfide on HRP activity with o-Phenylenediamine (OPD) as a substrate. The resulted HRP/NPG/GCE bioelectrode achieved a wide linear range of 0.1–40 μM in sulfide detection with a high sensitivity of 1720 μA mM‑1 cm‑2 and a low detection limit of 0.027 μM. Additionally, the inhibition of sulfide on HRP is competitive inhibition with OPD as a substrate by Michaelis-Menten analysis. Notably, the recovery of HRP activity was quickly achieved by washing the HRP/NPG/GCE bioelectrode using differential pulse voltammetry (DPV) technique in deaerated PBS (50 mM, pH 7.0) for only 60 s. Furthermore, the real sample analysis of sulfide by the HRP/NPG/GCE bioelectrode was achieved. Based on above results, the HRP/NPG/GCE bioelectrode could be a better choice for the real determination of sulfide compared to inhibitive biosensors previously reported.

  4. 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

  5. Hydrogen sulfide intervention in focal cerebral ischemia/reperfusion injury in rats

    Directory of Open Access Journals (Sweden)

    Xin-juan Li

    2015-01-01

    Full Text Available The present study aimed to explore the mechanism underlying the protective effects of hydrogen sulfide against neuronal damage caused by cerebral ischemia/reperfusion. We established the middle cerebral artery occlusion model in rats via the suture method. Ten minutes after middle cerebral artery occlusion, the animals were intraperitoneally injected with hydrogen sulfide donor compound sodium hydrosulfide. Immunofluorescence revealed that the immunoreactivity of P2X 7 in the cerebral cortex and hippocampal CA1 region in rats with cerebral ischemia/reperfusion injury decreased with hydrogen sulfide treatment. Furthermore, treatment of these rats with hydrogen sulfide significantly lowered mortality, the Longa neurological deficit scores, and infarct volume. These results indicate that hydrogen sulfide may be protective in rats with local cerebral ischemia/reperfusion injury by down-regulating the expression of P2X 7 receptors.

  6. Synthesis of rare earth sulfides and their UV-vis absorption spectra

    Institute of Scientific and Technical Information of China (English)

    YUAN Haibin; ZHANG Jianhui; YU Ruijin; SU Qiang

    2009-01-01

    Rare earth sulfides were systematically synthesized via the sulfurization of their commercial oxide powders using CS2 gas to shorten sulfurization time, and their UV-vis absorption spectra were investigated. The appropriate sulfurization conditions were studied. For the rare earth sulfides with the same crystal structure, the sulfurization temperature showed increasing tendency with the decrease of rare earth element atomic radii. The UV-vis absorption spectra of rare earth sulfides did not depend on the crystal structure of rare earth sulfides, but on the 4f electronic structure of rare earth element. The data showed that the optical band gaps of rare earth sulfides were irregular, and the values ranged from 1.65 to 3.75 eV.

  7. Hydrogen sulfide intervention in focal cerebral ischemia/reperfusion injury in rats.

    Science.gov (United States)

    Li, Xin-Juan; Li, Chao-Kun; Wei, Lin-Yu; Lu, Na; Wang, Guo-Hong; Zhao, Hong-Gang; Li, Dong-Liang

    2015-06-01

    The present study aimed to explore the mechanism underlying the protective effects of hydrogen sulfide against neuronal damage caused by cerebral ischemia/reperfusion. We established the middle cerebral artery occlusion model in rats via the suture method. Ten minutes after middle cerebral artery occlusion, the animals were intraperitoneally injected with hydrogen sulfide donor compound sodium hydrosulfide. Immunofluorescence revealed that the immunoreactivity of P2X7 in the cerebral cortex and hippocampal CA1 region in rats with cerebral ischemia/reperfusion injury decreased with hydrogen sulfide treatment. Furthermore, treatment of these rats with hydrogen sulfide significantly lowered mortality, the Longa neurological deficit scores, and infarct volume. These results indicate that hydrogen sulfide may be protective in rats with local cerebral ischemia/reperfusion injury by down-regulating the expression of P2X7 receptors.

  8. Anoxic Transformations of Radiolabeled Hydrogen-Sulfide in Marine and Fresh-Water Sediments

    DEFF Research Database (Denmark)

    ELSGAARD, L.; JØRGENSEN, BB

    1992-01-01

    oxidation to sulfate. Thiosulfate was partly turned over by oxidation or disproportionation and was found to be an intermediate in the (SO4=)-S-35 formation. The results demonstrate that oxidative and reductive sulfur cycling may occur simultaneously in marine and freshwater sediments. When added......Radiolabeled hydrogen sulfide (HS-)-S-35 was used to trace the anoxic sulfur transformations in marine and freshwater sediment slurries. Time course studies consistently showed a rapid (S2O3=)-S-35 formation and a progressive accumulation of (SO4=)-S-35 and thus indicated an anoxic sulfide...... as exogenous oxidant, nitrate (NO3-) stimulated the anoxic sulfide oxidation to sulfate. Ferric iron, added in the form of lepidocrocite (gamma-FeOOH), caused the precipitation of iron sulfides and only partial sulfide oxidation to pyrite and elemental sulfur....

  9. Non-hydrolytic Sol-gel Synthesis of Tin Sulfides

    Science.gov (United States)

    Kaur, Rajvinder

    systematic study was carried out to understand the influence of all reaction variables, which include tin halides, thioethers, solvents, time, temperature, stoichiometry and concentration. Fine tuning of all reaction variables was carried out. The crystallization and phase stability of the as-recovered products was further studied by heat treatments of the samples. A detailed investigation of synthetic variables during NHSG reactions resulted in controlled synthesis of two crystalline tin sulfide polymorphs, SnS and SnS2. A third polymorph, Sn2S3, could be obtained after heat treatments in the temperature range of 400 to 500 °C. Conditions for the targeted synthesis of particles with various sizes and morphologies were established. Samples were characterized by powder X-ray diffraction, electron microscopy in combination with EDS, CHNS analysis and thermo gravimetric/differential thermal analysis.

  10. 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

  11. 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

  12. 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

  13. Synthetic and Mechanistic Studies of Strained Heterocycle Opening Reactions Mediated by Zirconium(IV) Imido Complexes

    OpenAIRE

    Blum, Suzanne A.; Rivera, Vicki A.; Ruck, Rebecca T.; Michael, Forrest E.; Bergman, Robert G.

    2005-01-01

    The reactions of the bis(cyclopentadienyl)(tert-butylimido)zirconium complex (Cp2Zr=N-t-Bu)(THF) (1) with epoxides, aziridines, and episulfides were investigated. Heterocycles without accessible β-hydrogens undergo insertion/protonation of the C–X bond to produce 1,2-amino alcohols (X = O) and 1,2-diamines (X = NR), whereas heterocycles with accessible β-hydrogens undergo elimination/protonation to produce allylic alcohols (X = O) and allylic sulfides (X = S). Mechanistic investigations suppo...

  14. Inhibition of bladder cancer cell proliferation by allyl isothiocyanate (mustard essential oil)

    Energy Technology Data Exchange (ETDEWEB)

    Sávio, André Luiz Ventura, E-mail: savio.alv@gmail.com [UNESP – Universidade Estadual Paulista, Faculdade de Medicina de Botucatu, Departamento de Patologia, Botucatu, SP (Brazil); Nicioli da Silva, Glenda [UFOP – Universidade Federal de Ouro Preto, Escola de Farmácia, Departamento de Análises Clínicas, Ouro Preto, MG (Brazil); Salvadori, Daisy Maria Fávero [UNESP – Universidade Estadual Paulista, Faculdade de Medicina de Botucatu, Departamento de Patologia, Botucatu, SP (Brazil)

    2015-01-15

    Highlights: • AITC inhibits mutant and wild-type TP53 cell proliferation. • Morphological changes and cells debris were observed after AITC treatment in both cells. • BAX and BCL2 expression modulation was observed in wild-type TP53 cells. • BCL2, BAX and ANLN increased and S100P decreased expression was detected in mutated TP53 cells. • AITC effects in gene modulation are dependent TP53 gene status. - Abstract: Natural compounds hold great promise for combating antibiotic resistance, the failure to control some diseases, the emergence of new diseases and the toxicity of some contemporary medical products. Allyl isothiocyanate (AITC), which is abundant in cruciferous vegetables and mustard seeds and is commonly referred to as mustard essential oil, exhibits promising antineoplastic activity against bladder cancer, although its mechanism of action is not fully understood. Therefore, the aim of this study was to investigate the effects of AITC activity on bladder cancer cell lines carrying a wild type (wt; RT4) or mutated (T24) TP53 gene. Morphological changes, cell cycle kinetics and CDK1, SMAD4, BAX, BCL2, ANLN and S100P gene expression were evaluated. In both cell lines, treatment with AITC inhibited cell proliferation (at 62.5, 72.5, 82.5 and 92.5 μM AITC) and induced morphological changes, including scattered and elongated cells and cellular debris. Gene expression profiles revealed increased S100P and BAX and decreased BCL2 expression in RT4 cells following AITC treatment. T24 cells displayed increased BCL2, BAX and ANLN and decreased S100P expression. No changes in SMAD4 and CDK1 expression were observed in either cell line. In conclusion, AITC inhibits cell proliferation independent of TP53 status. However, the mechanism of action of AITC differed in the two cell lines; in RT4 cells, it mainly acted via the classical BAX/BCL2 pathway, while in T24 cells, AITC modulated the activities of ANLN (related to cytokinesis) and S100P. These data confirm

  15. New [Mo(eta3-allyl)(CO)2L3]+ complexes with monodentate or tridentate nitrogen-donor ligands.

    Science.gov (United States)

    Pérez, Julio; Morales, Dolores; Nieto, Sonia; Riera, Lucía; Riera, Víctor; Miguel, Daniel

    2005-03-01

    Cationic complexes [Mo(eta(3)-allyl)(CO)2L3]+ (L3 = either nitrogen-donor tridentate ligand or three monodentate ligands) were prepared in high yield and under mild conditions using as precursors either the triflato complex [Mo(eta(3)-allyl)(OTf)(CO)2(NCMe)2] or the combination of the chloro complex [Mo(eta(3)-allyl)Cl(CO)2(NCMe)2] and the salt NaBAr'(4)(Ar'= 3,5-bis(trifluoromethyl)phenyl). The tridentate ligands employed were 2,2':6',2'-terpyridine (terpy) and cis,cis-1,3,5-cyclohexanetriamine (CHTA), whereas the monodentate ligands imidazole (im) and 3,5-dimethylpyrazole (dmpz) were chosen. In order to stabilize the labile intermediates, an excess of acetonitrile was used in most of the syntheses. However, the pyrazole complex was prepared through a nitrile-free route to avoid reactions at the coordinated nitrile. The solid state structures of [Mo(eta(3)-methallyl)(CO)2(terpy)]OTf (2), [Mo(eta(3)-methallyl)(CO)2(CHTA)]BAr'4 (3), [Mo(eta(3)-methallyl)(CO)2(NCMe)3]BAr'4 (4), [Mo(eta(3)-allyl)(CO)2(im)3]OTf (5) and [Mo(eta(3)-allyl)(CO)2(dmpz)3]BAr'4 (6) were determined by means of single-crystal X-ray diffraction. PMID:15726140

  16. A randomized clinical study assessing the effects of the antioxidants, resveratrol or SG1002, a hydrogen sulfide prodrug, on idiopathic oligoasthenozoospermia

    Institute of Scientific and Technical Information of China (English)

    Arturo Morales Martinez; Luis H. Sordia-Hernández; Juan A. Morales; Martha Merino; Oscar Vidal; Manuel R. García Garza; Otto Valdés

    2015-01-01

    Objective: To determine whether subjects suffering from oligoasthenozoospermia would benefit from antioxidant treatment with resveratrol, a natural-occurring polyphenol, and hydrogen sulfide. Methods: A randomized controlled clinical trial involving 54 men with Oligoasthenozoospermia. We randomly assigned resveratrol (n=18), SG 1002 (n=18), and placebo (n=18) for 75 days. Sperm analysis was performed after treatment. Statistical analysis was made with chi square test. Results: When compared to the placebo treated group, SG1002 treatment led to an increase in sperm concentration (11.18 í 106 vs. 17.01 í 106, P < 0.05), sperm motility (10.06 í 106 vs. 20.06 í 106, P<0.05) and motile forms recovery (0.33 í 106 vs. 1.62 í 106, P<0.05). Resveratrol treatment did not significantly affect any of the parameters. Conclusions: SG1002 may reverse oligoasthenozoospermia. It seems to be more potent antioxidant than resveratrol. This findings need be supported by further clinical investigation.

  17. In vitro study on arsenic sulfide (realgar)-induced apoptosis of retinoic acid susceptible or resistant acute promyelocytic leukemia cell lines

    Institute of Scientific and Technical Information of China (English)

    CHEN Si-yu; LIU Shan-xi; LI Xin-min

    2002-01-01

    Objective: To further understand the possible mechanisms of arsenic sulfide (realgar) in the treatment of acute promyelocytic leukemia (APL). Methods: All-trans retinoic acid (ATRA)-susceptible APL cell line (NB4 cells) and ATRA-resistant APL cell line (MR2 subclone) were used as models in vitro. At various times after incubated with various concentrations of realgar, NB4 and MR2 cells were observed by cell viability, cell proliferation and cell morphology; cell cycle and the expression of Annexin V were assayed by flow cytometry. Results: Cell viability and proliferation of NB4 and MR2 cells were inhibited after the treatment,to some extent, in a dose and time dependent manner. 177-711 μg/L of realgar treated NB4 and MR2 cell presented morphologically some features of apoptotic cells such as intact cell membrane, chromatin condensation and nuclear fragmentation, apoptosis body could be found by electron microscopy as well. Sub-G1 ceils andcell cycle arrest were observed by flow cytometry. The proportion of Annexin V -FITC+/PI cells, which represent apoptotic cells, was up-regulated. Conclusion: Realgar could induce apoptosis of acute promyelocytic leukemia cell despite its susceptibility to retinoic acid in the way that may be different from retinoic acid.

  18. Magmatic sulfides in the porphyritic chondrules of EH enstatite chondrites

    CERN Document Server

    Piani, Laurette; Libourel, Guy; Tissandier, Laurent

    2016-01-01

    The nature and distribution of sulfides within 17 porphyritic chondrules of the Sahara 97096 EH3 enstatite chondrite have been studied by backscattered electron microscopy and electron microprobe in order to investigate the role of gas-melt interactions in the chondrule sulfide formation. Troilite (FeS) is systematically present and is the most abundant sulfide within the EH3 chondrite chondrules. It is found either poikilitically enclosed in low-Ca pyroxenes or scattered within the glassy mesostasis. Oldhamite (CaS) and niningerite [(Mg,Fe,Mn)S] are present in about 60% of the chondrules studied. While oldhamite is preferentially present in the mesostasis, niningerite associated with silica is generally observed in contact with troilite and low-Ca pyroxene. The chondrule mesostases contain high abundances of alkali and volatile elements as well as silica. Our data suggest that most of the sulfides found in EH3 chondrite chondrules are magmatic minerals that formed after the dissolution of S from a volatile-r...

  19. Micelle Mediated Trace Level Sulfide Quantification through Cloud Point Extraction

    Directory of Open Access Journals (Sweden)

    Samrat Devaramani

    2012-01-01

    Full Text Available A simple cloud point extraction protocol has been proposed for the quantification of sulfide at trace level. The method is based on the reduction of iron (III to iron (II by the sulfide and the subsequent complexation of metal ion with nitroso-R salt in alkaline medium. The resulting green-colored complex was extracted through cloud point formation using cationic surfactant, that is, cetylpyridinium chloride, and the obtained surfactant phase was homogenized by ethanol before its absorbance measurement at 710 nm. The reaction variables like metal ion, ligand, surfactant concentration, and medium pH on the cloud point extraction of the metal-ligand complex have been optimized. The interference effect of the common anions and cations was studied. The proposed method has been successfully applied to quantify the trace level sulfide in the leachate samples of the landfill and water samples from bore wells and ponds. The validity of the proposed method has been studied by spiking the samples with known quantities of sulfide as well as comparing with the results obtained by the standard method.

  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. 内蒙古某氧硫混合铜矿选矿试验研究%Study on the Beneficiation of a Sulfide - oxidized Copper Ore in Inner Mongolia

    Institute of Scientific and Technical Information of China (English)

    贾凤梅; 王林祥; 任大鹏

    2012-01-01

    针对内蒙古氧硫混合铜矿高氧化率、高碱性脉石、高含泥量等特点,着重对控泥、强化活化、强化捕收以及浮选流程进行了系统的研究.在硫酸铵、硫化钠的联合作用下,在捕收剂强化捕收作用下,当磨矿细度-0.074 mm至85%时,采用一次粗选、三次扫选、两次精选、中矿顺序返回的闭路流程,取得了铜精矿品位20.65%、铜回收率85.49%的较好技术指标.%In light of the characteristics of a sulfide - oxidized copper ore in Inner Mongolia, such as high oxidation rate, high alkali gangue, and high content of slime, a systematic study was made for the ore on controlling mud, strengthening activation and collecting. Under the combined action of the ammonium sulfate, sodium sulfide and the action of strengthening collecting, when the percentage of the grinding particle less than 0.074 mm was over 85% , copper concentrate of Cu 20. 65% with a recovery of 85.49% was obtained through the closed circuit process of once roughing, three times scavenging, twain cleaning and middlings returned in order.

  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. Enhanced performance of the catalytic conversion of allyl alcohol to 3-hydroxypropionic acid using bimetallic gold catalysts.

    Science.gov (United States)

    Falletta, Ermelinda; Della Pina, Cristina; Rossi, Michele; He, Qian; Kiely, Christopher J; Hutchings, Graham J

    2011-01-01

    One of the strategic building blocks in organic synthesis is 3-hydroxypropionic acid, which is particularly important for the manufacture of high performance polymers. However, to date, despite many attempts using both biological and chemical routes, no large scale effective process for manufacturing 3-hydroxypropionic acid has been developed. One potentially useful starting point is from allyl alcohol, as this can be obtained in principle from the dehydration of glycerol, thereby presenting a bio-renewable green pathway to this important building block. The catalytic transformation of allyl alcohol to 3-hydroxypropionic acid presents interesting challenges in catalyst design, particularly with respect to the control of selectivity among the products that can be expected, as acrylic acid, acrolein and glyceric acid can also be formed. In this paper, we present a novel eco-sustainable catalytic pathway leading to 3-hydroxypropionic acid, which highlights the outstanding potential of gold-based and bimetallic catalysts in the aerobic oxidation of allyl alcohol. PMID:22455056

  5. Reaction of zearalenone and α-zearalenol with allyl isothiocyanate, characterization of reaction products, their bioaccessibility and bioavailability in vitro.

    Science.gov (United States)

    Bordin, K; Saladino, F; Fernández-Blanco, C; Ruiz, M J; Mañes, J; Fernández-Franzón, M; Meca, G; Luciano, F B

    2017-02-15

    This study investigates the reduction of zearalenone (ZEA) and α-zearalenol (α-ZOL) on a solution model using allyl isothiocyanate (AITC) and also determines the bioaccessibility and bioavailability of the reaction products isolated and identified by MS-LIT. Mycotoxin reductions were dose-dependent, and ZEA levels decreased more than α-ZOL, ranging from 0.2 to 96.9% and 0 to 89.5% respectively, with no difference (p⩽0.05) between pH 4 and 7. Overall, simulated gastric bioaccessibility was higher than duodenal bioaccessibility for both mycotoxins and mycotoxin-AITC conjugates, with duodenal fractions representing ⩾63.5% of the original concentration. Simulated bioavailability of reaction products (α-ZOL/ZEA-AITC) were lower than 42.13%, but significantly higher than the original mycotoxins. The cytotoxicity of α-ZOL and ZEA in Caco-2/TC7 cells was also evaluated, with toxic effects observed at higher levels than 75μM. Further studies should be performed to evaluate the toxicity and estrogenic effect of α-ZOL/ZEA-AITC. PMID:27664682

  6. Synthesis, structural characterization and biological activities of organotin(IV) complexes with 5-allyl-2-hydroxy-3-methoxybenzaldehyde-4-thiosemicarbazone

    Indian Academy of Sciences (India)

    Rosenani A Haque; M A Salam

    2015-09-01

    The organotin(IV) complexes [MeSnCl(L)] (2), [BuSnCl(L)] (3), [PhSnCl(L)] (4) and [Me2Sn(L)] (5) were synthesized by reacting organotin(IV) chloride(s) with 5-allyl-2-hydroxy-3-methoxybenzaldehyde- 4-thiosemicarbazone [H2L], (1)] in presence of KOH in 1:2:1 molar ratio (metal salt: base:ligand). All the complexes have been characterized by elemental analyses, UV-Vis, FT-IR, 1H, 13C and 119Sn NMR spectral studies. The molecular structure of complex 5 has been confirmed by single crystal X-ray diffraction analysis. The ligand, H2L coordinates to Sn(IV) in thiolate form through phenoxide-O, azomethine-N and thiolate-S atoms. The C-Sn-C angle measured from coupling constant 1 (119Sn, 13C) for dimethyltin(IV) complex 5 is 123.4°. The 2 (119Sn, 1H) coupling constant values for complex 2 and 5 are 72.4 and 76.3 Hz, respectively. Proposed geometry for five coordinated Sn(IV) atom is a strongly distorted trigonal bipyramid. Biological studies were preformed in vitro against four bacterial strains which have shown better activities and potential as antibacterial agents.

  7. Polymer-Supported Chiral Monodentate Phosphoramidites in Palladium-Catalyzed Allylic Alkylation Reactions

    Institute of Scientific and Technical Information of China (English)

    JIANG,Zhi-Dong; MENG,Zhao-Hai

    2007-01-01

    A new and simple method for immobilization of monodentate chiral ligand on the cheap resin has been developed.A series of resin-immobilized phosphoramidite ligands based on BINOL and TADDOL backbones have been synthesized and characterized with gel-phase NMR.The immobilized ligands have been applied to the Pd-catalyzed asymmetric allylic alkylation of 1,3-diphenyl-2-propenyl acetate.Among four ligands,the supported bulky monodentate phosphoramidite ligand based on TADDOL backbone afforded the chiral product with ee up to 65%;moreover,this ligand could be recycled for 3 times without substantial decrease of the conversion and ee.

  8. Synthesis of Aminophosphine Ligands with Binaphthyl Backbones for Silver(I)-catalyzed Enantioselective Allylation of Benzaldehyde

    Institute of Scientific and Technical Information of China (English)

    WANG,Yi(王以); JI,Bao-Ming(吉保明); DING,Kui-Ling(丁奎岭)

    2002-01-01

    A series of aminophosphine ligands was synthesized from 2amino-2′-hydroxy-1,1′-binaphthyl (NOBIN). Their asymmetric induction efficiency was examined for silver(I)catalyzed enantioselective allylation reaction of benzaldehyde with allyltributyltin.Under the optimized reaction conditions,quantitative yield as well as moderate ee value (54.5% ee)of product was achieved by the catalysis with silver(I)/3 complex. The effects of the binaphthyl backbone and the substituted situated at chelating N, Patoms on enantioselectivity of the reaction were also discussed.

  9. Unusual selectivity-determining factors in the phosphine-free Heck arylation of allyl ethers

    DEFF Research Database (Denmark)

    Ambrogio, I.; Fabrizi, G.; Cacchi, S.;

    2008-01-01

    The Heck reaction of aryl iodides and bromides with allyl ethers has been investigated. Using phosphinefree Pd(OAc)(2) in DNIF at 90 degrees C in the presence of Bu4NOAc, the reaction gave cinnamyl derivatives, usually in good to high yields, with a wide range of aryl halides. The reaction tolera...... for cinnamyl ether over enol ether products. Interestingly, it was found that the product selectivity does not arise from competing beta-hydride eliminations but rather from a competition between beta-elimination and hindered single-bond rotation in the initial carbopalladation product....

  10. Non-thermal plasma destruction of allyl alcohol in waste gas: kinetics and modelling

    Science.gov (United States)

    DeVisscher, A.; Dewulf, J.; Van Durme, J.; Leys, C.; Morent, R.; Van Langenhove, H.

    2008-02-01

    Non-thermal plasma treatment is a promising technique for the destruction of volatile organic compounds in waste gas. A relatively unexplored technique is the atmospheric negative dc multi-pin-to-plate glow discharge. This paper reports experimental results of allyl alcohol degradation and ozone production in this type of plasma. A new model was developed to describe these processes quantitatively. The model contains a detailed chemical degradation scheme, and describes the physics of the plasma by assuming that the fraction of electrons that takes part in chemical reactions is an exponential function of the reduced field. The model captured the experimental kinetic data to less than 2 ppm standard deviation.

  11. Lanthanum triflate triggered synthesis of tetrahydroquinazolinone derivatives of N-allyl quinolone and their biological assessment

    Directory of Open Access Journals (Sweden)

    Jardosh Hardik H.

    2012-01-01

    Full Text Available A series of 24 derivatives of tetrahydroquinazolinone has been synthesized by one-pot cyclocondensation reaction of N-allyl quinolones, cyclic β-diketones and (thiourea/N-phenylthiourea in presence of lanthanum triflate catalyst. This methodology allowed us to achieve the products in excellent yield by stirring at room temperature. All the synthesized compounds were investigated against a representative panel of pathogenic strains using broth microdilution MIC (minimum inhibitory concentration method for their in vitro antimicrobial activity. Amongst these sets of heterocyclic compounds 5h, 6b, 6h, 5f, 5l, 5n and 6g found to have admirable activity.

  12. Nano-Aluminum Powder Mediated Allylation of Carbonyl Compounds in Aqueous Media

    Institute of Scientific and Technical Information of China (English)

    YUAN Shi-Zhen; LIU Jin

    2008-01-01

    A new and effective Barbier-Grignard allylation of aldehydes or ketones has been carried out with nano-aluminum powder in aqueous 0.1 mol·L-1 NH4Cl (aq.) under an atmosphere of nitrogen. Aromatic carbonyl compounds gave homoallylic alcohols in good yields. The effectiveness of reaction was strongly influenced by the steric environment surrounding the carbonyl group. Aliphatic carbonyl compounds proceeded in low yields. The dominant stereoisomer was an erythro-isomer when an ortho-hydroxyl carbonyl compound was reacted under such a reaction condition.

  13. Non-thermal plasma destruction of allyl alcohol in waste gas: kinetics and modelling

    International Nuclear Information System (INIS)

    Non-thermal plasma treatment is a promising technique for the destruction of volatile organic compounds in waste gas. A relatively unexplored technique is the atmospheric negative dc multi-pin-to-plate glow discharge. This paper reports experimental results of allyl alcohol degradation and ozone production in this type of plasma. A new model was developed to describe these processes quantitatively. The model contains a detailed chemical degradation scheme, and describes the physics of the plasma by assuming that the fraction of electrons that takes part in chemical reactions is an exponential function of the reduced field. The model captured the experimental kinetic data to less than 2 ppm standard deviation

  14. Organocatalytic Enantioselective Nucleophilic Alkynylation of Allyl Fluorides Affording Chiral Skipped Ene-ynes.

    Science.gov (United States)

    Okusu, Satoshi; Okazaki, Hiroki; Tokunaga, Etsuko; Soloshonok, Vadim A; Shibata, Norio

    2016-06-01

    Asymmetric methods for preparation of chiral alkynyl-containing compounds are in extremely high demand in many sectors of chemical research. In this work, we report the discovery of a general organocatalytic enantioselective alkynylation based on the idea of Si/F activation of the allylic C-F bond. This approach features reasonably broad substrate scope, functional group tolerance, and relatively neutral, mild, and operationally convenient reaction conditions; all of which bode well for the synthetic value of the discovered method. In particular, this method provides unique chiral skipped 1,4-ene-ynes having two kinds of versatile functional groups. PMID:27111713

  15. Combined experimental and theoretical mechanistic investigation of the Barbier allylation in aqueous media

    DEFF Research Database (Denmark)

    Dam, Johan Hygum; Fristrup, Peter; Madsen, Robert

    2008-01-01

    -determining step. For Zn, In, Sn, Sb, and Bi, an inverse secondary kinetic isotope effect was found (k(H)/k(D) = 0.75-0.95), which was compatible with the formation of a discrete organometallic species prior to allylation via a closed six-membered transition state. With Mg, a significantly larger build...... with the effect of solvent described by a polarized continuum model. The calculated secondary deuterium isotope effects based on this mechanism were found to be in good agreement with experimental values, thus adding further support to this mechanistic scenario....

  16. Direct asymmetric allylic alkenylation of N-itaconimides with Morita-Baylis-Hillman carbonates

    KAUST Repository

    Yang, Wenguo

    2012-08-03

    The asymmetric allylic alkenylation of Morita-Baylis-Hillman (MBH) carbonates with N-itaconimides as nucleophiles has been developed using a commercially available Cinchona alkaloid catalyst. A variety of multifunctional chiral α-methylene-β-maleimide esters were attained in moderate to excellent yields (up to 99%) and good to excellent enantioselectivities (up to 91% ee). The origin of the regio- and stereoselectivity was verified by DFT methods. Calculated geometries and relative energies of various transition states strongly support the observed regio- and enantioselectivity. © 2012 American Chemical Society.

  17. Synthesis of Aryl Allyl Ether in the Recyclable Ionic Liquid [bmim]PF6

    Institute of Scientific and Technical Information of China (English)

    Zhou Mei-Yun; Li Yi-Qun; Xu Xin-Ming

    2004-01-01

    Ionic liquids, especially imidazonium salts, have recently gained recognition as possible environmentally benign alternative chemical process solvents. This is mainly due to their nonvolatile nature, insolubility in some solvents as well as their ability to dissolve a wide range of organic and inorganic materials, allowing the ionic liquids easy recovery and recycling. Examples of their application in organic reactions have been summarized in a number of recent review articles.1Aryl allyl ether is very useful intermediate in organic synthesis. The Williamson reaction is a well knows method for the preparation ethers. However, the reaction of alkylating agents with the phenoxide ions was conventionally carried out in the organic solvents. The usual solvents for this type of reaction are DCM, 2 DMSO, 3 DMF, 4 CH3CN5 etc. With the current desire to avoid the use of organic molecular solvents in organic synthesis, we decide to investigate the use of the ionic liquid for the alternative solvent for the Williamson reaction to prepare the aryl allyl ethers. The ionic liquid employed here was the moisture stable 1-butyl-3-methylimidazolium hexafluorophosphate [bmim]PF6.6 The ionic liquid is non-volatile, thermally stable, and depending on the anion, can present low immiscible with water,alkanes and dialky ethers. We have now found that aryl allyl ethers can have been obtained from various phenols and allyl bromide in the presence of potassium hydroxide in [bmim]PF6 as a replacement for classical organic solvents in the ambient temperature. The results are shown in Scheme 1.The reaction were carried out by simple mixing the phenolwith the ally bromide and potassium hydroxide in [bmim]PF6 and stirred at room temperature for 4h. The results are summarized in Table 1.In conclusion, Williamson reaction can be successfully conducted in ionic liquid [bmim]PF6 with a number of advantages: the procedure is simple, the reaction condition is mild and the yields are excellent

  18. 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.

  19. 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.

  20. Electrogenerative leaching of nickel sulfide concentrate with ferric chloride

    Institute of Scientific and Technical Information of China (English)

    王少芬; 方正; 王云燕; 陈阳国

    2004-01-01

    In order to utilize the chemical energy in hydrometallurgical process of sulfide minerals reasonably and to simplify the purifying process, the electrogenerative process was applied and a dual cell system was introduced to investigate FeCl3 leaching of nickel sulfide concentrate. Some factors influencing the electrogenerative leaching, such as electrode structure, temperature and solution concentration were studied. The results show that a certain quantity of electrical energy accompanied with the leached products can be acquired in the electrogenerative leaching process.The output current and power increase with the addition of acetylene black to the electrode. Varying the components of electrode just affects the polarization degree of anode. Increasing FeCl3 concentration results in a sharp increase in the output of the leaching cell when c(FeCl3) is less than 0.1 mol/L. The optimum value of NaCl concentration for electrogenerative leaching nickel sulfide concentrate with FeCl3 is 3.0 mol/L. Temperature influences electrogenerative leaching by affecting anodic and cathodic polarization simultaneously. The apparent activation energy is determined to be 34.63 kJ/mol in the range of 298 K to 322 K. The leaching rate of Ni2+ is 29.3% after FeCl3 electrogenerative leaching of nickel sulfide concentrate for 620 min with a filter bag electrode.

  1. Selective Sulfidation of Lead Smelter Slag with Sulfur

    Science.gov (United States)

    Han, Junwei; Liu, Wei; Wang, Dawei; Jiao, Fen; Qin, Wenqing

    2016-02-01

    The selective sulfidation of lead smelter slag with sulfur was studied. The effects of temperature, sulfur dosage, carbon, and Na salts additions were investigated based on thermodynamic calculation. The results indicated that more than 96 pct of zinc in the slag could be converted into sulfides. Increasing temperature, sulfur dosage, or Na salts dosage was conducive to the sulfidation of the zinc oxides in the slag. High temperature and excess Na salts would result in the more consumption of carbon and sulfur. Carbon addition not only promoted the selective sulfidation but reduced the sulfur dosage and eliminated the generation of SO2. Iron oxides had a buffering role on the sulfur efficient utilization. The transformation of sphalerite to wurtzite was feasible under reducing condition at high temperature, especially above 1273 K (1000 °C). The growth of ZnS particles largely depended upon the roasting temperature. They were significantly increased when the temperature was above 1273 K (1000 °C), which was attributed to the formation of a liquid phase.

  2. Sulfide toxicity kinetics of a uasb reactor

    Directory of Open Access Journals (Sweden)

    D. R. Paula Jr.

    2009-12-01

    Full Text Available The effect of sulfide toxicity on kinetic parameters of anaerobic organic matter removal in a UASB (up-flow anaerobic sludge blanket reactor is presented. Two lab-scale UASB reactors (10.5 L were operated continuously during 12 months. The reactors were fed with synthetic wastes prepared daily using glucose, ammonium acetate, methanol and nutrient solution. One of the reactors also received increasing concentrations of sodium sulfide. For both reactors, the flow rate of 16 L.d-1 was held constant throughout the experiment, corresponding to a hydraulic retention time of 15.6 hours. The classic model for non-competitive sulfide inhibition was applied to the experimental data for determining the overall kinetic parameter of specific substrate utilization (q and the sulfide inhibition coefficient (Ki. The application of the kinetic parameters determined allows prediction of methanogenesis inhibition and thus the adoption of operating parameters to minimize sulfide toxicity in UASB reactors.

  3. [3,3]-sigmatropic rearrangements of fluorinated allyl (Thio)cyanates - a tool for the synthesis of fluorinated (Thio)ureas.

    Science.gov (United States)

    Ramb, Daniel C; Kost, Lisa; Haufe, Günter

    2014-01-01

    The first (thio)cyanate to iso(thio)cyanate rearrangements based on 2-fluoroallylic alcohols are presented. Long-chain 2-fluoroallylic alcohols were converted to corresponding N-unsubstituted carbamates by treatment with trichloroacetyl isocyanate. Dehydration using trifluoroacetic anhydride in the presence of triethylamine formed intermediate allylic cyanates, which immediately underwent sigmatropic rearrangement to fluorinated allyl isocyanates. Without isolation the latter delivered fluorinated ureas by addition of amines. The thiocyanate to isothiocyanate rearrangements started from the same fluorinated allylic alcohols, which were first converted to mesylates. Heating in THF with potassium thiocyanate led to fluorinated allyl isothiocyanates, via [3,3]-sigmatropic rearrangement of intermediate allyl thiocyanates. The formed products were further reacted with amines to fluorinated thioureas.

  4. Replacive sulfide formation in anhydrite chimneys from the Pacmanus hydrothermal field, Papua New Guinea

    Science.gov (United States)

    Los, Catharina; Bach, Wolfgang; Plümper, Oliver

    2016-04-01

    Hydrothermal flow within the oceanic crust is an important process for the exchange of energy and mass between the lithosphere, hydrosphere and biosphere. Infiltrated seawater heats up and interacts with wall rock, causing mineral replacement reactions. These play a large role in the formation of ore deposits; at the discharge zone, a hot, acidic and metal-rich potential ore fluid exits the crust. It mixes with seawater and forms chimneys, built up of sulfate minerals such as anhydrite (CaSO4), which are subsequently replaced by sulfide minerals. Sulfide formation is related to fluid pathways, defined by cracks and pores in the sulfate chimney. Over time, these systems might develop into massive sulfide deposits. The big question is then: how is sulfate-sulfide replacement related to the evolution of rock porosity? To address this question, sulfide-bearing anhydrite chimneys from the Pacmanus hydrothermal field (Manus Basin, Papua New Guinea) were studied using X-ray tomography, EMPA, FIB-SEM and -TEM. The apparently massive anhydrite turns out highly porous on the micro scale, with sulfide minerals in anhydrite cleavage planes and along grain boundaries. The size of the sulfide grains relates to the pores they grew into, suggesting a tight coupling between dissolution (porosity generation) and growth of replacive minerals. Some of the sulfide grains are hollow and apparently used the dissolving anhydrite as a substrate to start growth in a pore. Another mode of sulfide development is aggregates of euhedral pyrite cores surrounded by colloform chalcopyrite. This occurrence implies that fluid pathways have remained open for some time to allow several stages of precipitation during fluid evolution. To start the replacement and to keep it going, porosity generation is crucial. Our samples show that dissolution of anhydrite occurred along pathways where fluid could enter, such as cleavage planes and grain boundaries. It appears that fluids ascending within the inner

  5. The effect of sulfide dissolved in silicate melts on enhancing the solubility of the Highly Siderophile Elements

    Science.gov (United States)

    O'Neill, H. S.

    2015-12-01

    There are large inconsistencies among experimental studies of Highly Siderophile Element (HSE) partitioning relations between silicates and metal or sulfide phases, which has usually been attributed to "micronuggets", a general term for sub-optical (approximately HSE sulfide-melt/silicate-melt partition coefficients, where results range over several orders of magnitude. Moreover, nearly all the reported results of directly determined sulfide-melt/silicate-melt partition coefficients are considerably lower than values calculated by combining metal/silicate-melt with metal/sulfide-melt partition coefficients. This discrepancy has been attributed to large effects of S dissolved as sulfide in the silicate melts on HSE solubilities. As such large effects are not expected from the thermodynamic modeling of sulfide solubilities in silicate melts, it has been proposed that HSEs dissolve in sulfide-containing silicate melts by forming HSE-S complexes. This idea has been tested by experiments that compare the solubilities of Ir, Re and Ru in a high-TiO2 silicate melt both with and without dissolved sulfide at 1400 to 1600ºC at atmospheric pressure. The high TiO2 suppresses micronuggets. Experiments were analysed by LA-ICP-MS, with detection limits approaching 2 ppb. For Ir, the results show that at fO2 low enough to enable measurable sulfide in the melt, the presence of the sulfide just raises the level of dissolved Ir above detection limits. These results suggest a fairly large influence of the sulfide, but are not quantitative. By contrast, the experiments on Ru and Re clearly show only a modest effect of dissolved sulfide.

  6. Synthesis and structural characterization of magnetic cadmium sulfide-cobalt ferrite nanocomposite, and study of its activity for dyes degradation under ultrasound

    Science.gov (United States)

    Farhadi, Saeed; Siadatnasab, Firouzeh

    2016-11-01

    Cadmium sulfide-cobalt ferrite (CdS/CFO) nanocomposite was easily synthesized by one-step hydrothermal decomposition of cadmium diethyldithiocarbamate complex on the CoFe2O4 nanoparticles at 200 °C. Spectroscopic techniques of powder X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), UV-visible spectroscopy, field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET), and magnetic measurements were applied for characterizing the structure and morphology of the product. The results of FT-IR, XRD and EDX indicated that the CdS/CFO was highly pure. SEM and TEM results revealed that the CdS/CFO nanocomposite was formed from nearly uniform and sphere-like nanoparticles with the size of approximately 20 nm. The UV-vis absorption spectrum of the CdS/CFO nanocomposite showed the band gap of 2.21 eV, which made it suitable for sono-/photo catalytic purposes. By using the obtained CdS/CFO nanocomposite, an ultrasound-assisted advanced oxidation process (AOP) has been developed for catalytic degradation of methylene blue (MB), Rhodamine B (RhB), and methyl orange (MO)) in the presence of H2O2 as a green oxidant. CdS/CFO nanocomposite exhibited excellent sonocatalytic activity, so that, dyes were completely degraded in less than 10 min. The influences of crucial factors such as the H2O2 amount and catalyst dosage on the degradation efficiency were evaluated. The as-prepared CdS/CFO nanocomposite exhibited higher catalytic activity than pure CdS nanoparticles. Moreover, the magnetic property of CoFe2O4 made the nanocomposite recyclable.

  7. From a Sequential to a Concurrent Reaction in Aqueous Medium: Ruthenium-Catalyzed Allylic Alcohol Isomerization and Asymmetric Bioreduction.

    Science.gov (United States)

    Ríos-Lombardía, Nicolás; Vidal, Cristian; Liardo, Elisa; Morís, Francisco; García-Álvarez, Joaquín; González-Sabín, Javier

    2016-07-18

    The ruthenium-catalyzed redox isomerization of allylic alcohols was successfully coupled with the enantioselective enzymatic ketone reduction (mediated by KREDs) in a concurrent process in aqueous medium. The overall transformation, formally the asymmetric reduction of allylic alcohols, took place with excellent conversions and enantioselectivities, under mild reaction conditions, employing commercially and readily available catalytic systems, and without external coenzymes or cofactors. Optimization resulted in a multistep approach and a genuine cascade reaction where the metal catalyst and biocatalyst coexist from the beginning. PMID:27258838

  8. Iodine-Catalyzed Decarboxylative Amidation of β,γ-Unsaturated Carboxylic Acids with Chloramine Salts Leading to Allylic Amides.

    Science.gov (United States)

    Kiyokawa, Kensuke; Kojima, Takumi; Hishikawa, Yusuke; Minakata, Satoshi

    2015-10-26

    The iodine-catalyzed decarboxylative amidation of β,γ-unsaturated carboxylic acids with chloramine salts is described. This method enables the regioselective synthesis of allylic amides from various types of β,γ-unsaturated carboxylic acids containing substituents at the α- and β-positions. In the reaction, N-iodo-N-chloroamides, generated by the reaction of a chloramine salt with I2 , function as a key active species. The reaction provides an attractive alternative to existing methods for the synthesis of useful secondary allylic amine derivatives. PMID:26493878

  9. Computational insight into complex structures of thorium coordination with N, N'- bis(3-allyl salicylidene)-o-phenylenediamine.

    Science.gov (United States)

    Lan, Wenbo; Gao, Sha; Lin, Ying-Wu; Liao, Lifu; Wang, Xiaofeng; Nie, Changming

    2016-09-01

    Theoretical calculations on the structure of Th(IV) complex containing N, N'- bis(3-allyl salicylidene)-o-phenylenediamine (BASPDA) were performed using density functional theory (DFT) at the B3LYP/6-311G** level. The geometrical structural parameters and infrared spectra results of the Th(BASPDA)2 from the calculation were compared with the parallel dislocated structure (PDS) obtained in laboratory. The calculated structural parameters were in good agreement with the experimental results. In addition, based on the calculations, a stereoisomer SFS (staggered finger " + " structure) of the Th(BASPDA)2 complex was forecasted by the analysis of a comprehensive method. The charge distribution, structural parameters, bond order indices, spectral properties and thermodynamic properties as well as the molecular orbitals of the two possible crystal structures of Th(BASPDA)2 were also systematically studied. It was expected that this work could provide insightful information for understanding the properties of Th (BASPDA)2 complex at the molecular level.

  10. Influence of the antimicrobial compound allyl isothiocyanate against the Aspergillus parasiticus growth and its aflatoxins production in pizza crust.

    Science.gov (United States)

    Quiles, Juan M; Manyes, Lara; Luciano, Fernando; Mañes, Jordi; Meca, Giuseppe

    2015-09-01

    Aflatoxins (AFs) are secondary metabolites produced by different species of Aspergillus, such as Aspergillus flavus and Aspergillus parasiticus, which possess mutagenic, teratogenic and carcinogenic activities in humans. In this study, active packaging devices containing allyl isothiocyanate (AITC) or oriental mustard flour (OMF) + water were tested to inhibit the growth of A. parasiticus and AFs production in fresh pizza crust after 30 d. The antimicrobial and anti-aflatoxin activities were compared to a control group (no antimicrobial treatment) and to a group added with commercial preservatives (sorbic acid + sodium propionate). A. parasiticus growth was only inhibited after 30 d by AITC in filter paper at 5 μL/L and 10 μL/L, AITC sachet at 5 μL/L and 10 μL/L and OMF sachet at 850 mg + 850 μL of water. However, AFs production was inhibited by all antimicrobial treatments in a dose-dependent manner. More importantly, AITC in a filter paper at 10 μL/L, AITC sachet at 10 μL/L, OMF sachet at 850 mg + 850 μL of water and sorbic acid + sodium propionate at 0.5-2.0 g/Kg completely inhibited AFs formation. The use of AITC in active packaging devices could be a natural alternative to avoid the growth of mycotoxinogenic fungi in refrigerated bakery products in substitution of common commercial preservatives.

  11. Statistic evaluation of cysteine and allyl alcohol as additives for Cu-Zn coatings from citrate baths

    Directory of Open Access Journals (Sweden)

    Julyana Ribeiro Garcia

    2013-04-01

    Full Text Available In the present work, cysteine and allyl alcohol were added to citrate baths as additives to Cu-Zn coatings on steel substrates. In order to verify the effects of the deposition parameters (current density, mechanical stirring speed, and additives on the coating composition, electrochemical behavior, morphology, and microstructure properties of Cu-Zn coatings, the electrodeposition of the alloy was carried out using an experimental composite design 2³, in which these parameters were considered the entry variables and the measured properties were the response variables. The confidence level was 95% and the results were shown as response surface diagrams. It was possible to verify that the current density affected the zinc content in the coating, while the coating produced from cysteine-contained bath presented the worse anticorrosive performance. In a general way, it was possible to observe that the studied parameters affected the morphology, grain size, and the electrochemical behavior of these coatings, although only a few response variables were statistically influenced by them.

  12. Statistic evaluation of cysteine and allyl alcohol as additives for Cu-Zn coatings from citrate baths

    Directory of Open Access Journals (Sweden)

    Julyana Ribeiro Garcia

    2012-01-01

    Full Text Available In the present work, cysteine and allyl alcohol were added to citrate baths as additives to Cu-Zn coatings on steel substrates. In order to verify the effects of the deposition parameters (current density, mechanical stirring speed, and additives on the coating composition, electrochemical behavior, morphology, and microstructure properties of Cu-Zn coatings, the electrodeposition of the alloy was carried out using an experimental composite design 2³, in which these parameters were considered the entry variables and the measured properties were the response variables. The confidence level was 95% and the results were shown as response surface diagrams. It was possible to verify that the current density affected the zinc content in the coating, while the coating produced from cysteine-contained bath presented the worse anticorrosive performance. In a general way, it was possible to observe that the studied parameters affected the morphology, grain size, and the electrochemical behavior of these coatings, although only a few response variables were statistically influenced by them.

  13. Mesoporous sol-gel WO{sub 3} thin films via poly(styrene-co-allyl-alcohol) copolymer templates

    Energy Technology Data Exchange (ETDEWEB)

    Ozkan Zayim, Esra [Department of Physics, Faculty of Science and Letters, Istanbul Technical University, Maslak, Istanbul 80626 (Turkey); Liu, Ping; Lee, Se-Hee; Tracy, C. Edwin; Pitts, J. Roland; Deb, Satyen K. [National Renewable Energy Laboratory, Golden, CO 80401 (United States); Turner, John A.

    2003-12-01

    In this study a copolymer poly(styrene-co-allyl-alcohol), [-CH{sub 2}CH(C{sub 6}H{sub 5})-]{sub x}[-CH{sub 2}CH-(CH{sub 2}OH)-]{sub y} has been employed as a novel template in a sol-gel synthesis process to direct the formation of mesoporous tungsten oxide. The copolymer, due to its rigid hydrophobic block of polystyrene, is a more effective surfactant in an alcohol solution than polypropylene oxide-polyethylene oxide based compounds. The films have been prepared by a spin-coating technique from an ethanol solution of tungsten hexachloride. At room temperature, ultraviolet illumination method has been found to be very suitable for removing the polymer template, leading to the formation of a high-quality mesoporous structure. The electrochromic and optical properties of the mesoporous films are described and compared to standard sol-gel tungsten oxide films. Mesoporous materials exhibit superior high-rate ion-insertion performance when used as electrochromic layers.

  14. Structure formation of soil dispersions in the presence of polyelectrolytes on the basis of allyl alcohol and acryl acid derivatives

    Directory of Open Access Journals (Sweden)

    Amankait Asanov

    2015-09-01

    Full Text Available Some changes of structural composition and surface properties of soil dispersions in the presence of polyelectrolytes, based on allyl alcohol and acryl acid derivatives, have been studied. The results show, that the changes in the structure of soil dispersions composition are connected with the added concentration and pH value, that depend on mole ratio and nature of functional groups, as well as on the nature of counterions and concomitant electrolytes, changing with the conditions of polymer analogous conversion and neutralization reaction. Experimental data show, that the change in the conformational state and the length of the macromolecule has a significant impact on the structure-forming effect and the amount of polyelectrolyte, needed to achieve the same degree of structure-forming effect of soil dispersions. The causes for the revealed reasons are shown on the basis of the results of the experiment. Along with this, it was found that particular changes of structural composition and surface properties of the soil dispersions depend on the type and concentration of the added polyelectrolyte.

  15. Influence of the antimicrobial compound allyl isothiocyanate against the Aspergillus parasiticus growth and its aflatoxins production in pizza crust.

    Science.gov (United States)

    Quiles, Juan M; Manyes, Lara; Luciano, Fernando; Mañes, Jordi; Meca, Giuseppe

    2015-09-01

    Aflatoxins (AFs) are secondary metabolites produced by different species of Aspergillus, such as Aspergillus flavus and Aspergillus parasiticus, which possess mutagenic, teratogenic and carcinogenic activities in humans. In this study, active packaging devices containing allyl isothiocyanate (AITC) or oriental mustard flour (OMF) + water were tested to inhibit the growth of A. parasiticus and AFs production in fresh pizza crust after 30 d. The antimicrobial and anti-aflatoxin activities were compared to a control group (no antimicrobial treatment) and to a group added with commercial preservatives (sorbic acid + sodium propionate). A. parasiticus growth was only inhibited after 30 d by AITC in filter paper at 5 μL/L and 10 μL/L, AITC sachet at 5 μL/L and 10 μL/L and OMF sachet at 850 mg + 850 μL of water. However, AFs production was inhibited by all antimicrobial treatments in a dose-dependent manner. More importantly, AITC in a filter paper at 10 μL/L, AITC sachet at 10 μL/L, OMF sachet at 850 mg + 850 μL of water and sorbic acid + sodium propionate at 0.5-2.0 g/Kg completely inhibited AFs formation. The use of AITC in active packaging devices could be a natural alternative to avoid the growth of mycotoxinogenic fungi in refrigerated bakery products in substitution of common commercial preservatives. PMID:26146190

  16. Feasibility of sulfide control in sewers by reuse of iron rich drinking water treatment sludge.

    Science.gov (United States)

    Sun, Jing; Pikaar, Ilje; Sharma, Keshab Raj; Keller, Jürg; Yuan, Zhiguo

    2015-03-15

    Dosage of iron salt is the most commonly used method for sulfide control in sewer networks but incurs high chemical costs. In this study, we experimentally investigate the feasibility of using iron rich drinking water treatment sludge for sulfide control in sewers. A lab-scale rising main sewer biofilm reactor was used. The sulfide concentration in the effluent decreased from 15.5 to 19.8 mgS/L (without dosing) to below 0.7-2.3 mgS/L at a sludge dosing rate achieving an iron to total dissolved inorganic sulfur molar ratio (Fe:S) of 1:1, with further removal of sulfide possible by prolonging the reaction time. In fact, batch tests revealed an Fe consumption to sulfide removal ratio of 0.5 ± 0.02 (mole:mole), suggesting the possible occurrence of other reactions involving the removal of sulfide. Modelling revealed that the reaction between iron in sludge and sulfide has reaction orders of 0.65 ± 0.01 and 0.77 ± 0.02 with respect to the Fe and sulfide concentrations, respectively. The addition of sludge slightly increased the total chemical oxidation demand (tCOD) concentration (by approximately 12%) as expected, but decreased the soluble chemical oxidation demand (sCOD) concentration and methane formation by 7% and 20%, respectively. Some phosphate removal (13%) was also observed at the sludge dosing rate of 1:1 (Fe:S), which is beneficial to nutrient removal from the wastewater. Overall, this study suggests that dosing iron-rich drinking water sludge to sewers could be an effective strategy for sulfide removal in sewer systems, which would also reduce the sludge disposal costs for drinking water treatment works. However, its potential side-effects on sewer sedimentation and on the wastewater treatment plant effluent remain to be investigated. PMID:25616115

  17. Sulfidation Roasting of Hemimorphite with Pyrite for the Enrichment of Zn and Pb

    Science.gov (United States)

    Min, Xiao-Bo; Xue, Ke; Ke, Yong; Zhou, Bo-Sheng; Li, Yang-Wen-Jun; Wang, Qing-Wei

    2016-09-01

    With the increasing consumption of zinc and the depletion of zinc sulfide ores, the exploitation of low-grade zinc oxide ores may be important for the sustainability of the zinc industry. Hemimorphite, a zinc hydroxyl silicate hydrate, is a significant source of Zn and Pb. It is difficult to obtain Zn and Pb from the hemimorphite using traditional technology. In this work, for the first time, sulfidation roasting of hemimorphite with pyrite was studied for the enrichment of Zn and Pb by a flotation process. Four stages of sulfidation roasting were determined based on x-ray diffraction and thermogravimetry analysis. Then, the effects of sulfidation temperature, pyrite dosage and reaction time on the sulfidation percentages were investigated at the laboratory scale. The experimental results showed that the sulfidation percentages of Pb and Zn were as high as 98.08% and 90.55% under optimum conditions, respectively. Finally, a flotation test was performed to enrich Zn and Pb in the sulfidation product. A flotation concentrate with 8.78% Zn and 9.25% Pb was obtained, and the recovery of Zn and Pb reached 56.14% and 75.94%, respectively.

  18. In Vitro Antiparasitic and Apoptotic Effects of Antimony Sulfide Nanoparticles on Leishmania infantum

    Directory of Open Access Journals (Sweden)

    Saied Soflaei

    2012-01-01

    Full Text Available Visceral leishmaniasis is one of the most important sever diseases in tropical and subtropical countries. In the present study the effects of antimony sulfide nanoparticles on Leishmania infantum in vitro were evaluated. Antimony sulfide NPs (Sb2S5 were synthesized by biological method from Serratia marcescens bacteria. Then the cytotoxicity effects of different concentrations (5, 10, 25, 50, and 100 μg/mL of this nanoparticle were assessed on promastigote and amastigote stages of L. infantum. MTT method was used for verification results of promastigote assay. Finally, the percentages of apoptotic, necrotic, and viable cells were determined by flow cytometry. The results indicated the positive effectiveness of antimony sulfide NPs on proliferation of promastigote form. The IC50 (50% inhibitory concentration of antimony sulfide NPs on promastigotes was calculated 50 μg/mL. The cytotoxicity effect was dose-dependent means by increasing the concentration of antimony sulfide NPs, the cytotoxicity curve was raised and the viability curve of the parasite dropped simultaneously. Moreover, the IC50 of antimony sulfide NPs on amastigote stage was calculated 25 μg/mL. On the other hand, however, antimony sulfide NPs have a low cytotoxicity effect on uninfected macrophages but it can induce apoptosis in promastigote stage at 3 of 4 concentrations.

  19. Indium sulfide precipitation from hydrochloric acid solutions of calcium and sodium chlorides

    International Nuclear Information System (INIS)

    The effect of precipitation duration, acid concentration, indium complexing with chloride ions on the process of indium sulfide chemical precipitation in hydrochloric acid solutions, precipitate composition and dispersity are studied. It is established that indium sulfide solubility increases in solutions with acid concentration exceeding 0.40-0.45 mol/l. Calcium and indium chloride addition to diluted hydrochloric solutions greatly increases the solubility of indium sulfide. The effect of calcium chloride on In2S3 solubility is higher than that of sodium chloride

  20. Ni-sulfide particles in NaY-zeolite for combined hydrodesulfurization and hydrocracking purposes

    Science.gov (United States)

    de Bont, P. W.; Vissenberg, M. J.; Boellaard, E.; de Beer, V. H. J.; van Veen, J. A. R.; van Santen, R. A.; van der Kraan, A. M.

    1998-12-01

    The influence of physisorbed water on the formation of nickel-sulfide species in a 57Co doped ion exchange type 57Co:NiNaY catalyst is studied by Mössbauer Emission Spectroscopy. The absence or presence of physisorbed water during sulfidation seems to have no influence on the local nickel environment of the formed Ni-sulfide species. This result is confirmed by EXAFS measurements. In spite of the resemblance found in MES and EXAFS a large difference is found for the initial HDS activities, which is explained by the different particle sizes (HREM) found at the outer surface of the zeolite.

  1. Activation of AhR-mediated toxicity pathway by emerging pollutants polychlorinated diphenyl sulfides

    Science.gov (United States)

    Polychlorinated diphenyl sulfides (PCDPSs) are a group of environmental pollutants for which limited toxicological information is available. This study tested the hypothesis that PCDPSs could activate the mammalian aryl hydrocarbon receptor (AhR) mediated toxicity pathways. Eight...

  2. Direct rapid determination of traces of sulfide in environment samples

    Institute of Scientific and Technical Information of China (English)

    郭方遒; 黄兰芳; 梁逸曾

    2002-01-01

    An improved ethylene blue method for determination of sulfide is developed. It has been adapted to a direct determination of sulfide by both common spectrophotometric method and total differential spectrophotometric method. In common spectrophotometric method, the calibration curve is A=1.69ρ+0.006 and the correlation coefficient is 0.9994.The apparent molar absorptivity is 5.42×104 L*mol-1*cm-1 and calibration curve is liner when ρ is in the range of 0-0.9 mg*L-1. In total differential spectrophotometric method, the calibration curve is A=9.25ρ+0.004 and the correlation coefficient is 0.9996. The apparent molar absorptivity is 2.96×105 L*mol-1*cm-1and calibration curve is liner when ρ is in the range of 0-0.10 mg*L-1. The sensitivity of this method is increased significantly compared with the former ethylene blue method. The speed of reaction is also faster than the former one. The limit of detection is found to be 1.0 ng*mL-1 by both common spectrophotometric method and total differential spectrophotometric method. Ten replicate analyses of a sample solution containing 100 ng*mL-1sulfide give a relative standard deviation of 1.8%. The effects of various cations and anions on the determination of sulfide are studied and procedures for removal of interference is described. The method is used for the determination of sulfide in environment samples with satisfactory results.

  3. Role of allyl group in the hydroxyl and peroxyl radical scavenging activity of S-allylcysteine.

    Science.gov (United States)

    Maldonado, Perla D; Alvarez-Idaboy, J Raúl; Aguilar-González, Adriana; Lira-Rocha, Alfonso; Jung-Cook, Helgi; Medina-Campos, Omar Noel; Pedraza-Chaverrí, José; Galano, Annia

    2011-11-17

    S-Allylcysteine (SAC) is the most abundant compound in aged garlic extracts, and its antioxidant properties have been demonstrated. It is known that SAC is able to scavenge different reactive species including hydroxyl radical (•OH), although its potential ability to scavenge peroxyl radical (ROO•) has not been explored. In this work the ability of SAC to scavenge ROO• was evaluated, as well as the role of the allyl group (-S-CH(2)-CH═CH(2)) in its free radical scavenging activity. Two derived compounds of SAC were prepared: S-benzylcysteine (SBC) and S-propylcysteine (SPC). Their abilities to scavenge •OH and ROO• were measured. A computational analysis was performed to elucidate the mechanism by which these compounds scavenge •OH and ROO•. SAC was able to scavenge •OH and ROO•, in a concentration-dependent way. Such activity was significantly ameliorated when the allyl group was replaced by benzyl or propyl groups. It was shown for the first time that SAC is able to scavenge ROO•.

  4. Further exploration of the heterocyclic diversity accessible from the allylation chemistry of indigo

    Directory of Open Access Journals (Sweden)

    Alireza Shakoori

    2015-04-01

    Full Text Available Diversity-directed synthesis based on the cascade allylation chemistry of indigo, with its embedded 2,2’-diindolic core, has resulted in rapid access to new examples of the hydroxy-8a,13-dihydroazepino[1,2-a:3,4-b']diindol-14(8H-one skeleton in up to 51% yield. Additionally a derivative of the novel bridged heterocycle 7,8-dihydro-6H-6,8a-epoxyazepino[1,2-a:3,4-b']diindol-14(13H-one was produced when the olefin of the allylic substrate was terminally disubstituted. Further optimisation also produced viable one-pot syntheses of derivatives of the spiro(indoline-2,9'-pyrido[1,2-a]indol-3-one (65% and pyrido[1,2,3-s,t]indolo[1,2-a]azepino[3,4-b]indol-17-one (72% heterocyclic systems. Ring-closing metathesis of the N,O-diallylic spiro structure and subsequent Claisen rearrangement gave rise to the new (1R,8aS,17aS-rel-1,2-dihydro-1-vinyl-8H,17H,9H-benz[2',3']pyrrolizino[1',7a':2,3]pyrido[1,2-a]indole-8,17-(2H,9H-dione heterocyclic system.

  5. Further exploration of the heterocyclic diversity accessible from the allylation chemistry of indigo

    Science.gov (United States)

    Shakoori, Alireza; Bremner, John B; Abdel-Hamid, Mohammed K; Willis, Anthony C; Haritakun, Rachada

    2015-01-01

    Summary Diversity-directed synthesis based on the cascade allylation chemistry of indigo, with its embedded 2,2’-diindolic core, has resulted in rapid access to new examples of the hydroxy-8a,13-dihydroazepino[1,2-a:3,4-b']diindol-14(8H)-one skeleton in up to 51% yield. Additionally a derivative of the novel bridged heterocycle 7,8-dihydro-6H-6,8a-epoxyazepino[1,2-a:3,4-b']diindol-14(13H)-one was produced when the olefin of the allylic substrate was terminally disubstituted. Further optimisation also produced viable one-pot syntheses of derivatives of the spiro(indoline-2,9'-pyrido[1,2-a]indol)-3-one (65%) and pyrido[1,2,3-s,t]indolo[1,2-a]azepino[3,4-b]indol-17-one (72%) heterocyclic systems. Ring-closing metathesis of the N,O-diallylic spiro structure and subsequent Claisen rearrangement gave rise to the new (1R,8aS,17aS)-rel-1,2-dihydro-1-vinyl-8H,17H,9H-benz[2',3']pyrrolizino[1',7a':2,3]pyrido[1,2-a]indole-8,17-(2H,9H)-dione heterocyclic system. PMID:25977722

  6. Polymerizations of beta-substituted allylic arsonium ylides with catalytic amounts of organoboron compounds

    International Nuclear Information System (INIS)

    My Ph.D. work consisted in the generalization and optimization of a new polymerization reaction involving allylic arsonium ylides and catalytic amounts of various boron compounds. Thus, various β-substituted allylic arsonium salts were produced according to synthetic strategies that depended on the nature of the functional group born by the salt. These salts were converted in situ to the corresponding arsonium ylides which were then treated with boron compounds to yield polymers. Our new method of polymerization afforded either non conjugated polyenes that are functionalized every three atoms of carbon, or statistic copolymers, depending on the nature of the group R born on the β position of the ylide. These new polymers cannot be synthesized by usual methods of polymerization. Initial molar ratios of reactants were found to give molar mass control of the synthesized polymers. This controlled polymerization allowed us to produce several bloc copolymers. All the polymers were characterized by NMR techniques, by size exclusion chromatography and, for some of them, by mass spectrometry. Investigation of their physicochemical properties will need additional experiments. (author)

  7. Influence of oceanic dimethyl sulfide emissions on cloud condensation nuclei concentrations and seasonality over the remote Southern Hemisphere oceans: A global model study

    Science.gov (United States)

    Korhonen, Hannele; Carslaw, Kenneth S.; Spracklen, Dominick V.; Mann, Graham W.; Woodhouse, Matthew T.

    2008-08-01

    We use a global chemical transport model with size-resolved aerosol microphysics to investigate the sources of cloud condensation nuclei (CCN) in the Southern Hemisphere remote marine boundary layer (MBL). Long-term observations of CCN number at Cape Grim (40°41'S, 144°41'E) show a clear seasonal cycle with a 2-3 times higher concentration in summer than in winter, which has been attributed to seasonal changes in the dimethyl sulfide (DMS) ocean-to-atmosphere flux. We find that this cycle at Cape Grim and also throughout the 30°-45°S latitude band is caused mostly by changes in the regional-scale DMS ocean water concentration. In this latitude band, DMS emissions increase the simulated CCN concentrations from November to April, with a maximum effect of 46% in January (calculated at 0.23% supersaturation). Farther south, the impact of DMS on CCN is apparent only from December to February and increases the CCN concentration at most by 18% at 45°-60°S and by 40% at 60°-75°S. These model-derived contributions of DMS to Southern Ocean summertime CCN are smaller than the 80% derived from correlations between satellite-observed chlorophyll and column CCN, which we explain in terms of nonlinear behavior of CCN from the free troposphere (FT). We show that the main microphysical pathway of DMS influence on CCN number is nucleation of DMS-derived H2SO4 in the FT and subsequent growth of formed particles by condensation and coagulation during entrainment into the MBL. Our simulations suggest that >90% of the increase in MBL CCN when DMS is added to the model is formed in this way. The growth of ultrafine sea spray particles to CCN sizes due to condensation of DMS-derived H2SO4 in the MBL affects the simulated CCN concentrations by less than 6%. Overall, entrainment of nucleated sulfate aerosol into the MBL from the FT accounts for 43-65% of the summer zonal mean CCN concentrations but only 7-20% of the winter CCN over the Southern Hemisphere oceans.

  8. Re-Os sulfide (chalcopyrite, pyrite and molybdenite) systematics and fluid inclusion study of the Duobaoshan porphyry Cu (Mo) deposit, Heilongjiang Province, China

    Science.gov (United States)

    Liu, Jun; Wu, Guang; Li, Yuan; Zhu, Mingtian; Zhong, Wei

    2012-04-01

    The Duobaoshan porphyry deposit, located in the northwestern part of the Lesser Hinggan Range, is one of the biggest porphyry Cu (Mo) deposits in the Central Asian orogenic belt in China. The Duobaoshan porphyry deposit occurs in granodiorite and volcanic rocks of the Middle Ordovician Duobaoshan Formation. Six types of veins have been identified in three ore-forming stages as follows: a quartz-potassic feldspar vein in the early ore-forming stage, an early stage quartz-molybdenite vein, late stage quartz-molybdenite and quartz-chalcopyrite-pyrite veins in the middle ore-forming stage, and quartz-pyrite and calcite-quartz veins in the late ore-forming stage. The following four types of fluid inclusions are distinguished from various quartz veins: two-phase aqueous, pure gas phase, CO2-bearing and daughter mineral-bearing inclusions. The ore-forming fluid for the early ore-forming stage belongs to the H2O-CO2-NaCl system, which is characterized by high temperatures (>550 °C), intermediate salinities (16.2-18.1 wt% NaCl eqv.) and high CO2 content. The ore-forming fluid from the middle ore-forming stage evolved to the H2O-CO2-NaCl system, which is characterized by intermediate to high temperatures (230-450 °C) and high/low salinities (0.8 to >65.3 wt% NaCl eqv.) and is also rich in CO2 and metals. The ore-forming fluid finally reached cool temperatures (110-200 °C), low salinities (3.9-8.4 wt% NaCl eqv.) and was CO2-poor. Intensive fluid immiscibility or boiling occurred when the ore-forming fluid with temperatures of 230-450 °C and pressures of 10-41 MPa ascended to 4.1 km, inducing the escape of CO2, depressing the solubility of fluid, and depositing abundant metal sulfides. The total Re and Os concentrations of chalcopyrite and pyrite range from 0.15 to 2.95 μg/g and 0.74 to 15.01 ng/g, respectively. Analyses of seven chalcopyrite and pyrite samples yielded isochron ages of 482-486 Ma, and the model age of one molybdenite sample is 485.6 ± 3.7 Ma. The

  9. 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.

  10. 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.

  11. 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.

  12. 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......: (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...

  13. 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...... 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....

  14. Kinetics of Indigenous Nitrate Reducing Sulfide Oxidizing Activity in Microaerophilic Wastewater Biofilms.

    Directory of Open Access Journals (Sweden)

    Desirée Villahermosa

    Full Text Available Nitrate decreases sulfide release in wastewater treatment plants (WWTP, but little is known on how it affects the microzonation and kinetics of related microbial processes within the biofilm. The effect of nitrate addition on these properties for sulfate reduction, sulfide oxidation, and oxygen respiration were studied with the use of microelectrodes in microaerophilic wastewater biofilms. Mass balance calaculations and community composition analysis were also performed. At basal WWTP conditions, the biofilm presented a double-layer system. The upper microaerophilic layer (~300 μm showed low sulfide production (0.31 μmol cm-3 h-1 and oxygen consumption rates (0.01 μmol cm-3 h-1. The anoxic lower layer showed high sulfide production (2.7 μmol cm-3 h-1. Nitrate addition decreased net sulfide production rates, caused by an increase in sulfide oxidation rates (SOR in the upper layer, rather than an inhibition of sulfate reducing bacteria (SRB. This suggests that the indigenous nitrate reducing-sulfide oxidizing bacteria (NR-SOB were immediately activated by nitrate. The functional vertical structure of the biofilm changed to a triple-layer system, where the previously upper sulfide-producing layer in the absence of nitrate split into two new layers: 1 an upper sulfide-consuming layer, whose thickness is probably determined by the nitrate penetration depth within the biofilm, and 2 a middle layer producing sulfide at an even higher rate than in the absence of nitrate in some cases. Below these layers, the lower net sulfide-producing layer remained unaffected. Net SOR varied from 0.05 to 0.72 μmol cm-3 h-1 depending on nitrate and sulfate availability. Addition of low nitrate concentrations likely increased sulfate availability within the biofilm and resulted in an increase of both net sulfate reduction and net sulfide oxidation by overcoming sulfate diffusional limitation from the water phase and the strong coupling between SRB and NR

  15. Kinetics of Indigenous Nitrate Reducing Sulfide Oxidizing Activity in Microaerophilic Wastewater Biofilms

    Science.gov (United States)

    Villahermosa, Desirée; Corzo, Alfonso; Garcia-Robledo, Emilio; González, Juan M.; Papaspyrou, Sokratis

    2016-01-01

    Nitrate decreases sulfide release in wastewater treatment plants (WWTP), but little is known on how it affects the microzonation and kinetics of related microbial processes within the biofilm. The effect of nitrate addition on these properties for sulfate reduction, sulfide oxidation, and oxygen respiration were studied with the use of microelectrodes in microaerophilic wastewater biofilms. Mass balance calaculations and community composition analysis were also performed. At basal WWTP conditions, the biofilm presented a double-layer system. The upper microaerophilic layer (~300 μm) showed low sulfide production (0.31 μmol cm-3 h-1) and oxygen consumption rates (0.01 μmol cm-3 h-1). The anoxic lower layer showed high sulfide production (2.7 μmol cm-3 h-1). Nitrate addition decreased net sulfide production rates, caused by an increase in sulfide oxidation rates (SOR) in the upper layer, rather than an inhibition of sulfate reducing bacteria (SRB). This suggests that the indigenous nitrate reducing-sulfide oxidizing bacteria (NR-SOB) were immediately activated by nitrate. The functional vertical structure of the biofilm changed to a triple-layer system, where the previously upper sulfide-producing layer in the absence of nitrate split into two new layers: 1) an upper sulfide-consuming layer, whose thickness is probably determined by the nitrate penetration depth within the biofilm, and 2) a middle layer producing sulfide at an even higher rate than in the absence of nitrate in some cases. Below these layers, the lower net sulfide-producing layer remained unaffected. Net SOR varied from 0.05 to 0.72 μmol cm-3 h-1 depending on nitrate and sulfate availability. Addition of low nitrate concentrations likely increased sulfate availability within the biofilm and resulted in an increase of both net sulfate reduction and net sulfide oxidation by overcoming sulfate diffusional limitation from the water phase and the strong coupling between SRB and NR-SOB syntrophic

  16. Controls on Highly Siderophile Element Concentrations in Martian Basalt: Sulfide Saturation and Under-Saturation

    Science.gov (United States)

    Righter, Kevin

    2009-01-01

    Highly siderophile elements (HSE; Re, Au and the platinum group elements) in shergottites exhibit a wide range from very high, similar to the terrestrial mantle, to very low, similar to sulfide saturated mid ocean ridge basalt (e.g., [1]). This large range has been difficult to explain without good constraints on sulfide saturation or under-saturation [2]. A new model for prediction of sulfide saturation places new constraints on this problem [3]. Shergottite data: For primitive shergottites, pressure and temperature estimates are between 1.2-1.5 GPa, and 1350-1470 C [4]. The range of oxygen fugacities is from FMQ-2 to IW, where the amount of Fe2O3 is low and thus does not have a significant effect on the S saturation values. Finally, the bulk compositions of shergottites have been reported in many recent studies (e.g., [5]). All of this information will be used to test whether shergottites are sulfide saturated [3]. Modeling values and results: The database for HSE partition coefficients has been growing with many new data for silicates and oxides [6-8] to complement a large sulfide database [9- 11]. Combining these data with simple batch melting models allows HSE contents of mantle melts to be estimated for sulfide-bearing vs. sulfide-free mantle. Combining such models with fractional crystallization modeling (e.g., [12]) allows HSE contents of more evolved liquids to be modeled. Most primitive shergottites have high HSE contents (and low S contents) that can be explained by sulfide under-saturated melting of the mantle. An exception is Dhofar 019 which has high S contents and very low HSE contents suggesting sulfide saturation. Most evolved basaltic shergottites have lower S contents than saturation, and intermediate HSE contents that can be explained by olivine, pyroxene, and chromite fractionation. An exception is EET A79001 lithology B, which has very low HSE contents and S contents higher than sulfide saturation values . evidence for sulfide saturation

  17. S-33 constraints on the seawater sulfate contribution in modern seafloor hydrothermal vent sulfides

    Science.gov (United States)

    Ono, Shuhei; Shanks, Wayne C.; Rouxel, O.J.; Rumble, D.

    2007-01-01

    Sulfide sulfur in mid-oceanic ridge hydrothermal vents is derived from leaching of basaltic-sulfide and seawater-derived sulfate that is reduced during high temperature water rock interaction. Conventional sulfur isotope studies, however, are inconclusive about the mass-balance between the two sources because 34S/32S ratios of vent fluid H2S and chimney sulfide minerals may reflect not only the mixing ratio but also isotope exchange between sulfate and sulfide. Here, we show that high-precision analysis of S-33 can provide a unique constraint because isotope mixing and isotope exchange result in different ??33S (?????33S-0.515 ??34S) values of up to 0.04??? even if ??34S values are identical. Detection of such small ??33S differences is technically feasible by using the SF6 dual-inlet mass-spectrometry protocol that has been improved to achieve a precision as good as 0.006??? (2??). Sulfide minerals (marcasite, pyrite, chalcopyrite, and sphalerite) and vent H2S collected from four active seafloor hydrothermal vent sites, East Pacific Rise (EPR) 9-10??N, 13??N, and 21??S and Mid-Atlantic Ridge (MAR) 37??N yield ??33S values ranging from -0.002 to 0.033 and ??34S from -0.5??? to 5.3???. The combined ??34S and ??33S systematics reveal that 73 to 89% of vent sulfides are derived from leaching from basaltic sulfide and only 11 to 27% from seawater-derived sulfate. Pyrite from EPR 13??N and marcasite from MAR 37??N are in isotope disequilibrium not only in ??34S but also in ??33S with respect to associated sphalerite and chalcopyrite, suggesting non-equilibrium sulfur isotope exchange between seawater sulfate and sulfide during pyrite precipitation. Seafloor hydrothermal vent sulfides are characterized by low ??33S values compared with biogenic sulfides, suggesting little or no contribution of sulfide from microbial sulfate reduction into hydrothermal sulfides at sediment-free mid-oceanic ridge systems. We conclude that 33S is an effective new tracer for interplay among

  18. Dynamics of wood fall colonization in relation to sulfide concentration in a mangrove swamp.

    Science.gov (United States)

    Laurent, Mélina C Z; Le Bris, Nadine; Gaill, Françoise; Gros, Olivier

    2013-01-01

    Wood debris are an important component of mangrove marine environments. Current knowledge of the ecological role of wood falls is limited by the absence of information on metazoan colonization processes over time. The aim of this study was to provide insights to their temporal dynamics of wood eukaryotic colonization from a shallow water experiment in a mangrove swamp. Combined in situ chemical monitoring and biological surveys revealed that the succession of colonizers in the mangrove swamp relates with the rapid evolution of sulfide concentration on the wood surface. Sulfide-tolerant species are among the first colonizers and dominate over several weeks when the sulfide content is at its maximum, followed by less tolerant opportunistic species when sulfide decreases. This study supports the idea that woody debris can sustain chemosynthetic symbioses over short time-scale in tropical shallow waters. PMID:23623161

  19. 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.

  20. Asymmetric allylic alkylation in combination with ring-closing metathesis for the preparation of chiral N-heterocycles

    NARCIS (Netherlands)

    Teichert, Johannes F.; Zhang, Suyan; Zijl, Anthoni W. van; Slaa, Jan Willem; Minnaard, Adriaan J.; Feringa, Bernard

    2010-01-01

    Asymmetric copper-catalyzed allylic substitution with methylmagnesium bromide is employed in combination with ring-closing olefin metathesis or ene-yne metathesis to achieve the synthesis of chiral, unsaturated nitrogen heterocycles. The resulting six- to eight-membered chiral heterocycles are acces

  1. The NBS Reaction: A Simple Explanation for the Predominance of Allylic Substitution over Olefin Addition by Bromine at Low Concentrations.

    Science.gov (United States)

    Wamser, Carl C.; Scott, Lawrence T.

    1985-01-01

    Examines mechanisms related to use of N-bromosuccinimide (NBS) for bromination at an allylic position. Also presents derived rate laws for three possible reactions of molecular bromine with an alkene: (1) free radical substitution; (2) free radical addition; and (3) electrophilic addition. (JN)

  2. Organoselenium-catalyzed, hydroxy-controlled regio- and stereoselective amination of terminal alkenes: efficient synthesis of 3-amino allylic alcohols.

    Science.gov (United States)

    Deng, Zhimin; Wei, Jialiang; Liao, Lihao; Huang, Haiyan; Zhao, Xiaodan

    2015-04-17

    An efficient route to prepare 3-amino allylic alcohols in excellent regio- and stereoselectivity in the presence of bases by orangoselenium catalysis has been developed. In the absence of bases α,β-unsaturated aldehydes were formed in up to 97% yield. Control experiments reveal that the hydroxy group is crucial for the direct amination. PMID:25849818

  3. Aldehyde Selective Wacker Oxidations of Phthalimide Protected Allylic Amines : A New Catalytic Route to beta(3)-Amino Acids

    NARCIS (Netherlands)

    Weiner, Barbara; Baeza Garcia, Alejandro; Jerphagnon, Thomas; Feringa, Ben L.

    2009-01-01

    A new method for the synthesis of B-3-amino acids is presented. Phthalimide protected allylic amines are oxidized under Wacker conditions selectively to aldehydes using PdCl2 and CuCl or Pd(MeCN)(2)Cl(NO2) and CuCl2 as complementary catalyst systems. The aldehydes are produced in excellent yields an

  4. Synthesis of novel chiral phosphine-triazine ligand derived from α-phenylethylamine for Pd-catalyzed asymmetric allylic alkylation

    Institute of Scientific and Technical Information of China (English)

    Jia Di Huang; Xiang Ping Hu; Zhuo Zheng

    2008-01-01

    A novel chiral phosphine-triazine ligand was synthesized from chiral model reaction of Pd-catalyzed allylic alkylation of rac-l,3-diphenylprop-2-en-l-yl pivalate with dimethyl malonate, good enantioselectivity (90% e.e.) was obtained by using this ligand.

  5. Growth behavior prediction of fresh catfish fillet with Pseudomonas aeruginosa under stresses of allyl isothiocyanate, temperature and modified atmosphere

    Science.gov (United States)

    Pseudomonas aeruginosa, a common spoilage microorganism in fish, grows rapidly when temperature rises above 4 degree C. The combination of allyl isothiocyanate (AIT) and modified atmosphere (MA) was applied and proved to be effective to retard the growth of P. aeruginosa. The objective of this resea...

  6. Antimicrobial activity of allyl isothiocyanate used to coat biodegradable composite films as affected by storage and handling conditions

    Science.gov (United States)

    We evaluated the effects of storage and handling conditions on the antimicrobial activity of biodegradable composite films (polylactic acid and sugar beet pulp) coated with allyl isothiocyanate (AIT). Polylactic acid (PLA) and chitosan were incorporated with AIT and coated on one side of the film. T...

  7. Nanoscale Zero-Valent Iron for Sulfide Removal from Digested Piggery Wastewater

    Directory of Open Access Journals (Sweden)

    Sheng-Hsun Chaung

    2014-01-01

    Full Text Available The removal of dissolved sulfides in water and wastewater by nanoscale zero-valent iron (nZVI was examined in the study. Both laboratory batch studies and a pilot test in a 50,000-pig farm were conducted. Laboratory studies indicated that the sulfide removal with nZVI was a function of pH where an increase in pH decreased removal rates. The pH effect on the sulfide removal with nZVI is attributed to the formation of FeS through the precipitation of Fe(II and sulfide. The saturated adsorption capacities determined by the Langmuir model were 821.2, 486.3, and 359.7 mg/g at pH values 4, 7, and 12, respectively, for nZVI, largely higher than conventional adsorbents such as activated carbon and impregnated activated carbon. The surface characterization of sulfide-laden nZVI using XPS and TGA indicated the formation of iron sulfide, disulfide, and polysulfide that may account for the high adsorption capacity of nZVI towards sulfide. The pilot study showed the effectiveness of nZVI for sulfide removal; however, the adsorption capacity is almost 50 times less than that determined in the laboratory studies during the testing period of 30 d. The complexity of digested wastewater constituents may limit the effectiveness of nZVI. Microbial analysis suggested that the impact of nZVI on the change of microbial species distribution was relatively noticeable after the addition of nZVI.

  8. 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

  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. Time-resolved fluorescence sensing of pesticides chlorpyrifos, crotoxyphos and endosulfan by the luminescent Eu(III)-8-allyl-3-carboxycoumarin probe

    Science.gov (United States)

    Azab, Hassan A.; Khairy, Gasser M.; Kamel, Rasha M.

    2015-09-01

    This work describes the application of time resolved fluorescence in microtiter plates for investigating the interactions of europium-allyl-3-carboxycoumarin with pesticides chlorpyrifos, endosulfan and crotoxyphos. Stern-Volmer studies at different temperatures for chlorpyrifos and crotoxyphos shows dynamic and static quenching mechanisms respectively. Direct methods for the determination of the pesticides under investigation have been developed using the luminescence variations of the probe in solution. The detection limits are 6.53, 0.004, 3.72 μmol/L for chlorpyrifos, endosulfan, and crotoxyphos, respectively. The binding constants and thermodynamic parameters of the pesticides with probe were evaluated. A thermodynamic analysis showed that the reaction is spontaneous with negative ΔG. Effect of some relevant interferents on the detection of pesticides has been investigated. The new method was applied to the determination of the pesticides in different types of water samples (tap, mineral, and waste water).

  11. 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)

  12. Sites and reactivity of sulfides in hydro-treatment catalysis: theoretical ab-initio study; Sites et reactivite des sulfures en catalyse d`hydrotraitement: etude theorique ab-initio

    Energy Technology Data Exchange (ETDEWEB)

    Raybaud, P.

    1998-10-28

    Ab-initio calculations within the DFT and GGA have been carried out in an attempt to understand better which property sets the activity of transition metal sulfides (TMS) in the hydro-desulfurization reaction (HDS), a most important step in the refining of crude oil. A systematic study of the structural cohesive and electronic properties of more than thirty bulk TMS has allowed us to find a new simple relationship between the experimental catalytic activities known in HDS, and the properly defined sulfur-metal (S-M) bond energy. On this volcano curve reminiscent of the Sabatier principles, ionic metallic sulfides (as Ni{sub 3}S{sub 2}, Ci{sub 9}S{sub 8}) exhibit the weakest bonds whereas ion-covalent semi-conductors (as MoS{sub 2}) exhibit the strongest bonds: the highest activities correspond to intermediate bond strengths (RuS{sub 2}). Our study of the electronic structure of the MoS{sub 2} edge surfaces has revealed acceptor surface states localized on Coordinatively Unsaturated Mo ions and the significance of those states for the activation of hetero-aromatic molecules like thiophene. On such surfaces, the energetic profiles we establish for the thiophene HDS reaction point out the surface anionic vacancy regeneration steps as rate determining. We have calculated the optimal positions of Co (Ni) in decoration on the MoS{sub 2} edge planes, in excellent agreement with available EXAFS data on real catalysts. Introducing the promoter Co (Ni) induces a lower optimal sulfur coverage and a lower surface S-M bond strength in proportion of the Co (Ni) coverage, and lower for Ni than for Co. Simplified energy profiles for the thiophene HDS reactions on promoted (101-bar 0) surfaces show that the C-S scission step is likely to become rate determining. Our results show altogether that bulk and surface S-M strengths in TMS systems show similar trends, insofar as they are primarily determined by the local electronic structure. (author)

  13. Removal of Sulfide and COD from a Crude Oil Wastewater Model by Aluminum and Iron Electrocoagulation

    Directory of Open Access Journals (Sweden)

    K. I. Dermentzis

    2016-04-01

    Full Text Available The treatment of petroleum wastewater was studied using the electrocoagulation process with aluminum and iron electrodes aiming to simultaneous removal of sulfide and COD. All affecting parameters, such as solution pH, applied current density, time of electroprocessing, electrode material and addition of surfactant, were investigated. Sulfide was rapidly and effectively removed using iron electrodes. The removal of COD was effectively effectively enhanced by performing the electrocoagulation process after addition of the surfactant polyethylene glycol oleate.

  14. 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.

  15. 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.

  16. 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.

  17. Sulfidation of 310 stainless steel at sulfur potentials encountered in coal conversion systems

    Science.gov (United States)

    Rao, D. B.; Nelson, H. G.

    1976-01-01

    The sulfidation of SAE 310 stainless steel was carried out in gas mixtures of hydrogen and hydrogen sulfide over a range of sulfur potentials anticipated in advanced coal gasification processes. The kinetics, composition, and morphology of sulfide scale formation were studied at a fixed temperature of 1065 K over a range of sulfur potentials from .00015N/sqm to 900N/sqm. At all sulfur potentials investigated, the sulfide scales were found to be multilayered. The relative thickness of the individual layers as well as the composition was found to depend on the sulfur potential. The reaction was found to obey the parabolic rate law after an initial transient period. Considerably longer transient periods were found to be due to unsteady state conditions resulting from compositional variations in the spinel layer.

  18. Biological removal of air loaded with a hydrogen sulfide and ammonia mixture

    Institute of Scientific and Technical Information of China (English)

    CHEN Ying-xu; YIN Jun; FANG Shi

    2004-01-01

    The nuisance impact of air pollutant emissions from wastewater pumping stations is a major issue of concern to China. Hydrogen sulfide and ammonia are commonly the primary odor and are important targets for removal. An alternative control technology, biofiltration, was studied. The aim of this study is to investigate the potential of unit systems packed with compost in terms of ammonia and hydrogen sulfide emissions treatment, and to establish optimal operating conditions for a full-scale conceptual design. The laboratory scale biofilter packed with compost was continuously supplied with hydrogen sulfide and ammonia gas mixtures. A volumetric load of less than 150 gH2S/(m3· d) and 230 gNH3/(m3· d) was applied for about fifteen weeks. Hydrogen sulfide and ammonia elimination occurred in the biofilter simultaneously. The removal efficiency, removal capacity and removal kinetics in the biofilter were studied. The hydrogen sulfide removal efficiency reached was very high above 99%, and ammonia removal efficiency was about 80%. Hydrogen sulfide was oxidized into sulphate. The ammonia oxidation products were nitrite and nitrate. Ammonia in the biofilter was mainly removed by adsorption onto the carrier material and by absorption into the water fraction of the carrier material. High percentages of hydrogen sulfide or ammonia were oxidized in the first section of the column. Through kinetics analysis, the presence of amrronia did not hinder the hydrogen sulfide removal. According to the relationship between pressure drop and gas velocity for the biofilter and Reynolds number, non-Darcy flow can be assumed to represent the flow in the medium.

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

    Directory of Open Access Journals (Sweden)

    Mohammad Ali Rajabzadeh

    2015-10-01

    Full Text Available 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 concentrate them in specific lithological zones. The lack of exploration for sulfides in this environment suggests that sulfide saturation is rarely attained in ophiolite-related magmas. Some ophiolites, however, contain sulfide deposits, such as at Acoje in Philippines, and Cliffs in Shetland, U.K. (Evans, 2000; Naldrett, 2004. The Faryab ophiolite complex in southern Kerman Province, the most important mining area for chromite deposits in Iran, is located in the southwest part of the Makran Zone. Evidence of sulfide mineralization has been reported there by some authors (e.g. Rajabzadeh and Moosavinasab, 2013. This paper discusses the genesis of sulfides in the Faryab ophiolite using mineral chemistry of the major mineral phases in different rocks of the ophiolite column in order to determine the possible lithological location of sulfide deposits. Materials and methods Seventy three rock samples from cumulate units were collected from surficial occurrences and drill core. The samples were studied using conventional microscopic methods and the mineralogy confirmed by x-ray diffraction. Electron microprobe analysis was carried out on different mineral phases in order to determine the chemistry of the minerals used in the interpretation of magma evolution in the Faryab ophiolite. Lithologically, the Faryab ophiolite complex is divided into two major parts: the northern part includes magmatic rocks and the southern part is comprised of rocks residual after partial

  20. Microbial communities and arsenic biogeochemistry at the outflow of an alkaline sulfide-rich hot spring

    Science.gov (United States)

    Jiang, Zhou; Li, Ping; van Nostrand, Joy D.; Zhang, Ping; Zhou, Jizhong; Wang, Yanhong; Dai, Xinyue; Zhang, Rui; Jiang, Dawei; Wang, Yanxin

    2016-04-01

    Alkaline sulfide-rich hot springs provide a unique environment for microbial community and arsenic (As) biogeochemistry. In this study, a representative alkaline sulfide-rich hot spring, Zimeiquan in the Tengchong geothermal area, was chosen to study arsenic geochemistry and microbial community using Illumina MiSeq sequencing. Over 0.26 million 16S rRNA sequence reads were obtained from 5-paired parallel water and sediment samples along the hot spring’s outflow channel. High ratios of As(V)/AsSum (total combined arsenate and arsenite concentrations) (0.59-0.78), coupled with high sulfide (up to 5.87 mg/L), were present in the hot spring’s pools, which suggested As(III) oxidation occurred. Along the outflow channel, AsSum increased from 5.45 to 13.86 μmol/L, and the combined sulfide and sulfate concentrations increased from 292.02 to 364.28 μmol/L. These increases were primarily attributed to thioarsenic transformation. Temperature, sulfide, As and dissolved oxygen significantly shaped the microbial communities between not only the pools and downstream samples, but also water and sediment samples. Results implied that the upstream Thermocrinis was responsible for the transformation of thioarsenic to As(III) and the downstream Thermus contributed to derived As(III) oxidation. This study improves our understanding of microbially-mediated As transformation in alkaline sulfide-rich hot springs.

  1. 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.

  2. Research on Industrial Catalytic Synthesis of Allyl Isothiocyanate%烯丙基异硫氰酸酯的工业催化合成研究

    Institute of Scientific and Technical Information of China (English)

    王咏梅

    2014-01-01

    Allyl isothiocyanate is an important Intermediate products in organic Production , it is widely used in va-rious fields such as pesticides , medicine and soil disinfection etc . This paper describes different methods from dif -ferent starting materials and routes of synthesis of isothiocyanates , and the temperature , pressure , ratio of raw materials was studied in detail . We also made the effect for the catalyst in this reaction , the influences of solvents on the reaction . Under catalytic conditions , to stage a way of industrial synthesis of allyl isothiocyanate , achieves better purification and reduce the cost of products of dual urpose .%烯丙基异硫氰酸酯是一种重要的有机合成中间体,在合成农药、医药等方面都有比较重要的用途,在土壤消毒方面也有应用。本文叙述了用不同起始原料,不同技术路线合成异硫氰酸酯的方法,并对温度、压力、配料比进行了细致的研究试验。特别研究了催化剂对反应的影响,探讨了溶剂对反应的影响。在催化条件下,以阶段升温的方式工业合成烯丙基异硫氰酯的方法,达到了纯化产品和降低成本的双重目的。

  3. Enantioselective construction of quaternary N-heterocycles by palladium-catalysed decarboxylative allylic alkylation of lactams

    KAUST Repository

    Behenna, Douglas C.

    2011-12-18

    The enantioselective synthesis of nitrogen-containing heterocycles (N-heterocycles) represents a substantial chemical research effort and resonates across numerous disciplines, including the total synthesis of natural products and medicinal chemistry. In this Article, we describe the highly enantioselective palladium-catalysed decarboxylative allylic alkylation of readily available lactams to form 3,3-disubstituted pyrrolidinones, piperidinones, caprolactams and structurally related lactams. Given the prevalence of quaternary N-heterocycles in biologically active alkaloids and pharmaceutical agents, we envisage that our method will provide a synthetic entry into the de novo asymmetric synthesis of such structures. As an entry for these investigations we demonstrate how the described catalysis affords enantiopure quaternary lactams that intercept synthetic intermediates previously used in the synthesis of the Aspidosperma alkaloids quebrachamine and rhazinilam, but that were previously only available by chiral auxiliary approaches or as racemic mixtures. © 2012 Macmillan Publishers Limited. All rights reserved.

  4. Hydrogen sulfide releasing capacity of natural isothiocyanates: is it a reliable explanation for the multiple biological effects of Brassicaceae?

    Science.gov (United States)

    Citi, Valentina; Martelli, Alma; Testai, Lara; Marino, Alice; Breschi, Maria C; Calderone, Vincenzo

    2014-06-01

    Hydrogen sulfide is an endogenous pleiotropic gasotransmitter, which mediates important physiological effects in the human body. Accordingly, an impaired production of endogenous hydrogen sulfide contributes to the pathogenesis of important disorders. To date, exogenous compounds, acting as hydrogen sulfide-releasing agents, are viewed as promising pharmacotherapeutic agents. In a recent report, the hydrogen sulfide-releasing properties of some synthetic aryl isothiocyanate derivatives have been reported, indicating that the isothiocyanate function can be viewed as a suitable slow hydrogen sulfide-releasing moiety, endowed with the pharmacological potential typical of this gasotransmitter. Many isothiocyanate derivatives (deriving from a myrosinase-mediated transformation of glucosinolates) are well-known secondary metabolites of plants belonging to the family Brassicaceae, a large botanical family comprising many edible species. The phytotherapeutic and nutraceutic usefulness of Brassicaceae in the prevention of important human diseases, such as cancer, neurodegenerative processes and cardiovascular diseases has been widely discussed in the scientific literature. Although these effects have been largely attributed to isothiocyanates, the exact mechanism of action is still unknown. In this experimental work, we aimed to investigate the possible hydrogen sulfide-releasing capacity of some important natural isothiocyanates, studying it in vitro by amperometric detection. Some of the tested natural isothiocyanates exhibited significant hydrogen sulfide release, leading us to hypothesize that hydrogen sulfide may be, at least in part, a relevant player accounting for several biological effects of Brassicaceae.

  5. Fractal characteristics of nanocrystalline indium and gallium sulfide particles

    Energy Technology Data Exchange (ETDEWEB)

    Sastry, P.U., E-mail: psastry@barc.gov.i [Solid State Physics Division, Mumbai 400085 (India); Dutta, Dimple P. [Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)

    2009-11-13

    The structure of nano-sized powders of indium sulfide (In{sub 2}S{sub 3}) and gallium sulfide (Ga{sub 2}S{sub 3}), prepared by single source precursor route has been investigated by small angle X-ray scattering technique. The particle morphology shows interesting fractal nature. For In{sub 2}S{sub 3}, the nanoparticle aggregates show a mass fractal with fractal dimension 2.0 that increases with longer time of thermal treatment. Below the length scale of about 20 nm, the particles have a rough surface with a surface fractal dimension of 2.8. Unlike In{sub 2}S{sub 3}, structure of Ga{sub 2}S{sub 3} exhibits a single surface fractal over whole q-range of study. The estimated particle sizes are in range of 5-15 nm and the results are supported by transmission electron microscope.

  6. Synthesis and characterization of cerium sulfide thin film

    Institute of Scientific and Technical Information of China (English)

    Ιshak Afsin Kariper

    2014-01-01

    Cerium sulfide (CexSy) polycrystalline thin film is coated with chemical bath deposition on substrates (commercial glass). Transmittance, absorption, optical band gap and refractive index are examined by using UV/VIS. Spectrum. The hexagonal form is observed in the structural properties in XRD. The structural and optical properties of cerium sulfide thin films are analyzed at different pH. SEM and EDX analyses are made for surface analysis and elemental ratio in films. It is observed that some properties of films changed with different pH values. In this study, the focus is on the observed changes in the properties of films. The pH values were scanned at 6–10. The optical band gap changed with pH between 3.40 to 3.60 eV. In addition, the film thickness changed with pH at 411 nm to 880 nm.

  7. Study on the Process Conditions Extraction of Sulphur from Lead Slag Using Ammonium sulfide%硫化铵提取铅渣中硫工艺条件的研究

    Institute of Scientific and Technical Information of China (English)

    蒋兴荣; 任兴丽; 朱复跃; 魏红军

    2012-01-01

    To study leaching of sulfur using ammonium sulphate,and explore the optimum process conditions of extracting sulfur from lead slag.The results showed that the optimum conditions were liquid to solid ratio was 3∶1,concentration of ammonium sulphate was 140 g/L,molar ratio of sulfur and ammonium sulfide was 1∶0.4,leaching time was 25 minutes.%研究硫化铵浸取单质硫,探求铅渣中提取硫最佳工艺条件。结果表明:硫化铵浸取单质硫最佳工艺条件是液固比为3∶1,硫化铵溶液浓度为140g/L,硫与硫化铵的摩尔比为1∶0.4,浸出时间为25min,硫的浸出率达到98%。

  8. Study on the Dealing and Controlling Measures of Hydrogen Sulfide in High 95 Well%高95井硫化氢处理及防治措施研究

    Institute of Scientific and Technical Information of China (English)

    谢立志; 张磊; 顾晓强; 赵荣

    2012-01-01

    This article analyzes and concludes the influence of hydrogen sulfide on the drilling and the precautions for the drilling.Main controlling measures are proposed for the six-time highly displayed hydrogen sulfide in the core drilling process of the high 95 well in Shengli Oilfield,which is highly relevant to the wells of mass hydrogen sulfide in the block.%文章分析总结了硫化氢对钻井的影响及在钻井中应注意的事项,并结合胜利油田高95井现场取芯钻井过程中硫化氢六次高显示的处理工艺,提出了主要防治措施,对该区块的高含硫化氢井有参考借鉴价值.

  9. Hydrogen sulfide can inhibit and enhance oxygenic photosynthesis in a cyanobacterium from sulfidic springs

    NARCIS (Netherlands)

    Klatt, Judith M.; Haas, Sebastian; Yilmaz, Pelin; de Beer, Dirk; Polerecky, Lubos

    2015-01-01

    We used microsensors to investigate the combinatory effect of hydrogen sulfide (H2S) and light on oxygenic photosynthesis in biofilms formed by a cyanobacterium from sulfidic springs. We found that photosynthesis was both positively and negatively affected by H2S: (i) H2S accelerated the recovery of

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

    NARCIS (Netherlands)

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

    2014-01-01

    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

  11. Sulfide-driven autotrophic denitrification significantly reduces N2O emissions.

    Science.gov (United States)

    Yang, Weiming; Zhao, Qing; Lu, Hui; Ding, Zhi; Meng, Liao; Chen, Guang-Hao

    2016-03-01

    The Sulfate reduction-Autotrophic denitrification-Nitrification Integrated (SANI) process build on anaerobic carbon conversion through biological sulfate reduction and autotrophic denitrification by using the sulfide byproduct from the previous reaction. This study confirmed extra decreases in N2O emissions from the sulfide-driven autotrophic denitrification by investigating N2O reduction, accumulation, and emission in the presence of different sulfide/nitrate (S/N) mass ratios at pH 7 in a long-term laboratory-scale granular sludge autotrophic denitrification reactor. The N2O reduction rate was linearly proportional to the sulfide concentration, which confirmed that no sulfide inhibition of N2O reductase occurred. At S/N = 5.0 g-S/g-N, this rate resulted by sulfide-driven autotrophic denitrifying granular sludge (average granule size = 701 μm) was 27.7 mg-N/g-VSS/h (i.e., 2 and 4 times greater than those at 2.5 and 0.8 g-S/g-N, respectively). Sulfide actually stimulates rather than inhibits N2O reduction no matter what granule size of sulfide-driven autotrophic denitrifying sludge engaged. The accumulations of N2O, nitrite and free nitrous acid (FNA) with average granule size 701 μm of sulfide-driven autotrophic denitrifying granular sludge engaged at S/N = 5.0 g-S/g-N were 4.7%, 11.4% and 4.2% relative to those at 3.0 g-S/g-N, respectively. The accumulation of FNA can inhibit N2O reduction and increase N2O accumulation during sulfide-driven autotrophic denitrification. In addition, the N2O gas emission level from the reactor significantly increased from 14.1 ± 0.5 ppmv (0.002% of the N load) to 3707.4 ± 36.7 ppmv (0.405% of the N load) as the S/N mass ratio in the influent decreased from 2.1 to 1.4 g-S/g-N over the course of the 120-day continuous monitoring period. Sulfide-driven autotrophic denitrification may significantly reduce greenhouse gas emissions from biological nutrient removal when sulfur conversion processes are applied. PMID

  12. Ab Initio Investigation of Methanthiol and Dimethyl Sulfide Adsorption on Zeolite

    Institute of Scientific and Technical Information of China (English)

    Lü Renqing

    2006-01-01

    The Hartree-Fock and cluster model methods have been employed to investigate interactions of methanthiol or dimethyl sulfide on zeolites. Molecular complexes formed by adsorption of methanthiol on silanol H3SiOSi(OH)2OSiH3 with five coordination forms and dimethyl sulfide on silanol H3SiOSi(OH)2OSiH3 with four coordination forms, and Br(o)nsted acid sites of bridging hydroxyl H3Si(OH)Al(OH)2OSiH3 entering into interactions with methanthiol or dimethyl sulfide have been investigated. Full optimization and frequency analysis of all cluster models have been carried out using the Hartree-Fock method at 6-31 +G** basis set level for hydrogen, silicon, aluminum, oxygen, carbon, and sulfur atoms. The structures and energy changes of different coordination forms derived from methanthiol and H3Si(OH)Al(OH)2OSiH3, dimethyl sulfide and H3Si(OH)Al(OH)2OSiH3, methanthiol and H3SiOSi(OH)2OSiH3, dimethyl sulfide and H3SiOSi(OH)2OSiH3 complexes have been comparatively studied. The calculated results showed that the nature of interactions leading to the formation of the bridging hydroxyl-methanthiol, silanol-methanthiol,bridging hydroxyl-dimethyl sulfide, silanol-dimethyl sulfide complexes was governed by the Van der Waals force as confirmed by a small change in geometric structures and properties. Methanthiol and dimethyl sulfide molecules were adsorbed on bridging hydroxyl group prior to silanol group as evidenced by the heat of adsorption, and the protonization of methanthiol adsorption on bridging hydroxyl model, which was supposed in the literature, was not found.

  13. The Effect of Allylic Sulfide-Mediated IrreversibleAddition-Fragment Chain Transfer on the EmulsionPolymerization Kinetics of Styrene

    Directory of Open Access Journals (Sweden)

    Li An

    2015-09-01

    Full Text Available The effect of the irreversible addition-fragment chain transfer agent, butyl(2-phenylallylsulfane (BPAS, on the course of the emulsion polymerization of styrene and on the product molecular weight was investigated. The emulsion polymerizations were performed using various amounts of sodium dodecyl sulfate (SDS as the surfactant and potassium peroxodisulfate (KPS as the initiator. The relationships between the rates of polymerization (\\(R_{p} \\ and the number of particles per volume (\\(N_{c} \\ with respect to the concentrations of KPS, SDS, and BPAS were found to be \\(R_{p} \\propto \\left\\lbrack KPS \\right\\rbrack^{0.29} \\, \\(N_{c} \\propto \\left\\lbrack KPS \\right\\rbrack^{0.26} \\,\\(R_{p} \\propto \\left\\lbrack SDS \\right\\rbrack^{0.68} \\, \\(N_{c} \\propto \\left\\lbrack SDS \\right\\rbrack^{0.72} \\, and \\(R_{p} \\propto \\left\\lbrack BPAS \\right\\rbrack^{- 0.73} \\ . The obtained relationships can be attributed to the exit of the leaving group radicals on BPAS from the polymer particles. The experimental values of the average number of radicals per particle (\\(\\overset{\\_}{n} \\ were strongly dependent on the BPAS concentration and were in good agreement with the theoretical values (\\({\\overset{\\_}{n}}_{theo} \\ from model calculations. The number-average molecular weight (\\(\\overset{\\_}{M_{n}} \\ can be controlled by BPAS over nearly the entire conversion range, which is also in agreement with the mathematical model. In addition, the transfer rate coefficient (\\(k_{tr} \\ of BPAS can be estimated as 326 L/mol/s at 70 \\(^\\circ\\C. Moreover, similar good results were found for the tested redox reactions at 30 \\(^\\circ\\C.

  14. 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

  15. Potential for biogeochemical cycling of sulfur, iron and carbon within massive sulfide deposits below the seafloor.

    Science.gov (United States)

    Kato, Shingo; Ikehata, Kei; Shibuya, Takazo; Urabe, Tetsuro; Ohkuma, Moriya; Yamagishi, Akihiko

    2015-05-01

    Seafloor massive sulfides are a potential energy source for the support of chemosynthetic ecosystems in dark, deep-sea environments; however, little is known about microbial communities in these ecosystems, especially below the seafloor. In the present study, we performed culture-independent molecular analyses of sub-seafloor sulfide samples collected in the Southern Mariana Trough by drilling. The depth for the samples ranged from 0.52 m to 2.67 m below the seafloor. A combination of 16S rRNA and functional gene analyses suggested the presence of chemoautotrophs, sulfur-oxidizers, sulfate-reducers, iron-oxidizers and iron-reducers. In addition, mineralogical and thermodynamic analyses are consistent with chemosynthetic microbial communities sustained by sulfide minerals below the seafloor. Although distinct bacterial community compositions were found among the sub-seafloor sulfide samples and hydrothermally inactive sulfide chimneys on the seafloor collected from various areas, we also found common bacterial members at species level including the sulfur-oxidizers and sulfate-reducers, suggesting that the common members are widely distributed within massive sulfide deposits on and below the seafloor and play a key role in the ecosystem function.

  16. Investigation of the Electrocatalytic Activity of Rhodium Sulfide for Hydrogen Evolution and Hydrogen Oxidation

    International Nuclear Information System (INIS)

    We report the synthesis of unsupported and carbon-supported, mixed phase, rhodium sulfide, using both a hydrogen sulfide source and a solid sulfur source. Samples with several different distributions of rhodium sulfide phases (Rh2S3, Rh17S15, RhS2 and metallic Rh) were obtained by varying the temperature and exposure time to H2S or sulfur to rhodium ratio when using solid sulfur. Samples were characterized by X-ray diffraction (XRD), and the unsupported rhodium sulfide compounds studied using Raman spectroscopy to link Raman spectra to catalyst phases. The electrocatalytic activity of the rhodium sulfide compounds for hydrogen evolution and oxidation was measured using rotating disk electrode measurements in acidic conditions to simulate use in a flow cell. The most active phases for hydrogen evolution were found to be Rh3S4 and Rh17S15 (−0.34 V vs. Ag/AgCl required for 20 mA/cm2), while Rh2S3 and RhS2 phases were relatively inactive (−0.46 V vs. Ag/AgCl required for 20 mA/cm2 using RhS2/C). The hydrogen oxidation activity of all rhodium sulfide phases is significantly lower than the hydrogen evolution activity and is not associated with conductivity limitations

  17. Inhibition of Listeria monocytogenes on cooked cured chicken breasts by acidified coating containing allyl isothiocyanate or deodorized Oriental mustard extract.

    Science.gov (United States)

    Olaimat, Amin N; Holley, Richard A

    2016-08-01

    Ready-to-eat meats are considered foods at high risk to cause life-threatening Listeria monocytogenes infections. This study screened 5 L. monocytogenes strains for their ability to hydrolyze sinigrin (a glucosinolate in Oriental mustard), which formed allyl isothiocyanate (AITC) and reduced L. monocytogenes viability on inoculated vacuum-packed, cooked, cured roast chicken slices at 4 °C. Tests involved incorporation of 25-50 μl/g AITC directly or 100-250 mg/g Oriental mustard extract in 0.5% (w/v) κ-carrageenan/2% (w/v) chitosan-based coatings prepared using 1.5% malic or acetic acid. L. monocytogenes strains hydrolyzed 33.6%-48.4% pure sinigrin in MH broth by 21 d at 25 °C. Acidified κ-carrageenan/chitosan coatings containing 25-50 μl/g AITC or 100-250 mg/g mustard reduced the viability of L. monocytogenes and aerobic bacteria on cooked, cured roast chicken slices by 4.1 to >7.0 log10 CFU/g compared to uncoated chicken stored at 4 °C for 70 d. Coatings containing malic acid were significantly more antimicrobial than those with acetic acid. During storage for 70 d, acidified κ-carrageenan/chitosan coatings containing 25-50 μl/g AITC or 250 mg/g mustard extract reduced lactic acid bacteria (LAB) numbers 3.8 to 5.4 log10 CFU/g on chicken slices compared to uncoated samples. Acidified κ-carrageenan/chitosan-based coatings containing either AITC or Oriental mustard extract at the concentrations tested had the ability to control L. monocytogenes viability and delay growth of potential spoilage bacteria on refrigerated, vacuum-packed cured roast chicken. PMID:27052706

  18. 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

  19. Selective Facet Reactivity During Cation Exchange in Cadmium Sulfide Nanorods

    Energy Technology Data Exchange (ETDEWEB)

    Sadtler, Bryce; Demchenko, Denis; Zheng, Haimei; Hughes, Steven; Merkle, Maxwell; Dahmen, Ulrich; Wang, Lin-Wang; Alivisatos, A. Paul

    2008-12-18

    The partial transformation of ionic nanocrystals through cation exchange has been used to synthesize nanocrystal heterostructures. We demonstrate that the selectivity for cation exchange to take place at different facets of the nanocrystal plays an important role in determining the resulting morphology of the binary heterostructure. In the case of copper I (Cu+) cation exchange in cadmium sulfide (CdS) nanorods, the reaction starts preferentially at the ends of the nanorods such that copper sulfide (Cu2S) grows inwards from either end. The resulting morphology is very different from the striped pattern obtained in our previous studies of silver I (Ag+) exchange in CdS nanorods where non-selective nucleation of silver sulfide (Ag2S) occurs. From interface formation energies calculated for several models of epitaxialconnections between CdS and Cu2S or Ag2S, we infer the relative stability of each interface during the nucleation and growth of Cu2S or Ag2S within the CdS nanorods. The epitaxial connections of Cu2S to the end facets of CdS nanorods minimize the formation energy, making these interfaces stable throughout the exchange reaction. However, as the two end facets of wurtzite CdS nanorods are crystallographically nonequivalent, asymmetric heterostructures can be produced.

  20. [The balneotherapeutic components of sulfide-containing mineral waters].

    Science.gov (United States)

    Khutoryansky, V A; Gorshkov, A G

    2015-01-01

    It has been suggested in an early study that sulfanes may serve as a source of sulfur contained in hydrogen sulfide sources. We have performed derivatization of sulfanes, known to be present in the "Novonukutskaya" mineral water. The presence of polysulfanes in balneotherapeutic sulfide waters was confirmed by the HPLC-UV and chromato-mass spectrometric techniques. Derivatization of inorganic polysulfides was achieved by using the reaction with methyl iodide. It was shown that polysulfanes contained in the examined samples were metastable and disintegrated into So and H2S. Almost all molecular zero-valent sulfur was present in the form of S8. The application of HPLC allowed to determine the equilibrium concentration of molecular sulfur. The presence of the above compounds in therapeutic sulfide waters raises the question of the mechanism of their curative action. The authors hypothesize that it may be related to the high therapeutic potency of the substances obtained by steam distillation from the "Novonukutskaya" mineral water. PMID:26841531

  1. Dihydrogen Activation by Titanium Sulfide Complexes

    Science.gov (United States)

    Sweeney, Zachary K.; Polse, Jennifer L.; Bergman*, Robert G.; Andersen*, Richard A.

    2005-01-01

    The titanocene sulfido complex Cp*2Ti(S)py (1, Cp* = pentamethylcyclopentadienyl; py = pyridine) is synthesized by addition of a suspension of S8 to a toluene solution of Cp*2Ti-(CH2CH2) (2) and py. The rate of rotation of the pyridine ligand in solution was determined by 1H NMR spectroscopy, and the structure of 1 was determined by X-ray crystallography. Complex 1 reacts reversibly with dihydrogen to give Cp*2Ti(H)SH (6) and py. Reaction of 1 with HD gives an equilibrium mixture of Cp*2Ti(D)SH and Cp*2Ti(H)SD; H2 and D2 are not formed in this reaction. 1D 1H NMR magnetization transfer spectra and 2D EXSY 1H NMR spectra of 6 in the presence of H2 show that in solution the H2, hydride, and hydrosulfido hydrogen atoms exchange. A four-center mechanism for this exchange is proposed. The EXSY studies show that the Ti–H and S–H hydrogens exchange with each other more rapidly than either of those hydrogens exchanges with external H2. A transient dihydrogen complex intermediate is proposed to explain this observation. The infrared spectrum of 6 shows an absorption assigned to the Ti–H stretching mode at 1591 cm−1 that shifts upon deuteration to 1154 cm−1. Reaction of 1 with trimethylsilane, diethylsilane, or dimethylsilane gives Cp*2-Ti(H)SSiMe3 (7), Cp*2Ti(H)SSiHEt2 (8), or Cp*2Ti(H)SSiHMe2 (9), respectively. The isotope effect for the reaction producing 7 has been measured, and a mechanism is proposed. Treatment of 1 with an additional equivalent of S8 results in the formation of the disulfide Cp*2Ti(S2) (4). Acetylene inserts into the Ti–S bond of 4 to produce the vinyl disulfide complex 5. The structures of 4 and 5 have been determined by X-ray diffraction. Compound 4 reacts with 2 in the presence of py to produce 1. Phosphines react with 4 in the presence of H2 to provide 6 and the corresponding phosphine sulfide. Reaction of hydrogen with 4 gives Cp*2-Ti(SH)2 (3). The reactions of 1 and 4 with dihydrogen provide a model for possible mechanisms of H2

  2. 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

  3. Formation of gold clusters on La-Ni mixed oxides and its catalytic performance for isomerization of allylic alcohols to saturated aldehydes

    International Nuclear Information System (INIS)

    Au/NiO catalyzed the isomerization of allylic alcohols to afford saturated aldehydes. La-Ni mixed oxide could stabilize Au(III) and afford gold clusters smaller than 1 nm by H2 reduction. The resulting Au clusters on La-Ni-O exhibited superior catalytic performance to Au/NiO for the isomerization of internal allylic alcohol, 2-octen-1-ol to octanal. (author)

  4. An Efficient Protocol for the Palladium-catalyzed Asymmetric Decarboxylative Allylic Alkylation Using Low Palladium Concentrations and a Palladium(II) Precatalyst

    OpenAIRE

    Marziale, Alexander N.; Duquette, Douglas C.; Craig, Robert A.; Kim, Kelly E.; Liniger, Marc; Numajiri, Yoshitaka; Stoltz, Brian M.

    2015-01-01

    Enantioselective catalytic allylic alkylation for the synthesis of 2-alkyl-2-allylcycloalkanones and 3,3-disubstituted pyrrolidinones, piperidinones and piperazinones has been previously reported by our laboratory. The efficient construction of chiral all-carbon quaternary centers by allylic alkylation was previously achieved with a catalyst derived in situ from zero valent palladium sources and chiral phosphinooxazoline (PHOX) ligands. We now report an improved reaction protocol with broad a...

  5. Synthesis of magnetic rhenium sulfide composite nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Tang Naimei [Division of Molecular and Materials Simulation, Key Lab for Nanomaterials, Ministry of Education, Beijing University of Chemical Technology, Beijing 100029 (China); Tu Weixia [Division of Molecular and Materials Simulation, Key Lab for Nanomaterials, Ministry of Education, Beijing University of Chemical Technology, Beijing 100029 (China)], E-mail: tuwx@mail.buct.edu.cn

    2009-10-15

    Rhenium sulfide nanoparticles are associated with magnetic iron oxide through coprecipitation of iron salts with tetramethylammonium hydroxide. Sizes of the formed magnetic rhenium sulfide composite particles are in the range 5.5-12.5 nm. X-ray diffraction and energy-dispersive analysis of X-rays spectra demonstrate the coexistence of Fe{sub 3}O{sub 4} and ReS{sub 2} in the composite particle, which confirm the formation of the magnetic rhenium sulfide composite nanoparticles. The association of rhenium sulfide with iron oxide not only keeps electronic state and composition of the rhenium sulfide nanoparticles, but also introduces magnetism with the level of 24.1 emu g{sup -1} at 14 kOe. Surface modification with monocarboxyl-terminated poly(ethylene glycol) (MPEG-COOH) has the role of deaggregating the composite nanoparticles to be with average hydrodynamic size of 27.3 nm and improving the dispersion and the stability of the composite nanoparticles in water.

  6. Effect of inoculum and sulfide type on simultaneous hydrogen sulfide removal from biogas and nitrogen removal from swine slurry and microbial mechanism.

    Science.gov (United States)

    Wang, Lan; Wei, Benping; Chen, Ziai; Deng, Liangwei; Song, Li; Wang, Shuang; Zheng, Dan; Liu, Yi; Pu, Xiaodong; Zhang, Yunhong

    2015-12-01

    Four reactors were initiated to study the effect of inoculum and sulfide type on the simultaneous hydrogen sulfide removal from biogas and nitrogen removal from swine slurry (Ssu-Nir) process. Anaerobic sludge, aerobic sludge, and water were used as inocula, and Na2S and biogas were used as a sulfide substrate, respectively. Additionally, 454 pyrosequencing of the 16S rRNA gene was used to explore the bacterial diversity. The results showed that sulfur-oxidizing bacteria (Thiobacillus, 42.2-84.4 %) were dominant in Ssu-Nir process and led to the excellent performance. Aerobic sludge was more suitable for inoculation of the Ssu-Nir process because it is better for rapidly enriching dominant sulfur-oxidizing bacteria (Thiobacillus, 54.4 %), denitrifying sulfur-oxidizing bacteria (40.0 %) and denitrifiers (23.9 %). Lower S(2-) removal efficiency (72.6 %) and NO3 (-) removal efficiency (biogas as a sulfide substrate than when Na2S was used. For the Ssu-Nir process with biogas as the sulfide substrate, limiting H2S absorption caused a high relative abundance of sulfur-oxidizing bacteria, Thiobacillus (84.8 %) and Thiobacillus sayanicus (39.6 %), which in turn led to low relative abundance of denitrifiers (1.6 %) and denitrifying sulfur-oxidizing bacteria (24.4 %), low NO3 (-) removal efficiency, and eventually poor performance.

  7. Sulfide Capacities of CaO-MgO-Al2O3-SiO2-CrO x Slags

    Science.gov (United States)

    Wang, Lijun; Wang, Yaxian; Chou, Kuo-chih; Seetharaman, Seshadri

    2016-08-01

    The sulfide capacities of CaO-MgO-Al2O3-SiO2-CrO x slags were measured by gas-slag equilibration method in the temperature range of 1823 K to 1898 K (1550 °C to 1625 °C) to reveal the effect of CrO x on the sulfide capacities of slags. Both higher basicity and temperature enhanced sulfide capacities. The CrO x additions in the range of 0 to 5 mass pct increased the sulfide capacity, but, further increase of CrO x contents to 7 pct was found to lower the sulfide capacity. Utilizing the relationship for estimating the ratio of Cr(II)/Cr(III) put forward by the present authors, the influence of Cr(II) on the sulfide capacities of the slags studied is discussed.

  8. Hydrogen sulfide monitoring and the effects of oil and gas activities on migratory birds in southeastern New Mexico [draft

    Data.gov (United States)

    US Fish and Wildlife Service, Department of the Interior — This study examined the effects of hydrogen sulfide (H2S), emitted by oil and gas activities, by focusing on migratory birds in southeastern New Mexico. Study sites...

  9. 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.

  10. One-pot synthesis of enantiomerically pure N-protected allylic amines from N-protected α-amino esters

    Science.gov (United States)

    Silveira-Dorta, Gastón; Álvarez-Méndez, Sergio J; Martín, Víctor S

    2016-01-01

    Summary An improved protocol for the synthesis of enantiomerically pure allylic amines is reported. N-Protected α-amino esters derived from natural amino acids were submitted to a one-pot tandem reduction–olefination process. The sequential reduction with DIBAL-H at −78 °C and subsequent in situ addition of organophosphorus reagents yielded the corresponding allylic amines without the need to isolate the intermediate aldehyde. This circumvents the problem of instability of the aldehydes. The method tolerates well both Wittig and Horner–Wadsworth–Emmons organophosphorus reagents. A better Z-(dia)stereoselectivity was observed when compared to the previous one-pot method. The (dia)stereoselectivity of the process was affected neither by the reaction solvent nor by the amount of DIBAL-H employed. The method is compatible with the presence of free hydroxy groups as shown with serine and threonine derivatives. PMID:27340486

  11. 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.

  12. 肝脏缺血再灌注损伤中硫化氢的作用新研究%To Study the Role of Hydrogen Sulfide in the Injury of Hepatic Ischemia Reperfusion

    Institute of Scientific and Technical Information of China (English)

    王佩; 王与胜

    2015-01-01

    Liver ischemia-reperfusion (hepatic ischemia reperfusion, HIRI) can cause serious damage to the liver function, especial y when suf ering from cir hosis of the liver, risk wil increase. Reasonable amounts of hydrogen sulfide (H2S) on the human body can protect liver. In this paper, through the analysis of the occurrence of liver ischemia-reperfusion injury mechanism and the biological mechanism of hydrogen sulfide, the brief analysis of the hydrogen sulfide is applied to the role of liver ischemia-reperfusion injury. Through the analysis, in order to can cause the at ention of the relevant researchers of hydrogen sulfide, and hydrogen sulfide in the clinical application of the way, promote the development of clinical research.%肝脏缺血再灌注(hepatic ischemia reperfusion,HIRI)会对肝功能造成严重损伤,尤其是当患有肝硬化时,风险便会加剧。合理剂量的硫化氢(H2S)对人体肝脏可起到保护作用。本文通过分析肝脏缺血再灌注损伤的发生机制和硫化氢的生物作用机制,简要分析了硫化氢应用于肝脏缺血再灌注损伤中的作用。以期通过分析,能引起相关研究人员对硫化氢的注意,从而扩展硫化氢在临床上的应用途径,促进临床治疗研究发展。

  13. 肝脏缺血再灌注损伤中硫化氢的作用新研究%To Study the Role of Hydrogen Sulfide in the Injury of Hepatic Ischemia Reperfusion

    Institute of Scientific and Technical Information of China (English)

    王佩; 王与胜

    2015-01-01

    肝脏缺血再灌注(hepatic ischemia reperfusion,HIRI)会对肝功能造成严重损伤,尤其是当患有肝硬化时,风险便会加剧。合理剂量的硫化氢(H2S)对人体肝脏可起到保护作用。本文通过分析肝脏缺血再灌注损伤的发生机制和硫化氢的生物作用机制,简要分析了硫化氢应用于肝脏缺血再灌注损伤中的作用。以期通过分析,能引起相关研究人员对硫化氢的注意,从而扩展硫化氢在临床上的应用途径,促进临床治疗研究发展。%Liver ischemia-reperfusion (hepatic ischemia reperfusion, HIRI) can cause serious damage to the liver function, especial y when suf ering from cir hosis of the liver, risk wil increase. Reasonable amounts of hydrogen sulfide (H2S) on the human body can protect liver. In this paper, through the analysis of the occurrence of liver ischemia-reperfusion injury mechanism and the biological mechanism of hydrogen sulfide, the brief analysis of the hydrogen sulfide is applied to the role of liver ischemia-reperfusion injury. Through the analysis, in order to can cause the at ention of the relevant researchers of hydrogen sulfide, and hydrogen sulfide in the clinical application of the way, promote the development of clinical research.

  14. Hydroxymethylation beyond Carbonylation: Enantioselective Iridium-Catalyzed Reductive Coupling of Formaldehyde with Allylic Acetates via Enantiotopic π-Facial Discrimination.

    Science.gov (United States)

    Garza, Victoria J; Krische, Michael J

    2016-03-23

    Chiral iridium complexes modified by SEGPHOS catalyze the 2-propanol-mediated reductive coupling of branched allylic acetates 1a-1o with formaldehyde to form primary homoallylic alcohols 2a-2o with excellent control of regio- and enantioselectivity. These processes, which rely on enantiotopic π-facial discrimination of σ-allyliridium intermediates, represent the first examples of enantioselective formaldehyde C-C coupling beyond aldol addition. PMID:26958737

  15. Statistic evaluation of cysteine and allyl alcohol as additives for Cu-Zn coatings from citrate baths

    OpenAIRE

    Julyana Ribeiro Garcia; Dalva Cristina Baptista do Lago; Fernando Lucas Gonçalves Silva; Eliane D'Elia; Aderval Severino Luna; Lilian Ferreira de Senna

    2013-01-01

    In the present work, cysteine and allyl alcohol were added to citrate baths as additives to Cu-Zn coatings on steel substrates. In order to verify the effects of the deposition parameters (current density, mechanical stirring speed, and additives) on the coating composition, electrochemical behavior, morphology, and microstructure properties of Cu-Zn coatings, the electrodeposition of the alloy was carried out using an experimental composite design 2³, in which these parameters were considere...

  16. 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.

  17. 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.

  18. 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.

  19. Use of biogenic sulfide for ZnS precipitation

    NARCIS (Netherlands)

    Esposito, G.; Veeken, A.; Weijma, J.; Lens, P.N.L.

    2006-01-01

    A 600 ml continuously stirred tank reactor was used to assess the performance of a zinc sulfide precipitation process using a biogenic sulfide solution (the effluent of a sulfate-reducing bioreactor) as sulfide source. In all experiments, a proportional-integral (PI) control algorithm was used to co

  20. 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.

  1. 含硫天然气净化厂硫化氢泄漏分析及对策%Study of hydrogen sulfide leakage and dispersion in sour gas purification plants and countermeasures

    Institute of Scientific and Technical Information of China (English)

    高少华; 邹兵; 严龙; 张贺; 王振

    2012-01-01

    Processing facilities with higher risk of H2S leakage were determined through analyzing purifying process and various causes that may result in leakage from one of the sour gas plants in Northeastern Sichuan. The feed gas in the desulphurization units and acid gas in the sulfur recovery units , mainly consisting of H2S and CO2 ,were selected for the simulation through comparing the process pressures, flow rates and material compositions. Weather conditions and terrains around the plant were studied. According to the statistics of local meteorological data during the last 5 years, low wind speed and cloudy weather were typical weather conditions, and Dl. 5m/s was selected for calculation of hydrogen sulfide dispersion at the plant. Surface roughness length recommended for small refineries by American Petroleum Institute was adopted. The Immediately Dangerous to Life or Health (IDLH ) zones resulted from the hazardous gas dispersions were calculated with PHAST based on three different leakage holes with lmin, 5min and 30min. The IDLH downwind distances range from 41m to 1190m with the farthest one resulting from the large hole release of feed gas from the desulphurization units under the typical weather. The effects of wind speeds and atmospheric stabilities on the H2S dispersion were also simulated and discussed with small hole release. Some suggestions were made for setting online leak detection and interlock systems in order to reduce the risk of H2S leakage It has instructive meanings in avoiding or reducing casualties due to hydrogen sulfide poisoning.%以川东北某含硫天然气净化厂为对象,通过分析该净化厂的处理工艺及可能造成泄漏的各种原因,确定了硫化氢泄漏危险较高的生产单元.通过工艺压力、流量、物料组分的比对,选取了脱硫单元原料气和硫磺回收单元酸性气作为模拟泄漏物料.对该厂所在地的气象条件和厂区的地形地貌进行了调查,净化厂当地近5年风速

  2. Simulation study to determine the feasibility of injecting hydrogen sulfide, carbon dioxide and nitrogen gas injection to improve gas and oil recovery oil-rim reservoir

    Science.gov (United States)

    Eid, Mohamed El Gohary

    This study is combining two important and complicated processes; Enhanced Oil Recovery, EOR, from the oil rim and Enhanced Gas Recovery, EGR from the gas cap using nonhydrocarbon injection gases. EOR is proven technology that is continuously evolving to meet increased demand and oil production and desire to augment oil reserves. On the other hand, the rapid growth of the industrial and urban development has generated an unprecedented power demand, particularly during summer months. The required gas supplies to meet this demand are being stretched. To free up gas supply, alternative injectants to hydrocarbon gas are being reviewed to support reservoir pressure and maximize oil and gas recovery in oil rim reservoirs. In this study, a multi layered heterogeneous gas reservoir with an oil rim was selected to identify the most optimized development plan for maximum oil and gas recovery. The integrated reservoir characterization model and the pertinent transformed reservoir simulation history matched model were quality assured and quality checked. The development scheme is identified, in which the pattern and completion of the wells are optimized to best adapt to the heterogeneity of the reservoir. Lateral and maximum block contact holes will be investigated. The non-hydrocarbon gases considered for this study are hydrogen sulphide, carbon dioxide and nitrogen, utilized to investigate miscible and immiscible EOR processes. In November 2010, re-vaporization study, was completed successfully, the first in the UAE, with an ultimate objective is to examine the gas and condensate production in gas reservoir using non hydrocarbon gases. Field development options and proces schemes as well as reservoir management and long term business plans including phases of implementation will be identified and assured. The development option that maximizes the ultimate recovery factor will be evaluated and selected. The study achieved satisfactory results in integrating gas and oil

  3. Kinetic model for simultaneous leaching of zinc sulfide and manganese dioxide in the presence of iron-oxidizing bacteria

    OpenAIRE

    KAI, Takami; Suenaga, Yo-ich; Migita, Atsuko; TAKAHASHI, Takeshige

    2000-01-01

    The effect of iron-oxidizing bacteria on the simultaneous leaching of zinc sulfide and manganese dioxide was studied. Some researchers have reported the enhancement of the leaching rate during the simultaneous leaching of metal oxides and metal sulfides. In the present study, we examined the effect of the presence of Thiobacillus ferrooxidans in the simultaneous leaching. We also examined the reaction rates during the simultaneous leaching in the presence of the bacteria in order to study the...

  4. Adsorption of dimethyl sulfide from aqueous solution by a cost-effective bamboo charcoal.

    Science.gov (United States)

    Wang, Ming; Huang, Zheng-Hong; Liu, Guangjia; Kang, Feiyu

    2011-06-15

    The adsorption of dimethyl sulfide from an aqueous solution by a cost-effective bamboo charcoal from Dendrocalamus was studied in comparison with other carbon adsorbents. The bamboo charcoal exhibited superior adsorption on dimethyl sulfide compared with powdered activated carbons at different adsorbent dosages. The adsorption characteristics of dimethyl sulfide onto bamboo charcoal were investigated under varying experimental conditions such as particle size, contact time, initial concentration and adsorbent dosage. The dimethyl sulfide removal was enhanced from 31 to 63% as the particle size was decreased from 24-40 to >300 mesh for the bamboo charcoal. The removal efficiency increased with increasing the adsorbent dosage from 0.5 to 10mg, and reached 70% removal efficiency at 10mg adsorbed. The adsorption capacity (μg/g) increased with increasing concentration of dimethyl sulfide while the removal efficiency decreased. The adsorption process conforms well to a pseudo-second-order kinetics model. The adsorption of dimethyl sulfide is more appropriately described by the Freundlich isotherm (R(2), 0.9926) than by the Langmuir isotherm (R(2), 0.8685). Bamboo charcoal was characterized by various analytical methods to understand the adsorption mechanism. Bamboo charcoal is abundant in acidic and alcohol functional groups normally not observed in PAC. A distinct difference is that the superior mineral composition of Fe (0.4 wt%) and Mn (0.6 wt%) was detected in bamboo charcoal-elements not found in PAC. Acidic functional group and specific adsorption sites would be responsible for the strong adsorption of dimethyl sulfide onto bamboo charcoal of Dendrocalamus origin. PMID:21549503

  5. Density Functional Investigation of Methanethiol and Dimethyl Sulfide Adsorption on Zeolite

    Institute of Scientific and Technical Information of China (English)

    Renqing Lü; Guangmin Qiu; Chenguang Liu

    2006-01-01

    The density functional theory and cluster model methods have been employed to investigate the interactions between methanethiol, dimethyl sulfide and zeolites. The molecular complexes formed by adsorption of methanethiol or dimethyl sulfide on silanol H3SiOSi(OH)2OSiH3 with five coordination forms or four coordination forms, and complexes formed by interactions of Br(o)nsted acid sites of bridging hydroxyl H3Si(OH)Al(OH)2OSiH3 with methanethiol or dimethyl sulfide have been investigated. Full optimization and frequency analysis of all cluster models have been carried out using the B3LYP hybrid method at 6-31+G (d,p) basis set level for hydrogen, silicon, aluminum, oxygen,carbon, and sulfur atoms. The structures and energy changes of different coordination forms between methanethiol and H3Si(OH)Al(OH)2OSiH3, dimethyl sulfide and H3Si(OH)Al(OH)2OSiH3, methanethiol and H3SiOSi(OH)2OSiH3, dimethyl sulfide and H3SiOSi(OH)2OSiH3 complexes have been comparatively studied. The calculated results showed the nature of interactions that led to the formation of all complexes was van der Waals force confirmed by an insignificant change of geometric structures and properties. The conclusions that methanethiol and dimethyl sulfide molecules were adsorbed on bridging hydroxyl group prior to silanol group were obtained on the basis of adsorption heat, the most stable adsorption models of a 6 ring structure for interaction between bridging hydroxyl and methanethiol, and a 7 ring structure for interaction between bridging hydroxyl and dimethyl sulfide.

  6. Transformation of iron sulfide to greigite by nitrite produced by oil field bacteria.

    Science.gov (United States)

    Lin, Shiping; Krause, Federico; Voordouw, Gerrit

    2009-05-01

    Nitrate, injected into oil fields, can oxidize sulfide formed by sulfate-reducing bacteria (SRB) through the action of nitrate-reducing sulfide-oxidizing bacteria (NR-SOB). When reservoir rock contains siderite (FeCO(3)), the sulfide formed is immobilized as iron sulfide minerals, e.g. mackinawite (FeS). The aim of our study was to determine the extent to which oil field NR-SOB can oxidize or transform FeS. Because no NR-SOB capable of growth with FeS were isolated, the well-characterized oil field isolate Sulfurimonas sp. strain CVO was used. When strain CVO was presented with a mixture of chemically formed FeS and dissolved sulfide (HS(-)), it only oxidized the HS(-). The FeS remained acid soluble and non-magnetic indicating that it was not transformed. In contrast, when the FeS was formed by adding FeCl(2) to a culture of SRB which gradually produced sulfide, precipitating FeS, and to which strain CVO and nitrate were subsequently added, transformation of the FeS to a magnetic, less acid-soluble form was observed. X-ray diffraction and energy-dispersive spectrometry indicated the transformed mineral to be greigite (Fe(3)S(4)). Addition of nitrite to cultures of SRB, containing microbially formed FeS, was similarly effective. Nitrite reacts chemically with HS(-) to form polysulfide and sulfur (S(0)), which then transforms SRB-formed FeS to greigite, possibly via a sulfur addition pathway (3FeS + S(0) --> Fe(3)S(4)). Further chemical transformation to pyrite (FeS(2)) is expected at higher temperatures (>60 degrees C). Hence, nitrate injection into oil fields may lead to NR-SOB-mediated and chemical mineral transformations, increasing the sulfide-binding capacity of reservoir rock. Because of mineral volume decreases, these transformations may also increase reservoir injectivity. PMID:19290520

  7. 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

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

    NARCIS (Netherlands)

    Tangerman, A.

    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

  9. Hydrogen Sulfide in Preeclampsia : Potential Therapeutic Implications

    NARCIS (Netherlands)

    Holwerda, Kim

    2015-01-01

    The thesis provide insights into the production and possible therapeutic effect of the gaseous molecule hydrogen sulfide (H2S) in preeclampsia (PE). H2S is an important molecule in the (human) body. It is among others involved in blood pressure regulation, stimulation of vascular growth and modulati

  10. 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.

  11. Increased presevation of sliced mozzarella cheese by antimibrobial sachet incorporated with allyl isothiocyanate

    Directory of Open Access Journals (Sweden)

    Ana Clarissa dos Santos Pires

    2009-12-01

    Full Text Available There is an increasing tendency to add natural antimicrobials of plant origin into food. The objective of this work was to develop a microbial sachet incorporated with allyl isothiocyanate (AIT, a volatile compound of plant origin, and to test its efficiency against growth of yeasts and molds, Staphylococcus sp. and psychrotrophic bacteria on sliced mozzarella cheese. Another objective was to quantify the concentration of AIT in the headspace of cheese packaging. A reduction of 3.6 log cycles was observed in yeasts and molds counts in the mozzarella packed with the antimicrobial sachet over 15-day storage time. The sachet also showed an antibacterial effect on Staphylococcus sp., reducing 2.4 log cycles after 12-day storage. Psychrotrophic bacteria species were the most resistant to the antimicrobial action. The highest concentration of AIT (0.08µg.mL-1 inside the active packaging system was observed at the 6-day of storage at 12 ºC ± 2 ºC. At the end of the storage time, AIT concentration decreased to only 10% of the initial concentration. Active packaging containing antimicrobial sachet has a potential use for sliced mozzarella, with molds and yeasts being the most sensitive to the antimicrobial effects.

  12. Merging allylic carbon-hydrogen and selective carbon-carbon bond activation

    Science.gov (United States)

    Masarwa, Ahmad; Didier, Dorian; Zabrodski, Tamar; Schinkel, Marvin; Ackermann, Lutz; Marek, Ilan

    2014-01-01

    Since the nineteenth century, many synthetic organic chemists have focused on developing new strategies to regio-, diastereo- and enantioselectively build carbon-carbon and carbon-heteroatom bonds in a predictable and efficient manner. Ideal syntheses should use the least number of synthetic steps, with few or no functional group transformations and by-products, and maximum atom efficiency. One potentially attractive method for the synthesis of molecular skeletons that are difficult to prepare would be through the selective activation of C-H and C-C bonds, instead of the conventional construction of new C-C bonds. Here we present an approach that exploits the multifold reactivity of easily accessible substrates with a single organometallic species to furnish complex molecular scaffolds through the merging of otherwise difficult transformations: allylic C-H and selective C-C bond activations. The resulting bifunctional nucleophilic species, all of which have an all-carbon quaternary stereogenic centre, can then be selectively derivatized by the addition of two different electrophiles to obtain more complex molecular architecture from these easily available starting materials.

  13. Theoretical kinetic estimates for the recombination of hydrogen atoms with propargyl and allyl radicals

    Energy Technology Data Exchange (ETDEWEB)

    Harding, L. B.; Klippenstein, S. J.

    2000-01-12

    Ab initio quantum chemical simulations are coupled with variational transition state theory in estimating rate constants for the H+C{sub 3}H{sub 3} and H+C{sub 3}H{sub 5} recombination reactions. The energy of interaction between the H atom and each of the radicals is evaluated at the CAS+1+2 level for the range of separations and relative orientations spanning the transition state region. An analytic representation of these interaction energies is then implemented in variable reaction coordinate transition state theory calculations of the high pressure limit recombination rate constant for temperatures ranging from 200 to 2000 K. For the propargyl reaction the overall addition rate is separated into contributions correlating with the initial formation of allene and propyne. These theoretical results are compared with the available experimental data as well as with corresponding theoretical estimates for the H+C{sub 2}H{sub 3} and H+C{sub 2}H{sub 5} reactions. The H+propargyl and H+allyl total recombination rates are remarkably similar, with both being greater than the H+vinyl and H+ethyl rates, due to the presence of twice as many addition channels.

  14. Allyl m-Trifluoromethyldiazirine Mephobarbital: An Unusually Potent Enantioselective and Photoreactive Barbiturate General Anesthetic

    Energy Technology Data Exchange (ETDEWEB)

    Savechenkov, Pavel Y.; Zhang, Xi; Chiara, David C.; Stewart, Deirdre S.; Ge, Rile; Zhou, Xiaojuan; Raines, Douglas E.; Cohen, Jonathan B.; Forman, Stuart A.; Miller, Keith W.; Bruzik, Karol S. (Harvard-Med); (Mass. Gen. Hosp.); (UIC)

    2012-12-10

    We synthesized 5-allyl-1-methyl-5-(m-trifluoromethyl-diazirynylphenyl)barbituric acid (14), a trifluoromethyldiazirine-containing derivative of general anesthetic mephobarbital, separated the racemic mixture into enantiomers by chiral chromatography, and determined the configuration of the (+)-enantiomer as S by X-ray crystallography. Additionally, we obtained the {sup 3}H-labeled ligand with high specific radioactivity. R-(-)-14 is an order of magnitude more potent than the most potent clinically used barbiturate, thiopental, and its general anesthetic EC{sub 50} approaches those for propofol and etomidate, whereas S-(+)-14 is 10-fold less potent. Furthermore, at concentrations close to its anesthetic potency, R-(-)-14 both potentiated GABA-induced currents and increased the affinity for the agonist muscimol in human {alpha}1{beta}2/3{gamma}2L GABA{sub A} receptors. Finally, R-(-)-14 was found to be an exceptionally efficient photolabeling reagent, incorporating into both {alpha}1 and {beta}3 subunits of human {alpha}1{beta}3 GABAA receptors. These results indicate R-(-)-14 is a functional general anesthetic that is well-suited for identifying barbiturate binding sites on Cys-loop receptors.

  15. Enhanced biocompatibility and wound healing properties of biodegradable polymer-modified allyl 2-cyanoacrylate tissue adhesive.

    Science.gov (United States)

    Lee, Young Ju; Son, Ho Sung; Jung, Gyeong Bok; Kim, Ji Hye; Choi, Samjin; Lee, Gi-Ja; Park, Hun-Kuk

    2015-06-01

    As poly L-lactic acid (PLLA) is a polymer with good biocompatibility and biodegradability, we created a new tissue adhesive (TA), pre-polymerized allyl 2-cyanoacrylate (PACA) mixed with PLLA in an effort to improve biocompatibility and mechanical properties in healing dermal wound tissue. We determined optimal mixing ratios of PACA and PLLA based on their bond strengths and chemical structures analyzed by the thermal gravimetric analysis (TGA) and Fourier transform infrared (FT-IR) spectroscopy. In vitro biocompatibility of the PACA/PLLA was evaluated using direct- and indirect-contact methods according to the ISO-10993 cytotoxicity test for medical devices. The PACA/PLLA have similar or even better biocompatibility than those of commercially available cyanoacrylate (CA)-based TAs such as Dermabond® and Histoacryl®. The PACA/PLLA were not different from those exposed to Dermabond® and Histoacryl® in Raman spectra when biochemical changes of protein and DNA/RNA underlying during cell death were compared utilizing Raman spectroscopy. Histological analysis revealed that incised dermal tissues of rats treated with PACA/PLLA showed less inflammatory signs and enhanced collagen formation compared to those treated with Dermabond® or Histoacryl®. Of note, tissues treated with PACA/PLLA were stronger in the tensile strength compared to those treated with the commercially available TAs. Therefore, taking all the results into consideration, the PACA/PLLA we created might be a clinically useful TA for treating dermal wounds. PMID:25842106

  16. Allyl functionalized phosphinite and phosphonite ligands: Synthesis, transition metal chemistry and orthopalladation reactions

    Indian Academy of Sciences (India)

    Singappagudem Govindaraju; Guddekoppa S Ananthnag; Susmita Naik; Shaikh M Mobin; Maravanji S Balakrishn

    2012-07-01

    Allyl functionalized phosphinite PPh2(OAr) [Ar=C6H4(-C3H5)] (1) and phosphonite PPh(OAr)2 (2) ligands were prepared by the reactions of 2-allylphenol with PPh2Cl and PPhCl2, respectively. The ruthenium(II) complexes, [Ru(6--cymene)(PPh2(OAr))Cl2] (3) and [Ru(6--cymene)(PPh(OAr)2Cl2)] (4) were obtained by reacting 1 or 2 with [Ru(6--cymene)Cl2]2 in 2:1 molar ratios, respectively. Reactions of 1 or 2 with AuCl(SMe2) gave [Au{PPh2(OAr)}Cl] (5) or [Au{PPh(OAr)2}Cl] (6) in good yield. The palladium complex, [Pd{PPh(OAr)2}2Cl2] (7) was prepared by reacting Pd(COD)Cl2 with 2 in 1:2 molar ratio. The reaction between Pd(COD)Cl2 and 1 yielded a mixture of orthopalladated cis- and trans-[Pd(Ph2P(OAr))Cl]2 (8a and 8b). The treatment of 8 with PPh3 and Ph2PCH2PPh2 resulted in the cleavage of chloro bridge to give respectively, [Ph2(OAr)PPd(PPh3)Cl] (9) and [Ph2(ArO)PPd(2-dppm)]OTf (10). Single crystal X-ray structure of the ruthenium complex 3 is described.

  17. 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.

  18. Selective Sulfidation of Lead Smelter Slag with Pyrite and Flotation Behavior of Synthetic ZnS

    Science.gov (United States)

    Han, Junwei; Liu, Wei; Wang, Dawei; Jiao, Fen; Zhang, Tianfu; Qin, Wenqing

    2016-08-01

    The selective sulfidation of lead smelter slag with pyrite in the presence of carbon and Na salts, and the flotation behavior of synthetic ZnS were studied. The effects of temperature, time, pyrite dosage, Na salts, and carbon additions were investigated based on thermodynamic calculation, and correspondingly, the growth mechanism of ZnS particles was studied at high temperatures. The results indicated that the zinc in lead smelter slag was selectively converted into zinc sulfides by sulfidation roasting. The sulfidation degree of zinc was increased until the temperature, time, pyrite, and carbon dosages reached their optimum values, under which it was more than 95 pct. The growth of ZnS particles largely depended upon roasting temperature, and the ZnS grains were significantly increased above 1373 K (1100 °C) due to the formation of a liquid phase. After the roasting, the zinc sulfides generated had a good floatability, and 88.34 pct of zinc was recovered by conventional flotation.

  19. Nuclear Spin Lattice Relaxation and Conductivity Studies of the Non-Arrhenius Conductivity Behavior in Lithium Fast Ion Conducting Sulfide Glasses

    Energy Technology Data Exchange (ETDEWEB)

    Benjamin Michael Meyer

    2003-05-31

    As time progresses, the world is using up more of the planet's natural resources. Without technological advances, the day will eventually arrive when these natural resources will no longer be sufficient to supply all of the energy needs. As a result, society is seeing a push for the development of alternative fuel sources such as wind power, solar power, fuel cells, and etc. These pursuits are even occurring in the state of Iowa with increasing social pressure to incorporate larger percentages of ethanol in gasoline. Consumers are increasingly demanding that energy sources be more powerful, more durable, and, ultimately, more cost efficient. Fast Ionic Conducting (FIC) glasses are a material that offers great potential for the development of new batteries and/or fuel cells to help inspire the energy density of battery power supplies. This dissertation probes the mechanisms by which ions conduct in these glasses. A variety of different experimental techniques give a better understanding of the interesting materials science taking place within these systems. This dissertation discusses Nuclear Magnetic Resonance (NMR) techniques performed on FIC glasses over the past few years. These NMR results have been complimented with other measurement techniques, primarily impedance spectroscopy, to develop models that describe the mechanisms by which ionic conduction takes place and the dependence of the ion dynamics on the local structure of the glass. The aim of these measurements was to probe the cause of a non-Arrhenius behavior of the conductivity which has been seen at high temperatures in the silver thio-borosilicate glasses. One aspect that will be addressed is if this behavior is unique to silver containing fast ion conducting glasses. more specifically, this study will determine if a non-Arrhenius correlation time, {tau}, can be observed in the Nuclear Spin Lattice Relaxation (NSLR) measurements. If so, then can this behavior be modeled with a new single

  20. 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......, sulfide emission and thereby potential hydrogen sulfide buildup in the sewer atmosphere is of particular importance in sewers constructed with large diameter pipes, in sewers constructed with steep slopes and in sewers conveying low pH wastewater. Precipitation of metal sulfides is only important when...

  1. 降低长坡选矿厂全浮硫化矿中锡损失的试验研究%Experimental study on reducing the loss of cassiterite in bulk flotation sulfides in Changpo plant

    Institute of Scientific and Technical Information of China (English)

    周德炎

    2012-01-01

    针对长坡选矿厂在全浮流程中添加大量药剂回收硫化矿,细粒、微细粒锡石易损失于全浮硫化矿中的特点,采用组合抑制剂BY-6抑制锡石,降低锡损失,使损失于全浮硫化矿中的锡石含量仅为13.48%。%In Changpo plant, amounts of agents were used to recover sulfides, which led to some fine or ultra-fme cassiterites loss in bulk flotation sulfides. In order to solve this problem, a combined depressant named BY-6 was adopted. The results showed the loss of fine or ultra-fine cassiterites could be effectively controlled and the mass ratio of cassiterite in bulk flotation sulfides was only 14.48%.

  2. Pressure Effects on Product Channels of the Allyl Radical Reactions; C3H5+C3H5 and C3H5+CH3

    Science.gov (United States)

    Halpern, J. B.; N'Doumi, M.; Fahr, A.

    2011-12-01

    Relatively large hydrocarbon molecules (C4, C6 and larger) have been detected in several planetary environments. The mechanism for the formation of such large molecular species and detailed mechanism for their potential destruction are not well understood and are of considerable current interest. Previously we have studied the kinetics and product channels of small unsaturated hydrocarbon radical (C2 and C3s) reactions relevant to planetary atmospheric modeling. Reactions of C2 radicals (such as vinyl, H2CCH and ethynyl C2H) and C3 radicals (such as propargyl, HCCCH2) can affect the abundances of a large number of stable observable C3, C4, C5, C6 and larger molecules, including linear, aromatic and even poly aromatic molecules. Pressure-dependent product yields have been determined experimentally for the self- and cross-radical reactions performed at 298 K and at pressures between ~4 Torr (0.5 kPa) and 760 Torr (101 kPa). Final reaction products were quantitatively determined using a gas chromatograph with mass spectrometry/flame ionization detection (GC/MS/FID). In some cases complementary computational studies extended the pressure and temperature range of the experiments and provided valuable information on the complex reaction mechanisms. Theses studies provide a systematic framework so that important energetic and structural parameters for radical-radical reactions can be assessed. Here we report recent results for the allyl radical reactions H2CCCH3+ H2CCCH3 and H2CCCH3+CH3. For the allyl radical self-reaction, at high pressures the "head -to-head", combination channel forming 1,5-hexadiene is dominant with a combination/disproportionation = 1,5-hexadiene/propyne ratio of about 24 at 500 Torr (67 kPa, T=298K). At low pressures the ratio is substantially reduced to about 1.2 (at 0.3 kPa) and other major products are observed including allene, propene, 1-butene and propyne.

  3. Dimethyl sulfide in the Amazon rain forest

    Science.gov (United States)

    Jardine, K.; Yañez-Serrano, A. M.; Williams, J.; Kunert, N.; Jardine, A.; Taylor, T.; Abrell, L.; Artaxo, P.; Guenther, A.; Hewitt, C. N.; House, E.; Florentino, A. P.; Manzi, A.; Higuchi, N.; Kesselmeier, J.; Behrendt, T.; Veres, P. R.; Derstroff, B.; Fuentes, J. D.; Martin, S. T.; Andreae, M. O.

    2015-01-01

    Surface-to-atmosphere emissions of dimethyl sulfide (DMS) may impact global climate through the formation of gaseous sulfuric acid, which can yield secondary sulfate aerosols and contribute to new particle formation. While oceans are generally considered the dominant sources of DMS, a shortage of ecosystem observations prevents an accurate analysis of terrestrial DMS sources. Using mass spectrometry, we quantified ambient DMS mixing ratios within and above a primary rainforest ecosystem in the central Amazon Basin in real-time (2010-2011) and at high vertical resolution (2013-2014). Elevated but highly variable DMS mixing ratios were observed within the canopy, showing clear evidence of a net ecosystem source to the atmosphere during both day and night in both the dry and wet seasons. Periods of high DMS mixing ratios lasting up to 8 h (up to 160 parts per trillion (ppt)) often occurred within the canopy and near the surface during many evenings and nights. Daytime gradients showed mixing ratios (up to 80 ppt) peaking near the top of the canopy as well as near the ground following a rain event. The spatial and temporal distribution of DMS suggests that ambient levels and their potential climatic impacts are dominated by local soil and plant emissions. A soil source was confirmed by measurements of DMS emission fluxes from Amazon soils as a function of temperature and soil moisture. Furthermore, light- and temperature-dependent DMS emissions were measured from seven tropical tree species. Our study has important implications for understanding terrestrial DMS sources and their role in coupled land-atmosphere climate feedbacks.

  4. Luminescence of high-doped calcium sulfide crystals

    International Nuclear Information System (INIS)

    Calcium sulfide crystals grown by high-temperatur mineralization tecnique have been studied. Bands peaked at 2.12 and 2.5-2.7 eV are considered the most invariable features of cathodoluminescence and photoluminescence spectra. It has been found that the 2.12 eV band is conditioned by optical electronic transitions in Mn2+ ions substituted for Ca2+ ions in the host lattice. The exciton mechanism of energy transfer to centers, that are responsible for the high-energy luminescence band, is discussed

  5. Dynamic corrosion of copper-nickel sulfide by Acidithiobacillus ferrooxidans

    Institute of Scientific and Technical Information of China (English)

    TONG Lin-lin; JIANG Mao-fa; YANG Hong-ying; YU Juan; FAN You-jing; ZHANG Yao

    2009-01-01

    The dynamic corrosion process of bio-oxidation of copper-nickel sulfide from Karatungk in northern Xinjiang Province of China was studied. The polished wafer of the copper-nickel sulphide was used to carry on a series of oxidation corrosion experiment by Acidithiobacillus ferrooxidans. The changes of superficial corrosion appearance and the mineral dynamic corrosion process were discovered by microscope observation. Then, the galvanic cell model was established, and the bio-oxidation activation order of typical copper-nickel sulphide minerals was ascertained as pyrrhotite>pentlandite>chalocopyrite.

  6. Bioconversion of high concentrations of hydrogen sulfide to elemental sulfur in airlift bioreactor.

    Science.gov (United States)

    Zytoon, Mohamed Abdel-Monaem; AlZahrani, Abdulraheem Ahmad; Noweir, Madbuli Hamed; El-Marakby, Fadia Ahmed

    2014-01-01

    Several bioreactor systems are used for biological treatment of hydrogen sulfide. Among these, airlift bioreactors are promising for the bioconversion of hydrogen sulfide into elemental sulfur. The performance of airlift bioreactors is not adequately understood, particularly when directly fed with hydrogen sulfide gas. The objective of this paper is to investigate the performance of an airlift bioreactor fed with high concentrations of H2S with special emphasis on the effect of pH in combination with other factors such as H2S loading rate, oxygen availability, and sulfide accumulation. H2S inlet concentrations between 1,008 ppm and 31,215 ppm were applied and elimination capacities up to 113 g H2S m(-3) h(-1) were achieved in the airlift bioreactor under investigation at a pH range 6.5-8.5. Acidic pH values reduced the elimination capacity. Elemental sulfur recovery up to 95% was achieved under oxygen limited conditions (DO bioreactor tolerated accumulated dissolved sulfide concentrations >500 mg/L at pH values 8.0-8.5, and near 100% removal efficiency was achieved. Overall, the resident microorganisms in the studied airlift bioreactor favored pH values in the alkaline range. The bioreactor performance in terms of elimination capacity and sulfur recovery was better at pH range 8-8.5.

  7. Pathways of sulfide oxidation by haloalkaliphilic bacteria in limited-oxygen gas lift bioreactors.

    Science.gov (United States)

    Klok, Johannes B M; van den Bosch, Pim L F; Buisman, Cees J N; Stams, Alfons J M; Keesman, Karel J; Janssen, Albert J H

    2012-07-17

    Physicochemical processes, such as the Lo-cat and Amine-Claus process, are commonly used to remove hydrogen sulfide from hydrocarbon gas streams such as landfill gas, natural gas, and synthesis gas. Biodesulfurization offers environmental advantages, but still requires optimization and more insight in the reaction pathways and kinetics. We carried out experiments with gas lift bioreactors inoculated with haloalkaliphilic sulfide-oxidizing bacteria. At oxygen-limiting levels, that is, below an O(2)/H(2)S mole ratio of 1, sulfide was oxidized to elemental sulfur and sulfate. We propose that the bacteria reduce NAD(+) without direct transfer of electrons to oxygen and that this is most likely the main route for oxidizing sulfide to elemental sulfur which is subsequently oxidized to sulfate in oxygen-limited bioreactors. We call this pathway the limited oxygen route (LOR). Biomass growth under these conditions is significantly lower than at higher oxygen levels. These findings emphasize the importance of accurate process control. This work also identifies a need for studies exploring similar pathways in other sulfide oxidizers such as Thiobacillus bacteria.

  8. Formation of Fe-sulfides in cultures of sulfate-reducing bacteria

    International Nuclear Information System (INIS)

    The purpose of this study was to synthesize Fe-sulfides produced with sulfate-reducing bacteria under experimental laboratory conditions. Fe-sulfides were precipitated with biologically produced sulfide in cultures growing at 22, 45, and 60 deg. C for up to 16 weeks. Abiotic controls were prepared by reacting liquid media with Na2S solutions. Precipitates were collected anaerobically, freeze-dried and analyzed by X-ray diffraction. Additional analyses included total Fe and S content, magnetic susceptibility, specific surface area, and scanning electron microscopy. Mackinawite (FeS) and greigite (Fe3S4) were the dominant iron sulfide phases formed in sulfate-reducing bacterial cultures. An increase in the incubation temperature from 22 to 60 deg. C enhanced the crystallinity of the Fe-sulfides. Generally, greigite was more prevalent in abiotic samples and mackinawite in biogenic materials. Pyrite (FeS2) was also found in abiotic precipitates. Abiotic samples had a higher magnetic susceptibility because of the greigite and displayed improved crystallinity compared to biotic materials.

  9. Modeling the Effect of Dissolved Hydrogen Sulfide on Mg2+-water Complex on Dolomite {104} Surfaces

    CERN Document Server

    Shen, Zhizhang; Brown, Philip E; Szlufarska, Izabela; Xu, Huifang

    2016-01-01

    The key kinetic barrier to dolomite formation is related to the surface Mg2+-H2O complex, which hinders binding of surface Mg2+ ions to the CO3 2- ions in solution. It has been proposed that this reaction can be catalyzed by dissolved hydrogen sulfide. To characterize the role of dissolved hydrogen sulfide in the dehydration of surface Mg 2+ ions, ab initio simulations based on density functional theory (DFT) were carried out to study the thermodynamics of competitive adsorption of hydrogen sulfide and water on dolomite (104) surfaces from solution. We find that water is thermodynamically more stable on the surface with the difference in adsorption energy of -13.6 kJ/mol (in vacuum) and -12.8 kJ/mol (in aqueous solution). However, aqueous hydrogen sulfide adsorbed on the surface increases the Mg2+-H2O distances on surrounding surface sites. Two possible mechanisms were proposed for the catalytic effects of adsorbed hydrogen sulfide on the anhydrous Ca-Mg-carbonate crystallization at low temperature.

  10. Formation of Fe-sulfides in cultures of sulfate-reducing bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Gramp, Jonathan P. [Department of Microbiology, Ohio State University, 484 W. 12th Avenue, Columbus, OH 43210 (United States); Bigham, Jerry M.; Jones, F. Sandy [School of Environment and Natural Resources, 2021 Coffey Road, Ohio State University, Columbus, OH 43210 (United States); Tuovinen, Olli H., E-mail: tuovinen.1@osu.edu [Department of Microbiology, Ohio State University, 484 W. 12th Avenue, Columbus, OH 43210 (United States) and Department of Chemistry and Bioengineering, Tampere University of Technology, P.O. Box 541, FI 33101 Tampere (Finland)

    2010-03-15

    The purpose of this study was to synthesize Fe-sulfides produced with sulfate-reducing bacteria under experimental laboratory conditions. Fe-sulfides were precipitated with biologically produced sulfide in cultures growing at 22, 45, and 60 deg. C for up to 16 weeks. Abiotic controls were prepared by reacting liquid media with Na{sub 2}S solutions. Precipitates were collected anaerobically, freeze-dried and analyzed by X-ray diffraction. Additional analyses included total Fe and S content, magnetic susceptibility, specific surface area, and scanning electron microscopy. Mackinawite (FeS) and greigite (Fe{sub 3}S{sub 4}) were the dominant iron sulfide phases formed in sulfate-reducing bacterial cultures. An increase in the incubation temperature from 22 to 60 deg. C enhanced the crystallinity of the Fe-sulfides. Generally, greigite was more prevalent in abiotic samples and mackinawite in biogenic materials. Pyrite (FeS{sub 2}) was also found in abiotic precipitates. Abiotic samples had a higher magnetic susceptibility because of the greigite and displayed improved crystallinity compared to biotic materials.

  11. Formation of Fe-sulfides in cultures of sulfate-reducing bacteria.

    Science.gov (United States)

    Gramp, Jonathan P; Bigham, Jerry M; Jones, F Sandy; Tuovinen, Olli H

    2010-03-15

    The purpose of this study was to synthesize Fe-sulfides produced with sulfate-reducing bacteria under experimental laboratory conditions. Fe-sulfides were precipitated with biologically produced sulfide in cultures growing at 22, 45, and 60 degrees C for up to 16 weeks. Abiotic controls were prepared by reacting liquid media with Na(2)S solutions. Precipitates were collected anaerobically, freeze-dried and analyzed by X-ray diffraction. Additional analyses included total Fe and S content, magnetic susceptibility, specific surface area, and scanning electron microscopy. Mackinawite (FeS) and greigite (Fe(3)S(4)) were the dominant iron sulfide phases formed in sulfate-reducing bacterial cultures. An increase in the incubation temperature from 22 to 60 degrees C enhanced the crystallinity of the Fe-sulfides. Generally, greigite was more prevalent in abiotic samples and mackinawite in biogenic materials. Pyrite (FeS(2)) was also found in abiotic precipitates. Abiotic samples had a higher magnetic susceptibility because of the greigite and displayed improved crystallinity compared to biotic materials. PMID:19962824

  12. Measurements of hydrogen sulfide (H2S) using PTR-MS: calibration, humidity dependence, inter-comparison and results from field studies in an oil and gas production region

    Science.gov (United States)

    Li, R.; Warneke, C.; Graus, M.; Field, R.; Geiger, F.; Veres, P. R.; Soltis, J.; Li, S.-M.; Murphy, S. M.; Sweeney, C.; Pétron, G.; Roberts, J. M.; de Gouw, J.

    2014-10-01

    Natural gas production is associated with emissions of several trace gases, some of them classified as air toxics. While volatile organic compounds (VOCs) have received much attention, hydrogen sulfide (H2S) can also be of concern due to the known health impacts of exposure to this hazardous air pollutant. Here, we present quantitative, fast time-response measurements of H2S using proton-transfer-reaction mass-spectrometry (PTR-MS) instruments. An ultra-light-weight PTR-MS (ULW-PTR-MS) in a mobile laboratory was operated for measurements of VOCs and H2S in a gas and oil field during the Uintah Basin Winter Ozone Study (UBWOS) 2012 campaign. Measurements of VOCs and H2S by a PTR-MS were also made at the Horse Pool ground site in the Uintah Basin during UBWOS 2013. The H2S measurement by PTR-MS is strongly humidity dependent because the proton affinity of H2S is only slightly higher than that of water. The H2S sensitivity of PTR-MS ranged between 0.6-1.4 ncps ppbv-1 during UBWOS 2013. We compare the humidity dependence determined in the laboratory with in-field calibrations and determine the H2S mixing ratios for the mobile and ground measurements. The PTR-MS measurements at Horse Pool are evaluated by comparison with simultaneous H2S measurements using a PTR time-of-flight MS (PTR-ToF-MS) and a Picarro cavity ring down spectroscopy (CRDS) instrument for H2S / CH4. On average 0.6 ± 0.3 ppbv H2S was present at Horse Pool during UBWOS 2013. The correlation between H2S and methane enhancements suggests that the source of H2S is associated with oil and gas extraction in the basin. Significant H2S mixing ratios of up to 9 ppmv downwind of storage tanks were observed during the mobile measurements. This study suggests that H2S emissions associated with oil and gas production can lead to short-term high levels close to point sources, and elevated background levels away from those sources. In addition, our work has demonstrated that PTR-MS can make reliable measurements of

  13. CuCl-Catalyzed Aerobic Oxidation of Allylic and Propargylic Alcohols to Aldehydes or Ketones with 1 : 1 Combination of Phenanthroline and Bipyridine as the Ligandst%CuCl-Catalyzed Aerobic Oxidation of Allylic and Propargylic Alcohols to Aldehydes or Ketones with 1 : 1 Combination of Phenanthroline and Bipyridine as the Ligandst

    Institute of Scientific and Technical Information of China (English)

    刘宇; 麻生明

    2012-01-01

    We developed a modified protocol for the oxidation of 2,3-allenyl alcohols using CuCI with l : 1 combination of phenanthroline and bipyridine as the catalyst. To further investigate the applicability of this system, other types of alcohols such as allylic and propargylic alcohols have been tested: we found that both allylic and propargylic alcohols may be oxidized to the corresponding aldehydes or ketones using molecular oxygen in air as the oxidant with moderate to excellent yields.

  14. Investigation of the O+allyl addition/elimination reaction pathways from the OCH(2)CHCH(2) radical intermediate.

    Science.gov (United States)

    Fitzpatrick, Benjamin L; Lau, Kai-Chung; Butler, Laurie J; Lee, Shih-Huang; Lin, Jim Jr-Min

    2008-08-28

    These experiments study the preparation of and product channels resulting from OCH(2)CHCH(2), a key radical intermediate in the O+allyl bimolecular reaction. The data include velocity map imaging and molecular beam scattering results to probe the photolytic generation of the radical intermediate and the subsequent pathways by which the radicals access the energetically allowed product channels of the bimolecular reaction. The photodissociation of epichlorohydrin at 193.3 nm produces chlorine atoms and c-OCH(2)CHCH(2) radicals; these undergo a facile ring opening to the OCH(2)CHCH(2) radical intermediate. State-selective resonance-enhanced multiphoton ionization (REMPI) detection resolves the velocity distributions of ground and spin-orbit excited state chlorine independently, allowing for a more accurate determination of the internal energy distribution of the nascent radicals. We obtain good agreement detecting the velocity distributions of the Cl atoms with REMPI, vacuum ultraviolet (VUV) photoionization at 13.8 eV, and electron bombardment ionization; all show a bimodal distribution of recoil kinetic energies. The dominant high recoil kinetic energy feature peaks near 33 kcalmol. To elucidate the product channels resulting from the OCH(2)CHCH(2) radical intermediate, the crossed laser-molecular beam experiment uses VUV photoionization and detects the velocity distribution of the possible products. The data identify the three dominant product channels as C(3)H(4)O (acrolein)+H, C(2)H(4)+HCO (formyl radical), and H(2)CO (formaldehyde)+C(2)H(3). A small signal from C(2)H(2)O (ketene) product is also detected. The measured velocity distributions and relative signal intensities at me=27, 28, and 29 at two photoionization energies show that the most exothermic product channel, C(2)H(5)+CO, does not contribute significantly to the product branching. The higher internal energy onset of the acrolein+H product channel is consistent with the relative barriers en route to

  15. Photocatalytic Activities of Copper Doped Cadmium Sulfide Microspheres Prepared by a Facile Ultrasonic Spray-Pyrolysis Method

    OpenAIRE

    Jinzhan Su; Tao Zhang; Yufeng Li; Yubin Chen; Maochang Liu

    2016-01-01

    Ultrasonic spray pyrolysis is a superior method for preparing and synthesizing spherical particles of metal oxide or sulfide semiconductors. Cadmium sulfide (CdS) photocatalysts with different sizes and doped-CdS with different dopants and doping levels have been synthesized to study their properties of photocatalytic hydrogen production from water. The CdS photocatalysts were characterized with scanning electron microscopy (SEM), X-ray fluorescence-spectrometry (XRF), UV-Vis absorption spect...

  16. Growth and chemosensory behavior of sulfate-reducing bacteria in oxygen-sulfide gradients

    DEFF Research Database (Denmark)

    Sass, Andrea M.; Wieland, Andrea Eschemann; Kühl, Michael;

    2002-01-01

    Growth and chemotactic behavior in oxic–anoxic gradients were studied with two freshwater and four marine strains of sulfate-reducing bacteria related to the genera Desulfovibrio, Desulfomicrobium or Desulfobulbus. Cells were grown in oxygen–sulfide counter-gradients within tubes filled with agar...... chemotactically to lactate, nitrate, sulfate and thiosulfate, and even sulfide functioned as an attractant. In oxic–anoxic gradients the bacteria moved away from high oxygen concentrations and formed bands at the outer edge of the oxic zone at low oxygen concentration (... to actively change the extension and slope of the gradients by oxygen reduction with lactate or even sulfide as electron donor. Generally, the chemotactic behavior was in agreement with a defense strategy that re-establishes anoxic conditions, thus promoting anaerobic growth and, in a natural community...

  17. Characterization of AISI 1005 corrosion films grown under cyclic voltammetry of low sulfide ion concentrations

    International Nuclear Information System (INIS)

    Highlights: •The corrosion of AISI 1005 in sulfide solutions was investigated. •The mechanism of film growth on carbon steel in sulfide solutions was studied. •Film growth was characterized using SEM, EDX, XRD and Mössbauer spectroscopy. •Growth of AISI 1005 corrosion films under cyclic voltammetry. -- Abstract: The mechanism of AISI 1005 corrosion in sulfide ion solutions has been investigated using cyclic voltammetry, electrochemical impedance spectroscopy, X-ray diffraction (XRD) and Mössbauer spectroscopy (MS). The proposed mechanism occurs with the initial formation of oxygenated ferrous species followed by adsorption of HS− species, precipitation of iron monosulfides and their partial conversion to bisulfide iron. This mechanism was demonstrated by XRD results that revealed Fe-O and Fe-S phases and by MS results that detected pyrite as the major proportion (94%) of the iron species in the corrosion product

  18. Genesis of hydrogen sulfide of the Dauletabad-Donmezskiy gas field

    Energy Technology Data Exchange (ETDEWEB)

    Semenovich, V.V.; Guriyeva, S.M.; Maksimov, S.P.; Mekhtiyeva, V.L.; Pankina, R.G.

    1983-01-01

    An analysis was made of the content of hydrogen sulfide in isotope composition of sulfur in samples of condensation water (from a separator) at the gas-condensate field of DauletabadDonmez. Hydrogen sulfide was very enriched with heavy isotope deltaS/sup 34/ (deltaS/sup 34/ from +9.3 to +15.8 0/00) and close to sulfur of the evaporites of the Jurassic age. The findings are compared to the data of studying isotope composition of sulfur in gas fields of the Maudarya syneclise. A hypothesis is advanced for the origin of hydrogen sulfide in the Dauletabad-Donmezskiy field because of migration from the underlying Jurassic deposits.

  19. Synthesis, molecular modeling and biological evaluation of novel 2-allyl amino 4-methyl sulfanyl butyric acid as α-amylase and α-glucosidase inhibitor

    Science.gov (United States)

    Balan, Kannan; Perumal, Perumal; Sundarabaalaji, Narayanan; Palvannan, Thayumanavan

    2015-02-01

    In the present study 2-allyl amino 4-methyl sulfanyl butyric acid (AMSB) was synthesized in good yield. AMSB was characterized by Fourier transforms infrared spectroscopy (FTIR), Nuclear magnetic resonance (NMR) (1H and 13C) and Liquid chromatography mass spectrometry (LCMS). The radical scavenging activity and reducing power assay of AMSB was assessed using 1-1-diphenyl 2-picryl hydrazyl (DPPH), 2,2‧-azino-bis (3-ethyl benzothiazoline-6-sulfonic acid) (ABTS) and ferric ion reducing antioxidant power assay (FRAP) and was found to be 44.1, 34.71 and 41.7 μg/ml respectively. The compound showed effective inhibition against α-amylase and α-glucosidase. AMSB was identified to be a reversible mixed noncompetitive inhibitor of α-amylase and α-glucosidase. The molecular docking study was carried out to evaluate the specific groove binding properties and affords valuable information of AMSB binding mode in the active site of α-glucosidase the study may lead to the which leads to the rational design of new class of antidiabetic drugs targeting α-glucosidase based on AMSB in near future.

  20. 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.

  1. Antibacterial activity of starch/acrylamide/allyl triphenyl phosphonium bromide copolymers synthesized by gamma irradiation

    International Nuclear Information System (INIS)

    Starch/acrylamide/allyl triphenyl phosphonium bromide (St/AM/TP) copolymers were synthesized by simultaneous gamma irradiation and characterized by FTIR and 1H NMR techniques, weight measurement and titration method. Moreover, their antibacterial activities against Staphylococcus aureus were explored by the viable cell counting method in sterile distilled water. At St/AM/TP 6:8.4:5.6 g, copolymers with higher graft ratio (G) and higher (AM+TP) graft efficiency (EAM+TP) were obtained at 3 and 6 kGy, while cationic degree (CD) and TP graft efficiency (ETP) continuously increased with absorbed dose from 1 to 6 kGy. All of the copolymers were capable of killing >99.75% of 107 CFU/ml S. aureus within 30 mins. Moreover, at 3 kGy, G, EAM+TP and ETP increased with AM/TP from 0:14 to 11.2:2.8 g at St/(AM+TP) 6:14 g, while the optimum CD and antibacterial activity were achieved at AM/TP 7:7 and 8.4:5.6 g. In addition, at 3 kGy, G, EAM+TP and CD increased with St/(AM+TP) from 6:3 to 6:18 g at AM/TP 8.4:5.6 g, while the optimum antibacterial activity was achieved at 6:10 to 6:18 g, and the optimum ETP was achieved at 6:14. - Highlights: • Cationic starch is prepared from AM and TP by Gamma irradiation. • Cationic starch is characterized by FTIR, NMR, weight method and titration method. • Grafting ratio and cationic degree depend on absorbed dose and composition. • Cationic starch shows good antibacterial activity against Staphylococcus aureus

  2. Diversity of Nitrate-Reducing and Denitrifying Bacteria in a Marine Aquaculture Biofilter and their Response to Sulfide

    DEFF Research Database (Denmark)

    Krieger, Bärbel; Schwermer, Carsten U.; Rezakhani, Nastaran;

    2006-01-01

    DIVERSITY OF NITRATE-REDUCING AND DENITRIFYING BACTERIA IN A MARINE AQUACULTURE BIOFILTER AND THEIR RESPONSE TO SULFIDE B.U. Krieger 1,5, C. Schwermer 2, N. Rezakhani 5, M.A. Horn 1, A. Gieseke 2, E. Cytryn 3, D. Minz 3, J. van Rijn 4, H.L. Drake 1, A. Schramm 5 1 Dept. of Ecological Microbiology...... was developed containing a 3-stage biofilter for nitrification, denitrification/anaerobic sludge digestion, and sulfide oxidation. Sulfate reduction in the anaerobic part of the system leads to sulfide concentrations exceeding 5 mM, which may affect nitrate reduction and denitrification. Sulfide can inhibit...... nitrous oxide reductase, trigger a shift from denitrification to dissimilatory nitrate reduction to ammonium (DNRA), or be used as electron donor for nitrate reduction. The goal of this study was to identify and isolate nitrate-reducing and denitrifying bacteria from the biofilter and to investigate...

  3. 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.

  4. 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.

  5. Speciation of arsenic in sulfidic waters

    Directory of Open Access Journals (Sweden)

    Ford Robert G

    2003-03-01

    Full Text Available Formation constants for thioarsenite species have been determined in dilute solutions at 25°C, ΣH2S from 10-7.5 to 10-3.0 M, ΣAs from 10-5.6 to 10-4.8 M, and pH 7 and 10. The principal inorganic arsenic species in anoxic aquatic systems are arsenite, As(OH30, and a mononuclear thioarsenite with an S/As ratio of 3:1. Thioarsenic species with S/As ratios of 1 : 1,2 : 1, and 4 : 1 are lesser components in sulfidic solutions that might be encountered in natural aquatic environments. Thioarsenites dominate arsenic speciation at sulfide concentrations > 10-4.3 M at neutral pH. Conversion from neutral As(OH30 to anionic thioarsenite species may regulate the transport and fate of arsenic in sulfate-reducing environments by governing sorption and mineral precipitation reactions.

  6. Iron-sulfide redox flow batteries

    Energy Technology Data Exchange (ETDEWEB)

    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.

  7. Studies for the synthesis of marine natural products*

    OpenAIRE

    Williams, David R.; Walsh, Martin J.; Claeboe, Christopher D.; Zorn, Nicolas

    2009-01-01

    The process of allylic transposition in SE′ reactions is a significant construct for synthesis. The flexibility of a variety of allylation strategies provides for the rational design of pathways to a diverse array of complex targets. Our recent studies of SE′ reactions will examine issues of stereoselectivity and efficiency in the context of applications toward the synthesis of marine natural products such as the xenicane diterpenes, which feature the strained E-cyclononene ring system, and p...

  8. On the inhibition of hydrogen sulfide corrosion of steel with Schiff Bases

    International Nuclear Information System (INIS)

    The number of the Schiff bases(above 20 compounds) is synthesized. Their impact on the kinetics of electrochemical reactions and steel corrosion behaviour in the two-phase systems electrolyte - hydrocarbon containing H2S, is studied. It is shown, that azomethines, synthesized by the Schiff reaction from aldehydes and aliphatic amines, may serve as water-soluble inhibitors in these systems. The efficiency of steel corrosion protection against hydrogen sulfide corrosion through azomethines depends on their chemical structure and pH media. The effective water-soluble inhibitor of the hydrogen sulfide corrosion - IFKhAN-62 - is developed

  9. 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.

  10. Modeling the Effect of Dissolved Hydrogen Sulfide on Mg2+-water Complex on Dolomite {104} Surfaces

    OpenAIRE

    Shen, Zhizhang; Liu, Yun; Brown, Philip E; Szlufarska, Izabela; Xu, Huifang

    2016-01-01

    The key kinetic barrier to dolomite formation is related to the surface Mg2+-H2O complex, which hinders binding of surface Mg2+ ions to the CO3 2- ions in solution. It has been proposed that this reaction can be catalyzed by dissolved hydrogen sulfide. To characterize the role of dissolved hydrogen sulfide in the dehydration of surface Mg 2+ ions, ab initio simulations based on density functional theory (DFT) were carried out to study the thermodynamics of competitive adsorption of hydrogen s...

  11. 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.

  12. 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...

  13. 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.

  14. Hydrogen sulfide prodrugs—a review

    Science.gov (United States)

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

    2015-01-01

    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

  15. Elucidation of the regio- and chemoselectivity of enzymatic allylic oxidations with Pleurotus sapidus – conversion of selected spirocyclic terpenoids and computational analysis

    Directory of Open Access Journals (Sweden)

    Verena Weidmann

    2013-10-01

    Full Text Available Allylic oxidations of olefins to enones allow the efficient synthesis of value-added products from simple olefinic precursors like terpenes or terpenoids. Biocatalytic variants have a large potential for industrial applications, particularly in the pharmaceutical and food industry. Herein we report efficient biocatalytic allylic oxidations of spirocyclic terpenoids by a lyophilisate of the edible fungus Pleurotus sapidus. This ‘’mushroom catalysis’’ is operationally simple and allows the conversion of various unsaturated spirocyclic terpenoids. A number of new spirocyclic enones have thus been obtained with good regio- and chemoselectivity and chiral separation protocols for enantiomeric mixtures have been developed. The oxidations follow a radical mechanism and the regioselectivity of the reaction is mainly determined by bond-dissociation energies of the available allylic CH-bonds and steric accessibility of the oxidation site.

  16. Antimicrobial activity of allyl isothiocyanate used to coat biodegradable composite films as affected by storage and handling conditions.

    Science.gov (United States)

    Li, Weili; Liu, Linshu; Jin, Tony Z

    2012-12-01

    We evaluated the effects of storage and handling conditions on the antimicrobial activity of biodegradable composite films (polylactic acid and sugar beet pulp) coated with allyl isothiocyanate (AIT). Polylactic acid and chitosan were incorporated with AIT and used to coat one side of the film. The films were subjected to different storage conditions (storage time, storage temperature, and packed or unpacked) and handling conditions (washing, abrasion, and air blowing), and the antimicrobial activity of the films against Salmonella Stanley in tryptic soy broth was determined. The films (8.16 μl of AIT per cm(2) of surface area) significantly (P packaging.

  17. Allyl- iso-propyltelluride, a new MOVPE precursor for CdTe, HgTe and (Hg,Cd)Te

    Science.gov (United States)

    Hails, Janet E.; Cole-Hamilton, David J.; Stevenson, John; Bell, William

    2000-06-01

    The use of allyl- iso-propyltelluride as the tellurium precursor for the growth of CdTe, HgTe and (Hg,Cd)Te by metal organic vapour-phase epitaxy has been investigated. It has proved to be an efficient source of tellurium with growth rates for HgTe and (Hg,Cd)Te of up to 10 μm h -1 at 300°C. The best CdTe was grown at 4.5 μm h -1 under Me 2Cd-rich conditions at 300°C in the presence of Hg vapour.

  18. Use of ferric sulfate: acid media for the desulfurization of model compounds of coal. [Dibenzothiophene, diphenyl sulfide, di-n-butyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Clary, L.R.; Vermeulen, T.; Lynn, S.

    1980-12-01

    The objective of this work has been to investigate the ability of ferric sulfate-acid leach systems to oxidize the sulfur in model compounds of coal. Ferric iron-acid leach systems have been shown to be quite effective at removal of inorganic sulfur in coal. In this study, the oxidative effect of ferric iron in acid-leach systems was studied using dibenzothiophene, diphenyl sulfide, and di-n-butyl sulfide as models of organic sulfur groups in coal. Nitrogen and oxygen, as well as various transition metal catalysts and oxidants, were utilized in this investigation. Dibenzothiophene was found to be quite refractory to oxidation, except in the case where metavanadate was added, where it appears that 40% oxidation to sulfone could have occurred per hour at 150/sup 0/C and mild oxygen pressure. Diphenyl sulfide was selectively oxidized to sulfoxide and sulfone in an iron and oxygen system. Approximately 15% conversion to sulfone occurred per hour under these conditions. Some of the di-n-butyl sulfide was cracked to 1-butene and 1-butanethiol under similar conditions. Zinc chloride and ferric iron were used at 200/sup 0/C in an attempt to desulfonate dibenzothiophene sulfone, diphenyl sulfone, and di-n-butyl sulfone. Di-n-butyl sulfone was completely desulfurized on one hour and fragmented to oxidized parafins, while dibenzothiophene sulfone and diphenyl sulfone were unaffected. These results suggest that an iron-acid leach process could only selectively oxidize aryl sulfides under mild conditions, representing only 20% of the organic sulfur in coal (8% of the total sulfur). Removal through desulfonation once selective sulfur oxidation had occurred was only demonstrated for alkyl sulfones, with severe oxidation of the fragmented paraffins also occurring in one hour.

  19. 烯丙基异硫氰酸酯的熏蒸毒力研究%FUMIGATION ACTIVITY OF THE ALLYL ISOTHIOCYANATE

    Institute of Scientific and Technical Information of China (English)

    陈春武; 谢令德; 陈雅群; 何君; 贺艳萍

    2012-01-01

    以玉米象和赤拟谷盗作为实验对象,采用熏蒸方式对烯丙基异硫氰酸酯的毒力进行测定.结果表明,烯丙基异硫氰酸酯对所研究的两种害虫有较好的快速致死作用,同时研究发现在相同熏蒸时间内烯丙基异硫氰酸酯对玉米象熏蒸的LC50和LC99均小于对赤拟谷盗的LC50和LC99,这说明烯丙基异硫氰酸酯对玉米象的熏蒸效果比对赤拟谷盗的好.%Chosing Si tophilus zesmais (Motschulsky) and Tribolium castaneun (Herbst) as experimental objects, the toxicity for the allyl isothiocyanate (AITC) is tested systematically by fumigation method. The result demonstrates that the allyl isothiocyanate presents rapid lethal effect against both of the two types of insects. The research also shows that both the LC50 and the LC99 of the fumigation of the allyl isothiocyanate to the Sitophilus zeamais are less than those of the allyl isothiocyanate to the Tribolium castaneum exposuring the same fumigating time, which indicates that the fumigating effect of the allyl isothiocyanate to the Sitophilus zeamais is more effective than that of the allyl isothiocyanate to the Tribolium castaneum.

  20. 长坡选矿厂锌浮选尾矿硫砷分离试验研究%Experimental study on the separation of pyrite and arsenopyrite for the tailings of zinc sulfides flotation in Changpo plant

    Institute of Scientific and Technical Information of China (English)

    周德炎; 陈志文

    2012-01-01

    In Changpo plant, the arsenic-sulfur minerals were associated with each other and part minerals were not yet hberated m the tailings of zinc sulfides flotation. According to this problem, a new flowsheet was proposed that bulk flotation was firstly adopted, and then the sulfides concentrate was processed for the separation of arsenic-sulfur minerals. In this experiment, a combined agent of hydrogen peroxide and sodium humate (1:1) was used as an arsenic depressant. The results showed when the depressant dosage was 900g/t, desirable indexes could be achieved that the grade and recovery of sulfide concentrate were respectively 44.86% and 87.88%, and the arsenic content could be reduced to below 1%.%针对长坡选矿厂锌浮选尾矿硫砷矿物相互伴生且部分矿物未单体解离的特点,考虑全浮硫化矿,全浮精矿再硫砷分离的原则流程,在硫砷浮选分离过程中采用过氧化氢与腐殖酸钠1:1药剂组合抑制砷矿物,在用量仅为900g/t条件下,硫精矿品位达到44.86%,回收率达到87.88%,硫精矿中砷含量可降低到1%以下。