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Sample records for allyl sulfides studies

  1. Allyl sulfides modify cell growth.

    PubMed

    Knowles, L M; Milner, J A

    2000-01-01

    Extensive evidence points to the ability of allyl sulfides from garlic to suppress tumor proliferation both in vitro and in vivo. This antineoplastic effect is generally greater for lipid-soluble than water-soluble allyl sulfides. Both concentration and duration of exposure can increase the antiproliferative effects of lipid- and water-soluble allyl sulfides. Part of their antiproliferative effects may relate to an increase in membrane fluidity and a suppression of integrin glycoprotein IIb-IIIa mediated adhesion. Alterations in cholesterol, arachidonic acid, phospholipids and/or thiols may account for these changes in membrane function. Allyl sulfides are also recognized for their ability to suppress cellular proliferation by blocking cells in the G2/M phase and by the induction of apoptosis. This increase in the G2/M and apoptotic cell populations correlates with depressed p34cdc2 kinase activity, increased histone acetylation, increased intracellular calcium and elevated cellular peroxide production. While impressive pre-clinical data exist about the antineoplastic effects of allyl sulfur compounds, considerably more attention needs to be given to their effects in humans. The composition of the entire diet and a host of genetic/epigenetic factors will likely determine the true benefits that might arise from allyl sulfur compounds from garlic and other Allium foods.

  2. Do garlic-derived allyl sulfides scavenge peroxyl radicals?

    PubMed

    Amorati, Riccardo; Pedulli, Gian Franco

    2008-03-21

    The chain-breaking antioxidant activities of two garlic-derived allyl sulfides, i.e. diallyl disulfide (1), the main component of steam-distilled garlic oil, and allyl methyl sulfide (3) were evaluated by studying the thermally initiated autoxidation of cumene or styrene in their presence. Although the rate of cumene oxidation was reduced by addition of both 1 and 3, the dependence on the concentration of the two sulfides could not be explained on the basis of the classic antioxidant mechanism as with phenolic antioxidants. The rate of oxidation of styrene, on the other hand, did not show significant changes upon addition of either 1 or 3. This unusual behaviour was explained in terms of the co-oxidant effect, consisting in the decrease of the autoxidation rate of a substrate forming tertiary peroxyl radicals (i.e. cumene) upon addition of little amounts of a second oxidizable substrate giving rise instead to secondary peroxyl radicals. The relevant rate constants for the reaction of ROO(.) with 1 and 3 were measured as 1.6 and 1.0 M(-1) s(-1), respectively, fully consistent with the H-atom abstraction from substituted sulfides. It is therefore concluded that sulfides 1 and 3 do not scavenge peroxyl radicals and therefore cannot be considered chain-breaking antioxidants.

  3. Effects of different garlic-derived allyl sulfides on peroxidative processes and anaerobic sulfur metabolism in mouse liver.

    PubMed

    Iciek, Małgorzata B; Kowalczyk-Pachel, Danuta; Kwiecień, Inga; Dudek, Magdalena B

    2012-03-01

    Biological activity of garlic has been attributed to organosulfur compounds, most of all to oil-soluble allyl sulfides, such as diallyl sulfide (DAS), diallyl disulfide (DADS) and diallyl trisulfide (DATS). This study evaluated the effectiveness of garlic-derived allyl sulfides in influencing peroxidative processes, levels of thiols and sulfane sulfur and its metabolic enzymes in normal mouse liver cells. Various allyl sulfides (DAS, DADS and DATS) dissolved in corn oil were given intraperitoneally to mice for 10 days. After sacrificing the mice, biochemical assays were performed in liver homogenates and in plasma in order to establish liver function. All allyl sulfides under study had a beneficial effect in the mouse liver since they decreased reactive oxygen species and malondialdehyde levels and increased glutathione S-transferase activity and non-protein sulfhydryl group level. Moreover, DADS and DATS elevated total sulfane sulfur pool and activity of sulfane sulfur biosynthetic enzymes. The increase in sulfane sulfur level entailed augmentation of its antioxidant and regulatory capacities. Garlic-derived allyl sulfides exhibited antioxidant action in the liver and elevated anaerobic cysteine metabolism leading to the formation of sulfane sulfur-containing compounds. Thus, DADS and DATS showed beneficial action in the liver, which can be used for protection of normal liver cells during chemotherapy or for alleviation of liver damage. Copyright © 2011 John Wiley & Sons, Ltd.

  4. Theoretical Comparative Study of the Structure, Dynamics and Electronic Properties of Five Ally Molecules: Allicin, Methyl Propyl Disulfide (MPD), Allyl Methyl Sulfide (AMS), S-allyl cysteine (SAC) and S-allyl mercaptocysteine (SAMC)

    NASA Astrophysics Data System (ADS)

    Deniz Calisir, Emine; Erkoc, Sakir; Yildirim, Handan; Kara, Abdelkader; Rahman, Talat S.; Selvi, Mahmut; Erkoc, Figen

    2006-03-01

    The structural, dynamics and electronic properties of five allyl molecules have been investigated theoretically by performing semi-empirical molecular orbital (AM1 and PM3), ab-initio (RHF) and density functional theory calculations. The geometry of the molecules have been optimized, the vibrational spectra and the electronic properties of the molecules have been calculated in their ground states in gas phase. For each molecule, we found that the optimized geometries resulting from calculations based on the three levels of accuracy, to be very similar. However, we found that an accurate description of the vibrational properties of these molecules necessitates calculations at the ab-initio level. The electronic structures of these molecules were performed at the DFT level, resulting in an accurate description of the HOMO-LUMO gap and the local charges.

  5. Molecular mechanisms of garlic-derived allyl sulfides in the inhibition of skin cancer progression

    PubMed Central

    Wang, Hsiao-Chi; Pao, Jung; Lin, Shuw-Yuan; Sheen, Lee-Yan

    2012-01-01

    Skin cancer is a serious concern whose incidence is increasing at an alarming rate. Allyl sulfides—i.e., sulfur metabolites in garlic oil—have been demonstrated to have anticancer activity against several cancer types, although the mechanisms underlying these effects remain enigmatic. Our previous study showed that diallyl trisulfide (DATS) is more potent than mono- and disulfides against skin cancer. DATS inhibits cell growth of human melanoma A375 cells and basal cell carcinoma (BCC) cells by increasing the levels of intracellular reactive oxygen species (ROS) and DNA damage and by inducing G2/M arrest, endoplasmic reticulum (ER) stress, and mitochondria-mediated apoptosis, including the caspase-dependent and -independent pathways. This short review focuses on the molecular mechanisms of garlic-derived allyl sulfides on skin cancer prevention. PMID:23050963

  6. One pot iridium-catalyzed asymmetrical double allylations of sodium sulfide: a fast and economic way to construct chiral C2-symmetric bis(1-substituted-allyl)sulfane.

    PubMed

    Zheng, Shengcai; Huang, Weiqing; Gao, Ning; Cui, Ruimin; Zhang, Min; Zhao, Xiaoming

    2011-06-28

    One pot asymmetrical double allylations of sodium sulfide catalyzed by an iridium complex along with a combination of caesium fluoride and water in dichloromethane have been realized and the double allylation products with two C-S bond chiral centers were obtained in 67-99% yields with b/l 81/19-99/1, dr 85/15-99/1, and 96-99% ee.

  7. Effect of allyl sulfides from garlic essential oil on intracellular ca2+ levels in renal tubular cells.

    PubMed

    Jan, Chung-Ren; Lo, Horng-Ren; Chen, Chung-Yi; Kuo, Soong-Yu

    2012-12-28

    Diallyl sulfide (1), diallyl disulfide (2), and diallyl trisulfide (3), which are major organosulfur compounds of garlic (Allium sativum), are recognized as a group of potential chemopreventive compounds. In this study, the early signaling effects of 3 were examined on Madin-Darby canine kidney (MDCK) cells loaded with the Ca(2+)-sensitive dye fura-2. It was found that 3 caused an immediate and sustained increase of [Ca(2+)](i) in a concentration-dependent manner (EC(50) = 40 μM). Compound 3 also induced a [Ca(2+)](i) elevation when extracellular Ca(2+) was removed, but the magnitude was reduced by 45%. In Ca(2+)-free medium, the 3-induced [Ca(2+)](i) level was abolished by depleting stored Ca(2+) with 1 μM thapsigargin (an endoplasmic reticulum Ca(2+) pump inhibitor). Elevation of [Ca(2+)](i) caused by 3 in the Ca(2+)-containing medium was not affected by modulation of protein kinase C activity. The 3-induced Ca(2+) influx was inhibited by nifedipine and nicardipine (1 μM). U73122, an inhibitor of phospholipase C, abolished ATP (but not the 3-induced [Ca(2+)](i) level). These findings suggest that 3 induced a significant [Ca(2+)](i) elevation in MDCK renal tubular cells by stimulating both extracellular Ca(2+) influx and thapsigargin-sensitive intracellular Ca(2+) release via as yet unidentified mechanisms. Furthermore, the order of the allyl sulfide-induced [Ca(2+)](i) elevation and cell viability was 1 < 2 < 3. The differential effect of allyl sulfides on Ca(2+) signaling and cell death appears to correlate with the number of sulfur atoms in the structure of these allyl sulfides.

  8. Biocatalytic Synthesis of Allylic and Allenyl Sulfides through a Myoglobin-Catalyzed Doyle-Kirmse Reaction.

    PubMed

    Tyagi, Vikas; Sreenilayam, Gopeekrishnan; Bajaj, Priyanka; Tinoco, Antonio; Fasan, Rudi

    2016-10-17

    The first example of a biocatalytic [2,3]-sigmatropic rearrangement reaction involving allylic sulfides and diazo reagents (Doyle-Kirmse reaction) is reported. Engineered variants of sperm whale myoglobin catalyze this synthetically valuable C-C bond-forming transformation with high efficiency and product conversions across a variety of sulfide substrates (e.g., aryl-, benzyl-, and alkyl-substituted allylic sulfides) and α-diazo esters. Moreover, the scope of this myoglobin-mediated transformation could be extended to the conversion of propargylic sulfides to give substituted allenes. Active-site mutations proved effective in enhancing the catalytic efficiency of the hemoprotein in these reactions as well as modulating the enantioselectivity, resulting in the identification of the myoglobin variant Mb(L29S,H64V,V68F), which is capable of mediating asymmetric Doyle-Kirmse reactions with an enantiomeric excess up to 71 %. This work extends the toolbox of currently available biocatalytic strategies for the asymmetric formation of carbon-carbon bonds.

  9. The Effects of Different Garlic-Derived Allyl Sulfides on Anaerobic Sulfur Metabolism in the Mouse Kidney

    PubMed Central

    Iciek, Małgorzata; Bilska-Wilkosz, Anna; Górny, Magdalena; Sokołowska-Jeżewicz, Maria; Kowalczyk-Pachel, Danuta

    2016-01-01

    Diallyl sulfide (DAS), diallyl disulfide (DADS) and diallyl trisulfide (DATS) are major oil-soluble organosulfur compounds of garlic responsible for most of its pharmacological effects. The present study investigated the influence of repeated intraperitoneally (ip) administration of DAS, DADS and DATS on the total level of sulfane sulfur, bound sulfur (S-sulfhydration) and hydrogen sulfide (H2S) and on the activity of enzymes, which catalyze sulfane sulfur formation and transfer from a donor to an acceptor in the normal mouse kidney, i.e., γ-cystathionase (CSE) and rhodanese (TST). The activity of aldehyde dehydrogenase (ALDH), which is a redox-sensitive protein, containing an –SH group in its catalytic center, was also determined. The obtained results indicated that all tested compounds significantly increased the activity of TST. Moreover, DADS and DATS increased the total sulfane sulfur level and CSE activity in the normal mouse kidney. ALDH activity was inhibited in the kidney after DATS administration. The results indicated also that none of the studied allyl sulfides affected the level of bound sulfur or H2S. Thus, it can be concluded that garlic-derived DADS and DATS can be a source of sulfane sulfur for renal cells but they are not connected with persulfide formation. PMID:27929399

  10. The magnesium-ene cyclization stereochemically directed by an allylic oxyanionic group and its application to a highly stereoselective synthesis of (+/-)-matatabiether. Allylmagnesium compounds by reductive magnesiation of allyl phenyl sulfides.

    PubMed

    Cheng, D; Zhu, S; Yu, Z; Cohen, T

    2001-01-10

    The first example of a magnesium-ene cyclization stereochemically directed by an allylic oxyanionic group is demonstrated by a highly stereoselective synthesis of the bicyclic terpene matatabiether 10. The synthetic method is particularly valuable, not only because of the stereochemical control and the utility of the versatile hydroxyl group introduced into the product, but also because the precursor of the allylmagnesium is an allyl phenyl sulfide, which is more stable and more easily prepared in a connective fashion than the usual allyl halide precursor. Since the presence of lithium ions encourages undesirable proton transfer to the cyclized organometallic and is detrimental to the stereochemical control, the conversion of the allylic thioether to the allylmagnesium utilizes a lithium-free method involving direct reductive magnesiation in the presence of the magnesium-anthracene complex.

  11. Allyl astatide

    SciTech Connect

    Norseev, Yu.V.; Vasaros, L.; Syuch, Z.

    1988-11-01

    Allyl astatide was prepared by the interhalogen exchange method, by replacement of the bromine in allyl bromide with astatide ion. The most favorable conditions for the synthesis were found by variations of the method that uses hydrazine hydrate and sodium formaldehyde sulfoxylate as reductants. A by-product is formed by the reaction of allyl bromide with excited astatine-211 which forms by disintegration of radon-211. Allyl astatide was identified by radio gas-liquid chromatography. Its retention indexes on nonpolar and weakly polar liquid phases were found. The stability of this newly prepared astatine compound was studied. The extrapolated boiling point of allyl astatide is 129 +/- 2/sup 0/C.

  12. Single pulse shock tube study of allyl radical recombination.

    PubMed

    Fridlyand, Aleksandr; Lynch, Patrick T; Tranter, Robert S; Brezinsky, Kenneth

    2013-06-13

    The recombination and disproportionation of allyl radicals has been studied in a single pulse shock tube with gas chromatographic measurements at 1-10 bar, 650-1300 K, and 1.4-2 ms reaction times. 1,5-Hexadiene and allyl iodide were used as precursors. Simulation of the results using derived rate expressions from a complementary diaphragmless shock tube/laser schlieren densitometry study provided excellent agreement with precursor consumption and formation of all major stable intermediates. No significant pressure dependence was observed at the present conditions. It was found that under the conditions of these experiments, reactions of allyl radicals in the cooling wave had to be accounted for to accurately simulate the experimental results, and this unusual situation is discussed. In the allyl iodide experiments, higher amounts of allene, propene, and benzene were found at lower temperatures than expected. Possible mechanisms are discussed and suggest that iodine containing species are responsible for the low temperature formation of allene, propene, and benzene.

  13. Modulation of the multidrug efflux pump EmrD-3 from Vibrio cholerae by Allium sativum extract and the bioactive agent allyl sulfide plus synergistic enhancement of antimicrobial susceptibility by A. sativum extract.

    PubMed

    Bruns, Merissa M; Kakarla, Prathusha; Floyd, Jared T; Mukherjee, Mun Mun; Ponce, Robert C; Garcia, John A; Ranaweera, Indrika; Sanford, Leslie M; Hernandez, Alberto J; Willmon, T Mark; Tolson, Grace L; Varela, Manuel F

    2017-04-21

    The causative agent of cholera, Vibrio cholerae, is a public health concern. Multidrug-resistant V. cholerae variants may reduce chemotherapeutic efficacies of severe cholera. We previously reported that the multidrug efflux pump EmrD-3 from V. cholerae confers resistance to multiple structurally distinct antimicrobials. Medicinal plant compounds are potential candidates for EmrD-3 efflux pump modulation. The antibacterial activities of garlic Allium sativum, although poorly understood, predicts that a main bioactive component, allyl sulfide, modulates EmrD-3 efflux. Thus, we tested whether A. sativum extract acts in synergy with antimicrobials and that a main bioactive component allyl sulfide inhibits EmrD-3 efflux. We found that A. sativum extract and allyl sulfide inhibited ethidium bromide efflux in cells harboring EmrD-3 and that A. sativum lowered the MICs of multiple antibacterials. We conclude that A. sativum and allyl sulfide inhibit EmrD-3 and that A. sativum extract synergistically enhances antibacterial agents.

  14. Effects of allyl sulfide, germanium and NaCl on the development of glutathion S-transferase P-positive rat hepatic foci initiated by diethylnitrosamine.

    PubMed

    Jang, J J; Cho, K J; Kim, S H

    1989-01-01

    The modification potentials of allyl sulfide, germanium and NaCl on the development of preneoplastic hepatic enzyme altered foci were examined in an in vivo mid-term assay system. Rats were initially given a single dose (200 mg/kg), intraperitoneal injection of diethylnitrosamine (DEN) and, starting 2 weeks later, were treated with allyl sulfide, germanium and NaCl at a concentration of 0.5%, 0.05% and 5%, respectively, in the diet for 6 weeks and then killed. All rats were subjected to two-thirds partial hepatectomy at week 3. The modifying potential was scored by comparing the number and area per cm2 of induced glutathione S-transferase placental form-positive (GST-P+) foci in the liver with those of the corresponding control group given DEN alone. Allyl sulfide exerted an obvious inhibition of the development of GST-P+ foci as regards both number and area. On the contrary, germanium showed a significant increase in the number of GST-P+ foci, although the data for area were not altered. NaCl had no modifying effect on their development.

  15. Regio- and stereoselective palladium-pincer complex catalyzed allylation of sulfonylimines with trifluoro(allyl)borates and allylstannanes: a combined experimental and theoretical study.

    PubMed

    Wallner, Olov A; Szabó, Kálmán J

    2006-09-06

    Regio- and stereoselective palladium-pincer complex catalyzed allylation of sulfonylimines has been performed by using substituted trifluoro(allyl)borates and trimethylallylstannanes. The reactions provide the corresponding branched allylic products with excellent regioselectivity. The stereoselectivity of these processes is very high when trifluoro(cinnamyl)borate and trimethyl cinnamyl stannane are employed as allylic precursors; however, the reaction with trifluoro(crotyl)borate results in poor stereoselectivity. The major diastereomer formed in these reactions was the syn isomer, while the (previously reported) reactions with aldehyde electrophiles afforded the anti products, indicating that the mechanism of the stereoselection is dependent on the applied electrophile. Therefore, we have studied the mechanistic aspects of the allylation reactions by experimental studies and DFT modeling. The experimental mechanistic studies have clearly shown that potassium trifluoro(allyl)borate undergoes transmetallation with palladium-pincer complex 1 a affording an eta(1)-allylpalladium-pincer complex (1 e). The mechanism of the transfer of the allyl moiety from palladium to the sulfonylimine substrate was studied by DFT calculations at the B3PW91/LANL2DZ+P level of theory. These calculations have shown that the electrophilic substitution of sulfonylimines proceeds in a one-step process with a relatively low activation energy. The topology of the potential energy surface in the vicinity of the transition-state structure proved to be rather complicated as nine different geometries with similar energies were located as first order saddle points. Our studies have also shown that the high stereoselectivity with cinnamyl metal reagents stems from steric interactions in the TS structure of the allylation reaction. In addition, these studies have revealed that the mechanism of the stereoselection in the allylation of aldehydes and sulfonylimines is fundamentally different.

  16. Actinobacillus pleuropneumoniae is impaired by the garlic volatile allyl methyl sulfide (AMS) in vitro and in-feed garlic alleviates pleuropneumonia in a pig model.

    PubMed

    Becker, Petra M; van Wikselaar, Piet G; Mul, Monique F; Pol, Arjan; Engel, Bas; Wijdenes, Jan W; van der Peet-Schwering, Carola M C; Wisselink, Henk J; Stockhofe-Zurwieden, Norbert

    2012-01-27

    Decomposition products of ingested garlic are to a certain extent excreted via the lungs. If the supposed health-supporting capacities associated with garlic extend to these exhaled sulfurous compounds, they could have an effect on the course of pneumonia. In this study, the garlic-derived volatile allyl methyl sulfide (AMS) as a lead compound of volatile garlic metabolites was shown to exhibit an antibacterial effect against the pig pathogen Actinobacillus pleuropneumoniae serotype 9. AMS caused a delay in the appearance of the optical density-monitored growth of A. pleuropneumoniae in medium when compared to unaffected growth curves, yet without lowering the stationary phase yield at the concentration range tested. At 1.1mM, AMS impaired the in vitro growth rate of A. pleuropneumoniae serotype 9 by 8% compared to unimpeded growth. In an animal trial, a garlic-fed group of 15 pigs that received a diet with 5% garlic feed component and a control group of 15 pigs that received a diet without garlic were infected with A. pleuropneumoniae serotype 2 via an aerosol and subsequently followed for 4 days. At the day of the challenge, blood AMS in the garlic-fed group amounted to 0.32 ± 0.13 μM. A beneficial, alleviating effect of garlic on the course and severity of an A. pleuropneumoniae infection in pigs was indicated by the reduced occurrence of characteristic pleuropneumonia lesions (27% of the lungs affected in the garlic-fed group vs. 47% in the control group) and a near to significant (p=0.06) lower relative lung weight post mortem in the garlic-fed group.

  17. Spectroscopic characterization of alumina-supported bis(allyl)iridium complexes : site-isolation, reactivity, and decomposition studies.

    SciTech Connect

    Trovitch, R. J.; Guo, N.; Janicke, M. T.; Li, H.; Marshall, C. L.; Miller, J. T.; Sattelberger, A. P.; John, K. D.; Baker, R. T.; LANL; Univ. of Ottawa

    2010-01-01

    The covalent attachment of tris(allyl)iridium to partially dehydroxylated ?-alumina is found to proceed via surface hydroxyl group protonation of one allyl ligand to form an immobilized bis(allyl)iridium moiety, (?AlO)Ir(allyl)2, as characterized by CP-MAS 13C NMR, inductively coupled plasma-mass spectrometry, and Ir L3 edge X-ray absorption spectroscopy. Extended X-ray absorption fine-structure (EXAFS) measurements taken on unsupported Ir(allyl)3 and several associated tertiary phosphine addition complexes suggest that the ?3-allyl ligands generally account for an Ir-C coordination number of 2 rather than 3, with an average Ir-C distance of 2.16 A. Using this knowledge, combined EXAFS and X-ray absorption near-edge structure studies reveal that a small amount of Ir0 is also formed upon reaction of Ir(allyl)3 with the surface. It was found that the addition of either 2,6-dimethylphenyl isocyanide or carbon monoxide to the supported complex allows spectroscopic identification of the supported bis(allyl)iridium complexes, (?AlO)Ir(allyl)2(CNAr) [Ar = 2,6-(CH3)2C6H4] and (?AlO)Ir(allyl)2(CO)2, respectively. Although samples of the supported bis(allyl)iridium complex are active for the dehydrogenation of cyclohexane to benzene at temperatures between 180 and 220C, in situ temperature-programmed reaction XAFS and continuous-flow reactor studies suggest that Ir0 nanoparticles, rather than a well-defined Ir3+ complex, are responsible for the observed activity.

  18. Spectroscopic characterization of alumina-supported bis(allyl)iridium complexes: site-isolation, reactivity, and decomposition studies.

    PubMed

    Trovitch, Ryan J; Guo, Neng; Janicke, Michael T; Li, Hongbo; Marshall, Christopher L; Miller, Jeffrey T; Sattelberger, Alfred P; John, Kevin D; Baker, R Thomas

    2010-03-01

    The covalent attachment of tris(allyl)iridium to partially dehydroxylated gamma-alumina is found to proceed via surface hydroxyl group protonation of one allyl ligand to form an immobilized bis(allyl)iridium moiety, (=AlO)Ir(allyl)(2), as characterized by CP-MAS (13)C NMR, inductively coupled plasma-mass spectrometry, and Ir L(3) edge X-ray absorption spectroscopy. Extended X-ray absorption fine-structure (EXAFS) measurements taken on unsupported Ir(allyl)(3) and several associated tertiary phosphine addition complexes suggest that the eta(3)-allyl ligands generally account for an Ir-C coordination number of 2 rather than 3, with an average Ir-C distance of 2.16 A. Using this knowledge, combined EXAFS and X-ray absorption near-edge structure studies reveal that a small amount of Ir(0) is also formed upon reaction of Ir(allyl)(3) with the surface. It was found that the addition of either 2,6-dimethylphenyl isocyanide or carbon monoxide to the supported complex allows spectroscopic identification of the supported bis(allyl)iridium complexes, (=AlO)Ir(allyl)(2)(CNAr) [Ar = 2,6-(CH(3))(2)C(6)H(4)] and (=AlO)Ir(allyl)(2)(CO)(2), respectively. Although samples of the supported bis(allyl)iridium complex are active for the dehydrogenation of cyclohexane to benzene at temperatures between 180 and 220 degrees C, in situ temperature-programmed reaction XAFS and continuous-flow reactor studies suggest that Ir(0) nanoparticles, rather than a well-defined Ir(3+) complex, are responsible for the observed activity.

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

    PubMed Central

    D’Souza, Malcolm J.; Givens, Aaron F.; Lorchak, Peter A.; Greenwood, Abigail E.; Gottschall, Stacey L.; Carter, Shannon E.; Kevill, Dennis N.

    2013-01-01

    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. PMID:23549265

  20. Structural studies in limestone sulfidation

    SciTech Connect

    Fenouil, Laurent A.

    1993-05-01

    This study investigates the sulfidation of limestone at high temperatures (700--900°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 CaCO3 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 CaCO3 calcination point (899°C at 1.03 bar CO2} partial pressure). It is then shown that CaS sinters rapidly at 750 to 900°C if CO2 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 CaCO3 grains that greatly hinders more H2S 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 H2S through the CaS layer, possibly by S2- ionic diffusion. The kinetics is then adequately described by a shrinking-core model, in which a sharp front of completely converted limestone is assumed to progress toward the center of the pellet. Finally, experimental evidence and computer simulations using simple sintering models suggest that the CaS sintering, responsible for the sharp decrease in the sulfidation rate, is surface-diffusion controlled.

  1. A new class of modular P,N-ligand library for asymmetric Pd-catalyzed allylic substitution reactions: a study of the key Pd-pi-allyl intermediates.

    PubMed

    Mazuela, Javier; Paptchikhine, Alexander; Tolstoy, Päivi; Pàmies, Oscar; Diéguez, Montserrat; Andersson, Pher G

    2010-01-11

    A new class of modular P,N-ligand library has been synthesized and screened in the Pd-catalyzed allylic substitution reactions of several substrate types. These series of ligands can be prepared efficiently from easily accessible hydroxyl-oxazole/thiazole derivatives. Their modular nature enables the bridge length, the substituents at the heterocyclic ring and in the alkyl backbone chain, the configuration of the ligand backbone, and the substituents/configurations in the biaryl phosphite moiety to be easily and systematically varied. By carefully selecting the ligand components, therefore, high regio- and enantioselectivities (ee values up to 96 %) and good activities are achieved in a broad range of mono-, di-, and trisubstituted linear hindered and unhindered substrates and cyclic substrates. The NMR spectroscopic and DFT studies on the Pd-pi-allyl intermediates provide a deeper understanding of the effect of ligand parameters on the origin of enantioselectivity.

  2. C1-symmetric carbohydrate diphosphite ligands for asymmetric Pd-allylic alkylation reactions. Study of the key Pd-allyl intermediates.

    PubMed

    Gual, Aitor; Castillón, Sergio; Pàmies, Oscar; Diéguez, Montserrat; Claver, Carmen

    2011-03-28

    A series of C(1)-symmetrical 1,3-diphosphite ligands with a furanoside backbone have been applied in the Pd-catalysed asymmetric allylic alkylation of mono- and disubstituted linear substrates. These diphosphite ligands were designed by selective modification of the successful diphosphite ligand L1a with the 6-deoxy-1,2-O-isopropylidene-glucofuranose backbone in order to study the effect of the ligand structure on the catalytic performance. The effect of the solvent, the substrate/metal ratio and ligand/metal ratio were also investigated. The results in the Pd-allylic alkylation of rac-1,3-diphenyl-3-acetoxyprop-1-ene showed that the ligand structure and the reaction conditions had a considerable effect on enantioselectivity and on the kinetics of the reaction producing the kinetic resolution of the substrate. The alkylated product 2 was therefore obtained in 95% ee at 53% conversion and the enantiopure substrate 1 was recovered in 99.9% ee. Furthermore, the effect of the ligand structure and solvent were also observed in the Pd-allylic alkylation of monosubstituted 1-phenyl-3-acetoxyprop-1-ene. The use of a pro-chiral nucleophile was also explored in this reaction leading to excellent regioselectivities but moderate enantioselectivities. Finally, in order to determine how the ligand structure affected the chiral pocket of the Pd-π-allyl intermediates, the complexes [Pd(η(3)-C(15)H(13))(L)]PF(6), where L = L1a, L5-L8a, were synthesised and characterised by NMR spectroscopy.

  3. Quantum chemical study on asymmetric allylation of benzaldehyde in the presence of chiral allylboronate

    PubMed Central

    Chen, Wan-suo; Chen, Zhi-rong

    2005-01-01

    The quantum chemical method is employed to study the modified asymmetric allylation of benzaldehyde controlled by diisopropyl D-(-)-tartrate auxiliary. All the structures are optimized completely at the B3LYP/6-31G(d,p) level. The (R)-secondary alcohol can be achieved mainly through a six-membered ring chair-like transition state structure. From the relative reaction rates theory the main product configuration predicted is in agreement with the experiment result. PMID:15909353

  4. Study on the sulfidation behavior of smithsonite

    NASA Astrophysics Data System (ADS)

    Wu, Dandan; Wen, Shuming; Deng, Jiushuai; Liu, Jian; Mao, Yingbo

    2015-02-01

    Zinc extraction from low-grade mineral resources of oxidized zinc has recently become a focus of study. Sulfidation is an important process in oxidized ore flotation. In this study, the influence of sulfur ion adsorption on smithsonite surface was investigated with the use of zeta potential, inductively coupled plasma (ICP), scanning electron microscope (SEM), and X-ray photoelectron spectroscopic studies. Zeta potential measurements of sodium sulfide showed that sulfur ions were adsorbed onto the surface of pure smithsonite, as evidenced by the increased negative charge and the decrease in the pHIEP of smithsonite from 7.7 to 6 after sodium sulfide treatment. The ICP test revealed the gradual reduction in sulfur ion adsorption onto the surface of smithsonite in pulp sulfur. After 30 min of absorption, CS in the solution declined from 1000 × 10-6 mol/L to 1.4 × 10-6 mol/L. SEM results showed that the mineral surface was partially changed to ZnS film after sodium sulfide treatment, whereas EDS analysis results showed that 2% S is contained on the smithsonite surface. X-ray photoelectron spectroscopy results indicated the presence of a characteristic signal peak of sulfur ions after sulfidation. Sulfur concentration increased to 11.89%, whereas oxygen concentration decreased from 42.31% to 13.74%. Sulfur ions were not only present during chemical adsorption, but were also incorporated into the crystal lattices of minerals by the exchange reaction between S2- and CO32- ions.

  5. Allyl chloride

    Integrated Risk Information System (IRIS)

    Allyl chloride ; CASRN 107 - 05 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Ef

  6. Allyl alcohol

    Integrated Risk Information System (IRIS)

    Allyl alcohol ; CASRN 107 - 18 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Eff

  7. A Spectroscopic and Theoretical Study of Weak Intramolecular OH\\cdots π Interactions in Allyl Carbinol and Methallyl Carbinol

    NASA Astrophysics Data System (ADS)

    Schroeder, Sidsel D.; Mackeprang, Kasper; Kjaergaard, Henrik G.

    2013-06-01

    The weak intramolecular OH\\cdots π interactions in allyl carbinol and methallyl carbinol have been studied using a combination of NIR spectroscopy and theory. The third OH-stretching overtone region of vapor phase allyl carbinol and methallyl carbinol have been recorded with intracavity laser photoacoustic spectroscopy to study the effect of an enhanced OH\\cdots π interaction in methallyl carbinol arising from the electron donating methyl group. Local mode calculations were employed to assign the observed bands. The OH-stretching transition frequency of methallyl carbinol was observed to be red shifted relative to the OH-stretching transition frequency of allyl carbinol. A red shift of the transition frequency is in this context normally interpreted as a signature of hydrogen bonding. Whether the OH\\cdots π interaction can be categorized as a hydrogen bond will be discussed in this talk.

  8. Chirality Transfer in Gold(I)-Catalysed Direct Allylic Etherifications of Unactivated Alcohols: Experimental and Computational Study

    PubMed Central

    Barker, Graeme; Johnson, David G; Young, Paul C; Macgregor, Stuart A; Lee, Ai-Lan

    2015-01-01

    Gold(I)-catalysed direct allylic etherifications have been successfully carried out with chirality transfer to yield enantioenriched, γ-substituted secondary allylic ethers. Our investigations include a full substrate-scope screen to ascertain substituent effects on the regioselectivity, stereoselectivity and efficiency of chirality transfer, as well as control experiments to elucidate the mechanistic subtleties of the chirality-transfer process. Crucially, addition of molecular sieves was found to be necessary to ensure efficient and general chirality transfer. Computational studies suggest that the efficiency of chirality transfer is linked to the aggregation of the alcohol nucleophile around the reactive π-bound Au–allylic ether complex. With a single alcohol nucleophile, a high degree of chirality transfer is predicted. However, if three alcohols are present, alternative proton transfer chain mechanisms that erode the efficiency of chirality transfer become competitive. PMID:26248980

  9. Chirality Transfer in Gold(I)-Catalysed Direct Allylic Etherifications of Unactivated Alcohols: Experimental and Computational Study.

    PubMed

    Barker, Graeme; Johnson, David G; Young, Paul C; Macgregor, Stuart A; Lee, Ai-Lan

    2015-09-21

    Gold(I)-catalysed direct allylic etherifications have been successfully carried out with chirality transfer to yield enantioenriched, γ-substituted secondary allylic ethers. Our investigations include a full substrate-scope screen to ascertain substituent effects on the regioselectivity, stereoselectivity and efficiency of chirality transfer, as well as control experiments to elucidate the mechanistic subtleties of the chirality-transfer process. Crucially, addition of molecular sieves was found to be necessary to ensure efficient and general chirality transfer. Computational studies suggest that the efficiency of chirality transfer is linked to the aggregation of the alcohol nucleophile around the reactive π-bound Au-allylic ether complex. With a single alcohol nucleophile, a high degree of chirality transfer is predicted. However, if three alcohols are present, alternative proton transfer chain mechanisms that erode the efficiency of chirality transfer become competitive.

  10. Preconditioning with subneurotoxic allyl nitrile: protection against allyl nitrile neurotoxicity.

    PubMed

    Tanii, H; Higashi, T; Saijoh, K

    2010-02-01

    High-dose cruciferous allyl nitrile can induce behavioral abnormalities in rodents, while repeated exposure to allyl nitrile at subneurotoxic levels can increase phase 2 detoxification enzymes in many tissues, although the brain has not been investigated yet. In the present study, we examined the effect of 5 days repeated exposure to subneurotoxic allyl nitrile (0-400 micromol/kg/day) on the brain. Elevated glutathione S-transferase activity was recorded in the striatum, hippocampus, medulla oblongata plus pons, and cortex. Enhancement of quinone reductase activity was observed in the medulla oblongata plus pons, hippocampus, and cortex. In the medulla oblongata plus pons, elevated glutathione levels were recorded. Following repeated subneurotoxic allyl nitrile exposure (0-400 micromol/kg/day), mice were administered a high-dose allyl nitrile (1.2 mmol/kg) which alone led to appearance of behavioral abnormalities. Compared with the 0 micromol/kg/day group, animals in the 200 and 400 micromol/kg/day pre-treatment groups exhibited decreased behavioral abnormalities and elevated GABA-positive cell counts in the substantia nigra pars reticulata and the interpeduncular nucleus. These data suggest that repeated exposure to subneurotoxic levels of allyl nitrile can induce phase 2 enzymes in the brain, which together with induction in other tissues, may contribute to protection against allyl nitrile neurotoxicity. Copyright 2009 Elsevier Ltd. All rights reserved.

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

    SciTech Connect

    John, Kevin D; Martin, Richard L; Obrey, Steven J; Scott, Brian L

    2008-01-01

    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{sup -}}{eta}{sup 1}, {eta}{sup 3} bonding mode; theoretical studies elucidate the role sof the {sigma}- and {pi}-donor ligands in the interplay of metal-allyl and metal-metal bonding.

  12. Study of an improved Allyl Di-Glycol carbonate sheet for high energy proton detection.

    PubMed

    Ohguchi, H; Juto, N; Fujisaki, S; Migita, S; Koguchi, Y; Takada, M

    2006-01-01

    An allyl di-glycol carbonate (ADC) sheet which has been utilised as a neutron detector for personal dosimetry has recently been studied for its application as a device for radiation exposure control for astronauts in space, where protons are the dominant radiation. It is known that the fabrication process, modified by adding some kind of antioxidant to improve the sensitivity of ADC to high energy protons, causes a substantial increase in false tracks, which disturb the automatic counting of proton tracks using the auto-image analyser. This made clear the difficulty of fabricating ADC sheets which have sufficient sensitivity to high energy protons, while maintaining a good surface. In this study, we have tried to modify the fabrication process to improve the sensitivity to high energy protons without causing a deterioration of the surface condition of ADC sheets. We have successfully created fairly good products.

  13. Impurity Studies in Single Crystal Cadmium Sulfide.

    DTIC Science & Technology

    1979-12-01

    widths and relative intensities carried out. While studying the exciton emission from pure cadmium sulfide at low temper- atures, Bliel and Broser ...A Ŗ ® tor ® i* or® 0 I jourt! 45 . leeOialdl Split ting Diatitdnl for lon i :d Donor in Cadmni um Sul1$idte AFML-TR-79-4104 B9-19-72(b) H I c CdS...Chem. Phys. 29, 1375 (1958). 4. C. E. Bleil and 1. Broser , Proceedings of the Seventh International Conference on the Physics of Semiconductors

  14. On the regiochemical differences between Pd-catalyzed heterocyclization-allylation and -arylation reactions of alkynylbenzamides: preparation of 4-allyl-isochromen-1-imines and computational study.

    PubMed

    Álvarez, Rosana; Vilar, Unai; Madich, Youssef; Aurrecoechea, José M

    2017-10-05

    The Pd(0)-catalyzed cyclization-allylation reactions of 2-alkynylbenzamides proceed with high regioselectivity to afford the 6-endo-cyclization-derived products 4-allyl-isochromen-1-imines. DFT calculations have been performed on this and the related arylation reaction, that has been reported to afford the products corresponding to an exo-cyclization under similarly Pd(0)-catalyzed conditions. Under the reaction conditions, these cyclizations are presumed to be triggered by activation of the C-C triple bond with either an allyl- or an aryl palladium complex, generated by oxidative addition of an allyl- or aryl halide to the Pd(0) catalyst. For reactions promoted by allylpalladium species, calculations predict a reversible cyclization, followed by a regioselectivity-determining endo-selective reductive elimination. In contrast, according to calculations, the corresponding arylations would proceed through irreversible exo-selective cyclization and reductive elimination steps. These predictions are consistent with the experimental observations. The divergent regiochemical outcome appears to have its origin in the differences caused on the intermediate palladium complexes by the groups derived from the coupling agents (allyl or aryl) and by the reaction conditions (solvent and ligands) through a subtle interplay of polarity and coordinative effects.

  15. Allyl nitrile: Toxicity and health effects.

    PubMed

    Tanii, Hideji

    2017-03-28

    Allyl nitrile (3-butenenitrile) occurs naturally in the environment, in particular, in cruciferous vegetables, indicating a possible daily intake of the compound. There is no report on actual health effects of allyl nitrile in humans, although it is possible that individuals in the environment are at a risk of exposure to allyl nitrile. However, little is known about its quantitative assessment for the environment and bioactivity in the body. This study provides a review of previous accumulated studies on allyl nitrile. Published literature on allyl nitrile was examined for findings on toxicity, metabolism, risk of various cancers, generation, intake estimates, and low-dose effects in the body. High doses of allyl nitrile produce toxicity characterized by behavioral abnormalities, which are considered to be produced by an active metabolite, 3,4-epoxybutyronitrile. Cruciferous vegetables have been shown to have a potential role in reducing various cancers. Hydrolysis of the glucosinolate sinigrin, rich in cruciferous vegetables, results in the generation of allyl nitrile. An intake of allyl nitrile is estimated at 0.12 μmol/kg body weight in Japan. Repeated exposure to low doses of allyl nitrile upregulates antioxidant/phase II enzymes in various tissues; this may contribute to a reduction in neurotoxicity and skin inflammation. These high and low doses are far more than the intake estimate. Allyl nitrile in the environment is a compound with diverse bioactivities in the body, characterized by inducing behavioral abnormalities at high doses and some antioxidant/phase II enzymes at low doses.

  16. Spectroscopic and structural studies of allyl urethane derivative of Monensin A sodium salt

    NASA Astrophysics Data System (ADS)

    Huczyński, Adam; Janczak, Jan; Brzezinski, Bogumil; Bartl, Franz

    2013-07-01

    A new derivative of polyether antibiotic Monensin A sodium salt its allyl urethane (MON-UR2-Na) was synthesised and its structure was studied by X-ray, FT-IR, NMR, and ESI-MS methods. The results of these studies demonstrated that the oxygen atom of the Cdbnd O urethane group is not engaged in the coordination of the Na+ as postulated previously. The crystal space group is P21 with a = 12.0378(11), b = 12.4495(11), c = 14.9690(14), β = 94.791(8) and Z = 2. The structure determined in the present study exhibits significant differences with respect to the earlier published structure of phenyl urethane of Monensin. A comparison of these structures clearly shows that not only the functional urethane group but also its substituent strongly influence the structure of this type of derivatives of Monensin A. X-ray data and spectroscopic and spectrometric behaviour of the new derivative of Monensin A are discussed in detail and compared to the structure of phenyl urethane of Monensin A sodium salt.

  17. Cross coupling of magnesium diacetylenides with functional allylic and halide-containing compounds catalyzed by transition metal complexes

    SciTech Connect

    Dzhemilev, U.M.; Ibragimov, A.G.; Saraev, R.A.

    1986-08-20

    An efficient method has been developed for the synthesis of 1,4-enynes, conjugated acetylenes and aryl acetylenes by the cross coupling of magnesium diacetylenides with allyl ethers and esters, alkyl halides, allyl halides, aryl halides, allyl sulfides, and allylsulfones, using Ni and Pd complexes as the catalyst.

  18. Platinum-catalyzed direct amination of allylic alcohols under mild conditions: ligand and microwave effects, substrate scope, and mechanistic study.

    PubMed

    Ohshima, Takashi; Miyamoto, Yoshiki; Ipposhi, Junji; Nakahara, Yasuhito; Utsunomiya, Masaru; Mashima, Kazushi

    2009-10-14

    Transition metal-catalyzed amination of allylic compounds via a pi-allylmetal intermediate is a powerful and useful method for synthesizing allylamines. Direct catalytic substitution of allylic alcohols, which forms water as the sole coproduct, has recently attracted attention for its environmental and economical advantages. Here, we describe the development of a versatile direct catalytic amination of both aryl- and alkyl-substituted allylic alcohols with various amines using Pt-Xantphos and Pt-DPEphos catalyst systems, which allows for the selective synthesis of various monoallylamines, such as the biologically active compounds Naftifine and Flunarizine, in good to high yield without need for an activator. The choice of the ligand was crucial toward achieving high catalytic activity, and we demonstrated that not only the large bite-angle but also the linker oxygen atom of the Xantphos and DPEphos ligands was highly important. In addition, microwave heating dramatically affected the catalyst activity and considerably decreased the reaction time compared with conventional heating. Furthermore, several mechanistic investigations, including (1)H and (31)P{(1)H} NMR studies; isolation and characterization of several catalytic intermediates, Pt(xantphos)Cl(2), Pt(eta(2)-C(3)H(5)OH)(xantphos), etc; confirmation of the structure of [Pt(eta(3)-allyl)(xantphos)]OTf by X-ray crystallographic analysis; and crossover experiments, suggested that formation of the pi-allylplatinum complex through the elimination of water is an irreversible rate-determining step and that the other processes in the catalytic cycle are reversible, even at room temperature.

  19. Catalytic Enantioselective [2,3]-Rearrangements of Allylic Ammonium Ylides: A Mechanistic and Computational Study

    PubMed Central

    2017-01-01

    A mechanistic study of the isothiourea-catalyzed enantioselective [2,3]-rearrangement of allylic ammonium ylides is described. Reaction kinetic analyses using 19F NMR and density functional theory computations have elucidated a reaction profile and allowed identification of the catalyst resting state and turnover-rate limiting step. A catalytically relevant catalyst–substrate adduct has been observed, and its constitution elucidated unambiguously by 13C and 15N isotopic labeling. Isotopic entrainment has shown the observed catalyst–substrate adduct to be a genuine intermediate on the productive cycle toward catalysis. The influence of HOBt as an additive upon the reaction, catalyst resting state, and turnover-rate limiting step has been examined. Crossover experiments have probed the reversibility of each of the proposed steps of the catalytic cycle. Computations were also used to elucidate the origins of stereocontrol, with a 1,5-S···O interaction and the catalyst stereodirecting group providing transition structure rigidification and enantioselectivity, while preference for cation−π interactions over C–H···π is responsible for diastereoselectivity. PMID:28230365

  20. Catalytic Enantioselective [2,3]-Rearrangements of Allylic Ammonium Ylides: A Mechanistic and Computational Study.

    PubMed

    West, Thomas H; Walden, Daniel M; Taylor, James E; Brueckner, Alexander C; Johnston, Ryne C; Cheong, Paul Ha-Yeon; Lloyd-Jones, Guy C; Smith, Andrew D

    2017-03-10

    A mechanistic study of the isothiourea-catalyzed enantioselective [2,3]-rearrangement of allylic ammonium ylides is described. Reaction kinetic analyses using (19)F NMR and density functional theory computations have elucidated a reaction profile and allowed identification of the catalyst resting state and turnover-rate limiting step. A catalytically relevant catalyst-substrate adduct has been observed, and its constitution elucidated unambiguously by (13)C and (15)N isotopic labeling. Isotopic entrainment has shown the observed catalyst-substrate adduct to be a genuine intermediate on the productive cycle toward catalysis. The influence of HOBt as an additive upon the reaction, catalyst resting state, and turnover-rate limiting step has been examined. Crossover experiments have probed the reversibility of each of the proposed steps of the catalytic cycle. Computations were also used to elucidate the origins of stereocontrol, with a 1,5-S···O interaction and the catalyst stereodirecting group providing transition structure rigidification and enantioselectivity, while preference for cation-π interactions over C-H···π is responsible for diastereoselectivity.

  1. Why platinum catalysts involving ligands with large bite angle are so efficient in the allylation of amines: design of a highly active catalyst and comprehensive experimental and DFT study.

    PubMed

    Mora, Guilhem; Piechaczyk, Olivier; Houdard, Romaric; Mézailles, Nicolas; Le Goff, Xavier-Frederic; le Floch, Pascal

    2008-01-01

    The platinum-catalyzed allylation of amines with allyl alcohols was studied experimentally and theoretically. The complexes [Pt(eta(3)-allyl)(dppe)]OTf (2) and [Pt(eta(3)-allyl)(DPP-Xantphos)]PF(6) (5) were synthesized and structurally characterized, and their reactivity toward amines was explored. The bicyclic aminopropyl complex [Pt(CH(2)CH(2)CH(2)NHBn-kappa-C,N)(dppe)]OTf (3) was obtained from the reaction of complex 2 with an excess of benzylamine, and this complex was shown to be a deactivated form of catalyst 2. On the other hand, reaction of complex 5 with benzylamine and allyl alcohol led to formation of the 16-VE platinum(0) complex [Pt(eta(2)-C(3)H(5)OH)(DPP-Xantphos)] (7), which was structurally characterized and appears to be a catalytic intermediate. A DFT study showed that the mechanism of the platinum-catalyzed allylation of amines with allyl alcohols differs from the palladium-catalyzed process, since it involves an associative ligand-exchange step involving formation of a tetracoordinate 18-VE complex. This DFT study also revealed that ligands with large bite angles disfavor the formation of platinum hydride complexes and therefore the formation of a bicyclic aminopropyl complex, which is a thermodynamic sink. Finally, a combination of 5 and a proton source was shown to efficiently catalyze the allylation of a broad variety of amines with allyl alcohols under mild conditions.

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

    PubMed

    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.

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

    PubMed Central

    Timoshenko, Mariya A.; Kharitonov, Yurii V.; Shakirov, Makhmut M.; Bagryanskaya, Irina Yu.

    2015-01-01

    Abstract 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

  4. Surface Charge Development on Transition Metal Sulfides: An Electrokinetic Study

    NASA Astrophysics Data System (ADS)

    Bebie, Joakim; Schoonen, Martin A. A.; Fuhrmann, Mark; Strongin, Daniel R.

    1998-02-01

    The isoelectric points, pH i.e.p., of ZnS, PbS, CuFeS 2, FeS, FeS 2, NiS 2, CoS 2, and MnS 2 in NaCl supported electrolyte solutions are estimated to be between pH 3.3 and 0.6, with most of the isoelectric points below pH 2. The first electrokinetic measurements on NiS 2, CoS 2, and MnS 2 are reported here. Below pH i.e.p. the metal-sulfide surfaces are positively charged, above pH i.e.p. the surfaces are negatively charged. The addition of Me 2+ ions shifts the pH i.e.p. and changes the pH dependence considerably. The isoelectric points of the measured transition metal sulfides in the absence of metal ions or dissolved sulfide (H 2S or HS -) are in agreement with those found in earlier studies. The pH range of observed isoelectric points for metal sulfides (0.6-3.3) is compared to the considerably wider pH i.e.p. range (2-12) found for oxides. The correlation between pH i.e.p. and the electronegativities of the metal sulfides suggests that all metal sulfides will have an isoelectric point between pH 0.6 and 3.3. Compared to metal oxides, sulfides exhibit an isoelectric point that is largely independent of the nature of the metal cation in the solid.

  5. Dehydrative cross-coupling reactions of allylic alcohols with olefins.

    PubMed

    Gumrukcu, Yasemin; de Bruin, Bas; Reek, Joost N H

    2014-08-25

    The direct dehydrative activation of allylic alcohols and subsequent cross-coupling with alkenes by using palladium catalyst containing a phosphoramidite ligand is described. The activation of the allyl alcohol does not require stoichiometric additives, thus allowing clean, waste-free reactions. The scope is demonstrated by application of the protocol to a series allylic alcohols and vinyl arenes, leading to variety of 1,4-diene products. Based on kinetic studies, a mechanism is proposed that involves a palladium hydride species that activates the allyl alcohol to form the allyl intermediate.

  6. Study of point defects in alkaline-earth sulfides

    SciTech Connect

    Pandey, R.; Kunz, A.B.; Vail, J.M.

    1988-11-01

    The results of a computer simulation study of point defects including vacancy, interstitial, and F/sup +/ center in alkaline-earth sulfides are presented. The study is based on ICECAP/HADES simulation procedures and uses empirical interionic potentials obtained from the analysis of macroscopic data for these materials. The results predict the dominance of Schottky disorder and suggest that vacancy migration predominates in alkaline-earth sulfides. Furthermore, the calculated F/sup +/ center absorption energy is in good agreement with the experimental data deduced from the optical stimulated studies in these materials.

  7. Iridium-Catalyzed Allylic Substitution

    NASA Astrophysics Data System (ADS)

    Hartwig, John F.; Pouy, Mark J.

    Iridium-catalyzed asymmetric allylic substitution has become a valuable method to prepare products from the addition of nucleophiles at the more substituted carbon of an allyl unit. The most active and selective catalysts contain a phosphoramidite ligand possessing at least one arylethyl substituent on the nitrogen atom of the ligand. In these systems, the active catalyst is generated by a base-induced cyclometalation at the methyl group of this substituent to generate an iridium metalacycle bound by the COD ligand of the [Ir(COD)Cl]2 precursor and one additional labile dative ligand. Such complexes catalyze the reactions of linear allylic esters with alkylamines, arylamines, phenols, alcohols, imides, carbamates, ammonia, enolates and enolate equivalents, as well as typical stabilized carbon nucleophiles generated from malonates and cyanoesters. Iridium catalysts for enantioselective allylic substitution have also been generated from phosphorus ligands with substituents bound by heteroatoms, and an account of the studies of such systems, along with a description of the development of iridium catalysts is included.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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).

  10. A study of the stability of cadmium sulfide/copper sulfide and cadmium sulfide copper-indium-diselenide solar cells

    NASA Astrophysics Data System (ADS)

    Noel, G.; Richard, N.; Gaines, G.

    1984-08-01

    Groups of high efficiency cadmium sulfide/copper sulfide solar cells were exposed to combinations of stresses designed to isolate and accelerate intrinsic degradation mechanisms. Stresses included elevated temperature, illumination intensity, and cell loading conditions. All stress exposures and tests were conducted in a benign (high purity argon) atmosphere. Two primary intrinsic modes of degradation were identified: degradation of the open circuit voltage under continuous illumination and nonzero loading was found to be self recovering upon interruption of illumination or upon shorting or reverse biasing the cells. It was attributed to traps in the depletion region. Recovery from decay of light generated current was not spontaneous but could be partially accomplished by annealing in a reducing (hydrogen) environment. It was attributed to changes in the stoichiometry of the copper sulfide under the influence of electric fields and currents.

  11. Comparative studies on mitochondrial electron transport chain complexes of Sitophilus zeamais treated with allyl isothiocyanate and calcium phosphide.

    PubMed

    Zhang, Chao; Wu, Hua; Zhao, Yuan; Ma, Zhiqing; Zhang, Xing

    2016-01-01

    With Sitophilus zeamais as the target organism, the present study for the first time attempted to elucidate the comparative effects between allyl isothiocyanate (AITC) and calcium phosphide (Ca3P2), exposure on mitochondrial electron transport chain (ETC.) complex I & IV and their downstream effects on enzymes relevant to reactive oxygen species (ROS). In vivo, both AITC and Ca3P2 inhibited complex I and IV with similar downstream effects. In contrast with Ca3P2, the inhibition of complex I caused by AITC was dependent on time and dose. In vitro, AITC inhibited complex IV more significantly than complex I. These results indicate that mitochondrial complex IV is the primary target of AITC, and that complex I is another potential target. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Study of copper sulfide crystallization in PEO-SDS solutions.

    PubMed

    Orphanou, Maria; Leontidis, Epameinondas; Kyprianidou-Leodidou, Tasoula; Koutsoukos, Petros; Kyriacou, Kyriacos C

    2004-06-22

    The crystallization of copper sulfide in aqueous supersaturated solutions in the presence of the polymer poly(ethylene oxide), PEO, and the surfactant sodium dodecyl sulfate, SDS, was investigated. In these systems, copper sulfide precipitation competes with the reaction between copper cations and dodecyl sulfate anions. The competition of the two reactions may affect the reaction products significantly; therefore it is important to study the properties of the surfactant salt, copper dodecyl sulfate (Cu(DS)2), in detail. The thermodynamic solubility constant of Cu(DS)2 was measured at 8 degrees C and was equal to (2.4 +/- 0.4) x 10(-10) M3. The Krafft point of Cu(DS)2 and its solubility curve (precipitation temperature for a range of concentrations) were also measured. The latter was found to be very close to room temperature. Temperature is thus a very significant parameter in these systems and must be carefully controlled in all experiments. The crystallization of copper sulfide in PEO-SDS solutions was investigated in solutions with compositions above and below the solubility curve. Copper sulfide nanoparticles predominate and are stabilized at temperatures above the solubility curve. Surprisingly, at temperatures below the solubility curve CuxS coexists with Cu(DS)2, which appears in the form of lamellar crystals. The system is further complicated by the presence of at least two different types of copper sulfides corresponding to different oxidation states of copper. Our results suggest that the predominance of Cu(DS)2 at lower temperatures is due to its limited solubility and is modified by the CuI/CuII redox equilibrium in combination with the solution pH.

  13. Kinetic studies of sulfide mineral oxidation and xanthate adsorption

    NASA Astrophysics Data System (ADS)

    Mendiratta, Neeraj K.

    2000-10-01

    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 pyrrhotite, are few of the most abundant minerals, yet economically insignificant. Their existence with other sulfide minerals leads to an inefficient separation process as well as environmental problems, such as acid mine drainage during mining and processing and SO 2 emissions during smelting process. A part of the present study is focused on understanding their behavior, which leads to undesired flotation and difficulties in separation. The major reasons for the undesired flotation are attributed to the collectorless hydrophobicity and the activation with heavy metal ions. To better understand the collectorless hydrophobicity of pyrite, Electrochemical Impedance Spectroscopy (EIS) of freshly fractured pyrite electrodes was used to study the oxidation and reduction of the mineral. The EIS results showed that the rate of reaction increases with oxidation and reduction. At moderate oxidizing potentials, the rate of reaction is too slow to replenish hydrophilic iron species leaving hydrophobic sulfur species on the surface. However, at higher potentials, iron species are replaced fast enough to depress its flotation. Effects of pH and polishing were also explored using EIS. Besides collectorless hydrophobicity, the activation of pyrrhotite with nickel ions and interaction with xanthate ions makes the separation more difficult. DETA and SO2 are commonly used as pyrrhotite depressants; however, the mechanism is not very well understood. Contact angle measurements, cyclic voltammetry and Tafel

  14. Morphology and thermal studies of zinc sulfide and cadmium sulfide nanoparticles in polyvinyl alcohol matrix

    NASA Astrophysics Data System (ADS)

    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.

  15. Enantioselective Iridium-Catalyzed Carbonyl Allylation from the Alcohol or Aldehyde Oxidation Level Using Allyl Acetate as an Allyl Metal Surrogate

    PubMed Central

    Kim, In Su; Ngai, Ming-Yu; Krische, Michael J.

    2010-01-01

    A method for carbonyl allylation and crotylation from the alcohol oxidation state via allyl acetate-alcohol transfer hydrogenative C-C coupling is described. Exposure of allyl acetate to benzylic and allylic alcohols 1a-9a in the presence of an iridium catalyst derived from [IrCl(cod)]2 and BIPHEP delivers products of C-allylation 1b-9b. Similarly, 3-acetoxy-1-butene couples to allylic alcohols 1a-9a to furnish crotylation products 1c-9c. The ability of this allylation protocol to transcend the boundaries imposed by oxidation level are demonstrated by the coupling of allyl acetate to aldehydes 1d-3d under standard conditions, but employing isopropanol as terminal reductant. The products of C-allylation 1b-3b are obtained in isolated yields comparable to those obtained in the corresponding alcohol coupling reactions. These studies contribute to a paradigm shift in carbonyl addition chemistry that defines a departure from preformed organometallic reagents. PMID:18444616

  16. Synthesis, radioiodination and in vitro and in vivo sigma receptor studies of N-1-allyl-N´-4-phenethylpiperazine analogs.

    PubMed

    Lever, Susan Z; Xu, Rong; Fan, Kuo-Hsien; Fergason-Cantrell, Emily A; Carmack, Terry L; Watkinson, Lisa D; Lever, John R

    2012-04-01

    Sigma-1 (σ(1)) receptor radioligands are useful for basic pharmacology studies and for imaging studies in neurology, psychiatry and oncology. We derived a hybrid structure, N-1-allyl-N´-4-phenethylpiperazine, from known ligands TPCNE and SA4503 for use as a scaffold for development of radioiodinated σ(1) receptor ligands. E-and Z-N-1-(3'-iodoallyl)-N´-4-(3″,4″-dimethoxyphenethyl)-piperazine (E-1 and Z-1), N-1-allyl-N´-4-(3',4'-dimethoxyphenethyl)-piperazine (2) and E-N-1-(3'-iodoallyl)-N´-4-(3″-methoxy-4'´-hydroxyphenethyl)-piperazine (3) were synthesized. Affinities for σ(1) and σ(2) receptors were determined. [(125)I]E-1 and [(125)I]Z-1 were prepared and evaluated in vivo in mice. [(125)I]E-1 was further evaluated in σ(1) receptor binding assays in vitro. E-1 displayed moderately high apparent affinity (15 nM) for σ(1) sites and 84-fold selectivity against σ(2) sites. Z-1 showed similar σ(1) affinity, but only 23-fold selectivity. In contrast, 2 exhibited poor binding to both subtypes, while 3 had good affinities but poor selectivity. E-1 profiled as a probable antagonist in the phenytoin shift assay. [(125)I]E-1 and [(125)I]Z-1 were prepared in good yields and with high specific radioactivities. Log D(7.4) values (2.25 and 2.27) fall within the optimal range for in vivo studies. Both radioligands selectively labeled σ(1) receptors in mouse brain and peripheral organs in vivo. [(125)I]E-1 showed a higher level of specific binding than [(125)I]Z-1 and displayed good metabolic stability. Further, [(125)I]E-1 selectively labeled σ(1) receptors in mouse brain homogenates (K(d) 3.79 nM; B(max)=599 fmol/mg protein). [(125)I]E-1 is a selective σ(1) receptor radioligand that exhibits properties amenable to in vitro and in vivo studies, with possible extension to single photon emission computed tomography using iodine-123. Copyright © 2012. Published by Elsevier Inc.

  17. Regiospecific decarboxylative allylation of nitriles

    PubMed Central

    Recio, Antonio; Tunge, Jon A.

    2009-01-01

    Palladium-catalyzed decarboxylative α-allylation of nitriles readily occurs using Pd2(dba)3 and rac-BINAP. This catalyst mixture also allows the highly regiospecific α-allylation of nitriles in the presence of much more acidic α-protons. Thus, the reported method provides access to compounds that are not readily available via base-mediated allylation chemistries. Lastly, mechanistic investigations indicate that there is a competition between C- and N-allylation of an intermediate nitrile-stabilized anion and that N-allylation is followed by a rapid [3,3]-sigmatropic rearrangement. PMID:19921827

  18. Kinetic studies of Micrococcus luteus B-P 26 undecaprenyl diphosphate synthase reaction using 3-desmethyl allylic substrate analogs.

    PubMed

    Fujikura, Keitaro; Maki, Yuji; Ohya, Norimasa; Satoh, Mikiya; Koyama, Tanetoshi

    2008-03-01

    In order to investigate the substrate binding feature of undecaprenyl diphosphate synthase from Micrococcus luteus B-P 26 with respect to farnesyl diphosphate and a reaction intermediate, (Z,E,E)-geranylgeranyl diphosphate, we examined the reactivity of artificial substrate analogs, 3-desmethyl farnesyl diphosphate and 3-desmethyl Z-geranylgeranyl diphosphate, which lack the methyl group at the 3-position of farnesyl diphosphate and Z-geranylgeranyl diphosphate, respectively. Undecaprenyl diphosphate synthase did not accept either of the 3-desmethyl analogs as the allylic substrate, indicating that the methyl group at the 3-position of the allylic substrate is important in the undecaprenyl diphosphate synthase reaction. These analogs showed different inhibition patterns in the cis-prenyl chain elongation reaction with respect to the reactions of farnesyl diphosphate and Z-geranylgeranyl diphosphate as allylic substrate. These results suggest that the binding site for the natural substrate farnesyl diphosphate and those for the intermediate allylic diphosphate, which contains the cis-prenyl unit, are different during the cis-prenyl chain elongation reaction.

  19. The Allyl Intermediate in Regioselective and Enantioselective Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

    PubMed Central

    Madrahimov, Sherzod T.; Markovic, Dean; Hartwig., John F.

    2010-01-01

    The isolation and structural characterization of metallacyclic allyl (2a) and crotyl (2b) iridium complexes are reported. Complexes 2a and 2b are rare examples of iriduim allyl complexes that undergo nucleophilic attack at terminal position, rather than the central position, of the allyl unit. Structures of 2a and 2b were obtained by X-ray diffraction. Nucleophilic attack was observed at the carbon that is bound to iridium trans to phosphorus through a longer Ir-C bond. However, the effect of the trans phosphine ligand on the Ir-C bond lengths was smaller than the effect of the substituent on the allyl group in 2b. The competence of complexes 2a and 2b to be intermediates in the catalytic asymmetric allylic substitutions was evaluated by studying their reactivity towards stabilized carbon and heteroatom nucleophiles and comparing the rates and selectivities to those of the catalytic reactions. The stereoselectivity and regioselectivity of stoichiometric reactions of 2b were similar to those of reactions catalyzed by the previously reported iridium catalysts, supporting their intermediacy in the catalytic reactions. Based on the structural data, a model is proposed for the origin of stereoselectivity in iridium-catalyzed asymmetric allylic substitution reactions. PMID:19432473

  20. The allyl intermediate in regioselective and enantioselective iridium-catalyzed asymmetric allylic substitution reactions.

    PubMed

    Madrahimov, Sherzod T; Markovic, Dean; Hartwig, John F

    2009-06-03

    The isolation and structural characterization of metallacyclic allyl (2a) and crotyl (2b) iridium complexes are reported. Complexes 2a and 2b are rare examples of iriduim allyl complexes that undergo nucleophilic attack at terminal position, rather than the central position, of the allyl unit. Structures of 2a and 2b were obtained by X-ray diffraction. Nucleophilic attack was observed at the carbon that is bound to iridium trans to phosphorus through a longer Ir-C bond. However, the effect of the trans phosphine ligand on the Ir-C bond lengths was smaller than the effect of the substituent on the allyl group in 2b. The competence of complexes 2a and 2b to be intermediates in the catalytic asymmetric allylic substitutions was evaluated by studying their reactivity toward stabilized carbon and heteroatom nucleophiles and comparing the rates and selectivities to those of the catalytic reactions. The stereoselectivity and regioselectivity of stoichiometric reactions of 2b were similar to those of reactions catalyzed by the previously reported iridium catalysts, supporting their intermediacy in the catalytic reactions. On the basis of the structural data, a model is proposed for the origin of stereoselectivity in iridium-catalyzed asymmetric allylic substitution reactions.

  1. Aerobic and anaerobic transformations of sulfide in a sewer system--field study and model simulations.

    PubMed

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

    2008-01-01

    The formation and fate of sulfide in a force main and a downstream-located gravity sewer were investigated in an extensive field study. Sulfide formation in the force main was significant. However, during 14 minutes of transport in the gravity sewer, the sulfide concentration decreased 30%, on average. An application of a conceptual sewer process model for simulating the formation and fate of sulfide was demonstrated. Overall, the model predicted that approximately 90% of the decrease of the sulfide concentration in the gravity sewer was the result of sulfide oxidation and that only a small fraction entered the sewer atmosphere, causing odor and corrosion. Even so, the model predicted concrete corrosion rates of up to 1.2 mm/y in the gravity sewer section.

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

    NASA Astrophysics Data System (ADS)

    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. Near-silence of isothiocyanate carbon in (13)C NMR spectra: a case study of allyl isothiocyanate.

    PubMed

    Glaser, Rainer; Hillebrand, Roman; Wycoff, Wei; Camasta, Cory; Gates, Kent S

    2015-05-01

    (1)H and (13)C NMR spectra of allyl isothiocyanate (AITC) were measured, and the exchange dynamics were studied to explain the near-silence of the ITC carbon in (13)C NMR spectra. The dihedral angles α = ∠(C1-C2-C3-N4) and β = ∠(C2-C3-N4-C5) describe the conformational dynamics (conformation change), and the bond angles γ = ∠(C3-N4-C5) and ε = ∠(N4-C5-S6) dominate the molecular dynamics (conformer flexibility). The conformation space of AITC contains three minima, Cs-M1 and enantiomers M2 and M2'; the exchange between conformers is very fast, and conformational effects on (13)C chemical shifts are small (νM1 - νM2 < 3 ppm). Isotropic chemical shifts, ICS(γ), were determined for sp, sp(x), and sp(2) N-hybridization, and the γ dependencies of δ(N4) and δ(C5) are very large (10-33 ppm). Atom-centered density matrix propagation trajectories show that every conformer can access a large region of the potential energy surface AITC(γ,ε,...) with 120° < γ < 180° and 155° < ε < 180°. Because the extreme broadening of the (13)C NMR signal of the ITC carbon is caused by the structural flexibility of every conformer of AITC, the analysis provides a general explanation for the near-silence of the ITC carbon in (13)C NMR spectra of organic isothiocyanates.

  4. Identification of allyl esters in garlic cheese.

    PubMed

    Herbrand, Klaus; Hammerschmidt, Franz J; Brennecke, Stefan; Liebig, Margit; Lösing, Gerd; Schmidt, Claus Oliver; Gatfield, Ian; Krammer, Gerhard; Bertram, Heinz-Jürgen

    2007-09-19

    This study describes the identification of six allyl esters in a garlic cheese preparation and in a commercial cream cheese. The extracts were prepared by liquid/liquid extraction and concentrated by the SAFE process. The identification of the allyl esters of acetic, butyric, hexanoic, heptanoic, octanoic, and decanoic acids is based on the correlation of their mass spectrometric data and chromatographic retention time data obtained from the extracts with those of authentic standards. In addition to the gas chromatography (GC)/mass spectrometry analysis, the flavor ingredients were characterized by GC sniffing by a trained flavorist. Some of the esters were isolated by preparative GC.

  5. Theoretical Studies on Heavy Metal Sulfides in Solution

    SciTech Connect

    Tossell, John A.

    2007-10-31

    concepts have been worked out and we are therefore proposing to move to a new area, that of humic acids (while continuing our studies complexes formed by As oxides and sulfides, now applied to functional groups present in humic acids).

  6. Adsorption of acrolein, propanal, and allyl alcohol on Pd(111): a combined infrared reflection-absorption spectroscopy and temperature programmed desorption study.

    PubMed

    Dostert, Karl-Heinz; O'Brien, Casey P; Mirabella, Francesca; Ivars-Barceló, Francisco; Schauermann, Swetlana

    2016-05-18

    Atomistic-level understanding of the interaction of α,β-unsaturated aldehydes and their derivatives with late transition metals is of fundamental importance for the rational design of new catalytic materials with the desired selectivity towards C[double bond, length as m-dash]C vs. C[double bond, length as m-dash]O bond partial hydrogenation. In this study, we investigate the interaction of acrolein, and its partial hydrogenation products propanal and allyl alcohol, with Pd(111) as a prototypical system. A combination of infrared reflection-absorption spectroscopy (IRAS) and temperature programmed desorption (TPD) experiments was applied under well-defined ultrahigh vacuum (UHV) conditions to obtain detailed information on the adsorption geometries of acrolein, propanal, and allyl alcohol as a function of coverage. We compare the IR spectra obtained for multilayer coverages, reflecting the molecular structure of unperturbed molecules, with the spectra acquired for sub-monolayer coverages, at which the chemical bonds of the molecules are strongly distorted. Coverage-dependent IR spectra of acrolein on Pd(111) point to the strong changes in the adsorption geometry with increasing acrolein coverage. Acrolein adsorbs with the C[double bond, length as m-dash]C and C[double bond, length as m-dash]O bonds lying parallel to the surface in the low coverage regime and changes its geometry to a more upright orientation with increasing coverage. TPD studies indicate decomposition of the species adsorbed in the sub-monolayer regime upon heating. Similar strong coverage dependence of the IR spectra were found for propanal and allyl alcohol. For all investigated molecules a detailed assignment of vibrational bands is reported.

  7. Adsorption of acrolein, propanal, and allyl alcohol on Pd(111): a combined infrared reflection–absorption spectroscopy and temperature programmed desorption study

    PubMed Central

    Dostert, Karl-Heinz; O'Brien, Casey P.; Mirabella, Francesca; Ivars-Barceló, Francisco

    2016-01-01

    Atomistic-level understanding of the interaction of α,β-unsaturated aldehydes and their derivatives with late transition metals is of fundamental importance for the rational design of new catalytic materials with the desired selectivity towards C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 C vs. CO bond partial hydrogenation. In this study, we investigate the interaction of acrolein, and its partial hydrogenation products propanal and allyl alcohol, with Pd(111) as a prototypical system. A combination of infrared reflection–absorption spectroscopy (IRAS) and temperature programmed desorption (TPD) experiments was applied under well-defined ultrahigh vacuum (UHV) conditions to obtain detailed information on the adsorption geometries of acrolein, propanal, and allyl alcohol as a function of coverage. We compare the IR spectra obtained for

  8. Palladium-Catalyzed Decarboxylative Asymmetric Allylic Alkylation of Enol Carbonates

    PubMed Central

    Trost, Barry M.; Xu, Jiayi; Schmidt, Thomas

    2009-01-01

    Palladium-catalyzed decarboxylative asymmetric allylic alkylation (DAAA) of allyl enol carbonates as a highly chemo-, regio- and enantio-selective process for the synthesis of ketones bearing either a quaternary or a tertiary α-stereogenic center has been investigated in detail. Chiral ligand L4 was found to be optimal in the DAAA of a broad scope of cyclic and acyclic ketones including simple aliphatic ketones with more than one enolizable proton. The allyl moiety of the carbonates has been extended to a variety of cyclic or acyclic di-substituted allyl groups. Our mechanistic studies reveal that, similar to the direct allylation of lithium enolates, the DAAA reaction proceeds through an “outer sphere” SN2 type of attack on the π-allylpalladium complex by the enolate. An important difference between the DAAA reaction and the direct allylation of lithium enolates is that in the DAAA reaction, the nucleophile and the electrophile were generated simultaneously. Since the π-allylpalladium cation must serve as the counterion for the enolate, the enolate probably exists as a tight-ion-pair. This largely prevents the common side reactions of enolates associated with the equilibrium between different enolates. The much milder reaction conditions as well as the much broader substrate scope also represent the advantages of the DAAA reaction over the direct allylation of preformed metal enolates. PMID:19928805

  9. Vibrational Spectroscopic Studies of Hydrogen, Carbon-Monoxide and Thiophene Adsorption on Ruthenium-Sulfide and Sulfided Ruthenium Catalysts.

    NASA Astrophysics Data System (ADS)

    Heise, William Herbert

    The "working surface" of ruthenium hydrodesulfurization (HDS) catalysts has been modeled by preadsorption of sulfur, carbon and carbon plus sulfur on Ru(0001). Adsorption and decomposition of thiophene over these surfaces have been investigated using TDS/TPRS, XPS and EELS. Thiophene is proposed to decompose via a three-step mechanism involving: (i) initial thiophene cracking at 120 K yielding surface sulfur and hydrocarbon species, (ii) hydrogen desorption near 230 K providing additional decomposition ensembles and (iii) continued decomposition to form "metallocycle -like" intermediates which retain EELS features similar to thiophene. Preadsorbed carbon or carbon plus sulfur are not as effective for passivation of the surface toward metallocycle formation as preadsorbed sulfur alone. This result is attributed to the fact that carbon deposited from butadiene annealed and decomposed at 700 K forms islands, while sulfur establishes a well-ordered superlattice on the surface. The decrease in metallocycle formation with increasing poison levels appears to explain HDS selectivity and specific activity trends observed in our laboratory from mildly sulfided (10% H_2S/H_2 , 673 K, 2h) ruthenium catalysts retaining submonolayers of sulfur. Incoherent inelastic neutron scattering (IINS) has been used to characterize hydrogen adsorption sites on ruthenium sulfide. Hydrogen resides on sulfur anions to form SH groups, yielding two non-degenerate bending modes at 600 and 710 cm^{-1}. Complementary hydrogen adsorption and H_2/D _2 exchange data suggest that the active sites for hydrogen adsorption may be coordinatively unsaturated S-S anion pairs. Comparison of CO adsorption on sulfided Ru/Al _2O_3 to sulfur precovered Ru(0001) reveals an adsorption site related to edge/corner atoms directly perturbed by sulfur, consistent with previous kinetic studies demonstrating higher specific activity for thiophene HDS over smaller ruthenium crystallites.

  10. Radical cations of sulfides and disulfides: An ESR study

    SciTech Connect

    Bonazzola, L.; Michaut, J.P.; Roncin, J.

    1985-09-15

    Exposure of dilute solutions of dimethylsulfide, methanethiol, tetrahydrothiophene, terbutyl and diterbutyl-sulfides, dimethyl-disulfide, and diterbutyldisulfide, in freon at 77 K to /sup 60/Co ..gamma.. rays gave the corresponding cations. From the reported ESR spectra, g tensors were obtained. It was found that both sulfide and disulfide cations exhibit the same g tensor: (g/sub max/ = 2.034 +- 0.002, g/sub int/ = 2.017 +- 0.001, g/sub min/ = 2.001 +- 0.005). From this result it has been shown that the disulfide cation is planar. This finding was supported by fully optimized geometry ab initio calculations.

  11. Tsuji-Trost N-allylation with allylic acetates using cellulose-Pd catalyst

    EPA Science Inventory

    Allylic amines are synthesized using heterogeneous cellulose-Pd catalyst via N-allylation of amines; aliphatic and benzyl amines undergo facile reaction with substituted and unsubstituted allyl acetates in high yields.

  12. Tsuji-Trost N-allylation with allylic acetates using cellulose-Pd catalyst

    EPA Science Inventory

    Allylic amines are synthesized using heterogeneous cellulose-Pd catalyst via N-allylation of amines; aliphatic and benzyl amines undergo facile reaction with substituted and unsubstituted allyl acetates in high yields.

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

    PubMed

    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.

  14. Branched/linear selectivity in palladium-catalyzed allyl-allyl cross-couplings: The role of ligands.

    PubMed

    Ardolino, Michael J; Morken, James P

    2015-09-16

    While Pd-catalyzed allyl-allyl cross-couplings in the presence of small-bite-angle bidentate ligands reliably furnish the branched regioisomer with high levels of selectivity, cross-couplings in the presence of large-bite-angle bidentate ligands give varying, often unpredictable, levels of selectivity. In a combined computational and experimental study, we probe the underlying features that govern the regioselectivity in these metal-catalyzed cross-couplings.

  15. Structural studies of copper sulfide films: effect of ambient atmosphere

    PubMed Central

    Kundu, Manisha; Hasegawa, Tsuyoshi; Terabe, Kazuya; Yamamoto, Kazuhiro; Aono, Masakazu

    2008-01-01

    We examined the structural properties of copper sulfide films as a function of the sulfurization time of 70-nm-thick Cu films. Copper sulfide films with various phases such as mixed metallic Cu-chalcocite, chalcocite, roxbyite, and covellite phases were formed with increasing sulfurization time. To evaluate the structural stability of various films, all the films were exposed to the ambient atmosphere for the same amount of time. Although the phase structure and stoichiometry of the films were maintained at a greater depth, the near-surface region of the films was oxidized and covered with overlayers of oxide, hydroxide, and/or sulfate species due to the exposure and reaction with the ambient atmosphere. The oxygen uptake and its reactivity with the copper sulfide film surfaces were enhanced with increasing sulfur content of the films. In addition, the type of divalent state of copper formed on the film surfaces depended on the phase structure, composition, and stoichiometry of the films. PMID:27878008

  16. Asymmetric Allylic C-H Oxidation for the Synthesis of Chromans.

    PubMed

    Wang, Pu-Sheng; Liu, Peng; Zhai, Yu-Jia; Lin, Hua-Chen; Han, Zhi-Yong; Gong, Liu-Zhu

    2015-10-14

    An enantioselective intramolecular allylic C-H oxidation to generate optically active chromans has been accomplished under the cooperative catalysis of a palladium complex of chiral phosphoramidite ligand and 2-fluorobenzoic acid. Mechanistic studies suggest that this reaction commences with a Pd-catalyzed allylic C-H activation event and then undergoes asymmetric allylic alkoxylation. The synthetic significance of the method has been embodied by concisely building up a key chiral intermediate to access (+)-diversonol.

  17. Palladium-Catalyzed Aminocarbonylation of Allylic Alcohols.

    PubMed

    Li, Haoquan; Neumann, Helfried; Beller, Matthias

    2016-07-11

    A benign and efficient palladium-catalyzed aminocarbonylation reaction of allylic alcohols is presented. The generality of this novel process is demonstrated by the synthesis of β,γ-unsaturated amides including aliphatic, cinnamyl, and terpene derivatives. The choice of ligand is crucial for optimal carbonylation processes: Whereas in most cases the combination of PdCl2 with Xantphos (L6) gave best results, sterically hindered substrates performed better in the presence of simple triphenylphosphine (L10), and primary anilines gave the best results using cataCXium® PCy (L8). The reactivity of the respective catalyst system is significantly enhanced by addition of small amounts of water. Mechanistic studies and control experiments revealed a tandem allylic alcohol amination/C-N bond carbonylation reaction sequence.

  18. Mechanistic study of microbial control of hydrogen sulfide production in oil reservoirs.

    PubMed

    Nemati, M; Jenneman, G E; Voordouw, G

    2001-09-05

    Microbial control of biogenic production of hydrogen sulfide in oil fields was studied in a model system consisting of pure cultures of the nitrate-reducing, sulfide-oxidizing bacterium (NR-SOB) Thiomicrospira sp. strain CVO and the sulfate-reducing bacterium (SRB) Desulfovibrio sp. strain Lac6, as well as in microbial cultures enriched from produced water of a Canadian oil reservoir. The presence of nitrate at concentrations up to 20 mM had little effect on the rate of sulfate reduction by a pure culture of Lac6. Addition of CVO imposed a strong inhibition effect on production of sulfide. In the absence of added nitrate SRB we were able to overcome this effect after an extended lag phase. Simultaneous addition of CVO and nitrate stopped the production of H2S immediately. The concentration of sulfide decreased to a negligible level due to nitrate-dependent sulfide oxidation activity of CVO. This was not prevented by raising the concentration of Na-lactate, the electron donor for sulfate reduction. Similar results were obtained with enrichment cultures. Enrichments of produced water with sulfide and nitrate were dominated by CVO, whereas enrichments with sulfate and Na-lactate were dominated by SRB. Addition of an NR-SOB enrichment to an SRB enrichment inhibited the production of sulfide. Subsequent addition of sufficient nitrate caused the sulfide concentration to drop to zero. A similar response was seen in the presence of nitrate alone, although after a pronounced lag time, it was needed for emergence of a sizable CVO population. The results of the present study show that two mechanisms are involved in microbial control of biogenic sulfide production. First, addition of NR-SOB imposes an inhibition effect, possibly by increasing the environmental redox potential to levels which are inhibitory for SRB. Second, in the presence of sufficient nitrate, NR-SOB oxidize sulfide, leading to its complete removal from the environment. Successful microbial control of H2S in

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

    PubMed Central

    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

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

    PubMed

    Fremerey, Peter; Jess, Andreas; Moos, Ralf

    2015-10-23

    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.

  1. Nickel-Catalyzed Allylic Alkylation with Diarylmethane Pronucleophiles: Reaction Development and Mechanistic Insights.

    PubMed

    Sha, Sheng-Chun; Jiang, Hui; Mao, Jianyou; Bellomo, Ana; Jeong, Soo A; Walsh, Patrick J

    2016-01-18

    Palladium-catalyzed allylic substitution reactions are among the most efficient methods to construct C-C bonds between sp(3)-hybridized carbon atoms. In contrast, much less work has been done with nickel catalysts, perhaps because of the different mechanisms of the allylic substitution reactions. Palladium catalysts generally undergo substitution by a "soft"-nucleophile pathway, wherein the nucleophile attacks the allyl group externally. Nickel catalysts are usually paired with "hard" nucleophiles, which attack the metal before C-C bond formation. Introduced herein is a rare nickel-based catalyst which promotes substitution with diarylmethane pronucleophiles by the soft-nucleophile pathway. Preliminary studies on the asymmetric allylic alkylation are promising.

  2. Dissolution of cellulose in 1-allyl-3-methylimizodalium carboxylates at room temperature: a structure-property relationship study.

    PubMed

    Zhang, Yajuan; Xu, Airong; Lu, Benlian; Li, Zhiyong; Wang, Jianji

    2015-03-06

    The development of highly efficient cellulose solvents is imperative to the effective utilization of cellulose. In this work, ionic liquids (ILs) with the same 1-allyl-3-methylimidazolium cation ([Amim](+)) but different carboxylate anions, such as formate ([HCOO](-)), acetate ([CH3COO](-)), propionate ([CH3CH2COO](-)), butyrate ([CH3CH2CH2COO](-)), glycollate ([HOCH2COO](-)), lactate ([CH3CHOHCOO](-)) and benzoate ([C6H5COO](-)) were synthesized, and their thermal properties and viscosities were determined. Then these ILs were used to investigate the effect of anion structure on solubility of cellulose in the ILs. It was shown that the viscosity and cellulose solubility depended strongly on the anion structure of the ILs. For example, at 30 °C solubility of cellulose in [Amim][CH3CH2COO] was as high as 19.0%, whereas cellulose was not soluble in [Amim][HOCH2COO], [Amim][CH3CHOHCOO] and [Amim][C6H5COO]. In addition, solvatochromic UV/vis probe and (13)C NMR measurements were performed to demonstrate dissolution mechanism of cellulose in the ILs. The results suggested that although cations of the ILs have un-negligible contribution to the highly efficient dissolution of cellulose, hydrogen bonding interactions of anions of the ILs with cellulose is predominant.

  3. Palladium-catalyzed allylation of acidic and less nucleophilic anilines using allylic alcohols directly.

    PubMed

    Hsu, Yi-Chun; Gan, Kim-Hong; Yang, Shyh-Chyun

    2005-10-01

    The direct activation of C-O bonds in allylic alcohols by palladium complexes has been accelerated by carrying out the reactions in the presence of titanium(IV) isoproxide and 4 A molecular sieves. The acidic and less nucleophilic anilines such as diphenylamine, phenothiazine, 4-cyanoaniline, and nitroanilines are efficiently allylated under palladium catalysis using allylic alcohols as allylating reagents.

  4. Indium-Mediated Stereoselective Allylation.

    PubMed

    Kumar, Dinesh; Vemula, Sandeep R; Balasubramanian, Narayanaganesh; Cook, Gregory R

    2016-10-04

    Stereoselective indium-mediated organic reactions have enjoyed tremendous growth in the last 25 years. This is in part due to the insensitivity of allylindium to moisture, affording facile and practical reaction conditions coupled with outstanding functional group tolerance and minimal side reactions. Despite the plethora of articles about allylindium, there is much yet to be discovered and exploited for efficient and sustainable synthesis. In this Account, we describe indium-mediated synthetic methods for the preparation of chiral amines with the aim to present a balance of practical method development, novel asymmetric chemistry, and mechanistic understanding that impact multiple chemical and materials science disciplines. In 2005, we demonstrated the indium-mediated allylation of chiral hydrazones with complete diastereoselectivity (>99:1) and quantitative yields. Further, we revealed the first example of enantioselective indium-mediated allylation of hydrazones using catalytic (R)-3,3'-bis(trifluoromethyl)-BINOL ligands to afford homoallylic amines with high enantioselectivity. The use of enantiopure perfluoroalkylsulfonate BINOLs greatly improved the indium-mediated allylation of N-acylhydrazones with exquisite enantiocontrol (99% yield, 99% ee). This laboratory has also investigated indium-mediated asymmetric intramolecular cyclization in the presence of amino acid additives to deliver biologically relevant chromanes with excellent diastereoselectivity (dr >99:1). The effect of amino acid additives (N-Boc-glycine) was further investigated during the indium-mediated allylation of isatins with allyl bromide to yield homoallylic alcohols in excellent yields in a short time with a wide range of functional group tolerance. Critical mechanistic insight was gained, and evidence suggests that the additive plays two roles: (1) to increase the rate of formation of allylindium from allyl bromide and In(0) and (2) to increase the nucleophilicity of the allylindium

  5. Palladium-catalyzed amination of allyl alcohols.

    PubMed

    Ghosh, Raju; Sarkar, Amitabha

    2011-10-21

    An efficient catalytic amination of aryl-substituted allylic alcohols has been developed. The complex [(η(3)-allyl)PdCl](2) modified by a bis phosphine ligand, L, has been used as catalyst in the reaction that afforded a wide range of allyl amines in good to excellent yield under mild conditions.

  6. Sulfide and sulfoxide oxidations by mono- and diperoxo complexes of molybdenum. A density functional study.

    PubMed

    Sensato, Fabrício R; Custodio, Rogério; Longo, E; Safont, Vicent S; Andres, Juan

    2003-07-25

    The molecular mechanism for the oxidation of sulfides to sulfoxides and subsequent oxidation to sulfones by diperoxo, MoO(O(2))(2)(OPH(3)) (I), and monoperoxo, MoO(2)(O(2))(OPH(3)) (II), complexes of molybdenum was studied using density functional calculations at the b3lyp level and the transition state theory. Complexes I and II were both found to be active species. Sulfide oxidation by I or II shows similar activation free energy values of 18.5 and 20.9 kcal/mol, respectively, whereas sulfoxides are oxidized by I (deltaG = 20.6 kcal/mol) rather than by II (deltaG = 30.3 kcal/mol). Calculated kinetic and thermodynamic parameters account for the spontaneous overoxidation of sulfides to sulfones as has been experimentally observed. The charge decomposition analysis (CDA) of the calculated transition structures of sulfide and sulfoxide oxidations revealed that I and II are stronger electrophilic oxidants toward sulfides than they are toward sulfoxides.

  7. Study on phase transformation pathways of iron sulfide minerals

    NASA Astrophysics Data System (ADS)

    Lin, M. Y.; Chen, Y. H.

    2016-12-01

    The iron sulfide minerals, including mackinawite, greigite, pyrite etc., are critical role in global sulfur cycle, recorders of geomagnetic fields and paleoenvironment in sedimentary rocks. However, due to lots of factors like oxygen pressure, pH, concentration and temperature etc., the transformation process mechanism and pathway were still unknown. Co-precipitation method was used to synthesize precursor (amorphous FeS) and pH value, time, temperature were adjusted to observe transformation process. For ex-situ X-ray diffraction (XRD) results of iron sulfide growth, it was observed the initially appearing phase was mackinawite at acidic and neutral conditions, but mackinawite along with magnetite occurred at the alkaline condition. While the reaction time was increased from 1 hour to 3 days and 20 days, it displayed the transformation phase from mackinawite to greigite, finally marcasite and pyrite were appeared in acidic condition. It showed that the transformation rate in the acidic environment is faster than that in neutral and alkaline conditions. For in-situ X-ray diffraction (XRD) results, it had the same phase transition pathway as mackinawite transformed into greigite at 80oC, and then pyrite appeared at 100oC in the acidic medium. However, it always kept the same phases in neutral and alkaline conditions during 3 hours at 80oC and 100oC, which indicated that mackinawite was very unstable and performed visible transformation sequence under acidic conditions. It concluded that the reaction time, pH value, and temperature indeed influenced the Fe-S formation pathway.

  8. Study of upscaling possibilities for antimony sulfide solid state sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Nikolakopoulou, Archontoula; Raptis, Dimitrios; Dracopoulos, Vasilios; Sygellou, Lamprini; Andrikopoulos, Konstantinos S.; Lianos, Panagiotis

    2015-03-01

    Solid state solar cells of inverted structure were constructed by successive deposition of nanoparticulate titania, antimony sulfide sensitizer and P3HT on FTO electrodes with PEDOT:PSS:Ag as counter electrode. Sensitized photoanode electrodes were characterized by XRD, Raman, XPS, FESEM and UV-vis. Small laboratory scale cells were first constructed and optimized. Functional cells were obtained by annealing the antimony sulfide film either in air or in inert atmosphere. High short-circuit currents were recorded in both cases with air-annealed sample producing more current but lower voltage. Small unit cells were combined to form cell modules. Connection of unit cells in parallel increased current but not proportionally to that of the unit cell. Connection in series preserved current and generated voltage multiplication. Cells were constructed and studied under ambient conditions, without encapsulation. The results encourage upscaling of antimony sulfide solar cells.

  9. Iron-Catalyzed Allylic Amination Directly from Allylic Alcohols.

    PubMed

    Emayavaramban, Balakumar; Roy, Moumita; Sundararaju, Basker

    2016-03-14

    Allylic amination, directly from alcohols, has been demonstrated without any Lewis acid activators using an efficient and regiospecific molecular iron catalyst. Various amines and alcohols were employed and the reaction proceeded through the oxidation/reduction (redox) pathway. A direct one-step synthesis of common drugs, such as cinnarizine and nafetifine, was exhibited from cinnamyl alcohol that produced water as side product.

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

    NASA Astrophysics Data System (ADS)

    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 > CH2 ≈ 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.

  11. Allyl-silica Hybrid Monoliths For Chromatographic Application

    NASA Astrophysics Data System (ADS)

    Guo, Wenjuan

    Column technology continues to be the most investigated topics in the separation world, since the column is the place where the chromatographic separation happens, making it the heart of the separation system. Allyl-silica hybrid monolithic material has been exploited as support material and potential stationary phases for liquid chromatography; the stationary phase anchored to the silica surface by Si-C bond, which is more pH stable than traditional stationary phase. First, nuclear magnetic resonance spectroscopy has been used to study the sol in the synthesis of allyl-silica hybrid monoliths. Allyl-trimethoxysilane (allyl-TrMOS), dimethyldimethoxysilane (DMDMOS) and tetramethoxysilane (TMOS) have been served as co-precursors in the sol-gel synthesis of organo-silica hybrid monolithic columns for liquid chromatography (LC). 29Si nuclear magnetic resonance (NMR) and 1H NMR spectroscopy were employed to monitor reaction profiles for the acid-catalyzed hydrolysis and initial condensation reactions of the individual precursor and the hybrid system. 29Si-NMR has also been used to identify different silane species formed during the reactions. The overall hydrolysis rate has been found to follow the trend DMDMOS > allyl-TrMOS > TMOS, if each precursor is reacted individually (homo-polymerization). Precursors show different hydrolysis rate when reacted together in the hybrid system than they are reacted individually. Cross-condensation products of TMOS and DMDMOS (QD) arise about 10 minutes of initiation of the reaction. The allyl-silica monolithic columns for capillary liquid chromatography can only be prepared in capillaries with 50 im internal diameter with acceptable performance. One of the most prominent problems related to the synthesis of silica monolithic structures is the volume shrinkage. The synthesis of allylfunctionalized silica hybrid monolithic structures has been studied in an attempt to reduce the volume shrinkage during aging, drying and heat treatment

  12. Reflectivity and microhardness of sulfide minerals as genetic information source (case study: pyrite and arsenopyrite)

    NASA Astrophysics Data System (ADS)

    Sinkina, E. A.; Korovkin, M. V.; Savinova, O. V.; Makarova, A. A.

    2016-03-01

    Reflectivity and microhardness of pyrite and arsenopyrite of black shale gold-ore deposits in Chertovo Koryto (Patom upland) were studied. It was found that sulfides of different generations are characterized by different values of above-mentioned parameters which is associated mechanical and isomorphic impurities.

  13. Kinetic studies on the oxidation of aryl methyl sulfides and sulfoxides by dimethyldioxirane; absolute rate constants and activation parameters for 4-nitrophenyl methyl sulfide and sulfoxide.

    PubMed

    Hanson, Peter; Hendrickx, Ramon A A J; Lindsay Smith, John R

    2008-02-21

    The oxidations of methyl 4-nitrophenyl sulfide and sulfoxide by dimethyldioxirane, in acetone and mixtures of acetone with water, methanol, acetonitrile and hexane, have been followed by UV-Vis spectroscopy to monitor the decay of the substrates. The data show that, under all the conditions studied, both oxidations obey second-order kinetics. Grunwald-Winstein and Kamlet-Taft analyses of the influence of solvents on the second-order rate constants have been used to obtain mechanistic information on the two reactions. Activation parameters for the two oxidations in acetone and aqueous acetone have been calculated from rate constants for reactions in the temperature range 283-313 K and compared with those from sulfide and sulfoxide oxidations with other oxidants. For sulfoxide oxidations in acetone and 1-20% v/v water in acetone, the results support a concerted nucleophilic displacement by sulfur of oxygen from dimethyldioxirane with the rate being dependent on the solvent's polarity. Sulfide oxidations in acetone and 1-5% v/v water in acetone also proceed by a concerted mechanism. However, in the most polar solvent system studied, 20% v/v water in acetone, the mechanism changes in favour of a two-step reaction involving a betaine intermediate. Importantly, the sulfide oxidation shows a different solvent dependence to that of the sulfoxide, with the rate of oxidation being determined by the hydrogen bond donor capacity and electron-pair donicity of the solvent.

  14. Study on Fiber-optic Hydrogen Sulfide Gas Sensor

    NASA Astrophysics Data System (ADS)

    Zhou, Hong; Wen, Jun-Qing; Zhang, Xiao-Zhen; Wang, Wei; Feng, De-Quan; Wang, Qi; Jia, Fei

    We describe a novel fiber-optic gas sensor which hydrogen Sulfide (H2S) gas can be detected by a silver coated fiber bragg grating (FBG). The H2S sensitive material Ag can be coated on the cladding surrounding surface of FBG by conventional silver mirror reaction. The scanning electron microscope (SEM) was applied to analysis the Ag film structure before and after the interaction with H2S gas. By conducting the experiment of Ag-coated optical sensor (AOS), the relation between the H2S gas concentration and absorption spectrum was built. Result shows that while the concentration alters from 0 to 9.32%, a linear response of AOS signal to H2S concentration was observed with the response sensitivity of 0.332 dBm/% and linearity R2=0.9966. Such H2S sensor is suitable for monitoring the H2S hazard as a one time disposable logging-while-drilling sensor.

  15. Allyl isothiocyanate from mustard seed is effective in reducing the levels of volatile sulfur compounds responsible for intrinsic oral malodor.

    PubMed

    Tian, Minmin; Hanley, A Bryan; Dodds, Michael W J

    2013-06-01

    Oral malodor is a major social and psychological issue that affects general populations. Volatile sulfur compounds (VSCs), particularly hydrogen sulfide (H₂S) and methyl mercaptan (CH₃SH), are responsible for most oral malodor. The objectives for this study were to determine whether allyl isothiocyanate (AITC) at an organoleptically acceptable level can eliminate VSCs containing a free thiol moiety and further to elucidate the mechanism of action and reaction kinetics. The study revealed that gas chromatograph with a sulfur detector demonstrated a good linearity, high accuracy and sensitivity on analysis of VSCs. Zinc salts eliminate the headspace level of H₂S but not CH₃SH. AITC eliminates both H₂S and CH₃SH via a nucleophilic addition reaction. In addition, a chemical structure-activity relationship study revealed that the presence of unsaturated group on the side chain of the isothiocyanate accelerates the elimination of VSCs.

  16. A computational study of adhesion between rubber and metal sulfides at rubber-brass interface

    NASA Astrophysics Data System (ADS)

    Ling, Chian Ye; Hirvi, Janne T.; Suvanto, Mika; Bazhenov, Andrey S.; Ajoviita, Tommi; Markkula, Katriina; Pakkanen, Tapani A.

    2015-05-01

    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.

  17. Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature

    NASA Astrophysics Data System (ADS)

    Han, Junwei; Liu, Wei; Zhang, Tianfu; Xue, Kai; Li, Wenhua; Jiao, Fen; Qin, Wenqing

    2017-02-01

    The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1‑xFexS). The oxidation of synthetic Zn1‑xFexS is easier than marmatite in air.

  18. Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature

    PubMed Central

    Han, Junwei; Liu, Wei; Zhang, Tianfu; Xue, Kai; Li, Wenhua; Jiao, Fen; Qin, Wenqing

    2017-01-01

    The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1−xFexS). The oxidation of synthetic Zn1−xFexS is easier than marmatite in air. PMID:28186156

  19. Oxy-Allyl Cation Catalysis: An Enantioselective Electrophilic Activation Mode

    PubMed Central

    Liu, Chun; Oblak, E. Zachary; Vander Wal, Mark N.; Dilger, Andrew K.; Almstead, Danielle K.; MacMillan, David W. C.

    2016-01-01

    A generic activation mode for asymmetric LUMO-lowering catalysis has been developed using the long-established principles of oxy-allyl cation chemistry. Here, the enantioselective conversion of racemic α-tosyloxy ketones to optically enriched α-indolic carbonyls has been accomplished using a new amino alcohol catalyst in the presence of electron-rich indole nucleophiles. Kinetic studies reveal that the rate-determining step in this SN1 pathway is the catalyst-mediated α-tosyloxy ketone deprotonation step to form an enantiodiscriminant oxy-allyl cation prior to the stereodefining nucleophilic addition event. PMID:26797012

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

    PubMed

    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. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. Role of planar chirality of S,N- and P,N-ferrocene ligands in palladium-catalyzed allylic substitutions.

    PubMed

    You, Shu-Li; Hou, Xue-Long; Dai, Li-Xin; Yu, Yi-Hua; Xia, Wei

    2002-07-12

    Palladium-catalyzed asymmetric allylic substitutions using thioether and phosphino derivatives of ferrocenyloxazoline as ligands have been investigated with a focus on studying the role of planar chirality. In allylic alkylation, up to 98% ee and 95% ee were achieved with S,N- and P,N-ligands, respectively. In allylic amination, 97% ee was realized with P,N-ligands in the presence of TBAF. Several palladium allylic complexes were characterized by X-ray diffraction and/or solution NMR. Thioether derivatives of ferrocenyloxazolines with only planar chirality showed lower enantioselectivity in the allylic alkylation except 5c because of the formation of a new chirality on sulfur atom during the coordination of sulfur with palladium. On the other hand, in the planar chiral P,N-ligands without central chirality, (Sp)-11a-c there was no such disturbance and comparatively higher enantioselectivity in both palladium-catalyzed allylic alkylation and amination was provided.

  2. Regioselective hydroformylation of allylic alcohols.

    PubMed

    Lightburn, Thomas E; De Paolis, Omar A; Cheng, Ka H; Tan, Kian L

    2011-05-20

    A highly regioselective hydroformylation of allylic alcohols is reported toward the synthesis of β-hydroxy-acid and aldehyde products. The selectivity is achieved through the use of a ligand that reversibly binds to alcohols in situ, allowing for a directed hydroformylation to occur. The application to trisubstituted olefins was also demonstrated, which yields a single diastereomer product consistent with a stereospecific addition of CO and hydrogen.

  3. Enantioselective Allylation, Crotylation and Reverse Prenylation of Substituted Isatins via Iridium Catalyzed C-C Bond Forming Transfer Hydrogenation**

    PubMed Central

    Itoh, Junji; Han, Soo Bong; Krische, Michael J.

    2010-01-01

    Oxindoles with a Twist Transfer hydrogenation of substituted isatins in the presence of allyl acetate, α-methyl allyl acetate or 1,1,-dimethylallene employing an ortho-cyclometallated iridium catalyst modified by CTH-(R)-P-PHOS provides products of carbonyl allylation, crotylation and reverse prenylation, respectively, in highly enantiomerically enriched form. These studies represent the first use of activated ketones as electrophilic partners in asymmetric C-C bond forming transfer hydrogenation. PMID:19606435

  4. Chronoamperometric study of mild steel pitting in sodium sulfide aqueous solution

    SciTech Connect

    Otero, T.F.; Achucarro, C. . Dept. de Ciencia y Tecnologia de Polimeros)

    1994-08-01

    Mild steel samples were studied by chronoamperometry in sodium sulfide (Na[sub 2]S) aqueous solution. Pit nucleation and growth also were monitored by optical microscopy. The influence of variables such as temperature, polarization potential, surface roughness, the presence of electrochemically generated oxide layers, and the simultaneous presence of potassium hydroxide (KOH) was studied. The influence of each parameter on pit shape and growth was reviewed. Different reactions and competitive processes were proposed based on the experimental results.

  5. Selenium Sulfide

    MedlinePlus

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

  6. Kinetic and thermodynamic studies on the disulfide-bond reducing potential of hydrogen sulfide.

    PubMed

    Vasas, Anita; Dóka, Éva; Fábián, István; Nagy, Péter

    2015-04-30

    The significance of persulfide species in hydrogen sulfide biology is increasingly recognized. However, the molecular mechanisms of their formation remain largely elusive. The obvious pathway of the reduction of biologically abundant disulfide moieties by sulfide was challenged on both thermodynamic and kinetic grounds. Using DTNB (5,5'-dithiobis-(2-nitrobenzoic acid), also known as Ellman's reagent) as a model disulfide we conducted a comprehensive kinetic study for its reaction with sulfide. The bimolecular reaction is relatively fast with a second-order rate constant of 889 ± 12 M(-1)s(-1) at pH = 7.4. pH dependence of the rate law revealed that the reaction proceeds via the bisulfide anion species with an initial nucleophilic thiol-disulfide exchange reaction to give 5-thio-2-nitrobenzoic acid (TNB) and TNB-persulfide with a pH independent second-order rate constant of 1090 ± 12 M(-1)s(-1). However, kinetic studies and stoichiometric analyses in a wide range of reactant ratios together with kinetic simulations revealed that it is a multistep process that proceeds via kinetically driven, practically irreversible reactions along the disulfide → persulfide → inorganic polysulfides axis. The kinetic model postulated here, which is fully consistent with the experimental data, suggests that the TNB-persulfide is further reduced by sulfide with a second-order rate constant in the range of 5 × 10(3) - 5 × 10(4) M(-1)s(-1) at pH 7.4 and eventually yields inorganic polysulfides and TNB. The reactions of cystine and GSSG with sulfide were found to be significantly slower and to occur via more complicated reaction schemes. (1)H NMR studies suggest that these reactions also generate Cys-persulfide and inorganic polysulfide species, but in contrast with DTNB, in consecutive equilibrium processes that are sensitive to changes in the reactant and product ratios. Collectively, our results demonstrate that the reaction of disulfides with sulfide is a highly system

  7. Study of the chemical reduction of the fumonisins toxicity using allyl, benzyl and phenyl isothiocyanate in model solution and in food products.

    PubMed

    Azaiez, I; Meca, G; Manyes, L; Luciano, F B; Fernández-Franzón, M

    2013-03-01

    Fumonisins (FBs) are bioactive compounds produced by several strains of Fusarium spp. which contain a polyketide structure similar to sphinganine. These mycotoxins contain a free amino group that could work as an electron donor and react with the electrophile carbon present within the isothiocyanate (ITC) group. The objective of this study was to determine the effect of ITCs (allyl, benzyl and phenyl) on the stability of FB(1), FB(2) and FB(3). Firstly, PBS solutions at three pH levels (4, 7 and 9) were prepared and added with pairs of one FB (1 mg/L) plus one ITC (1 mg/L). Then, gaseous ITC was used to fumigate corn kernels and corn flour contaminated with FBs produced by Gibberella moniliformis CECT 2987 in situ. Mycotoxin levels were evaluated using liquid chromatography coupled to mass spectrometry in tandem (LC-MS/MS), while products formed from the reaction of FBs and ITCs were examined by liquid chromatography coupled to mass spectrometry-linear ion trap (LC-MS-LIT). The reduction of FB(1) and FB(2) in solution ranged from 42 to 100% on a time-dependent manner. This variance was greatly influenced by pH. In general, lower pH levels eased the reaction between ITCs and FBs. ITC fumigation treatment (50, 100 and 500 μL/L) was able to reduce 53-96% of FB(1) levels, 29-91% of FB(2) and 29-96% of FB(3). Four reaction products between the bioactive compounds employed in this study were identified, corresponding to FB + ITC conjugates. Copyright © 2012 Elsevier Ltd. All rights reserved.

  8. O-Allylation of phenols with allylic acetates in aqueous media using a magnetically separable catalytic system

    EPA Science Inventory

    Allylic ethers were synthesized in water using magnetically recoverable heterogeneous Pd catalyst via O-allylation of phenols with allylic acetates under ambient conditions. Aqueous reaction medium, easy recovery of the catalyst using an external magnet, efficient recycling, and ...

  9. O-Allylation of phenols with allylic acetates in aqueous media using a magnetically separable catalytic system

    EPA Science Inventory

    Allylic ethers were synthesized in water using magnetically recoverable heterogeneous Pd catalyst via O-allylation of phenols with allylic acetates under ambient conditions. Aqueous reaction medium, easy recovery of the catalyst using an external magnet, efficient recycling, and ...

  10. Interdisciplinary neurotoxicity inhalation studies: Carbon disulfide and carbonyl sulfide research in F344 rats

    SciTech Connect

    Sills, Robert C. . E-mail: sills@niehs.nih.gov; Harry, G. Jean; Valentine, William M.; Morgan, Daniel L.

    2005-09-01

    Inhalation studies were conducted on the hazardous air pollutants, carbon disulfide, which targets the central nervous system (spinal cord) and peripheral nervous system (distal portions of long myelinated axons), and carbonyl sulfide, which targets the central nervous system (brain). The objectives were to investigate the neurotoxicity of these compounds by a comprehensive evaluation of function, structure, and mechanisms of disease. Through interdisciplinary research, the major finding in the carbon disulfide inhalation studies was that carbon disulfide produced intra- and intermolecular protein cross-linking in vivo. The observation of dose-dependent covalent cross-linking in neurofilament proteins prior to the onset of lesions is consistent with this process contributing to the development of the neurofilamentous axonal swellings characteristic of carbon disulfide neurotoxicity. Of significance is that valine-lysine thiourea cross-linking on rat globin and lysine-lysine thiourea cross-linking on erythrocyte spectrin reflect cross-linking events occurring within the axon and could potentially serve as biomarkers of carbon disulfide exposure and effect. In the carbonyl sulfide studies, using magnetic resonance microscopy (MRM), we determined that carbonyl sulfide targets the auditory pathway in the brain. MRM allowed the examination of 200 brain slices and made it possible to identify the most vulnerable sites of neurotoxicity, which would have been missed in our traditional neuropathology evaluations. Electrophysiological studies were focused on the auditory system and demonstrated decreases in auditory brain stem evoked responses. Similarly, mechanistic studies focused on evaluating cytochrome oxidase activity in the posterior colliculus and parietal cortex. A decrease in cytochrome oxidase activity was considered to be a contributing factor to the pathogenesis of carbonyl sulfide neurotoxicity.

  11. Case Study: Microbial Ecology and Forensics of Chinese Drywall-Elemental Sulfur Disproportionation as Primary Generator of Hydrogen Sulfide.

    PubMed

    Tomei Torres, Francisco A

    2017-06-21

    Drywall manufactured in China released foul odors attributed to volatile sulfur compounds. These included hydrogen sulfide, methyl mercaptan, and sulfur dioxide. Given that calcium sulfate is the main component of drywall, one would suspect bacterial reduction of sulfate to sulfide as the primary culprit. However, when the forensics, i.e., the microbial and chemical signatures left in the drywall, are studied, the evidence suggests that, rather than dissimilatory sulfate reduction, disproportionation of elemental sulfur to hydrogen sulfide and sulfate was actually the primary cause of the malodors. Forensic evidence suggests that the transformation of elemental sulfur went through several abiological and microbial stages: (1) partial volatilization of elemental sulfur during the manufacture of plaster of Paris, (2) partial abiotic disproportionation of elemental sulfur to sulfide and thiosulfate during the manufacture of drywall, (3) microbial disproportionation of elemental sulfur to sulfide and sulfate resulting in neutralization of all alkalinity, and acidification below pH 4, (4) acidophilic microbial disproportionation of elemental sulfur to sulfide and sulfuric acid, and (5) hydrogen sulfide volatilization, coating of copper fixtures resulting in corrosion, and oxidation to sulfur dioxide.

  12. An XAFS study of the S Se exchange during the reaction of selenophene over Mo sulfide catalysts

    NASA Astrophysics Data System (ADS)

    Kubota, Takeshi; Hosomi, Naoto; Hamasaki, Yuya; Okamoto, Yasuaki

    2003-03-01

    The S-Se exchange during the hydrode-selenium (HD-Se) reaction of selenophene was investigated over MoS 2/Al 2O 3 and intrazeolite Mo sulfide clusters. The local structure of Se incorporated into the Mo sulfide catalysts was studied by means of Se K-edge XAFS. It was found that the capacity of S-Se exchange during the HD-Se reaction and dynamic behavior of Se incorporation strongly depend on the cluster size of Mo sulfides.

  13. Palladium-Catalyzed Chemoselective Allylic Substitution, Suzuki-Miyaura Cross-Coupling, and Allene Formation of Bifunctional 2-B(pin)-Substituted Allylic Acetate Derivatives

    PubMed Central

    Kim, Byeong-Seon; Hussain, Mahmud M.; Hussain, Nusrah

    2014-01-01

    A formidable challenge at the forefront of organic synthesis is the control of chemoselectivity to enable the selective formation of diverse structural motifs from a readily available substrate class. Presented herein is a detailed study of chemoselectivity with palladium-based phosphine catalysts and readily available 2-B(pin)-substituted allylic acetates, benzoates, and carbonates. Depending on the choice of reagents, catalysts and reaction conditions, 2-B(pin)-substituted allylic acetates and derivatives can be steered into one of three reaction manifolds: allylic substitution, Suzuki-Miyaura cross-coupling, or elimination to form allenes, all with excellent chemoselectivity. The studies on chemoselectivity of Pd catalysts in their reactivity with boron-bearing allylic acetate derivatives led to the development of diverse and practical reactions with potential utility in synthetic organic chemistry. PMID:25077980

  14. Activation mechanism of ammonium ions on sulfidation of malachite (-201) surface by DFT study

    NASA Astrophysics Data System (ADS)

    Wu, Dandan; Mao, Yingbo; Deng, Jiushuai; Wen, Shuming

    2017-07-01

    The activation mechanism of ammonium ions on the sulfidation of malachite (-201) was determined by density functional theory (DFT) calculations. Results of DFT calculations indicated that interlayer sulfidation occurs during the sulfidation process of malachite (-201). The absorption of both the ammonium ion and sulfide ion on the malachite (-201) surface is stronger than that of sulfur ion. After sulfidation was activated with ammonium ion, the Cu 3d orbital peak is closer to the Fermi level and characterized by a stronger peak value. Therefore, the addition of ammonium ions activated the sulfidation of malachite (-201), thereby improving the flotation performance.

  15. A study of the trace sulfide mineral assemblages in the Stillwater Complex, Montana, USA

    NASA Astrophysics Data System (ADS)

    Aird, Hannah M.; Ferguson, Katherine M.; Lehrer, Malia L.; Boudreau, Alan E.

    2016-07-01

    The sulfide assemblages of the Stillwater Complex away from the well-studied ore zones are composed mainly of variable proportions of pyrrhotite, chalcopyrite, pentlandite, and ±pyrite. Excluding vein assemblages and those affected by greenschist and lower temperature alteration, the majority can be classified into two broad assemblages, defined here as pristine (multiphase, often globular in shape) or volatile-bearing (multiphase, high-temperature, volatile-rich minerals such as biotite, hornblende, or an unmixed calcite-dolomite assemblage). The volatile-bearing assemblages are mainly found within and below the J-M reef, where native copper and sphalerite are also locally present. Pristine sulfides are found throughout the stratigraphy. Both groups can be affected by apparent S loss in the form of pyrite being converted to magnetite and chalcopyrite to a Cu-Fe-oxide (delafossite), with little to no silicate alteration. An upward trend from pentlandite-rich to pyrrhotite-rich to pyrite-rich assemblages is observed in the footwall rocks in upper GN-I, and the same trend repeats from just below the reef and continues into the overlying N-II and GN-II. Modeling suggests that the sulfide Ni in the Peridotite Zone is largely controlled by silicate Ni. When taken together, observations are most readily explained by the remobilization of selected elements by a high-temperature fluid with the apparent loss of S > Cu > Ni. This could concentrate ore metals by vapor refining, eventually producing a platinum group element-enriched sulfide ore zone, such as the J-M reef.

  16. A study of the trace sulfide mineral assemblages in the Stillwater Complex, Montana, USA

    NASA Astrophysics Data System (ADS)

    Aird, Hannah M.; Ferguson, Katherine M.; Lehrer, Malia L.; Boudreau, Alan E.

    2017-03-01

    The sulfide assemblages of the Stillwater Complex away from the well-studied ore zones are composed mainly of variable proportions of pyrrhotite, chalcopyrite, pentlandite, and ±pyrite. Excluding vein assemblages and those affected by greenschist and lower temperature alteration, the majority can be classified into two broad assemblages, defined here as pristine (multiphase, often globular in shape) or volatile-bearing (multiphase, high-temperature, volatile-rich minerals such as biotite, hornblende, or an unmixed calcite-dolomite assemblage). The volatile-bearing assemblages are mainly found within and below the J-M reef, where native copper and sphalerite are also locally present. Pristine sulfides are found throughout the stratigraphy. Both groups can be affected by apparent S loss in the form of pyrite being converted to magnetite and chalcopyrite to a Cu-Fe-oxide (delafossite), with little to no silicate alteration. An upward trend from pentlandite-rich to pyrrhotite-rich to pyrite-rich assemblages is observed in the footwall rocks in upper GN-I, and the same trend repeats from just below the reef and continues into the overlying N-II and GN-II. Modeling suggests that the sulfide Ni in the Peridotite Zone is largely controlled by silicate Ni. When taken together, observations are most readily explained by the remobilization of selected elements by a high-temperature fluid with the apparent loss of S > Cu > Ni. This could concentrate ore metals by vapor refining, eventually producing a platinum group element-enriched sulfide ore zone, such as the J-M reef.

  17. Ruthenium(IV)-catalyzed isomerization of the C=C bond of o-allylic substrates: a theoretical and experimental study.

    PubMed

    Varela-Álvarez, Adrián; Sordo, José A; Piedra, Estefanía; Nebra, Noel; Cadierno, Victorio; Gimeno, José

    2011-09-12

    A general mechanism to rationalize Ru(IV) -catalyzed isomerization of the C=C bond in O-allylic substrates is proposed. Calculations supporting the proposed mechanism were performed at the MPWB1K/6-311+G(d,p)+SDD level of theory. All experimental observations in different solvents (water and THF) and under different pH conditions (neutral and basic) can be interpreted in terms of the new mechanism. Theoretical analysis of the transformation from precatalyst to catalyst led to structural identification of the active species in different media. The experimentally observed induction period is related to the magnitudes of the energy barriers computed for that process. The theoretical energy profile for the catalytic cycle requires application of relatively high temperatures, as is experimentally observed. Participation of a water molecule in the reaction coordinate is mechanistically essential when the reaction is carried out in aqueous medium. The new mechanistic proposal helped to develop a new experimental procedure for isomerization of allyl ethers to 1-propenyl ethers under neutral aqueous conditions. This process is an unique example of efficient and selective catalytic isomerization of allyl ethers in aqueous medium.

  18. DFT study on the interaction between hydrogen sulfide ions and cerussite (110) surface

    NASA Astrophysics Data System (ADS)

    Feng, Qicheng; Wen, Shuming; Deng, Jiushuai; Zhao, Wenjuan

    2017-02-01

    The interaction between hydrogen sulfide ions (HS-) and the cerussite surface was simulated using density functional theory (DFT) calculations. The calculated results show that Pb atoms are the dominating active sites for the subsequent reaction on the cerussite (110) surface. The S atom in HS- ions can readily interact with the Pb atoms at the cerussite surface layers with the interaction energy of -5.19 eV, resulting in the formation of lead sulfide species. An obvious difference occurs when HS- ions interact with the various Pb atoms on the cerussite surface. The density of state analysis reveals that the Pb 6p orbital at the mineral surface layers and S 3p orbital from HS- ions are overlapped between -1.5 and 0.5 eV near the Fermi level, indicating a stable chemical adsorption. The Mulliken population result suggests that the electron transfer exists between the bonding atoms and the oxidation of the HS- ions is involved in the adsorption process. This study provides an insight into the sulfidization mechanism at an atomic level, and further confirms the experimental phenomenon proposed in our previous work.

  19. Enantioselective Conjugate Allylation of Cyclic Enones

    PubMed Central

    Taber, Douglass F.; Gerstenhaber, David A.; Berry, James F.

    2011-01-01

    Enantioselective organocatalytic 1,2-allylation of a cyclic enone followed by anionic oxy-Cope rearrangement delivered the ketone as a mixture of diastereomers. This appears to be a general method for the net enantioselective conjugate allylation of cyclic enones. PMID:21830779

  20. Palladium-catalyzed substitution of allylic fluorides.

    PubMed

    Hazari, Amaruka; Gouverneur, Véronique; Brown, John M

    2009-01-01

    As unusual substrates for the Tsuji-Trost allylation reaction, allylic fluorides are responsive to palladium-catalyzed substitution. Their activity towards this reaction fits in the series OCO(2)Me>OBz>F>OAc. The classic stereoretention mechanism that involves sequential inversions does not operate in this case. Several distinct cases are considered.

  1. The coordination chemistry of silyl-substituted allyl ligands.

    PubMed

    Solomon, Sophia A; Layfield, Richard A

    2010-03-14

    Metal allyl complexes in which the ligands carry bulky silyl substituents frequently show stability that cannot be achieved with unsubstituted analogues. As a result, it has been possible to characterize a large family of structurally diverse metal silyl-allyls from the s-, p-, d- and f-blocks of the Periodic Table, and to study the coordination chemistry of compounds that often have no counterparts without bulky substituents. The fact that the majority of compounds discussed in this Perspective have been published since 2000 reflects the newness of the area, and the article summarizes the main developments in the structural chemistry of metal silyl-allyls and also selected synthetic and catalytic applications. Although organometallic chemistry is often regarded as transcending traditional boundaries between 'organic' and 'inorganic' chemistry, an understanding persists that those working in the field can be labelled 'inorganic organometallic' chemists or 'organic organometallic' chemists. It is hoped that chemists from a broad range of backgrounds will be able to use this review as an entry point to an exciting new direction in metal allyl chemistry.

  2. Pt(ii) coordination complexes as visible light photocatalysts for the oxidation of sulfides using batch and flow processes.

    PubMed

    Casado-Sánchez, Antonio; Gómez-Ballesteros, Rocío; Tato, Francisco; Soriano, Francisco J; Pascual-Coca, Gustavo; Cabrera, Silvia; Alemán, José

    2016-07-12

    A new catalytic system for the photooxidation of sulfides based on Pt(ii) complexes is presented. The catalyst is capable of oxidizing a large number of sulfides containing aryl, alkyl, allyl, benzyl, as well as more complex structures such as heterocycles and methionine amino acid, with complete chemoselectivity. In addition, the first sulfur oxidation in a continuous flow process has been developed.

  3. Synthesis of nearly enantiopure allylic amines by aza-Claisen rearrangement of Z-configured allylic trifluoroacetimidates catalyzed by highly active ferrocenylbispalladacycles.

    PubMed

    Jautze, Sascha; Seiler, Paul; Peters, René

    2008-01-01

    The development of the first highly active enantioselective catalyst for the aza-Claisen rearrangement of Z-configured allylic trifluoroacetimidates generating valuable almost enantiopure protected allylic amines is described. Usually Z-configured allylic imidates react significantly slower than their E-configured counterparts, but in the present study the opposite effect was observed. Z-Configured olefins have the principal practical advantage that a geometrically pure C=C double bond can be readily obtained, for example, by semihydrogenations of alkynes. Our catalyst, a C(2)-symmetric planar chiral bispalladacycle complex, is rapidly prepared from ferrocene in four simple steps. Key step of this protocol is an unprecedented highly diastereoselective biscyclopalladation providing dimeric macrocyclic complexes of fascinating structure. In the present study as little as 0.1 mol % of catalyst precursor were sufficient for most of the alkyl substituted substrates to give in general almost quantitative yields. NMR investigations revealed a monomeric structure for the active catalyst species. The bispalladacycle can also be used for the formation of almost enantiomerically pure allylic amines (ee > or =96 %) substituted with important functional groups such as ester, ketone, ether, silyl ether, acetal or protected amino moieties providing high-added-value allylic amine building blocks in excellent yield (> or =94 %). The preparative advantages should render this methodology highly appealing as a practical and valuable tool for the formation of allylic amines in target oriented synthesis.

  4. Synthesis of complex allylic esters via C-H oxidation vs C-C bond formation.

    PubMed

    Vermeulen, Nicolaas A; Delcamp, Jared H; White, M Christina

    2010-08-18

    A highly general, predictably selective C-H oxidation method for the direct, catalytic synthesis of complex allylic esters is introduced. This Pd(II)/sulfoxide-catalyzed method allows a wide range of complex aryl and alkyl carboxylic acids to couple directly with terminal olefins to furnish (E)-allylic esters in synthetically useful yields and selectivities (16 examples, E/Z >or= 10:1) and without the use of stoichiometric coupling reagents or unstable intermediates. Strategic advantages of constructing allylic esters via C-H oxidation vs C-C bond-forming methods are evaluated and discussed in four "case studies".

  5. Lithium-alloy/iron sulfide battery design studies

    NASA Astrophysics Data System (ADS)

    Chilenskas, A. A.

    1984-10-01

    The DOE/EHV sponsored design studies carried out at Argonne and the integration of these studies with the EPRI program for the development of an advanced van battery are discussed. The design basis for the van battery is given. Some of the inputs are given which are required to derive the battery specifications. Modeling work to optimize the powr/energy ratio as a function of energy was performed. Energy efficiency of the battery is addressed, as is battery deprication. Recharging and reliability of the battery is discussed.

  6. Iridium-Catalyzed Kinetic Asymmetric Transformations of Racemic Allylic Benzoates

    PubMed Central

    Stanley, Levi M.; Bai, Chen; Ueda, Mitsuhiro; Hartwig, John F.

    2010-01-01

    Versatile methods for iridium-catalyzed, kinetic asymmetric substitution of racemic, branched allylic esters are reported. These reactions occur with a variety of aliphatic, aryl, and heteroaryl allylic benzoates to form the corresponding allylic substitution products in high yields (74–96%) with good to excellent enantioselectivity (84–98% ee) with a scope that encompasses a range of anionic carbon and heteroatom nucleophiles. These kinetic asymmetric processes occur with distinct stereochemical courses for racemic aliphatic and aromatic allylic benzoates, and the high reactivity of branched allylic benzoates enables enantioselective allylic substitutions that are slow or poorly selective with linear allylic electrophiles. PMID:20552969

  7. Nickel-Catalyzed α-Allylation of Aldehydes and Tandem Aldol Condensation/Allylation Reaction with Allylic Alcohols.

    PubMed

    Bernhard, Yann; Thomson, Brodie; Ferey, Vincent; Sauthier, Mathieu

    2017-06-19

    An additive-free nickel-catalyzed α-allylation of aldehydes with allyl alcohol is reported. The reaction is promoted by 1 mol % of in situ formed nickel complex in methanol, and water is the sole by-product of the reaction. The experimental conditions allow the conversion of various α-branched aldehydes and α,β-unsaturated aldehydes as nucleophiles. The same catalyst and reaction conditions enabled a tandem aldol condensation of aldehyde/α-allylation reaction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Involvement of cyclooxygenase-2 in the potentiation of allyl alcohol-induced liver injury by bacterial lipopolysaccharide.

    PubMed

    Ganey, P E; Barton, Y W; Kinser, S; Sneed, R A; Barton, C C; Roth, R A

    2001-07-15

    Bacterial endotoxin (lipopolysaccharide; LPS) augments the hepatotoxicity of a number of xenobiotics including allyl alcohol. The mechanism for this effect is known to involve the inflammatory response elicited by LPS. Upregulation of cyclooxygenase-2 (COX-2) and production of eicosanoids are important aspects of inflammation, therefore studies were undertaken to investigate the role of COX-2 in LPS-induced enhancement of liver injury from allyl alcohol. Rats were pretreated (iv) with a noninjurious dose of LPS or sterile saline vehicle and 2 h later were treated (ip) with a noninjurious dose of allyl alcohol or saline vehicle. COX-2 mRNA was determined by semiquantitative reverse transcriptase-polymerase chain reaction (RT-PCR), and liver injury was assessed from activities in serum of alanine and aspartate aminotransferases (ALT and AST, respectively) and from histology. Liver injury was observed only in rats cotreated with LPS and allyl alcohol. Serum ALT activity was increased by 4 h after administration of LPS and continued to increase through 8 h. COX-2 mRNA was detectable at low levels in livers from rats receiving only the vehicles at any time up to 8 h. Expression of COX-2 mRNA was increased by 30 min after administration of LPS and remained elevated through 6 h. Allyl alcohol treatment alone caused an increase in COX-2 mRNA at 4 h (2 h after allyl alcohol) that lasted less than 2 h. In livers from rats cotreated with LPS and allyl alcohol, levels of COX-2 mRNA were greater than levels seen with either LPS or allyl alcohol alone. The increased expression of COX-2 mRNA was accompanied by an increase in the concentration of prostaglandin (PG) D(2) in plasma. Plasma PGD(2) concentration was increased to a greater extent in rats treated with LPS plus allyl alcohol compared to allyl alcohol or LPS alone. Pretreatment with the COX-2 selective inhibitor, NS-398, abolished the increase in plasma PGD(2) and reduced the increase in ALT and AST activities observed in

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

    NASA Astrophysics Data System (ADS)

    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

  10. Regio- and Enantioselective N-Allylations of Imidazole, Benzimidazole, and Purine Heterocycles Catalyzed by Single-Component Metallacyclic Iridium Complexes

    PubMed Central

    Stanley, Levi M.

    2010-01-01

    Highly regio- and enantioselective iridium-catalyzed N-allylations of benzimidazoles, imidazoles, and purines have been developed. N-Allylated benzimidazoles and imidazoles were isolated in high yields (up to 97%) with high branched-to-linear selectivity (up to 99:1) and enantioselectivity (up to 98% ee) from the reactions of benzimidazole and imidazole nucleophiles with unsymmetrical allylic carbonates in the presence of single component, ethylene-bound, metallacyclic iridium catalysts. N-Allylated purines were also obtained in high yields (up to 91%) with high N9:N7 selectivity (up to 96:4), high branched-to-linear selectivity (98:2), and high enantioselectivity (up to 98% ee) under similar conditions. The reactions encompass a range of benzimidazole, imidazole, and purine nucleophiles, as well as a variety of unsymmetrical aryl, heteroaryl, and aliphatic allylic carbonates. Competition experiments between common amine nucleophiles and the heterocyclic nitrogen nucleophiles studied in this work illustrate the effect of nucleophile pKa on the rate of iridium-catalyzed N-allylation reactions. Kinetic studies on the allylation of benzimidazole catalyzed by metallacyclic iridium-phosphoramidite complexes, in combination with studies on the deactivation of these catalysts in the presence of heterocyclic nucleophiles, provide insight into the effects of the structure of the phosphoramidite ligands on the stability of the metallacyclic catalysts. The data obtained from these studies has led to the development of N-allylations of benzimidazoles and imidazoles in the absence of an exogenous base. PMID:19480431

  11. A DFT Study of the Photochemical Dimerization of Methyl 3-(2-Furyl)acrylate and Allyl Urocanate.

    PubMed

    D'Auria, Maurizio

    2014-12-08

    A DFT study of the photochemical dimerization of methyl 3-(2-furyl)acrylate is reported. The photochemical reaction gave a mixture of two dimers with high regioselectivity and good stereoselectivity. Calculations showed that benzophenone was able to act as a photosensitizer of the reaction. This compound populated the first excited triplet state of the substrate. The frontier orbitals interaction between LSOMO of the triplet state and HOMO of the ground state accounted for the observed high regioselectivity. Furthermore, the energy of all the possible triplet biradicals has been calculated, showing that the precursor of the main product was the triplet biradical with the lowest energy. The coupling of the atomic coefficients on the radical centres in the biradical intermediates allowed to justify the observed products. The same behavior was observed in the case of the photochemical dimerization of an urocanate ester and in the dimerization of liquid methyl cinnamate.

  12. Friedel-Crafts-type allylation of nitrogen-containing aromatic compounds with allylic alcohols catalyzed by a [Mo3S4Pd(η3-allyl)] cluster.

    PubMed

    Tao, Yinsong; Wang, Baomin; Zhao, Jinfeng; Song, Yuming; Qu, Lihong; Qu, Jingping

    2012-03-16

    With the direct use of allylic alcohols as allylating agents, the Friedel-Crafts-type allylic alkylation of nitrogen-containing aromatic compounds catalyzed by a [Mo(3)S(4)Pd(η(3)-allyl)] cluster is achieved. With a 3 mol % catalyst loading in acetonitrile at reflux or 60 °C, a variety of N,N-dialkylanilines and indoles reacted smoothly with allylic alcohols to afford the Friedel-Crafts-type allylation products in good to excellent yields with high levels of regioselectivity.

  13. Hydrogen sulfide and resolution of acute inflammation: A comparative study utilizing a novel fluorescent probe

    PubMed Central

    Dufton, Neil; Natividad, Jane; Verdu, Elena F.; Wallace, John L.

    2012-01-01

    Hydrogen sulfide is an essential gasotransmitter associated with numerous pathologies. We assert that hydrogen sulfide plays an important role in regulating macrophage function in response to subsequent inflammatory stimuli, promoting clearance of leukocyte infiltrate and reducing TNF-α levels in vivo following zymosan-challenge. We describe two distinct methods of measuring leukocyte hydrogen sulfide synthesis; methylene blue formation following zinc acetate capture and a novel fluorescent sulfidefluor probe. Comparison of these methods, using pharmacological tools, revealed they were complimentary in vitro and in vivo. We demonstrate the application of sulfidefluor probe to spectrofluorimetry, flow cytometry and whole animal imaging, to monitor the regulation of hydrogen sulfide synthesis in vivo during dynamic inflammatory processes. Both methodologies revealed that granulocyte infiltration negatively affects hydrogen sulfide synthesis. Our report offers an insight into the profile of hydrogen sulfide synthesis during inflammation and highlight opportunities raised by the development of novel fluorescent hydrogen sulfide probes. PMID:22787557

  14. Hydrogen sulfide and resolution of acute inflammation: A comparative study utilizing a novel fluorescent probe.

    PubMed

    Dufton, Neil; Natividad, Jane; Verdu, Elena F; Wallace, John L

    2012-01-01

    Hydrogen sulfide is an essential gasotransmitter associated with numerous pathologies. We assert that hydrogen sulfide plays an important role in regulating macrophage function in response to subsequent inflammatory stimuli, promoting clearance of leukocyte infiltrate and reducing TNF-α levels in vivo following zymosan-challenge. We describe two distinct methods of measuring leukocyte hydrogen sulfide synthesis; methylene blue formation following zinc acetate capture and a novel fluorescent sulfidefluor probe. Comparison of these methods, using pharmacological tools, revealed they were complimentary in vitro and in vivo. We demonstrate the application of sulfidefluor probe to spectrofluorimetry, flow cytometry and whole animal imaging, to monitor the regulation of hydrogen sulfide synthesis in vivo during dynamic inflammatory processes. Both methodologies revealed that granulocyte infiltration negatively affects hydrogen sulfide synthesis. Our report offers an insight into the profile of hydrogen sulfide synthesis during inflammation and highlight opportunities raised by the development of novel fluorescent hydrogen sulfide probes.

  15. Mechanistically Driven Development of Iridium Catalysts for Asymmetric Allylic Substitution

    PubMed Central

    Hartwig, John F.; Stanley, Levi M.

    2010-01-01

    Conspectus Enantioselective allylic substitution reactions comprise some of the most versatile methods for preparing enantiomerically enriched materials. These reactions form products that contain multiple functionalities by creating carbon–nitrogen, carbon–oxygen, carbon–carbon, and carbon–sulfur bonds. For many years, the development of catalysts for allylic substitution focused on palladium complexes. However, studies of complexes of other metals have revealed selectivities that often complement those of palladium systems. Most striking is the observation that reactions with unsymmetrical allylic electrophiles that typically occur with palladium catalysts at the less hindered site of an allylic electrophile occur at the more hindered site with catalysts based on other metals. In this Account, we describe an iridium precursor and a phosphoramidite ligand that catalyze reactions with a particularly broad scope of nucleophiles. The active form of this iridium catalyst is not generated by the simple binding of the phosphoramidite ligand to the metal precursor. Instead, the initial phosphoramidite and iridium precursor react in the presence of base to form a metallacyclic species that is the active catalyst. This species is generated either in situ or separately in isolated form by reactions with added base. The identification of the structure of the active catalyst led to the development of simplified catalysts as well as the most active form of the catalyst now available, which is stabilized by a loosely bound ethylene. Most recently, this structure was used to prepare intermediates containing allyl ligands, the structures of which provide a model for the enantioselectivities discussed here. Initial studies from our laboratory on the scope of iridium-catalyzed allylic substitution showed that reactions of primary and secondary amines, including alkylamines, benzylamines, and allylamines, and reactions of phenoxides and alkoxides occurred in high yields

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

    PubMed

    Tong, Guanghu; Zhu, Bo; Lee, Richmond; Yang, Wenguo; Tan, Davin; Yang, Caiyun; Han, Zhiqiang; Yan, Lin; Huang, Kuo-Wei; Jiang, Zhiyong

    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.

  17. The feasibility study of autotrophic denitrification with iron sludge produced for sulfide control.

    PubMed

    Wei, Yangyang; Dai, Ji; Mackey, Hamish R; Chen, Guang-Hao

    2017-10-01

    Ferric iron is widely dosed in wastewater treatment plants dealing with sulfide for septicity control, which generates a great amount of iron-rich chemical sludge that is challenging and costly to dispose. This study investigates the feasibility of using this iron sludge as the electron donor for autotrophic denitrification, not only realizing high nitrogen removal efficiency without additional carbon source requirement, but also partially mitigating iron-rich chemical sludge disposal and reduce sludge production by enriching low-yield autotrophic denitrifiers in the system. Both batch tests and performance monitoring of a lab-scale up-flow anaerobic sludge blanket reactor with a more than 300 days of operation were conducted. All the results confirmed the feasibility of using iron sludge as electron donor for autotrophic denitrification. The nitrate reduction rate with iron sludge was highly influenced by the type of ferrous electron donor and the electron donor/acceptor ratio. Ferrous hydroxide had significantly higher nitrate reduction rate than ferrous sulfide at the same electron donor/acceptor ratio. The nitrate reduction rate also accelerated with the increase of the electron donor/acceptor ratio. However, if the total surface area of the iron sludge is considered for comparison, it was shown that ferrous hydroxide and ferrous sulfide provided similar nitrate reduction rates of around 0.02 mmol N/m(2)/d in this study, indicating total surface area would be the key parameter for denitrification efficiency for the solid phase electron donor. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Control of Diastereoselectivity for Iridium-catalyzed Allylation of a Prochiral Nucleophile with a Phosphate Counterion

    PubMed Central

    Chen, Wenyong; Hartwig, John F.

    2013-01-01

    We report a highly diastereo- and enantioselective allylation of azlactones catalyzed by the combination of a metallayclic iridium complex and an optically inactive phosphate anion. The process demonstrates an approach to conduct diastereoselective reactions with prochiral nucleophiles in the presence of metallacyclic allyliridium complexes. The reaction provides access to an array of enantioenriched allylated azlactones containing adjacent tertiary and quaternary carbon centers. Preliminary mechanistic studies suggest that the phosphate and methyl carbonate anions together induce the unusually high diastereoselectivity. PMID:23286279

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

    NASA Astrophysics Data System (ADS)

    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.

  20. Cross coupling of dialkylmagnesium derivatives with allylic compounds catalyzed by copper salts

    SciTech Connect

    Ibragimov, A.G.; Dzhemilev, U.M.; Saraev, R.A.

    1985-07-20

    The reaction of allylic compounds with Grignard reagents catalyzed by salts of copper, nickel, iron and cobalt, titanium and palladium is a simple and efficient method for the preparation of unsaturated hydrocarbons. However, information concerning the use of dialkylmagnesium derivatives, which are more reactive than Grignard reagents, is extremely limited in these reactions. To continue a study of the cross-coupling of allylic compounds with dialkylmagnesium derivatives in an effort to expand the scope of this reaction and to elucidate the effect of the R/sub 2/Mg reagent structure on its reactivity, the authors investigated the reaction of dialkylmagnesium and diarlmagnesium reagents with allylic ethers and esters, thioethers, and amines, by the action of transition metal salts. This work demonstrates the feasibility of the preparation of unsaturated hydrocarbons of given structure by the cross-coupling of dialkylmagnesium derivatives with functional allylic compounds by the action of catalytic amounts of copper complexes.

  1. Sulfidation kinetics of silver nanoparticles reacted with metal sulfides.

    PubMed

    Thalmann, Basilius; Voegelin, Andreas; Sinnet, Brian; Morgenroth, Eberhard; Kaegi, Ralf

    2014-05-06

    Recent studies have documented that the sulfidation of silver nanoparticles (Ag-NP), possibly released to the environment from consumer products, occurs in anoxic zones of urban wastewater systems and that sulfidized Ag-NP exhibit dramatically reduced toxic effects. However, whether Ag-NP sulfidation also occurs under oxic conditions in the absence of bisulfide has not been addressed, yet. In this study we, therefore, investigated whether metal sulfides that are more resistant toward oxidation than free sulfide, could enable the sulfidation of Ag-NP under oxic conditions. We reacted citrate-stabilized Ag-NP of different sizes (10-100 nm) with freshly precipitated and crystalline CuS and ZnS in oxygenated aqueous suspensions at pH 7.5. The extent of Ag-NP sulfidation was derived from the increase in dissolved Cu(2+) or Zn(2+) over time and linked with results from X-ray absorption spectroscopy (XAS) analysis of selected samples. The sulfidation of Ag-NP followed pseudo first-order kinetics, with rate coefficients increasing with decreasing Ag-NP diameter and increasing metal sulfide concentration and depending on the type (CuS and ZnS) and crystallinity of the reacting metal sulfide. Results from analytical electron microscopy revealed the formation of complex sulfidation patterns that seemed to follow preexisting subgrain boundaries in the pristine Ag-NP. The kinetics of Ag-NP sulfidation observed in this study in combination with reported ZnS and CuS concentrations and predicted Ag-NP concentrations in wastewater and urban surface waters indicate that even under oxic conditions and in the absence of free sulfide, Ag-NP can be transformed into Ag2S within a few hours to days by reaction with metal sulfides.

  2. Kinetic study of the OH-initiated photo-oxidation of four unsaturated (allyl and vinyl) ethers under simulated atmospheric conditions

    NASA Astrophysics Data System (ADS)

    Peirone, Silvina A.; Aranguren Abrate, Juan P.; Taccone, Raúl A.; Cometto, Pablo M.; Lane, Silvia I.

    2011-09-01

    Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with n-propyl vinyl ether ( k1), 2-chloroethyl vinyl ether ( k2), allyl ether ( k3) and allyl ethyl ether ( k4) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using N 2 and ultra pure air as bath gas. Using isoprene, 1-methyl-1-cyclohexene, 2-methyl-2-butene, 3-buten-1-ol and 2-methyl-2-propen-1-ol as reference compounds, the following rate constants were derived: k1 = (11.0 ± 0.4) × 10 -11, k2 = (9 ± 1) × 10 -11, k3 = (6.8 ± 0.7) × 10 -11 and k4 = (4.2 ± 0.7) × 10 -11, in units of cm 3 molecule -1 s -1. This is the first experimental detcermination of k2- k4. The rate constants obtained are compared with the previous literature data for corresponding alkenes reactions with OH and the observed reactivity trends are discussed. The atmospheric implications of the results are considered.

  3. The effects of γ-irradiation on garlic oil content in garlic bulbs and on the radiolysis of allyl trisulfide

    NASA Astrophysics Data System (ADS)

    Genshuan, Wei; Guanghui, Wang; Ruipu, Yang; Jilan, Wu

    1996-02-01

    A study of the effects of γ-radiation on garlic oil content in garlic bulbs and on the radiolysis of allyl trisulfide and disulfide was carried out. The content of garlic oil in fresh garlic bulbs treated by gamma ray keeps nearly constant when stored for 10 months. The main components of garlic oil are allyl trisulfide (about 60%) and allyl disulfide (about 30%). The G values of radiolysis products of allyl disulfide and trisulfide in ethanol system were determined. The results show that allyl trisulfide is a very effective solvated electron scavenger and can oxidize CH 3CHOH radical into acetaldehyde, which means that the formation of 2,3-butanediol is extensively inhibited.

  4. Weathering processes and pickeringite formation in a sulfidic schist: a consideration in acid precipitation neutralization studies

    SciTech Connect

    Parnell, R.A. Jr.

    1983-01-01

    Extremely low abrasion pH values (2.8-3.3) characterize the weathering products of the Partridge Formation, a Middle-Ordovician metamorphosed, black, sulfidic shale. The local occurrence is observed of two sulfates that are rare in the Northeast: pickeringite and jarosite. X-ray diffraction studies of the weathering residues and the sulfate efflorescences have also identified dioctahedral and trioctahedral illite, kaolinite, vermiculite, and an 11-12 Angstrom phase, thought to be a type of randomly-interstratified biotite-vermiculite. From the mineralogical studies, qualitative weathering processes for the schist are formulated. A probable mechanism for the intense chemical weathering of the schist appears to be oxidation of iron sulfides to form iron oxide-hydroxides, sulfates, and sulfuric acid. This natural weathering process is proposed as an analog to anthropogenic low pH rock weathering resulting from acid precipitation. In the Northeast, natural weathering rates, may, in places, significantly affect the water chemistry and mineralogy used to quantify total (natural plus anthropogenic) weathering and leaching rates. 27 references, 4 figures.

  5. Structural evolution and stabilities of neutral and anionic clusters of lead sulfide: joint anion photoelectron and computational studies.

    PubMed

    Koirala, Pratik; Kiran, Boggavarapu; Kandalam, Anil K; Fancher, Charles A; de Clercq, Helen L; Li, Xiang; Bowen, Kit H

    2011-10-07

    The geometric and electronic structures of both neutral and negatively charged lead sulfide clusters, (PbS)(n)/(PbS)(n)(-) (n = 2-10) were investigated in a combined anion photoelectron spectroscopy and computational study. Photoelectron spectra provided vertical detachment energies (VDEs) for the cluster anions and estimates of electron affinities (EA) for their neutral cluster counterparts, revealing a pattern of alternating EA and VDE values in which even n clusters exhibited lower EA and VDE values than odd n clusters up until n = 8. Computations found neutral lead sulfide clusters with even n to be thermodynamically more stable than their immediate (odd n) neighbors, with a consistent pattern also being found in their HOMO-LUMO gaps. Analysis of neutral cluster dissociation energies found the Pb(4)S(4) cube to be the preferred product of the queried fragmentation processes, consistent with our finding that the lead sulfide tetramer exhibits enhanced stability; it is a magic number species. Beyond n = 10, computational studies showed that neutral (PbS)(n) clusters in the size range, n = 11-15, prefer two-dimensional stacking of face-sharing lead sulfide cubical units, where lead and sulfur atoms possess a maximum of five-fold coordination. The preference for six-fold coordination, which is observed in the bulk, was not observed at these cluster sizes. Taken together, the results show a preference for the formation of slightly distorted, fused cuboids among small lead sulfide clusters. © 2011 American Institute of Physics

  6. Structural evolution and stabilities of neutral and anionic clusters of lead sulfide: Joint anion photoelectron and computational studies

    NASA Astrophysics Data System (ADS)

    Koirala, Pratik; Kiran, Boggavarapu; Kandalam, Anil K.; Fancher, Charles. A.; de Clercq, Helen L.; Li, Xiang; Bowen, Kit. H.

    2011-10-01

    The geometric and electronic structures of both neutral and negatively charged lead sulfide clusters, (PbS)n/(PbS)n- (n = 2-10) were investigated in a combined anion photoelectron spectroscopy and computational study. Photoelectron spectra provided vertical detachment energies (VDEs) for the cluster anions and estimates of electron affinities (EA) for their neutral cluster counterparts, revealing a pattern of alternating EA and VDE values in which even n clusters exhibited lower EA and VDE values than odd n clusters up until n = 8. Computations found neutral lead sulfide clusters with even n to be thermodynamically more stable than their immediate (odd n) neighbors, with a consistent pattern also being found in their HOMO-LUMO gaps. Analysis of neutral cluster dissociation energies found the Pb4S4 cube to be the preferred product of the queried fragmentation processes, consistent with our finding that the lead sulfide tetramer exhibits enhanced stability; it is a magic number species. Beyond n = 10, computational studies showed that neutral (PbS)n clusters in the size range, n = 11-15, prefer two-dimensional stacking of face-sharing lead sulfide cubical units, where lead and sulfur atoms possess a maximum of five-fold coordination. The preference for six-fold coordination, which is observed in the bulk, was not observed at these cluster sizes. Taken together, the results show a preference for the formation of slightly distorted, fused cuboids among small lead sulfide clusters.

  7. Copper-Catalyzed Enantioselective Allyl-Allyl Coupling between Allylic Boronates and Phosphates with a Phenol/N-Heterocyclic Carbene Chiral Ligand.

    PubMed

    Yasuda, Yuto; Ohmiya, Hirohisa; Sawamura, Masaya

    2016-08-26

    Copper-catalyzed enantioselective allyl-allyl coupling between allylboronates and either Z-acyclic or cyclic allylic phosphates using a new chiral N-heterocyclic carbene ligand, bearing a phenolic hydroxy, is reported. This reaction occurs with exceptional SN 2'-type regioselectivities and high enantioselectivities to deliver chiral 1,5-diene derivatives with a tertiary stereogenic center at the allylic/homoallylic position.

  8. Oxidation state, aggregation, and heterolytic dissociation of allyl indium reagents.

    PubMed

    Koszinowski, Konrad

    2010-05-05

    Solutions of allyl indium reagents formed in the reactions of indium with allyl bromide and allyl iodide, respectively, in N,N-dimethylformamide, tetrahydrofuran, and water were analyzed by a combination of electrospray-ionization mass spectrometry, temperature-dependent (1)H NMR spectroscopy, and electrical conductivity measurements. Additional mass spectrometric experiments probed charge-tagged derivatives of the allyl indium reagents. The results obtained indicate the presence of allyl indium(+3) species, which undergo heterolytic dissociation to yield ions such as InR(2)(solv)(+) and InRX(3)(-) with R = allyl and X = Br and I. The extent of dissociation is greatest for N,N-dimethylformamide, whereas aggregation effects are more pronounced for the less polar tetrahydrofuran. The heterolytic dissociation of the allyl indium reagents supposedly enhances their reactivity by simultaneously providing highly Lewis acidic allyl indium cations and nucleophilic allyl indate anions.

  9. Novel palladium complex-catalyzed reaction of magnesium amides with allylic electrophiles

    SciTech Connect

    Dzhemilev, U.M.; Ibragimov, A.G.; Minsker, D.L.; Muslukhov, R.R.

    1987-08-20

    In order to develop an efficient method for the synthesis of higher order unsaturated tertiary amines, and also to explore a new method for the formation of C-N bonds, they have investigated the transition metal complex-catalyzed reaction of magnesium amides with electrophiles; the electrophiles selected for study included allyl ethers and esters, as well as sulfones, sulfides and quaternized allylamines. The effects of the nature and structure of the catalyst components, as well as of the reaction conditions, on product yield were examined in the case of the reaction of diethyl (bromomagnesium)amine with diallyl ether, and revealed that the highest yield of diethylallyl-amine (I) was achieved using Pd(acac)/sub 2/ (3-5 mole %) and Ph/sub 3/P (1:2) as catalyst in THF solution at 50/sup 0/C for 5 h. Other transition metal (Ni, Fe, Zr, Ti, Cu) compounds were also examined as catalysts, but the yield of (I) did not exceed 15% with these compounds. Bimetallic catalysts based on Zr (Cp/sub 2/ZrCl, Py/sub 2/ZrCl/sub 6/, (RO)/sub 4/Zr) and Ni (Ni(acac)/sub 2/ and NiCl/sub 2/) were successful in forming (I) from diethyl (bromomagnesium)amine and diallyl ether in 60% yield.

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

    EPA Science Inventory

    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...

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

    EPA Science Inventory

    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...

  12. In situ solvothermal growth of metal-organic framework-5 supported on porous copper foam for noninvasive sampling of plant volatile sulfides.

    PubMed

    Hu, Yuling; Lian, Haixian; Zhou, Langjun; Li, Gongke

    2015-01-06

    The present study reported on an in situ solvothermal growth method for immobilization of metal-organic framework MOF-5 on porous copper foam support for enrichment of plant volatile sulfides. The porous copper support impregnated with mother liquor of MOF-5 anchors the nucleation and growth of MOF crystallites at its surface, and its architecture of the three-dimensional channel enables accommodation of the MOF-5 crystallite seed. A continuous and well-intergrown MOF-5 layer, evidenced from scanning electron microscope imaging and X-ray diffraction, was successfully immobilized on the porous metal bar with good adhesion and high stability. Results show that the resultant MOF-5 coating was thermally stable up to 420 °C and robust enough for replicate extraction for at least 200 times. The MOF-5 bar was then applied to the headspace sorptive extraction of the volatile organic sulfur compounds in Chinese chive and garlic sprout in combination with thermal desorption-gas chromatography/mass spectrometry. It showed high extraction sensitivity and good selectivity to these plant volatile sulfides owing to the extraordinary porosity of the metal-organic framework as well as the interaction between the S-donor sites and the surface cations at the crystal edges. Several primary sulfur volatiles containing allyl methyl sulfide, dimethyl disulfide, diallyl sulfide, methyl allyl disulfide, and diallyl disulfide were quantified. Their limits of detection were found to be in the range of 0.2-1.7 μg/L. The organic sulfides were detected in the range of 6.0-23.8 μg/g with recoveries of 76.6-100.2% in Chinese chive and 11.4-54.6 μg/g with recoveries of 77.1-99.8% in garlic sprout. The results indicate the immobilization of MOF-5 on copper foam provides an efficient enrichment formats for noninvasive sampling of plant volatiles.

  13. Structure-Activity Relationship Study on Isothiocyanates: Comparison of TRPA1-Activating Ability between Allyl Isothiocyanate and Specific Flavor Components of Wasabi, Horseradish, and White Mustard.

    PubMed

    Terada, Yuko; Masuda, Hideki; Watanabe, Tatsuo

    2015-08-28

    Allyl isothiocyanate (ITC) (4) is the main pungent component in wasabi, and it generates an acrid sensation by activating TRPA1. The flavor and pungency of ITCs vary depending on the compound. However, the differences in activity to activate TRPA1 between ITCs are not known except for a few compounds. To investigate the effect of carbon chain length and substituents of ITCs, the TRPA1-activiting ability of 16 ITCs was measured. Since most of the ITCs showed nearly equal TRPA1-activiting potency, the ITC moiety is likely the predominant contributor to their TRPA1-activating abilities, and contributions of other functional groups to their activities to activate TRPA1 are comparatively small.

  14. Asymmetric synthesis of N-allylic indoles via regio- and enantioselective allylation of aryl hydrazines

    PubMed Central

    Xu, Kun; Gilles, Thomas; Breit, Bernhard

    2015-01-01

    The asymmetric synthesis of N-allylic indoles is important for natural product synthesis and pharmaceutical research. The regio- and enantioselective N-allylation of indoles is a true challenge due to the favourable C3-allylation. We develop here a new strategy to the asymmetric synthesis of N-allylic indoles via rhodium-catalysed N-selective coupling of aryl hydrazines with allenes followed by Fischer indolization. The exclusive N-selectivities and good to excellent enantioselectivities are achieved applying a rhodium(I)/DTBM-Segphos or rhodium(I)/DTBM-Binap catalyst. This method permits the practical synthesis of valuable chiral N-allylated indoles, and avoids the N- or C-selectivity issue. PMID:26137886

  15. Solubility, stability, and electrochemical studies of sulfur-sulfide solutions in organic solvents

    NASA Technical Reports Server (NTRS)

    Fielder, W. L.; Singer, J.

    1978-01-01

    A preliminary study of the sulfur electrode in organic solvents suggests that the system warrants further investigation for use in a low temperature (100 deg to 120 C) Na-S secondary battery. A qualitative screening was undertaken at 120 C to determine the solubilities and stabilities of Na2S and Na2S2 in representatives of many classes of organic solvents. From the screening and quantitative studies, two classes of solvents were selected for work; amides and cyclic polyalcohols. Voltammetric and Na-S cell charge discharge studies of sulfide solutions in organic solvents (e.g., N, N-dimethylformamide) at 120 C suggested that the reversibilities of the reactions on Pt or high density graphite were moderately poor. However, the sulfur electrode was indeed reducible (and oxidizable) through the range of elemental sulfur to Na2S. Reactions and mechanisms are proposed for the oxidation reduction processes occurring at the sulfur electrode.

  16. Acidification and sulfide formation control during reductive dechlorination of 1,2-dichloroethane in groundwater: Effectiveness and mechanistic study.

    PubMed

    Wang, S Y; Chen, S C; Lin, Y C; Kuo, Y C; Chen, J Y; Kao, C M

    2016-10-01

    To enhance the reductive dechlorination of 1,2-dichloroethane (DCA) in groundwater, substrate injection may be required. However, substrate biodegradation causes groundwater acidification and sulfide production, which inhibits the bacteria responsible for DCA dechlorination and results in an odor problem. In the microcosm study, the effectiveness of the addition of ferrous sulfate (FS), desulfurization slag (DS), and nanoscale zero-valent iron (nZVI) on acidification and sulfide control was studied during reductive dechlorination of DCA, and the emulsified substrate (ES) was used as the substrate. Up to 94% of the sulfide was removed with FS and DS addition (0.25 wt%) (initial DCA concentration = 13.5 mg/L). FS and DS amendments resulted in the formation of a metal sulfide, which reduced the hydrogen sulfide concentration as well as the subsequent odor problem. Approximately 96% of the DCA was degraded under reductive dechlorination with nZVI or DS addition using ES as the substrate. In microcosms with nZVI or DS addition, the sulfide concentration was reduced to less than 15 μg/L. Acidification can be controlled via hydroxide ions production after nZVI oxidation and reaction of free CaO (released from DS) with water, which enhanced DCA dechlorination. The quantitative polymerase chain reaction results confirmed that the microcosms with nZVI added had the highest Dehalococcoides population (up to 2.5 × 10(8) gene copies/g soil) due to effective acidification control. The α-elimination mechanism was the main abiotic process, and reductive dechlorination dominated by Dehalococcides was the biotic mechanism that resulted in DCA removal. More than 22 bacterial species were detected, and dechlorinating bacteria existed in soils under alkaline and acidic conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Structures of complexes of benzyl and allyl esters of monensin A with Mg 2+, Ca 2+, Sr 2+, Ba 2+ cations studied by ESI-MS and PM5 methods

    NASA Astrophysics Data System (ADS)

    Huczyński, Adam; Brzezinski, Bogumil; Bartl, Franz

    2008-08-01

    Benzyl ester of monensin A (MON3) and allyl ester of monensin A (MON4) were synthesized and their ability of forming complexes with divalent cations was studied by ESI mass spectrometry and by PM5 semi empirical calculations. The ESI-MS spectra indicate that MON3 as well as MON4 form stable 1:1 complexes with the divalent cations used in this study. The complexes of MON3 are stable to cv = 50 V and after this cv value no m/ z signals are more observed in the spectra. In contrast, with increasing cone voltage values, a fragmentation process of the MON4 complexes is simultaneously observed, where dehydration processes are the main events. The structures of the complexes are discussed in detail on the basis of conformational analysis together with the PM5 semiempirical calculations.

  18. Electrochemical behavior of silver sulfide

    SciTech Connect

    Drouven, B.U.E.

    1982-01-01

    The electrochemical behavior of silver sulfide in sulfuric acid as well as in nitric acid was studied using electrodes made from synthetic silver sulfide. The primary techniques used were potentiostatic, potentiodynamic, galvanostatic and corrosion cell experiments. The cathodic reaction of silver sulfide produces silver and hydrogen sulfide. This reaction mechanism is a sequential two step charge transfer involving a single electron in each step. Silver ions are produced from silver sulfide upon applying an anodic potential. The dissolution rate of silver sulfide can be so high that the formation of silver sulfate occurs which partially covers the silver sulfide surface and inhibits a further rate increase. The sulfur from the silver sulfide will be oxidized at low overpotentials to elemental sulfur; at high overpotentials, the oxidation to sulfate or bisulfate is observed. The results suggest that the catalysis of chalcopyrite by the addition of silver ions is caused by the formation and subsequent dissolution of silver sulfide leaving a porous layer behind. The understanding of the reaction mechanism of silver sulfide dissolution and its optimization will significantly improve the economic evaluation of industrial processes using the catalyzed leaching of chalcopyrite. The present knowledge of the catalysis indicates that other ions may be substituted for silver ions which would increase the feasibility of hydrometallurgical processes.

  19. Preliminary study of the electrolysis of aluminum sulfide in molten salts

    SciTech Connect

    Minh, N.Q.; Loutfy, R.O.; Yao, N.P.

    1983-02-01

    A preliminary laboratory-scale study of the electrolysis of aluminum sulfide in molten salts investigated the (1) solubility of Al/sub 2/S/sub 3/ in molten salts, (2) electrochemical behavior of Al/sub 2/S/sub 3/, and (3) electrolysis of Al/sub 2/S/sub 3/ with the determination of current efficiency as a function of current density. The solubility measurements show that MgCl/sub 2/-NaCl-KCl eutectic electrolyte at 1023 K can dissolve up to 3.3 mol % sulfide. The molar ratio of sulfur to aluminum in the eutectic is about one, which suggests that some sulfur remains undissolved, probably in the form of MgS. The experimental data and thermodynamic calculations suggest that Al/sub 2/S/sub 3/ dissolves in the eutectic to form AlS/sup +/ species in solution. Addition of AlCl/sub 3/ to the eutectic enhances the solubility of Al/sub 2/S/sub 3/; the solubility increases with increasing AlCl/sub 3/ concentration. The electrode reaction mechanism for the electrolysis of Al/sub 2/S/sub 3/ was elucidated by using linear sweep voltammetry. The cathodic reduction of aluminum-ion-containing species to aluminum proceeds by a reversible, diffusion-controlled, three-electron reaction. The anodic reaction involves the two-electron discharge of sulfide-ion-containing species, followed by the fast dimerization of sulfur atoms to S/sub 2/. Electrolysis experiments show that Al/sub 2/S/sub 3/ dissolved in molten MgCl/sub 2/-NaCl-KCl eutectic or in eutectic containing AlCl/sub 3/ can be electrolyzed to produce aluminum and sulfur. In the eutectic at 1023 K, the electrolysis can be conducted up to about 300 mA/cm/sup 2/ for the saturation solubility of Al/sub 2/S/sub 3/. Although these preliminary results are promising, additional studies are needed to elucidate many critical operating parameters before the technical potential of the electrolysis can be accurately assessed. 20 figures, 18 tables.

  20. O2-Promoted Allylic Acetoxylation of Alkenes: Assessment of “Push” vs. “Pull” Mechanisms and Comparison between O2 and Benzoquinone

    PubMed Central

    Diao, Tianning

    2014-01-01

    Palladium-catalyzed acetoxylation of allylic C–H bonds has been the subject of extensive study. These reactions proceed via allyl-palladium(II) intermediates that react with acetate to afford the allyl acetate product. Benzoquinone and molecular oxygen are two common oxidants for these reactions. Benzoquinone has been shown to promote allyl acetate formation from well-defined π-allyl palladium(II) complexes. Here, we assess the ability of O2 to promote similar reactions with a series of “unligated” π-allyl palladium(II) complexes (i.e., in the absence of ancillary phosphorus, nitrogen or related donor ligands). Stoichiometric and catalytic allyl acetate formation is observed under aerobic conditions with several different alkenes. Mechanistic studies are most consistent with a “pull” mechanism in which O2 traps the Pd0 intermediate following reversible C–O bond-formation from an allyl-palladium(II) species. A “push” mechanism, involving oxidatively induced C–O bond formation, does not appear to participate. These results and conclusions are compared with benzoquinone-promoted allylic acetoxylation, in which a “push” mechanism seems to be operative. PMID:25435646

  1. Cadmium Telluride, Cadmium Telluride/Cadmium Sulfide Core/Shell, and Cadmium Telluride/Cadmium Sulfide/Zinc Sulfide Core/Shell/Shell Quantum Dots Study

    NASA Astrophysics Data System (ADS)

    Yan, Yueran

    aqueous phase can quench CdTe/CdS QDs. Additionally, the stability of the different ligands capped CdTe/CdS QDs was tested by dialysis measurement, the hydrodynamic diameters of CdTe and CdTe/CdS core/shell QDs were measured by dynamic light scattering, and dissolving issue was found when CdTe and CdTe/CdS core/shell QDs were diluted in CHCl3. We have characterized the CdTe core and the CdTe/CdS core/shell QDs by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), small angle X-ray scattering (SAXS), and ICP-OES measurements. We have found that the CdTe core was of a zincblende structure, and the shell was a wurtzite structure. And the CdTe/CdS QDs were core/shell QDs instead of alloying QDs. We have also analyzed the photophysical properties of CdTe and CdTe/CdS core/shell QDs. Time-resolved photoluminescence (PL) measurements showed the emission decay lifetimes in the tens of nanoseconds. Additionally, ultrafast charge carrier relaxation dynamics of the CdTe core and CdTe/CdS core/shell QDs were studied by the femtosecond transient absorption (TA) spectroscopy. The transient absorption spectra of CdTe and CdTe/CdS core/shell QDs showed multiple bleaches, which have been assigned to the 1S3/2(h)-1S(e), 2S3/2(h)-1S(e), and 1P3/2(h)-1P(e) transitions. The spectral shifts of these bleaches after shell deposition have been analyzed in the context of a quasi-type-II carrier distribution in the core/shell samples, and interestingly the red shift was only contributed from the conduction band energy levels shifting to lower energy. In addition, the ultrafast evolution of these bleach features has been examined to extract electron cooling rates in these samples. A fast decay component in the 1S3/2(h)-1S(e) transition of the small CdTe QDs was discovered due to the hole being trapped by the defects on the surface of QD. Further, we have studied the PL quenching process of the air exposed CdTe QDs via the PL decay and transient absorption measurements. Oxygen

  2. Dynamic infrared study of polyphenylene sulfide using planar array infrared spectroscopy.

    PubMed

    Pesapane, Andrea; Snively, Christopher M; Ikeda, Richard M; Chase, D Bruce; Rabolt, John F

    2008-10-01

    Planar array infrared (PA-IR) spectroscopy was used to study polyphenylene sulfide (PPS) at room temperature during the application of a sinusoidal elastic deformation. All of the intensity in the dynamic spectra was contained within the in-phase spectrum, which was expected since the measurements were carried out at room temperature, far below the glass transition temperature. The contributions of chain orientation, sample thinning, and stress-induced band shifts were separated in the dynamic spectra. It was found that the effects of chain orientation and sample thinning canceled each other out. Stress-induced band shifts far below the spectral resolution, on the order of 0.01 cm(-1), were quantified and used to calculate the stress optical coefficients and mode Gruneisen parameters for PPS.

  3. First-principles study of superconducting hydrogen sulfide at pressure up to 500 GPa.

    PubMed

    Durajski, Artur P; Szczęśniak, Radosław

    2017-06-30

    We investigate the possibility of achieving the room-temperature superconductivity in hydrogen sulfide (H3S) through increasing external pressure, a path previously widely used to reach metallization and superconducting state in novel hydrogen-rich materials. The electronic properties and superconductivity of H3S in the pressure range of 250-500 GPa are determined by the first-principles calculations. The metallic character of a body-centered cubic Im[Formula: see text]m structure is found over the whole studied pressure. Moreover, the absence of imaginary frequency in phonon spectrum implies that this structure is dynamically stable. Furthermore, our calculations conducted within the framework of the Eliashberg formalism indicate that H3S in the range of the extremely high pressures is a conventional strong-coupling superconductor with a high superconducting critical temperature, however, the maximum critical temperature does not exceed the value of 203 K.

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

    NASA Astrophysics Data System (ADS)

    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

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

    NASA Astrophysics Data System (ADS)

    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

  6. The stability of allyl radicals following the photodissociation of allyl iodide at 193 nm.

    SciTech Connect

    Fan, H.; Pratt, S. T.; Chemistry

    2006-01-01

    The photodissociation of allyl iodide (C{sub 3}H{sub 5}I) at 193 nm was investigated by using a combination of vacuum-ultraviolet photoionization of the allyl radical, resonant multiphoton ionization of the iodine atoms, and velocity map imaging. The data provide insight into the primary C-I bond fission process and into the dissociative ionization of the allyl radical to produce C{sub 3}H{sup 3+}. The experimental results are consistent with the earlier results of Szpunar et al. [J. Chem. Phys. 119, 5078 (2003)], in that some allyl radicals with internal energies higher than the secondary dissociation barrier are found to be stable. This stability results from the partitioning of available energy between the rotational and vibrational degrees of freedom of the radical, the effects of a centrifugal barrier along the reaction coordinate, and the effects of the kinetic shift in the secondary dissociation of the allyl radical. The present results suggest that the primary dissociation of allyl iodide to allyl radicals plus I*({sup 2}P{sub 1/2}) is more important than previously suspected.

  7. Rh-Catalyzed Chemo- and Enantioselective Hydrogenation of Allylic Hydrazones.

    PubMed

    Hu, Qiupeng; Hu, Yanhua; Liu, Yang; Zhang, Zhenfeng; Liu, Yangang; Zhang, Wanbin

    2017-01-23

    A highly efficient P-stereogenic diphosphine-rhodium complex was applied to the chemo- and enantioselective hydrogenation of allylic hydrazones for the synthesis of chiral allylic hydrazines in 89-96 % yields and with 82-99 % ee values. This methodology was successfully applied to the preparation of versatile chiral allylic amine derivatives.

  8. A new portable sulfide monitor with a zinc-oxide semiconductor sensor for daily use and field study.

    PubMed

    Tanda, Naoko; Washio, Jumpei; Ikawa, Kyoko; Suzuki, Kengo; Koseki, Takeyoshi; Iwakura, Masaki

    2007-07-01

    For measuring oral malodor in daily clinical practice and in field study, we developed and evaluated a highly sensitive portable monitor system. We examined sensitivity and specificity of the sensor for volatile sulfur compounds (VSC) and obstructive gases, such as ethanol, acetone, and acetaldehyde. Each mouth air provided by 46 people was measured by this monitor, gas chromatography (GC), and olfactory panel and compared with each other. Based on the result, we used the monitor for mass health examination of a rural town with standardized measuring. The sensor detected hydrogen sulfide, methyl mercaptan, and dimethyl sulfide with 10-1000 times higher sensitivity than the other gases. The monitor's specificity was significantly improved by a VSC-selective filter. There were significant correlations between VSC concentration by the sulfide monitor and by GC, and by organoleptic score. Thirty-six percent of 969 examinees had oral malodor in a rural town. Seventy-eight percent of 969 examinees were motivated to take care of their oral condition by oral malodor measuring with the monitor. The portable sulfide monitor was useful to promote oral health care not only in clinics, but also in field study. The simple and quick operation system and the standardized measuring make it one of parameters of oral condition.

  9. Structural and optical studied of nano structured lead sulfide thin films prepared by the chemical bath deposition technique

    NASA Astrophysics Data System (ADS)

    Al Din, Nasser Saad; Hussain, Nabiha; Jandow, Nidhal

    2016-07-01

    Lead (II) Sulfide PbS thin films were deposited on glass substrates at 25°C by chemical bath deposition (CBD) method. The structural properties of the films were studied as a function of the concentration of Thiourea (CS (NH2)2) as Source of Sulfide and deposition time. The surface morphology of the films was characterized by X-ray diffraction and SEM. The obtained results showed that the as-deposited films Polycrystalline had cubic crystalline phase that belong to S.G: Fm3m. We found that they have preferred orientation [200]. Also the thickness of thin films decrease with deposition time after certain value and, it observed free sulfide had orthorhombic phase. Optical properties showed that the thin films have high transmission at visible range and low transmission at UV, IR range. The films of PbS have direct band gap (I.68 - 2.32 ev) at 300K the values of band energy decreases with increases thickness of the Lead (II) Sulfide films.

  10. Structural and optical studied of nano structured lead sulfide thin films prepared by the chemical bath deposition technique

    SciTech Connect

    Al Din, Nasser Saad Hussain, Nabiha; Jandow, Nidhal

    2016-07-25

    Lead (II) Sulfide PbS thin films were deposited on glass substrates at 25°C by chemical bath deposition (CBD) method. The structural properties of the films were studied as a function of the concentration of Thiourea (CS (NH{sub 2}){sub 2}) as Source of Sulfide and deposition time. The surface morphology of the films was characterized by X-ray diffraction and SEM. The obtained results showed that the as-deposited films Polycrystalline had cubic crystalline phase that belong to S.G: Fm3m. We found that they have preferred orientation [200]. Also the thickness of thin films decrease with deposition time after certain value and, it observed free sulfide had orthorhombic phase. Optical properties showed that the thin films have high transmission at visible range and low transmission at UV, IR range. The films of PbS have direct band gap (I.68 - 2.32 ev) at 300 K the values of band energy decreases with increases thickness of the Lead (II) Sulfide films.

  11. Enantioselective transformation of allyl carbonates into branched allyl carbamates by using amines and recycling CO2 under iridium catalysis.

    PubMed

    Zheng, Sheng-Cai; Zhang, Min; Zhao, Xiao-Ming

    2014-06-10

    Enantioselective transformation of allyl carbonates into branched allyl carbamates by using amines and recycling CO2 in the presence of an Ir complex and K3PO4 was accomplished. This provided branched allyl carbamates in fair to excellent yields with up to 98:2 regioselectivity and 93 % ee. The role of CO2 in this transformation is discussed as well.

  12. Asymmetric synthesis of allylic sulfonic acids: enantio- and regioselective iridium-catalyzed allylations of Na2SO3.

    PubMed

    Liu, Wei; Zhao, Xiao-ming; Zhang, Hong-bo; Zhang, Liang; Zhao, Ming-zhu

    2014-12-15

    An enantioselective allylation reaction of allylic carbonates with sodium sulfite (Na2 SO3 ) catalyzed by Ir complex was accomplished, providing allylic sulfonic acids in good to excellent yields with a high level of enantio- and regioselectivities. (R)-2-Phenyl-2-sulfoacetic acid, a key intermediate for the synthesis of Cefsulodin and Sulbenicillin, was synthesized as well.

  13. Soluble-sulfide precipitation study. Final report, Dec 85-Oct 86

    SciTech Connect

    Balasco, A.A.; Santhanam, C.J.; Stevens, J.I.; Walters, R.A.; Wolfrum, E.J.

    1986-12-30

    Based on the authors evaluation of the extensive amount of information available within the U.S. Army on metal finishing wastewater management at Army facilities and the open literature, they have prepared this report to provide information on the soluble sulfide precipitation (SSP) process for the removal of heavy metals from metal finishing wastewater. The hydroxide precipitation process is most broadly used today and employed at many U.S. Army facilities. Both soluble sulfide precipitation (SSP) and insoluble sulfide precipitation (ISP) processes are potentially applicable for treating metal finishing wastewaters. A decision methodology is outlined to permit a planner at any of the U.S. Army metal plating facilities to undertake a comparative evaluation of both the hydroxide and sulfide precipitation processes. Important environmental related issues to note are as follows: hydroxide precipitates are difficult to dewater and can potentially be leached from landfills; while sulfide precipitates are more difficult to leach, they have the potential to produce hydrogen sulfide (H2S), a toxic gas.

  14. [Study on dynamics of hydrogen sulfide and carbonyl sulfide emission fluxes from Suaeda salsa marsh in the Yellow River estuary].

    PubMed

    Li, Xin-Hua; Guo, Hong-Hai; Yang, Li-Ping; Zhu, Zhen-Lin; Sun, Xiao-Qing

    2014-02-01

    The H2S and COS emission fluxes from Suaeda salsa marsh in the Yellow River estuary were measured using the static chamber and Chromatogram method during the growth season (May to October), the results showed that the seasonal and diurnal variations of H2S and COS emission fluxes were obvious, and Suaeda salsa marsh in the Yellow River estuary was the sources for both H2S and COS during the growth time, and the mean H2S and COS emission fluxes from Suaeda salsa marsh were 4.97 microg x (m2 x h)(-1) and 0.92 microg x (m2 x h)(-1), respectively. Different environmental factors had different effects on the emission fluxes of H2S and COS from Suaeda salsa marsh, in which the SO4(2-) content and water content in the soil were the main factors that affected the H2S and COS emission fluxes, respectively. Sulfur gases emissions from Suaeda salsa marsh may be affected by many factors, such as plant, tide status and so on, so that should be further studied.

  15. Selenium sulfide

    Integrated Risk Information System (IRIS)

    Selenium sulfide ; CASRN 7446 - 34 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  16. Carbonyl sulfide

    Integrated Risk Information System (IRIS)

    Carbonyl sulfide ; CASRN 463 - 58 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  17. Hydrogen sulfide

    Integrated Risk Information System (IRIS)

    EPA / 635 / R - 03 / 005 www.epa.gov / iris TOXICOLOGICAL REVIEW OF HYDROGEN SULFIDE ( CAS No . 7783 - 06 - 4 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) June 2003 U.S . Environmental Protection Agency Washington , DC DISCLAIMER This document has been

  18. Resonance interactions in acyclic systems. 1. Energies and charge distributions in allyl anions and related compounds

    SciTech Connect

    Wiberg, K.B.; Breneman, C.M.; LePage, T.J. )

    1990-01-03

    The energies of dissociation of propane to 1-propyl cation and anion and of propene to allyl cation and anion may be satisfactorily reproduced via ab initio calculations at the MP4/6-311++G**//6-31G* level. The reaction of 1-propyl cation with propene to give the unconjugated allyl cation was found to be endothermic, whereas the corresponding reaction of the anion was exothermic. The rotational barrier for allyl cation was 36 kcal/mol, whereas that for the anion was 19 kcal/mol. These data were analyzed in terms of electron delocalization and the electrostatic energies of the ions, and it was concluded that whereas the cation had significant resonance stabilization, the anion had little stabilization. A series of allyl type anions were examined making use of 6-311++G** wave functions calculated at the 6-31G* geometries. Correction for electron correlation at the MP3 level led to calculated proton affinities which agreed well with the experimental values. Electronegative atoms at the central position had little affect on the proton affinities, but when they were at the terminal positions, there was a large change. The changes in electron population among the amions were studied via numerical integration of the charge densities within boundaries which may be assigned to the atoms in the ions. The more stable anions are characterized by a -+- charge distribution for the three atoms in the allylic system, leading to internal coulombic stabilization.

  19. Metallocene-catalyzed alkene polymerization and the observation of Zr-allyls.

    PubMed

    Landis, Clark R; Christianson, Matthew D

    2006-10-17

    Single-site polymerization catalysts enable exquisite control over alkene polymerization reactions to produce new materials with unique properties. Knowledge of catalyst speciation and fundamental kinetics are essential for full mechanistic understanding of zirconocene-catalyzed alkene polymerization. Currently the effect of activators on fundamental polymerization steps is not understood. Progress in understanding activator effects requires determination of fundamental kinetics for zirconocene catalysts with noncoordinating anions such as [B(C6F5)4]-. Kinetic NMR studies at low temperature demonstrate a very fast propagation rate for 1-hexene polymerization catalyzed by [(SBI)Zr(CH2SiMe3)][B(C6F5)4] [where SBI is rac-Me2Si(indenyl)2] with complete consumption of 1-hexene before the first NMR spectrum. Surprisingly, the first NMR spectrum reveals, aside from uninitiated catalyst, Zr-allyls as the sole catalyst-containing species. These Zr-allyls, which exist in two diastereomeric forms, have been characterized by physical and chemical methods. The mechanism of Zr-allyl formation was probed with a trapping experiment, leading us to favor a mechanism in which Zr-polymeryl undergoes beta-H transfer to metal without dissociation of coordinated alkene followed by sigma-bond metathesis to form H2 and Zr-allyl. Zr-allyl species undergo slow reactions with alkene but react rapidly with H2 to form hydrogenation products.

  20. Kinetic and mechanistic study of the reaction of atomic chlorine with dimethyl sulfide

    SciTech Connect

    Stickel, R.E.; Nicovich, J.M.; Wang, S.; Zhao, Z.; Wine, P.H.

    1992-11-26

    Time-resolved resonance fluorescence detection of Cl({sup 2}P{sub J}) following 266-nm laser flash photolysis of Cl{sub 2}CO/CH{sub 3}SCH{sub 3}(DMS)/N{sub 2} mixtures has been employed to study the kinetics of the title reaction over the temperature and pressure ranges 240-421 K and 3-700 Torr. The reaction is found to be very fast, occurring on essentially every Cl({sup 2}P{sub J}) + DMS encounter. The reaction rate increases with decreasing temperature and shows a significant pressure dependence. At 297 K, for example, the rate coefficient increases from a low-pressure limit value of approximately 1.8 x 10{sup {minus}10} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} to a value of (3.3 {+-} 0.5) x 10{sup {minus}10} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} at P = 700 Torr. A few experiments were carried out with CD{sub 3}SCD{sub 3} or C{sub 2}H{sub 5}SC{sub 2}H{sub 5} replacing DMS as the sulfide reactant; within experimental uncertainty, no dependence of the rate coefficient on the identity of the sulfide reactant was observed. In a separate study, time-resolved tunable diode laser spectroscopic detection of HCl has been coupled with 248-nm laser flash photolysis of Cl{sub 2}CO/DMS/CO{sub 2}/N{sub 2} mixtures to measure the HCl product yield from the title reaction as a function of pressure at T = 297 K. The HCl yield approaches unity as P {yields} 0 but decreases with increasing pressure to a value of {approximately}0.5 at P = 203 Torr. The yield experiments demonstrate that hydrogen abstraction is the dominant reaction mechanism in the low-pressure limit. With increasing pressure, stabilization of a (CH{sub 3}){sub 2}SCl adduct apparently becomes competitive with the hydrogen abstraction pathway. The potential role of the title reaction in marine atmospheric chemistry is discussed. 59 refs., 7 figs., 3 tabs.

  1. Morphological and Electrochemical Study of Sulfide/Nitride Nanostructure Deposited Through Pulsed Plasma Electrolysis

    NASA Astrophysics Data System (ADS)

    Tavakoli, H.; Sobhani, M.

    2017-04-01

    This study investigated the feasibility of coating a steel St12 substrate with a sulfide/nitride layer. The coating process was conducted through a plasma electrolysis technique with a pulsed regime applied at frequencies of 100, 500, and 1000 Hz. It was found that the use of higher frequencies in the mentioned process provides better control over workpiece surface temperature and leads to reduced extent of voltage variations required to achieve a fixed temperature. The coating deposited at the frequency of 1000 Hz and voltage of about 235 V exhibited a nanostructure composed of 50 nm particles. The deposited coating consisted of an outer porous layer and an inner relatively dense layer. The x-ray studies identified the phases of the coating as γ'-Fe4N, Fe2-3N and FeS. The presence of FeS phase reduces the friction coefficient of the surface to about half the value obtainable in its absence. Studying the electrochemical impedance of the layer revealed that using a higher frequency in the deposition process increases the stability of resulting layer against seven days of immersion in the corrosive solution.

  2. Morphological and Electrochemical Study of Sulfide/Nitride Nanostructure Deposited Through Pulsed Plasma Electrolysis

    NASA Astrophysics Data System (ADS)

    Tavakoli, H.; Sobhani, M.

    2017-03-01

    This study investigated the feasibility of coating a steel St12 substrate with a sulfide/nitride layer. The coating process was conducted through a plasma electrolysis technique with a pulsed regime applied at frequencies of 100, 500, and 1000 Hz. It was found that the use of higher frequencies in the mentioned process provides better control over workpiece surface temperature and leads to reduced extent of voltage variations required to achieve a fixed temperature. The coating deposited at the frequency of 1000 Hz and voltage of about 235 V exhibited a nanostructure composed of 50 nm particles. The deposited coating consisted of an outer porous layer and an inner relatively dense layer. The x-ray studies identified the phases of the coating as γ'-Fe4N, Fe2-3N and FeS. The presence of FeS phase reduces the friction coefficient of the surface to about half the value obtainable in its absence. Studying the electrochemical impedance of the layer revealed that using a higher frequency in the deposition process increases the stability of resulting layer against seven days of immersion in the corrosive solution.

  3. Comparative study of using different materials as bacterial carriers to treat hydrogen sulfide.

    PubMed

    Li, Zhiling; Sun, Tonghua; Zhu, Nanwen; Cao, Xinde; Jia, Jinping

    2008-12-01

    The use of support media for the immobilization of microorganisms is widely known to provide a surface for microbial growth and protect the microorganisms from inhibitory compounds. In this study, molecular sieve, granular porous carbon, and ferric oxide desulfurizer, immobilized with autotrophic bacteria capable of oxidizing ferrous iron to ferric iron, were developed to treat hydrogen sulfide (H(2)S). Their corresponding bioreactors were referred to as BMS, BPC, and BFO, respectively. H(2)S loading, gas retention time, hydrogen ion, and aluminous, ferric, and ferrous iron concentrations of recycling effluents were evaluated. Thermogravimetric analysis, Brauner-Emmett-Teller method, and scanning electron microscopy were used to characterize packing materials. Results showed that the elimination capacity was in the order of BFO > BPC > BMS. This study suggested that the material characteristics progressively influenced the deodorization capacities of bioreactors. H(2)S was oxidized into elemental sulfur and oxidized sulfur species, according to differences of carriers. Furthermore, this study revealed the potential application of simultaneously treating of H(2)S under extremely acidic conditions.

  4. Enantioselective construction of C-chiral allylic sulfilimines via the iridium-catalyzed allylic amination with S,S-diphenylsulfilimine: asymmetric synthesis of primary allylic amines.

    PubMed

    Grange, Rebecca L; Clizbe, Elizabeth A; Counsell, Emma J; Evans, P Andrew

    2015-01-01

    We have devised a highly regio- and enantioselective iridium-catalyzed allylic amination reaction with the sulfur-stabilized aza-ylide, S,S-diphenylsulfilimine. This process provides a robust and scalable method for the construction of aryl-, alkyl- and alkenyl-substituted C-chiral allylic sulfilimines, which are important functional groups for organic synthesis. Additionally, the combination of the allylic amination with an in situ deprotection of the sulfilimine constitutes a convenient one-pot protocol for the construction of chiral nonracemic primary allylic amines.

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

    NASA Astrophysics Data System (ADS)

    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

  6. Expanding insight into asymmetric palladium-catalyzed allylic alkylation of N-heterocyclic molecules and cyclic ketones.

    PubMed

    Bennett, Nathan B; Duquette, Douglas C; Kim, Jimin; Liu, Wen-Bo; Marziale, Alexander N; Behenna, Douglas C; Virgil, Scott C; Stoltz, Brian M

    2013-04-02

    Eeny, meeny, miny ... enaminones! Lactams and imides have been shown to consistently provide enantioselectivities substantially higher than other substrate classes previously investigated in the palladium-catalyzed asymmetric decarboxylative allylic alkylation. Several new substrates have been designed to probe the contributions of electronic, steric, and stereoelectronic factors that distinguish the lactam/imide series as superior alkylation substrates (see scheme). These studies culminated in marked improvements on carbocyclic allylic alkylation substrates.

  7. Genetic Targets of Hydrogen Sulfide in Ventilator-Induced Lung Injury – A Microarray Study

    PubMed Central

    Spassov, Sashko; Pfeifer, Dietmar; Strosing, Karl; Ryter, Stefan; Hummel, Matthias; Faller, Simone; Hoetzel, Alexander

    2014-01-01

    Recently, we have shown that inhalation of hydrogen sulfide (H2S) protects against ventilator-induced lung injury (VILI). In the present study, we aimed to determine the underlying molecular mechanisms of H2S-dependent lung protection by analyzing gene expression profiles in mice. C57BL/6 mice were subjected to spontaneous breathing or mechanical ventilation in the absence or presence of H2S (80 parts per million). Gene expression profiles were determined by microarray, sqRT-PCR and Western Blot analyses. The association of Atf3 in protection against VILI was confirmed with a Vivo-Morpholino knockout model. Mechanical ventilation caused a significant lung inflammation and damage that was prevented in the presence of H2S. Mechanical ventilation favoured the expression of genes involved in inflammation, leukocyte activation and chemotaxis. In contrast, ventilation with H2S activated genes involved in extracellular matrix remodelling, angiogenesis, inhibition of apoptosis, and inflammation. Amongst others, H2S administration induced Atf3, an anti-inflammatory and anti-apoptotic regulator. Morpholino mediated reduction of Atf3 resulted in elevated lung injury despite the presence of H2S. In conclusion, lung protection by H2S during mechanical ventilation is associated with down-regulation of genes related to oxidative stress and inflammation and up-regulation of anti-apoptotic and anti-inflammatory genes. Here we show that Atf3 is clearly involved in H2S mediated protection. PMID:25025333

  8. Allylic rearrangement of 1-alkenyl(ethynyl)carbinols catalyzed by polyvanadium organosiloxane

    SciTech Connect

    Gulyi, S.E.; Novikov, N.A.; Erman, M.B.

    1986-12-20

    Ethynylcarbinols upon heating with polyvanadium organosiloxanes and other esters of vanadic acid isomerize to unsaturated aldehydes, while 1-alkenylcarbinols under the same conditions undergo allylic rearrangement. The authors have studied the rearrangement of these carbinols capable of reacting by both pathways and thus serving as models for a study of intramolecular competition between these two type of processes. In the presence of polyvanadium organosiloxane, the carbinols undergo virtually complete isomerization to 2-hydroxy-3-alken-5-ynes. In other words, the allylic rearrangement predominates. No significant amounts of sorbinaldehydes, which would be formed as the products of the other reaction, were detected. An analysis of the NMR spectra is given.

  9. Waveguide Chirped-Pulse Fourier Transform Microwave Spectroscopy of Allyl Bromide

    NASA Astrophysics Data System (ADS)

    McCabe, Morgan N.; Shipman, Steven

    2014-06-01

    The rotational spectrum of allyl bromide was recorded from 8.7 to 26.5 GHz at -20 °C with a waveguide chirped-pulse Fourier transform microwave spectrometer. The rotational spectrum of allyl bromide has been previously studied by Niide and coworkers. However, previous assignments of this spectrum only extended to J = 12 and K_a = 1. Newly acquired data from our spectrometer has allowed us to extend the previous work to higher values of J and K_a, leading to significant improvements in the distortion constants in particular. Comparisons between the spectra and conformational preferences of the allyl halides will also be discussed. Y. Niide, M, Takano,T. Satoh, and Y. Sasada J. Mol. Spectrosc., 63, 108(1976) Niide, Yuzuru, J. Sci. Hiroshima Univ., Ser. A, 48, 1(1984)

  10. Mineralogical studies of sulfide samples and volatile concentrations of basalt glasses from the southern Juan de Fuca Ridge

    NASA Technical Reports Server (NTRS)

    Brett, Robin; Evans, Howard T., Jr.; Wandless, M. V.; Gibson, E. K., Jr.; Hedenquist, Jeffrey W.

    1987-01-01

    Sulfide samples obtained from Alvin dives on the southern Juan de Fuca Ridge were examined, showing the presence of two previously undiscovered minerals, both formed at low temperatures. The first detection of lizardite, starkeyite, and anatase in such an environment is also reported. Sulfide geothermometry involving the Cu-Fe-S system shows a vent temperature of less than 328 C for one sample. Ice-melting temperatures on inclusions from this sample are about -2.8 C, and fluid inclusion studies on crystals near this sample show pressure-corrected homogenization temperatures of 268 and 285 C. Volatile concentrations from vesicle-free basalt glass from the vent field are found to be about 0.0013 wt pct CO2 and 0.16 wt pct H2O.

  11. Sulfidation of silver nanoparticles

    NASA Astrophysics Data System (ADS)

    Levard, C.; Michel, F. M.; Brown, G. E.

    2010-12-01

    the kinetics of sulfidation and in solubility behavior. The results of this type of fundamental study are important for predicting the behavior and fate of Ag-NPs in natural ecosystems. For example, aggregation caused by sulfidation may limit transport in porous media such as soils. Modification of surface charge during the sulfidation process may have an important impact on electrostatic interactions between Ag-NPs and charged phases such as natural organic matter. Finally, it is well known that Ag+ has a greater toxicity than metallic Ag (3) and the observed decrease in solubility of Ag-NPs after sulfidation may strongly impact the toxicity of silver in the environment. (1) www.nanotechproject.org (2) F. Fievet, J.P. Lagier, B. Blin, B. Beaudoin and M. Figlarz, Solid State Ionics 32/33, 198 (1989) (3) G.A. Sotiriou and S.E. Pratsinis, Environmental Science & Technology 14, 5649 (2010).

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

    PubMed

    Vaitheeswari, S; Sriram, R; Brindha, P; Kurian, Gino A

    2015-01-01

    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. The antilithiatic activity of sodium hydrogen sulfide (NaSH), sodium thiosulfate (Na(2)S(2)O(3)) and sodium sulfate (Na(2)SO(4)) 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. 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>Na(2)S(2)O(3)>Na(2)SO(4). 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 S(2)O(3)(2)-and SO(4)(2)- moiety produced by the test compounds.

  13. Mineralogical and isotopic studies of base metal sulfides from the Jiawula Ag-Pb-Zn deposit, Inner Mongolia, NE China

    NASA Astrophysics Data System (ADS)

    Niu, Si-Da; Li, Sheng-Rong; Santosh, M.; Zhang, De-Hui; Li, Zeng-Da; Shan, Meng-Jie; Lan, Yi-Xiang; Gao, De-Rong; Zhao, Wen-Bin

    2016-01-01

    The Jiawula Ag-Pb-Zn deposit is located in the northern part of the Da Hinggan Mountains metallogenic belt in the eastern section of the Central Asian Orogenic Belt. Sphalerite, galena, pyrite, chalcopyrite, and arsenopyrite are the major sulfide minerals occurring in this deposit. Here we report results from electron probe micro-analysis (EPMA), thermoelectricity, and sulfur isotope studies of the constituent silver minerals and sulfide phases of the Jiawula deposit. Petrographic observations and EPMA study reveal abundant silver mineralization in the ore, especially within sphalerite and galena. Discrete grains of silver minerals (including argentite, pyrargyrite, and canfieldite) and isomorphism in silver-bearing sulfides are identified. Silver and tellurium contents in galena are relatively high and show interrelationship. Significant substitution of S by Te in the galena lattice facilitates silver entering the galena structure, which might have been promoted by relatively low lg fS2. The thermoelectric coefficient of pyrite shows a marked gradient from N-type to P-type from pre- to post-metallogenic stages. Pyrites in Jiawula are enriched in Co and As and in the absence of Ni, displaying features typical of epithermal deposits. The isotopic data present a close relationship between the sulfur source and magmatism.

  14. An advanced modeling study on the impacts and atmospheric implications of multiphase dimethyl sulfide chemistry

    NASA Astrophysics Data System (ADS)

    Hoffmann, Erik Hans; Tilgner, Andreas; Schrödner, Roland; Bräuer, Peter; Wolke, Ralf; Herrmann, Hartmut

    2016-10-01

    Oceans dominate emissions of dimethyl sulfide (DMS), the major natural sulfur source. DMS is important for the formation of non-sea salt sulfate (nss-SO42-) aerosols and secondary particulate matter over oceans and thus, significantly influence global climate. The mechanism of DMS oxidation has accordingly been investigated in several different model studies in the past. However, these studies had restricted oxidation mechanisms that mostly underrepresented important aqueous-phase chemical processes. These neglected but highly effective processes strongly impact direct product yields of DMS oxidation, thereby affecting the climatic influence of aerosols. To address these shortfalls, an extensive multiphase DMS chemistry mechanism, the Chemical Aqueous Phase Radical Mechanism DMS Module 1.0, was developed and used in detailed model investigations of multiphase DMS chemistry in the marine boundary layer. The performed model studies confirmed the importance of aqueous-phase chemistry for the fate of DMS and its oxidation products. Aqueous-phase processes significantly reduce the yield of sulfur dioxide and increase that of methyl sulfonic acid (MSA), which is needed to close the gap between modeled and measured MSA concentrations. Finally, the simulations imply that multiphase DMS oxidation produces equal amounts of MSA and sulfate, a result that has significant implications for nss-SO42- aerosol formation, cloud condensation nuclei concentration, and cloud albedo over oceans. Our findings show the deficiencies of parameterizations currently used in higher-scale models, which only treat gas-phase chemistry. Overall, this study shows that treatment of DMS chemistry in both gas and aqueous phases is essential to improve the accuracy of model predictions.

  15. An advanced modeling study on the impacts and atmospheric implications of multiphase dimethyl sulfide chemistry.

    PubMed

    Hoffmann, Erik Hans; Tilgner, Andreas; Schrödner, Roland; Bräuer, Peter; Wolke, Ralf; Herrmann, Hartmut

    2016-10-18

    Oceans dominate emissions of dimethyl sulfide (DMS), the major natural sulfur source. DMS is important for the formation of non-sea salt sulfate (nss-SO4(2-)) aerosols and secondary particulate matter over oceans and thus, significantly influence global climate. The mechanism of DMS oxidation has accordingly been investigated in several different model studies in the past. However, these studies had restricted oxidation mechanisms that mostly underrepresented important aqueous-phase chemical processes. These neglected but highly effective processes strongly impact direct product yields of DMS oxidation, thereby affecting the climatic influence of aerosols. To address these shortfalls, an extensive multiphase DMS chemistry mechanism, the Chemical Aqueous Phase Radical Mechanism DMS Module 1.0, was developed and used in detailed model investigations of multiphase DMS chemistry in the marine boundary layer. The performed model studies confirmed the importance of aqueous-phase chemistry for the fate of DMS and its oxidation products. Aqueous-phase processes significantly reduce the yield of sulfur dioxide and increase that of methyl sulfonic acid (MSA), which is needed to close the gap between modeled and measured MSA concentrations. Finally, the simulations imply that multiphase DMS oxidation produces equal amounts of MSA and sulfate, a result that has significant implications for nss-SO4(2-) aerosol formation, cloud condensation nuclei concentration, and cloud albedo over oceans. Our findings show the deficiencies of parameterizations currently used in higher-scale models, which only treat gas-phase chemistry. Overall, this study shows that treatment of DMS chemistry in both gas and aqueous phases is essential to improve the accuracy of model predictions.

  16. An advanced modeling study on the impacts and atmospheric implications of multiphase dimethyl sulfide chemistry

    PubMed Central

    Hoffmann, Erik Hans; Tilgner, Andreas; Schrödner, Roland; Bräuer, Peter; Wolke, Ralf; Herrmann, Hartmut

    2016-01-01

    Oceans dominate emissions of dimethyl sulfide (DMS), the major natural sulfur source. DMS is important for the formation of non-sea salt sulfate (nss-SO42−) aerosols and secondary particulate matter over oceans and thus, significantly influence global climate. The mechanism of DMS oxidation has accordingly been investigated in several different model studies in the past. However, these studies had restricted oxidation mechanisms that mostly underrepresented important aqueous-phase chemical processes. These neglected but highly effective processes strongly impact direct product yields of DMS oxidation, thereby affecting the climatic influence of aerosols. To address these shortfalls, an extensive multiphase DMS chemistry mechanism, the Chemical Aqueous Phase Radical Mechanism DMS Module 1.0, was developed and used in detailed model investigations of multiphase DMS chemistry in the marine boundary layer. The performed model studies confirmed the importance of aqueous-phase chemistry for the fate of DMS and its oxidation products. Aqueous-phase processes significantly reduce the yield of sulfur dioxide and increase that of methyl sulfonic acid (MSA), which is needed to close the gap between modeled and measured MSA concentrations. Finally, the simulations imply that multiphase DMS oxidation produces equal amounts of MSA and sulfate, a result that has significant implications for nss-SO42− aerosol formation, cloud condensation nuclei concentration, and cloud albedo over oceans. Our findings show the deficiencies of parameterizations currently used in higher-scale models, which only treat gas-phase chemistry. Overall, this study shows that treatment of DMS chemistry in both gas and aqueous phases is essential to improve the accuracy of model predictions. PMID:27688763

  17. Allylic Oxidations Catalyzed by Dirhodium Caprolactamate via Aqueous tert-Butyl Hydroperoxide: The Role of the tert-Butylperoxy Radical

    PubMed Central

    McLaughlin, Emily C.; Choi, Hojae; Wang, Kan; Chiou, Grace; Doyle, Michael P.

    2009-01-01

    Dirhodium(II) caprolactamate exhibits optimal efficiency for the production of the tert-butylperoxy radical, which is a selective reagent for hydrogen atom abstraction. These oxidation reactions occur with aqueous tert-butyl hydroperoxide (TBHP) without rapid hydrolysis of the caprolactamate ligands on dirhodium. Allylic oxidations of enones yield the corresponding enedione in moderate to high yields, and applications include allylic oxidations of steroidal enones. Although methylene oxidation to a ketone is more effective, methyl oxidation to a carboxylic acid can also be achieved. The superior efficiency of dirhodium(II) caprolactamate as a catalyst for allylic oxidations by TBHP (mol % catalyst, % conversion) is described in comparative studies with other metal catalysts that are also reported to be effective for allylic oxidations. That different catalysts produce essentially the same mixture of products with the same relative yields suggests that the catalyst is not involved in product forming steps. Mechanistic implications arising from studies of allylic oxidation with enones provide new insights into factors that control product formation. A previously undisclosed disproportionation pathway, catalyzed by the tert-butoxy radical, of mixed peroxides for the formation of ketone products via allylic oxidation has been uncovered. PMID:19072696

  18. Additive-Free Pd-Catalyzed α-Allylation of Imine-Containing Heterocycles.

    PubMed

    Kljajic, Marko; Puschnig, Johannes G; Weber, Hansjörg; Breinbauer, Rolf

    2017-01-06

    An additive-free Pd-catalyzed α-allylation of different imino-group-ontaining heterocycles is reported. The activation of α-CH pronucleophiles (pKa (DMSO) > 25) occurs without the addition of strong bases or Lewis acids using only the Pd/Xantphos catalyst system. The reaction scope has been studied for various 5- and 6-membered nitrogen-containing heterocycles (yields up to 96%). Mechanistic investigations suggest an initial allylation of the imine-N followed by a Pd-catalyzed formal aza-Claisen rearrangement.

  19. Additive-Free Pd-Catalyzed α-Allylation of Imine-Containing Heterocycles

    PubMed Central

    2016-01-01

    An additive-free Pd-catalyzed α-allylation of different imino-group-ontaining heterocycles is reported. The activation of α-CH pronucleophiles (pKa (DMSO) > 25) occurs without the addition of strong bases or Lewis acids using only the Pd/Xantphos catalyst system. The reaction scope has been studied for various 5- and 6-membered nitrogen-containing heterocycles (yields up to 96%). Mechanistic investigations suggest an initial allylation of the imine-N followed by a Pd-catalyzed formal aza-Claisen rearrangement. PMID:27936786

  20. Allylic Amines as Key Building Blocks in the Synthesis of (E)-Alkene Peptide Isosteres

    PubMed Central

    Skoda, Erin M.; Davis, Gary C.

    2012-01-01

    Nucleophilic imine additions with vinyl organometallics have developed into efficient, high yielding, and robust methodologies to generate structurally diverse allylic amines. We have used the hydrozirconation-transmetalation-imine addition protocol in the synthesis of allylic amine intermediates for peptide bond isosteres, phosphatase inhibitors, and mitochondria-targeted peptide mimetics. The gramicidin S-derived XJB-5-131 and JP4-039 and their analogs have been prepared on up to 160 g scale for preclinical studies. These (E)-alkene peptide isosteres adopt type II′ β-turn secondary structures and display impressive biological properties, including selective reactions with reactive oxygen species (ROS) and prevention of apoptosis. PMID:22323894

  1. Antimicrobial activity of allylic thiocyanates derived from the Morita-Baylis-Hillman reaction

    PubMed Central

    Sá, Marcus Mandolesi; Ferreira, Misael; Lima, Emerson Silva; dos Santos, Ivanildes; Orlandi, Patrícia Puccinelli; Fernandes, Luciano

    2014-01-01

    Bacterial resistance to commonly used antibiotics has been recognized as a significant global health issue. In this study, we carried out the screening of a family of allylic thiocyanates for their action against a diversity of bacteria and fungi with a view to developing new antimicrobial agents. Allylic thiocyanates bearing halogenated aryl groups, which were readily obtained in two steps from the Morita-Baylis-Hillman adducts, showed moderate-to-high activity against selective pathogens, including a methicillin-resistant S. aureus (MRSA) strain. In particular cases, methyl (Z)-3-(2,4-dichlorophenyl)-2-(thiocyanomethyl)-2-propenoate exhibited antimicrobial activity comparable to the reference antibiotic Imipenem. PMID:25477911

  2. Nanostructured metal sulfides for energy storage

    NASA Astrophysics Data System (ADS)

    Rui, Xianhong; Tan, Huiteng; Yan, Qingyu

    2014-08-01

    Advanced electrodes with a high energy density at high power are urgently needed for high-performance energy storage devices, including lithium-ion batteries (LIBs) and supercapacitors (SCs), to fulfil the requirements of future electrochemical power sources for applications such as in hybrid electric/plug-in-hybrid (HEV/PHEV) vehicles. Metal sulfides with unique physical and chemical properties, as well as high specific capacity/capacitance, which are typically multiple times higher than that of the carbon/graphite-based materials, are currently studied as promising electrode materials. However, the implementation of these sulfide electrodes in practical applications is hindered by their inferior rate performance and cycling stability. Nanostructures offering the advantages of high surface-to-volume ratios, favourable transport properties, and high freedom for the volume change upon ion insertion/extraction and other reactions, present an opportunity to build next-generation LIBs and SCs. Thus, the development of novel concepts in material research to achieve new nanostructures paves the way for improved electrochemical performance. Herein, we summarize recent advances in nanostructured metal sulfides, such as iron sulfides, copper sulfides, cobalt sulfides, nickel sulfides, manganese sulfides, molybdenum sulfides, tin sulfides, with zero-, one-, two-, and three-dimensional morphologies for LIB and SC applications. In addition, the recently emerged concept of incorporating conductive matrices, especially graphene, with metal sulfide nanomaterials will also be highlighted. Finally, some remarks are made on the challenges and perspectives for the future development of metal sulfide-based LIB and SC devices.

  3. Nanostructured metal sulfides for energy storage.

    PubMed

    Rui, Xianhong; Tan, Huiteng; Yan, Qingyu

    2014-09-07

    Advanced electrodes with a high energy density at high power are urgently needed for high-performance energy storage devices, including lithium-ion batteries (LIBs) and supercapacitors (SCs), to fulfil the requirements of future electrochemical power sources for applications such as in hybrid electric/plug-in-hybrid (HEV/PHEV) vehicles. Metal sulfides with unique physical and chemical properties, as well as high specific capacity/capacitance, which are typically multiple times higher than that of the carbon/graphite-based materials, are currently studied as promising electrode materials. However, the implementation of these sulfide electrodes in practical applications is hindered by their inferior rate performance and cycling stability. Nanostructures offering the advantages of high surface-to-volume ratios, favourable transport properties, and high freedom for the volume change upon ion insertion/extraction and other reactions, present an opportunity to build next-generation LIBs and SCs. Thus, the development of novel concepts in material research to achieve new nanostructures paves the way for improved electrochemical performance. Herein, we summarize recent advances in nanostructured metal sulfides, such as iron sulfides, copper sulfides, cobalt sulfides, nickel sulfides, manganese sulfides, molybdenum sulfides, tin sulfides, with zero-, one-, two-, and three-dimensional morphologies for LIB and SC applications. In addition, the recently emerged concept of incorporating conductive matrices, especially graphene, with metal sulfide nanomaterials will also be highlighted. Finally, some remarks are made on the challenges and perspectives for the future development of metal sulfide-based LIB and SC devices.

  4. High Temperature Study of Molecular Motion in Polyphenylene Sulfide by Thermally Stimulated Currents

    NASA Astrophysics Data System (ADS)

    Jurga, Jan; Hruszka, Przemysław; Hilczer, Bożena; Kułek, Jan

    1984-03-01

    Thermally stimulated currents (TSC) in polyphenylene sulfide were measured in unpolarized and polarized samples. The TSC thermograms show a rapid increase in current at about 200 °C with an activation energy of about 1.6 eV. Additionally, in polarized samples a peak at about 150 °C related with the reorientational motions of the chain was found.

  5. Origins of enantioselectivity during allylic substitution reactions catalyzed by metallacyclic iridium complexes.

    PubMed

    Madrahimov, Sherzod T; Hartwig, John F

    2012-05-16

    In depth mechanistic studies of iridium catalyzed regioselective and enantioselective allylic substitution reactions are presented. A series of cyclometalated allyliridium complexes that are kinetically and chemically competent to be intermediates in the allylic substitution reactions was prepared and characterized by 1D and 2D NMR spectroscopies and single-crystal X-ray difraction. The rates of epimerization of the less thermodynamically stable diastereomeric allyliridium complexes to the thermodynamically more stable allyliridium stereoisomers were measured. The rates of nucleophilic attack by aniline and by N-methylaniline on the isolated allyliridium complexes were also measured. Attack on the thermodynamically less stable allyliridium complex was found to be orders of magnitude faster than attack on the thermodynamically more stable complex, yet the major enantiomer of the catalytic reaction is formed from the more stable diastereomer. Comparison of the rates of nucleophilic attack to the rates of epimerization of the diastereomeric allyliridium complexes containing a weakly coordinating counterion showed that nucleophilic attack on the less stable allyliridium species is much faster than conversion of the less stable isomer to the more stable isomer. These observations imply that Curtin-Hammett conditions are not met during iridium catalyzed allylic substitution reactions by η(3)-η(1)-η(3) interconversion. Rather, these data imply that when these conditions exist for this reaction, they are created by reversible oxidative addition, and the high selectivity of this oxidative addition step to form the more stable diastereomeric allyl complex leads to the high enantioselectivity. The stereochemical outcome of the individual steps of allylic substitution was assessed by reactions of deuterium-labeled substrates. The allylic substitution was shown to occur by oxidative addition with inversion of configuration, followed by an outer sphere nucleophilic attack

  6. The importance of the Lewis base in lithium mediated metallation and bond cleavage reaction of allyl amines and allyl phosphines.

    PubMed

    Blair, V L; Stevens, M A; Thompson, C D

    2016-06-21

    Metallation of two analogous N- and P-allyl molecules Ph2NCH2CHCH2 and Ph2PCH2CHCH2 with nBuLi have shown contrasting reactivities based on the choice of Lewis donor. With metallation of the alpha carbon atom was achieved regardless of the Lewis donor used while in comparison metallation of showed an unexpected donor denticity dependence with P-C bond clevage induced with the tri-dentate PMDETA. Complementary DFT and solution studies rationalise this outcome.

  7. Transition-metal-catalyzed asymmetric allylic dearomatization reactions.

    PubMed

    Zhuo, Chun-Xiang; Zheng, Chao; You, Shu-Li

    2014-08-19

    Dearomatization reactions serve as powerful methods for the synthesis of highly functionalized, three-dimensional structures starting with simple planar aromatic compounds. Among processes of this type, catalytic asymmetric dearomatization (CADA) reactions are attractive owing to the large number of aromatic compounds that are readily available and the fact that they enable direct access to enantiopure polycycles and spirocycles, which frequently are key structural motifs in biologically active natural products and pharmaceuticals. However, as a consequence of their high stabilities, arenes only difficultly participate in dearomatization reactions that take place with high levels of enantioselectivity. Transition-metal-catalyzed asymmetric allylic substitution reactions have been demonstrated to be powerful methods for enantioselective formation of C-C and C-X (X = O, N, S, etc.) bonds. However, the scope of these processes has been explored mainly using soft carbon nucleophiles, some hard carbon nucleophiles such as enolates and preformed organometallic reagents, and heteroatom nucleophiles. Readily accessible aromatic compounds have been only rarely used directly as nucleophiles in these reactions. In this Account, we present the results of studies we have conducted aimed at the development of transition-metal-catalyzed asymmetric allylic dearomatization reactions. By utilizing this general process, we have devised methods for direct dearomatization of indoles, pyrroles, phenols, naphthols, pyridines, and pyrazines, which produce various highly functionalized structural motifs bearing all-carbon quaternary stereogenic centers in a straightforward manner. In mechanistic investigations of the dearomatization process, we found that the five-membered spiroindolenines serve as intermediates, which readily undergo stereospecific allylic migration to form corresponding tetrahydro-1H-carbazoles upon treatment with a catalytic amount of TsOH. It is worth noting that no

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

    NASA Astrophysics Data System (ADS)

    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

  9. Palladium-catalyzed Allylic Substitution with (η6-arene–CH2Z)Cr(CO)3-based Nucleophiles

    PubMed Central

    Zhang, Jiadi; Stanciu, Corneliu; Wang, Beibei; Hussain, Mahmud M.; Da, Chao-Shan; Carroll, Patrick J.; Dreher, Spencer D.; Walsh, Patrick J.

    2011-01-01

    Although the palladium-catalyzed Tsuji-Trost allylic substitution reaction has been intensively studied, there is a lack of general methods to employ simple benzylic nucleophiles. Such a method would facilitate access to “α-2-propenyl benzyl” motifs, which are common structural motifs in bioactive compounds and natural products. We report herein the palladium-catalyzed allylation reaction of toluene-derived pronucleophiles activated by tricarbonylchromium. A variety of cyclic and acyclic allylic electrophiles can be employed with in situ generated (η6-C6H5–CHLiR)Cr(CO)3 nucleophiles. Catalyst identification was performed by high throughput experimentation (HTE) and led to the Xantphos/palladium hit, which proved to be a general catalyst for this class of reactions. In addition to η6-toluene complexes, benzyl amine and ether derivatives (η6-C6H5–CH2Z)Cr(CO)3 (Z=NR2, OR) are also viable pronucleophiles, allowing C–C bond-formation alpha to heteroatoms with excellent yields. Finally, a tandem allylic substitution/demetallation procedure is described that affords the corresponding metal-free allylic substitution products. This method will be a valuable complement to the existing arsenal of nucleophiles with applications in allylic substitution reactions. PMID:22047504

  10. A DFT study on PBu3-catalyzed intramolecular cyclizations of N-allylic substituted α-amino nitriles for the formation of functionalized pyrrolidines: mechanisms, selectivities, and the role of catalysts.

    PubMed

    Zheng, Linjie; Tang, Mingsheng; Wang, Yang; Guo, Xiaokang; Wei, Donghui; Qiao, Yan

    2016-03-21

    The mechanisms and chemo- and stereo-selectivities of PBu3-catalyzed intramolecular cyclizations of N-allylic substituted α-amino nitriles leading to functionalized pyrrolidines (5-endo-trig cyclization, Mechanism A) and their competing reaction leading to another kind of pyrrolidine (5-exo-trig cyclization, Mechanism B) have been investigated using density functional theory (DFT). Multiple possible reaction pathways associated with four different isomers (RR, SR, RS, and SS) for Mechanism A, and two isomers (R and S) for Mechanism B have been studied. The calculated results indicate that the Gibbs free energy barriers of Mechanism A are remarkably lower than those of Mechanism B, and the reaction pathway leading to the RS-configured product has the lowest Gibbs free energy barrier, which is in agreement with the experiments. A C-H···π interaction has been identified to be responsible for the favorability of RS isomers by non-covalent interaction (NCI) analysis. Moreover, global reaction indexes (GRIs) and NBO analyses confirm that PBu3 acts as a Lewis base to strengthen the nucleophilicity of the reaction active site. The mechanistic insights gained in the present study should be valuable for the rational design of effective organocatalysts for this kind of reaction with high chemo- and stereo-selectivities.

  11. Transient overexpression of adh8a increases allyl alcohol toxicity in zebrafish embryos.

    PubMed

    Klüver, Nils; Ortmann, Julia; Paschke, Heidrun; Renner, Patrick; Ritter, Axel P; Scholz, Stefan

    2014-01-01

    Fish embryos are widely used as an alternative model to study toxicity in vertebrates. Due to their complexity, embryos are believed to more resemble an adult organism than in vitro cellular models. However, concerns have been raised with respect to the embryo's metabolic capacity. We recently identified allyl alcohol, an industrial chemical, to be several orders of magnitude less toxic to zebrafish embryo than to adult zebrafish (embryo LC50 = 478 mg/L vs. fish LC50 = 0.28 mg/L). Reports on mammals have indicated that allyl alcohol requires activation by alcohol dehydrogenases (Adh) to form the highly reactive and toxic metabolite acrolein, which shows similar toxicity in zebrafish embryos and adults. To identify if a limited metabolic capacity of embryos indeed can explain the low allyl alcohol sensitivity of zebrafish embryos, we compared the mRNA expression levels of Adh isoenzymes (adh5, adh8a, adh8b and adhfe1) during embryo development to that in adult fish. The greatest difference between embryo and adult fish was found for adh8a and adh8b expression. Therefore, we hypothesized that these genes might be required for allyl alcohol activation. Microinjection of adh8a, but not adh8b mRNA led to a significant increase of allyl alcohol toxicity in embryos similar to levels reported for adults (LC50 = 0.42 mg/L in adh8a mRNA-injected embryos). Furthermore, GC/MS analysis of adh8a-injected embryos indicated a significant decline of internal allyl alcohol concentrations from 0.23-58 ng/embryo to levels below the limit of detection (< 4.6 µg/L). Injection of neither adh8b nor gfp mRNA had an impact on internal allyl alcohol levels supporting that the increased allyl alcohol toxicity was mediated by an increase in its metabolization. These results underline the necessity to critically consider metabolic activation in the zebrafish embryo. As demonstrated here, mRNA injection is one useful approach to study the role of candidate enzymes involved in

  12. Iridium-Catalyzed Regioselective and Enantioselective Allylation of Trimethylsiloxyfuran

    PubMed Central

    Chen, Wenyong; Hartwig, John F.

    2012-01-01

    We report the regioselective and enantioselective allylation of an ester enolate, trimethylsiloxyfuran. This enolate reacts in the 3-position with linear aromatic allylic carbonates or aliphatic allylic benzoates to form the branched substitution products in the presence of a metallacyclic iridium catalyst. This process provides access to synthetically important 3-substituted butenolides in enantioenriched form. Stoichiometric reactions of the allyliridium intermediate imply that the trimethylsiloxyfuran is activated by the carboxylate leaving group. PMID:22954355

  13. Equilibriums between Cu, Fe, and Zn sulfides and oxides in chloride solution: A thermodynamic study

    NASA Astrophysics Data System (ADS)

    Strel'Tsova, N. I.

    2009-10-01

    The results of thermodynamic modeling of equilibriums between Cu, Fe, and Zn sulfides and oxides pertaining to the Cu-Fe-Zn-S-O2 system in water and aqueous chloride solution are presented. The system comprises solid phases of constant composition: pyrite, pyrrhotite, hematite, magnetite, wüstite, γ-iron, chalcocite, covellite, cuprite, native copper, chalcopyrite, and bornite, as well as more than 100 ions, complexes, and molecules in an aqueous solution. The GIBBS program with the UNITHERM thermodynamic dataset used in calculations allows numerical analysis of phase assemblages in a dry system and in equilibrium with an aqueous solution. How the temperature, pressure, and the composition of the solution in the system opened for oxygen and sulfur affects the composition of phase assemblages was considered in temperature and pressure ranges of 50-350 C and 100-1000 bar, respectively. Decrease in temperature leads to a shift in stability fields of the studied phases toward the region of elevated oxygen and sulfur partial pressures. Variation of temperature is an important factor affecting precipitation of ore minerals, primarily, Cu- and Zn-bearing. The calculation results are presented in tables and diagrams. Each point in the (log m_{S_{tot} } - log f_{O_2 } ) diagram is characterized by a single possible assemblage of phases equilibrated with a solution of the given composition within the considered temperature and pressure range. Since the composition of the mineral assemblage is controlled by physicochemical conditions at the moment of mineral formation, comparison of the calculation results with mineral assemblages at ore deposits makes it possible to estimate the parameters of ore deposition at the early stage of investigation, including oxygen and sulfur activity and, occasionally, the composition and salinity of the solution. These parameters control the formation of such assemblages.

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

    NASA Astrophysics Data System (ADS)

    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 H 2S from coal gas at 500 °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 CO 2, SO 2 and COS are detected by on-line FTIR spectroscopy during the initial and later stages of the sorption process. The formation of CO 2 is related to the water-shift reaction, and SO 2 is probably attributable to the reaction of organic matters and H 2S. 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 H 2S at a temperature of 500 °C.

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

    PubMed

    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.

  16. The microwave spectrum of allyl acetone

    NASA Astrophysics Data System (ADS)

    Tulimat, Layla; Mouhib, Halima; Kleiner, Isabelle; Stahl, Wolfgang

    2015-06-01

    Allyl acetone was investigated using a combination of quantum chemical calculations and molecular beam Fourier transform microwave spectroscopy. The microwave spectrum was recorded in the frequency range from 10.0 to 14.0 GHz. The most abundant conformer in the supersonic jet possesses a C1 symmetry and appears as a pair of enantiomers. The observed conformer does not correspond to the most abundant conformer observed for allyl acetate, which is structurally related to allyl acetone. Here, we report on its structure and dynamics, for which a set of highly accurate rotational and centrifugal distortion constants, as well as the barrier to internal rotation of the acetyl methyl group could be determined with high accuracy. Splittings due to the internal rotation of the methyl group of up to 360 MHz were observed in the spectrum. Using the programs XIAM and BELGI-C1, a barrier height (V3) of about 225 cm-1 as well as the other molecular parameters were determined. The results obtained from the different codes were subsequently compared to each other. Additionally, the experimental rotational constants were used to validate quantum chemical calculations at different levels of theory.

  17. Mineral-chemical studies of metamorphosed hydrothermal alteration in the Kristineberg volcanogenic massive sulfide district, Sweden

    NASA Astrophysics Data System (ADS)

    Hannington, Mark D.; Kjarsgaard, Ingrid M.; Galley, Alan G.; Taylor, Bruce

    2003-06-01

    The massive sulfide deposits of the Kristineberg area, Sweden, occur within a 2- to 3-km-thick succession of felsic volcaniclastic rocks belonging to the Skellefte Group. The volcanic pile is intruded by a synvolcanic Jorn-type granitoid (Viterliden intrusive complex) and is overlain by a thick sequence of metasedimentary rocks (Vargfors Group). Mineralization occurs at two main stratigraphic levels, at the base of the felsic volcanic succession and at the contact with the metasedimentary rocks of the Vargfors Group. The Kristineberg Cu-Zn mine is the largest deposit (approximately 21 Mt) and occurs at the base of the volcanic pile, close to the contact with the Viterliden intrusive complex. Four smaller deposits (Ravliden, Ravlidmyran, Horntrask and Nyliden) occur along the upper ore horizon. These deposits are thought to be related to a late intrusive phase of the Viterliden complex which cuts the altered volcanic rocks at the Kristineberg deposit. Within an area of about 50 km2 surrounding the Kristineberg deposit, felsic volcanic rocks between the two ore horizons are affected by extensive albite-destructive alteration (sodium depletion) and development of chlorite and muscovite (strong co-enrichment in magnesium and potassium). The Kristineberg deposit is enveloped by a large and partly transposed quartz-chlorite alteration zone, approximately 2 km in diameter, and a distal but coherent pyrite-quartz-muscovite alteration zone extending as far as 4 km from the deposit. Chlorite(±talc) in the mine area is notably magnesium-rich and contains anomalous F, Ba, Zn and Mn. High fluorine is also present in coexisting muscovite and phlogopite. The magnesium-rich chlorite alteration contrasts sharply with the iron enrichment observed in many other felsic, volcanic-hosted Precambrian massive sulfide deposits. This may indicate fixation of iron by large amounts of pyrite in the section or entrainment of large amounts of seawater in the hydrothermal upflow zones. Kyanite

  18. Assessment of DNA damage and repair in adults consuming allyl isothiocyanate or Brassica vegetables

    USDA-ARS?s Scientific Manuscript database

    Allyl isothiocyanate (AITC) is a dietary component with potentially important anti-cancer effects, though much of the information about AITC and cancer processes has been obtained from cell studies. To investigate the effect of AITC on DNA integrity and repair in vivo, a human feeding study was con...

  19. Sulfide stress corrosion study of a super martensitic stainless steel in H2S sour environments: Metallic sulfides formation and hydrogen embrittlement

    NASA Astrophysics Data System (ADS)

    Monnot, Martin; Nogueira, Ricardo P.; Roche, Virginie; Berthomé, Grégory; Chauveau, Eric; Estevez, Rafael; Mantel, Marc

    2017-02-01

    Thanks to their high corrosion resistance, super martensitic stainless steels are commonly used in the oil and gas industry, particularly in sour environments. Some grades are however susceptible to undergo hydrogen and mechanically-assisted corrosion processes in the presence of H2S, depending on the pH. The martensitic stainless steel EN 1.4418 grade exhibits a clear protective passive behavior with no sulfide stress corrosion cracking when exposed to sour environments of pH ≥ 4, but undergoes a steep decrease in its corrosion resistance at lower pH conditions. The present paper investigated this abrupt loss of corrosion resistance with electrochemical measurements as well as different physicochemical characterization techniques. Results indicated that below pH 4.0 the metal surface is covered by a thick (ca 40 μm) porous and defect-full sulfide-rich corrosion products layer shown to be straightforwardly related to the onset of hydrogen and sulfide mechanically-assisted corrosion phenomena.

  20. Characterization of porosity in sulfide ore minerals: A USANS/SANS study

    SciTech Connect

    Xia, Fang; Zhao, Jing; Etschmann, Barbara E.; Brugger, Joel; Garvey, Christopher J.; Rehm, Christine; Lemmel, Hartmut; Ilavsky, Jan; Han, Young-Soo; Pring, Allan

    2014-11-01

    Porosity plays a key role in the formation and alteration of sulfide ore minerals, yet our knowledge of the nature and formation of the residual pores is very limited. Herein, we report the application of ultra-small-angle neutron scattering and small-angle neutron scattering (USANS/SANS) to assess the porosity in five natural sulfide minerals (violarite, marcasite, pyrite, chalcopyrite, and bornite) possibly formed by hydrothermal mineral replacement reactions and two synthetic sulfide minerals (violarite and marcasite) prepared experimentally by mimicking natural hydrothermal conditions. USANS/SANS data showed very different pore size distributions for these minerals. Natural violarite and marcasite tend to possess less pores in the small size range (<100 nm) compared with their synthetic counterparts. This phenomenon is consistent with a higher degree of pore healing or diagenetic compaction experienced by the natural violarite and marcasite. Surprisingly, nanometer-sized (<20 nm) pores were revealed for a natural pyrite cube from La Rioga, Spain, and the sample has a pore volume fraction of ~7.7%. Both chalcopyrite and bornite from the massive sulfide assemblage of the Olympic Dam deposit in Roxby Downs, South Australia, were found to be porous with a similar pore volume fraction (~15%), but chalcopyrite tends to have a higher proportion of nanometer-size pores centered at ~4 nm while bornite tends to have a broader pore size distribution. The specific surface area is generally low for these minerals ranging from 0.94 to 6.28 m2/g, and the surfaces are generally rough as surface fractal behavior was observed for all these minerals. This investigation has demonstrated that USANS/SANS is a very useful tool for analyzing porosity in ore minerals. We believe that with this quantified porosity information a deeper understanding of the complex fluid flow behavior within the porous minerals can be expected.

  1. Volcanogenic Massive Sulfide Deposit Density

    USGS Publications Warehouse

    Mosier, Dan L.; Singer, Donald A.; Berger, Vladimir I.

    2007-01-01

    A mineral-deposit density model for volcanogenic massive sulfide deposits was constructed from 38 well-explored control areas from around the world. Control areas contain at least one exposed volcanogenic massive sulfide deposit. The control areas used in this study contain 150 kuroko, 14 Urals, and 25 Cyprus massive sulfide subtypes of volcanogenic massive sulfide deposits. For each control area, extent of permissive rock, number of exposed volcanogenic massive sulfide deposits, map scale, deposit age, and deposit density were determined. The frequency distribution of deposit densities in these 38 control areas provides probabilistic estimates of the number of deposits for tracts that are permissive for volcanogenic massive sulfide deposits-90 percent of the control areas have densities of 100 or more deposits per 100,000 square kilometers, 50 percent of the control areas have densities of 700 or more deposits per 100,000 square kilometers, and 10 percent of the control areas have densities of 3,700 or more deposits per 100,000 square kilometers. Both map scale and the size of the control area are shown to be predictors of deposit density. Probabilistic estimates of the number of volcanogenic massive sulfide deposits can be made by conditioning the estimates on sizes of permissive area. The model constructed for this study provides a powerful tool for estimating the number of undiscovered volcanogenic massive sulfide deposits when conducting resource assessments. The value of these deposit densities is due to the consistency of these models with the grade and tonnage and the descriptive models. Mineral-deposit density models combined with grade and tonnage models allow reasonable estimates of the number, size, and grades of volcanogenic massive sulfide deposits to be made.

  2. Glycosyl Cations versus Allylic Cations in Spontaneous and Enzymatic Hydrolysis.

    PubMed

    Danby, Phillip M; Withers, Stephen G

    2017-08-09

    Enzymatic prenyl and glycosyl transfer are seemingly unrelated reactions that yield molecules and protein modifications with disparate biological functions. However, both reactions employ diphosphate-activated donors and each proceed via cationic species: allylic cations and oxocarbenium ions, respectively. In this study, we explore the relationship between these processes by preparing valienyl ethers to serve as glycoside mimics that are capable of allylic rather than oxocarbenium cation stabilization. Rate constants for spontaneous hydrolysis of aryl glycosides and their analogous valienyl ethers were found to be almost identical, as were the corresponding activation enthalpies and entropies. This close similarity extended to the associated secondary kinetic isotope effects (KIEs), indicating very similar transition state stabilities and structures. Screening a library of over 100 β-glucosidases identified a number of enzymes that catalyze hydrolysis of these valienyl ethers with kcat values up to 20 s(-1). Detailed analysis of one such enzyme showed that ether hydrolysis occurs via the analogous mechanisms found for glycosides, and through a very similar transition state. This suggests that the generally lower rates of enzymatic cleavage of the cyclitol ethers reflects evolutionary specialization of these enzymes toward glycosides rather than inherent reactivity differences.

  3. Kinetics of the reaction of diethylene glycol bis-chloroformate with allyl alcohol

    SciTech Connect

    Alekseev, N.N.; Shtoda, N.F.; Dzumedzei, N.V.

    1988-10-01

    The kinetics of diethylene glycol bis-chloroformate solvolysis by excess allyl alcohol in toluene and carbon tetrachloride has been studied. Under conditions of a pseudofirst order reaction with respect to diethylene glycol bis-chloroformate the activation parameters confirm an addition-detachment mechanism.

  4. Pilot field-verification studies of the sodium sulfide/ferrous sulfate treatment process. Final report, September 1987-May 1988

    SciTech Connect

    Wiloff, P.M.; Suciu, D.F.; Prescott, D.S.; Schober, R.K.; Loyd, F.S.

    1988-09-01

    In previous project, jar and dynamic testing showed that the sodium sulfide/ferrous sulfate process was a viable method for reducing hexavalent chromium and removing heavy metals from the Tinker AFB industrial wastewater with significant decrease in sludge production and treatment costs. In this phase, pilot-plant field verification studies were conducted to evaluate the chemical and physical parameters of the chromium reduction process, the precipitation and clarification process, and the activated-sludge system. Sludge production was evaluated and compared to the sulfuric acid/sulfur dioxide/lime process.

  5. Sedimentary sulfides in dune sands of Spiekeroog Island, southern North Sea: A biogeochemical study of sulfur isotope partitioning

    NASA Astrophysics Data System (ADS)

    Seibert, Stephan; Schubert, Florian; Schmiedinger, Iris; Böttcher, Michael E.; Massmann, Gudrun

    2017-04-01

    The formation of iron sulfides in sandy sediments and the associated development of stable isotope signatures is still mechanistically not understood. In dune sands under impact of both fresh and saline water several physico-chemical gradients may develop leading to distinctly different biogeochemical zones. In the present study, a 10 m long core from a dune base at the North Eastern part of Spiekeroog Island, southern North Sea, was investigated for the elemental and stable isotope composition. The pyrite (TRIS) content was quantitatively extracted via an acidic Cr(II) distillation procedure and the stable sulfur isotope composition was determined by means of C-irmMS. The pore waters display a downcore increase in salt contents and a mixing between fresh and salt water. The accumulation of metabolites at depth indicate an increasing superimposition of mixing by microbial decomposition of dissolved organic matter with only limited net sulfate reduction. This indicates an essential open system with respect to dissolved sulfate. The sands were found to be very low in TOC, TIC, and TRIS and dominated by quartz minerals. Under the assumption that North Sea water sulfate was the only substantial sulfate source (d34S = + 21per mil), the sedimentary sulfides indicate an overall sulfur isotope discrimination upon microbial sulfate reduction between 39 and 52 per mil, which is within the range of results from other fully marine sands from the Spiekeroog area and laboratory studies with pure cultures of sulfate-reducing bacteria under low cellular sulfate reduction rates. Further investigations are on the way to understand the processes leading to the iron sulfide formation in these organic-poor substrates.

  6. Amination of allylic alcohols in water at room temperature.

    PubMed

    Nishikata, Takashi; Lipshutz, Bruce H

    2009-06-04

    The "trick" to carrying out regiocontrolled aminations of allylic alcohols in water as the only medium is use of a nanomicelle's interior as the organic reaction solvent. When HCO(2)Me is present, along with the proper base and source of catalytic Pd, allylic amines are cleanly formed at room temperature.

  7. Sulfide chemiluminescence detection

    DOEpatents

    Spurlin, S.R.; Yeung, E.S.

    1985-11-26

    A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

  8. Sulfide chemiluminescence detection

    DOEpatents

    Spurlin, Stanford R.; Yeung, Edward S.

    1985-01-01

    A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

  9. Origins of Enantioselectivity during Allylic Substitution Reactions Catalyzed by Metallacyclic Iridium Complexes

    PubMed Central

    Madrahimov, Sherzod T.; Hartwig, John F.

    2012-01-01

    In depth mechanistic studies of iridium catalyzed regioselective and enantioselective allylic substitution reactions are presented. A series of cyclometallated allyliridium complexes that are kinetically and chemically competent to be intermediates in the allylic substitution reactions was prepared and characterized by 1D and 2D NMR spectroscopies and solid state structural analysis. The rates of epimerization of the less thermodynamically stable diastereomeric allyliridium complexes to the thermodynamically more stable allyliridium stereoisomers were measured. The rates of nucleophilic attack by aniline and by N-methylaniline on the isolated allyliridium complexes were also measured. Attack on the thermodynamically less stable allyliridium complex was found to be orders of magnitude faster than attack on the thermodynamically more stable complex, yet the major enantiomer of the catalytic reaction is formed from the more stable diastereomer. Comparison of the rates of nucleophilic attack to the rates of epimerization of the diastereomeric allyliridium complexes containing a weakly-coordinating counterion showed that nucleophilic attack on the less stable allyliridium species is much faster than conversion of the less stable isomer to the more stable isomer. These observations imply that Curtin-Hammett conditions are not met during iridium catalyzed allylic substitution reactions by η3-η1-η3 interconversion. Rather, these data imply that when these conditions exist for this reaction, they are created by reversible oxidative addition and the high selectivity of this oxidative addition step to form the more stable diastereomeric allyl complex leads to the high enantioselectivity. The stereochemical outcome of the individual steps of allylic substitution was assessed by reaction of deuterium-labeled substrates. The reaction was shown to occur by oxidative addition with inversion of configuration, followed by an outer sphere nucleophilic attack that leads to a second

  10. Raising the pKa Limit of “Soft” Nucleophiles in Palladium-Catalyzed Allylic Substitutions. Application of Diarylmethane Pronucleophiles

    PubMed Central

    Sha, Sheng-Chun; Zhang, Jiadi; Carroll, Patrick J.

    2013-01-01

    The Tsuji-Trost allylic substitution reaction provides a useful and efficient approach to construct C-C bonds between sp3-hybridized carbons. The widely accepted paradigm for classifying the mode of attack of nucleophiles on palladium π-allyl intermediates in the Tsuji-Trost reaction is based on the pKa of the pronucleophile: (1) stabilized or “soft” carbon nucleophiles and heteroatom nucleophiles (e.g., pronucleophiles with pKa’s < 25), and (2) unstabilized or “hard” nucleophiles (those from pronucleophiles with pKa’s > 25). One of the keys to the continuing development of allylic substitution processes remains broadening the scope of “soft” nucleophiles. Herein we report a general method for the room temperature Pd-catalyzed allylic substitution with diarylmethane derivatives (pKa’s up to 32). The synthetic significance of the method is that it provides a rapid access to products containing allylated diarylmethyl motifs. The method is general for a wide range of nucleophiles derived from diarylmethanes and heterocyclic derivatives. A procedure for the Pd-catalyzed allylic substitutions to afford diallylation products with quaternary centers is also described. With triarylmethanes and, alkylated diarylmethanes the corresponding allylated products are isolated. We anticipate that the described method will be a valuable complement to the existing arsenal of nucleophiles in Pd-catalyzed allylic substitutions. Mechanistic studies show that the nucleophile derived from diphenylmethane undergoes external attack on π-allyl palladium species under our reaction conditions. This unexpected observation indicates that diarylmethane derivatives behave as “soft” or stabilized nucleophiles. The results of this study indicate that the cutoff between “soft” and “hard” nucleophiles should be raised from a pronucleophile pKa of 25 to at least 32. PMID:24147620

  11. Thermoelectric Properties of Lanthanum Sulfide

    NASA Technical Reports Server (NTRS)

    Wood, C.; Lockwood, R.; Parker, J. B.; Zoltan, A.; Zoltan, L. D.; Danielson, L.; Raag, V.

    1987-01-01

    Report describes measurement of Seebeck coefficient, electrical resistivity, thermal conductivity, and Hall effect in gamma-phase lanthanum sulfide with composition of La3-x S4. Results of study, part of search for high-temperature thermoelectric energy-conversion materials, indicate this sulfide behaves like extrinsic semiconductor over temperature range of 300 to 1,400 K, with degenerate carrier concentration controlled by stoichiometric ratio of La to S.

  12. Thermoelectric Properties of Lanthanum Sulfide

    NASA Technical Reports Server (NTRS)

    Wood, C.; Lockwood, R.; Parker, J. B.; Zoltan, A.; Zoltan, L. D.; Danielson, L.; Raag, V.

    1987-01-01

    Report describes measurement of Seebeck coefficient, electrical resistivity, thermal conductivity, and Hall effect in gamma-phase lanthanum sulfide with composition of La3-x S4. Results of study, part of search for high-temperature thermoelectric energy-conversion materials, indicate this sulfide behaves like extrinsic semiconductor over temperature range of 300 to 1,400 K, with degenerate carrier concentration controlled by stoichiometric ratio of La to S.

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

    PubMed

    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.

  14. Mineralogical studies of sulfide samples and volatile concentrations of basalt glasses from the southern Juan de Fuca Ridge.

    PubMed

    Brett, R; Evans, H T; Gibson, E K; Hedenquist, J W; Wandless, M V; Sommer, M A

    1987-10-10

    Sulfide samples obtained from the U.S. Geological Survey's DSRV Alvin dives on the southern Juan de Fuca Ridge closely resemble those from the same area described by Koski et al. (1984). Major minerals include sphalerite, wurtzite, pyrite, marcasite, isocubanite, anhydrite, and chalcopyrite. Equilibrium, if attained at all, during deposition of most sulfides was a transient event over a few tens of micrometers at most and was perturbed by rapid temperature and compositional changes of the circulating fluid. Two new minerals were found: one, a hydrated Zn, Fe hydroxy-chlorosulfate, and the other, a (Mn, Mg, Fe) hydroxide or hydroxy-hydrate. Both were formed at relatively low temperatures. Lizardite, starkeyite, and anatase were found for the first time in such an environment. Sulfide geothermometry involving the system Cu-Fe-S indicates a vent temperature of <328 degrees C for one sample. Fluid inclusion studies on crystals from the same vicinity of the same sample give pressure-corrected homogenization temperatures of 268 degrees and 285 degrees C. Ice-melting temperatures on inclusions from the same sample are about -2.8 degrees C, indicating that the equivalent salinity of the trapped fluid is about 50% greater than that of seawater. Volatile concentrations from vesicle-free basalt glass from the vent field are about 0.013 wt% CO2 and 0.16 wt% H2O, CO2 contents in these samples yield an entrapment depth of 2200 m of seawater, which is the depth from which the samples were collected.

  15. Highly Concentrated Catalytic Asymmetric Allylation of Ketones

    PubMed Central

    Wooten, Alfred J.; Kim, Jeung Gon; Walsh, Patrick J.

    2008-01-01

    We report the catalytic asymmetric allylation of ketones under highly concentrated reaction conditions with a catalyst generated from titanium tetraisopropoxide and BINOL (1:2 ratio) in the presence of isopropanol. This catalyst promotes the addition of tetraallylstannane to a variety of ketones to produce tertiary homoallylic alcohols in excellent yield (80–99%) with high enantioselectivities (79–95%). The resulting homoallylic alcohols can also be epoxidized in situ using tert-butyl hydroperoxide (TBHP) to afford cyclic epoxy alcohols in high yield (84–87%). PMID:17249767

  16. Highly concentrated catalytic asymmetric allylation of ketones.

    PubMed

    Wooten, Alfred J; Kim, Jeung Gon; Walsh, Patrick J

    2007-02-01

    [reaction: see text] We report the catalytic asymmetric allylation of ketones under highly concentrated reaction conditions with a catalyst generated from titanium tetraisopropoxide and BINOL (1:2 ratio) in the presence of isopropanol. This catalyst promotes the addition of tetraallylstannane to a variety of ketones to produce tertiary homoallylic alcohols in excellent yield (80-99%) with high enantioselectivities (79-95%). The resulting homoallylic alcohols can also be epoxidized in situ using tert-butyl hydroperoxide (TBHP) to afford cyclic epoxy alcohols in high yield (84-87%).

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

    PubMed

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

    2015-01-20

    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.

  18. Kinetic resolution of allyl fluorides by enantioselective allylic trifluoromethylation based on silicon-assisted C-F bond cleavage.

    PubMed

    Nishimine, Takayuki; Fukushi, Kazunobu; Shibata, Naoyuki; Taira, Hiromi; Tokunaga, Etsuko; Yamano, Akihito; Shiro, Motoo; Shibata, Norio

    2014-01-07

    Two birds, one stone! The first kinetic resolution of allyl fluorides was achieved by the development of an organocatalyzed enantioselective allylic trifluoromethylation. Two kinds of chiral fluorinated compounds, which incorporate C*F and C*CF3 units, respectively, can thus be accessed by a single transformation.

  19. [Studies on the structure-activity relationship of allyl substituted oxopyrimidines searching for the novel antagonist or agonist of barbiturates to the sleep mechanism based on the uridine receptor theory--barbituric acid to uridine (part I)].

    PubMed

    Yamamoto, Ikuo

    2005-01-01

    Thirty-six allyl substituted oxopyrimidine analogues such as barbituric acid (BA), barbiturates, uracil, thymine, and related derivatives including 13 new compounds were synthesized and their pharmacologic effects ([hypnotic activity, anticonvulsant activity against pentylentetrazol (PTZ)-induced seizures, and LD(50)]) and interactions with the barbiturates were evaluated in mice and rats. The results are briefly and parially summarized as follows. BA prolonged pentobarbital (PB)-induced sleep and had some central depressant effects. N,5,5-triallyl-BA exhibited some hypnotic and anticonvulsant activities, although the other 5,N-allyl-compounds did not show any activity except for allobarbital (AlloB). N-allyl-BA, 5-allyl-BA, N(1),N(3),5-triallyl-BA, N,5,5-triallyl-BA, and N(1),N(3),5,5-tetraallyl-BA also prolonged PB-induced sleep. Interestingly, N,5,5-triallyl-BA was the most potent in the interaction with AlloB, phenobarbital (PheB), amobarbital (AB), PB, and thiopental (TP) but not barbital (B). N(1),N(3),5,5-tetraallyl-BA prolonged AlloB-, PB-, and AB-induced sleep but not B-, PheB-, and TP-induced sleep. N(1),N(3),5-triallyl-B prolonged only PB- and TP-induced sleep. 5,5-diallyl-BA prolonged PheB- and TP-induced sleep. N,5-diallyl-BA prolonged only TP-induced sleep. In contrast, BA and N(1),N(3),5-triallyl-AB tended to antagonize AlloB, AB, and B. N(1),N(3),5,5-tetraallyl-BA also slightly antagonized B, PheB, and TP. 5,5-diallyl-BA antagonized only AB. The prolonging effects of BA, N,5,5-triallyl-BA, and N(1),N(3),5,5-tetraallyl-BA on PB-induced sleep were dose dependent. These results indicate that the position and number of allyl groups substituted on the structure of BA play an important role in their depressant activities. This review deals with the structure-activity relationship of allyl-substituted oxopyrimidines as part of our search for antagonists and agonists of barbiturates as well as their mechanisms of action.

  20. Metabolism, excretion, and pharmacokinetics of S-allyl-L-cysteine in rats and dogs.

    PubMed

    Amano, Hirotaka; Kazamori, Daichi; Itoh, Kenji; Kodera, Yukihiro

    2015-05-01

    The metabolism, excretion, and pharmacokinetics of S-allyl-l-cysteine (SAC), an active key component of garlic supplements, were examined in rats and dogs. A single dose of SAC was administered orally or i.v. to rats (5 mg/kg) and dogs (2 mg/kg). SAC was well absorbed (bioavailability >90%) and its four metabolites-N-acetyl-S-allyl-l-cysteine (NAc-SAC), N-acetyl-S-allyl-l-cysteine sulfoxide (NAc-SACS), S-allyl-l-cysteine sulfoxide (SACS), and l-γ-glutamyl-S-allyl-l-cysteine-were identified in the plasma and/or urine. Renal clearance values (<0.01 l/h/kg) of SAC indicated its extensive renal reabsorption, which contributed to the long elimination half-life of SAC, especially in dogs (12 hours). The metabolism of SAC to NAc-SAC, principal metabolite of SAC, was studied in vitro and in vivo. Liver and kidney S9 fractions of rats and dogs catalyzed both N-acetylation of SAC and deacetylation of NAc-SAC. After i.v. administration of NAc-SAC, SAC appeared in the plasma and its concentration declined in parallel with that of NAc-SAC. These results suggest that the rate and extent of the formation of NAc-SAC are determined by the N-acetylation and deacetylation activities of liver and kidney. Also, NAc-SACS was detected in the plasma after i.v. administration of either NAc-SAC or SACS, suggesting that NAc-SACS could be formed via both N-acetylation of SACS and S-oxidation of NAc-SAC. In conclusion, this study demonstrated that the pharmacokinetics of SAC in rats and dogs is characterized by its high oral bioavailability, N-acetylation and S-oxidation metabolism, and extensive renal reabsorption, indicating the critical roles of liver and kidney in the elimination of SAC.

  1. Pentacoordinated carboxylate π-allyl nickel complexes as key intermediates for the Ni-catalyzed direct amination of allylic alcohols.

    PubMed

    Kita, Yusuke; Sakaguchi, Hironobu; Hoshimoto, Yoichi; Nakauchi, Daisuke; Nakahara, Yasuhito; Carpentier, Jean-François; Ogoshi, Sensuke; Mashima, Kazushi

    2015-10-05

    Direct amination of allylic alcohols with primary and secondary amines catalyzed by a system made of [Ni(1,5-cyclooctadiene)2 ] and 1,1'-bis(diphenylphosphino)ferrocene was effectively enhanced by adding nBu4 NOAc and molecular sieves, affording the corresponding allyl amines in high yield with high monoallylation selectivity for primary amines and high regioselectivity for monosubstituted allylic alcohols. Such remarkable additive effects of nBu4 NOAc were elucidated by isolating and characterizing some nickel complexes, manifesting the key role of a charge neutral pentacoordinated η(3) -allyl acetate complex in the present system, in contrast to usual cationic tetracoordinated complexes earlier reported in allylic substitution reactions.

  2. Analytical and Numerical Modeling Study of Bioprotection From Zinc Toxicity in Sulfidic Systems

    NASA Astrophysics Data System (ADS)

    Schwarz, A. O.; Rittmann, B. E.

    2004-05-01

    In the context of increasing metal pollution, it is important to understand the role microbes play at metals-contaminated sites, particularly, in metal detoxification and immobilization. Bioprotection is a community relationship in which one microbial type protects a community by reducing the bioavailability of a toxic metal and, in return, receives a key community service (e.g., substrate) from other members. Bioprotection should be key in shaping community structure and function at metals-contaminated sites; moreover, induction of pore-water metal gradients should be a key microbial metal-resistance and bioprotection mechanism. Within a complex microbial community, sulfate-reducing bacteria (SRB) are outstanding candidates for providing bioprotection to the entire community, because they provide passive metal protection by producing sulfide, which forms sparingly soluble complexes with many toxic metals (e.g., Ni, Zn, Cd, Pb, Cu, and Hg). Additionally, SRB can also effect the direct and indirect reductive precipitation of metals (e.g., Cr and U). In order to understand how bioprotection from Zn toxicity ought to work in sulfidic systems, we describe the biogeochemistry of sulfidic systems, including stoichiometry and kinetics of reactive ligand (e.g., sulfide and functional groups of extracellular polymeric substances (EPS)) generation, Zn speciation, and Zn bioavailability and toxic response. Importantly, we use the biogeochemical portrayal possible with an expanded version of the numerical model CCBATCH to examine the effect of coupling one-dimensional steady-state groundwater flow with equilibrium- and kinetic-based reactions relevant when a microbial community and metals are present together. Analytical and numerical solutions to differential mass balances are the two key tools we exploit to test the bioprotection concepts. In this presentation, we describe how we use analytical solutions to derive metal-resistance criteria for two sulfidic systems: permeable

  3. Allyl 4-hydroxy­phenyl carbonate

    PubMed Central

    Flores Ahuactzin, Víctor Hugo; López, Delia; Bernès, Sylvain

    2009-01-01

    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 (10)ratio. 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. PMID:21582877

  4. Novel C2-symmetric planar chiral diphosphine ligands and their application in pd-catalyzed asymmetric allylic substitutions.

    PubMed

    Liu, Delong; Xie, Fang; Zhang, Wanbin

    2007-08-31

    Novel C(2)-symmetric diphosphine ligands possessing only the planar chirality of ruthenocene, 1,1'-bis(diphenylphosphino)-2,2'-disubstituted-ruthenocenes (4), were prepared. With this kind of ligands, excellent enantioselectivity and especially highly catalytic activity in palladium-catalyzed asymmetric allylic substitutions of rac-1,3-diphenyl-2-propenyl acetate (9) were observed, compared to their ferrocene analogues 1. Good enantioselectivity and highly catalytic activity were also obtained with 4 in palladium-catalyzed asymmetric allylic substitutions of cyclohexen-1-yl acetate (12). Further study on the effect of R in ester group on enantioselectivity of 4 showed an opposite trend compared with their ferrocene analogues 1 in asymmetric allylic substitutions. For ruthenocene ligands 4, the one with the smaller R in the ester group gave higher enantioselectivity for the palladium-catalyzed asymmetric allylic substitutions of 9, while a converse trend had been observed with 1. However, for the palladium-catalyzed asymmetric allylic substitutions of 12, ligand 4 with a larger R in the ester group resulted in somewhat higher enantioselectivity but still an opposite trend with ligand 1. The X-ray diffraction study of crystal structures of 4 and 1 with Pd(II) was carried out and showed that the enantioselectivity was correlated to the twist angle existing in the palladium complex.

  5. Diaza [1,4] Wittig-type rearrangement of N-allylic-N-Boc-hydrazines into γ-amino-N-Boc-enamines.

    PubMed

    Tayama, Eiji; Kobayashi, Yoshiaki; Toma, Yuka

    2016-08-18

    Diaza [1,4] Wittig-type rearrangement of N-allylic-N-Boc-hydrazines into γ-amino-N-Boc-enamines was demonstrated. The scope and limitation, experimental mechanistic studies, and a proposed reaction mechanism were also described.

  6. Chemical Kinetics of Hydrogen Atom Abstraction from Allylic Sites by (3)O2; Implications for Combustion Modeling and Simulation.

    PubMed

    Zhou, Chong-Wen; Simmie, John M; Somers, Kieran P; Goldsmith, C Franklin; Curran, Henry J

    2017-03-09

    calculated in this work have also been used in predicting the reactivity of the target fuels of 1-butene, 2-butene, isobutene, 2-methylfuran, 2,5-dimethylfuran, and toluene, and the results show that the ignition delay times for those fuels have been increased by a factor of 1.5-3. This work provides a first systematic study of one of the key initiation reaction for compounds containing allylic hydrogen atoms.

  7. Genome Wide Association Mapping in Arabidopsis thaliana Identifies Novel Genes Involved in Linking Allyl Glucosinolate to Altered Biomass and Defense

    PubMed Central

    Francisco, Marta; Joseph, Bindu; Caligagan, Hart; Li, Baohua; Corwin, Jason A.; Lin, Catherine; Kerwin, Rachel E.; Burow, Meike; Kliebenstein, Daniel J.

    2016-01-01

    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. PMID:27462337

  8. Genome Wide Association Mapping in Arabidopsis thaliana Identifies Novel Genes Involved in Linking Allyl Glucosinolate to Altered Biomass and Defense.

    PubMed

    Francisco, Marta; Joseph, Bindu; Caligagan, Hart; Li, Baohua; Corwin, Jason A; Lin, Catherine; Kerwin, Rachel E; Burow, Meike; Kliebenstein, Daniel J

    2016-01-01

    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.

  9. Mössbauer study of electrochemically deposited amorphous iron-sulfide-oxide thin films

    NASA Astrophysics Data System (ADS)

    Ichimura, Masaya; Kajima, Takahiro; Kawai, Shoichi; Mibu, Ko

    2016-03-01

    Iron-sulfide-oxide thin films, which are promising candidates for solar cell materials, were deposited by electrochemical deposition. As-deposited and annealed films were characterized by Mössbauer spectroscopy, X-ray diffraction (XRD), and Raman scattering at room temperature. The as-deposited film is amorphous, and the oxygen content is about 1/4 of the sulfur content (S/Fe ≈ 1.5, O/Fe ≈ 0.4). The Mössbauer spectrum for the as-deposited film is a doublet with a broad line profile having hyperfine parameters similar to those of FeS2 pyrite or marcasite. This indicates that Fe atoms are in the Fe2+ low-spin state, as in FeS2.

  10. 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.

    PubMed

    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.

  11. Iridium(I)-Catalyzed Regio- and Enantioselective Allylic Amidation

    PubMed Central

    Singh, Om V.; Han, Hyunsoo

    2009-01-01

    Ir(I)-catalyzed intermolecular allylic amidation of ethyl allylic carbonates with soft nitrogen nucleophiles under completely “salt-free” conditions is described. A combination of [Ir(COD)Cl]2, a chiral phosphoramidite ligand L*, and DBU as a base in THF effects the reaction. The reaction appears to be quite general, accommodating a wide variety of R-groups and soft nitrogen nucleophiles, and proceeds with excellent regio- and enantioselectivities to afford the branched N-protected allylic amines. The developed reaction was conveniently utilized in the asymmetric synthesis of Boc protected α- and β-amino acids as well as (−)-cytoxazone. PMID:19554202

  12. Palladium-catalyzed asymmetric synthesis of allylic fluorides.

    PubMed

    Katcher, Matthew H; Doyle, Abigail G

    2010-12-15

    The enantioselective fluorination of readily available cyclic allylic chlorides with AgF has been accomplished using a Pd(0) catalyst and Trost bisphosphine ligand. The reactions proceed with unprecedented ease of operation for Pd-mediated nucleophilic fluorination, allowing access to highly enantioenriched cyclic allylic fluorides that bear diverse functional groups. Evidence that supports a mechanism in which C-F bond formation occurs by an S(N)2-type attack of fluoride on a Pd(II)-allyl intermediate is presented.

  13. Can the hemoglobin characteristics of vesicomyid clam species influence their distribution in deep-sea sulfide-rich sediments? A case study in the Angola Basin

    NASA Astrophysics Data System (ADS)

    Decker, C.; Zorn, N.; Le Bruchec, J.; Caprais, J. C.; Potier, N.; Leize-Wagner, E.; Lallier, F. H.; Olu, K.; Andersen, A. C.

    2017-08-01

    Vesicomyids live in endosymbiosis with sulfur-oxidizing bacteria and therefore need hydrogen sulfide to survive. They can nevertheless live in a wide range of sulfide and oxygen levels and depths, which may explain the exceptional diversity of this clam family in deep-sea habitats. In the Gulf of Guinea, nine species of vesicomyid clams are known to live in cold-seep areas with pockmarks from 600 to 3200 m deep, as well as in the organic-rich sediments of the Congo deep-sea fan at 5000 m deep. Our previous study showed that two species living in a giant pockmark have different oxygen carriers, suggesting different adaptations to hypoxia. Here, we studied the hemoglobin structure and oxygen affinity in three other species, Calyptogena valdiviae, Elenaconcha guiness and Abyssogena southwardae to determine whether the characteristics of their oxygen carriers contribute to their distribution in sulfide-rich sediments at a regional scale. Documenting pairwise species associations in various proportions, we give a semi-quantitative account of their local distribution and oxygen and sulfide measurements at seven sites. Mass spectrometry showed that each vesicomyid species has four intracellular monomeric hemoglobin molecules of 15-16 kDa, all differing in their molecular mass. As expected, the monomers showed no cooperativity in oxygen binding. Their oxygen affinities were very high (below 1 Torr), but differed significantly. C. valdiviae had the highest affinity and was dominant in the Harp pockmark, the site with the lowest oxygen content (half the value of fully oxygenated water). A. southwardae dominated in the Congo Lobe area, the site with the deepest sulfides. We discuss how hemoglobin may favor an active, vertical distribution of vesicomyids in sulfide-rich sediments.

  14. Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism

    SciTech Connect

    Bai, Da -Chang; Yu, Fei -Le; Wang, Wan -Ying; Chen, Di; Li, Hao; Liu, Qing -Rong; Ding, Chang -Hua; Chen, Bo; Hou, Xue -Long

    2016-06-10

    The palladium-catalysed allylic substitution reaction is one of the most important reactions in transition-metal catalysis and has been well-studied in the past decades. Most of the reactions proceed through an outer-sphere mechanism, affording linear products when monosubstituted allyl reagents are used. Here, we report an efficient Palladium-catalysed protocol for reactions of beta-substituted ketones with monosubstituted allyl substrates, simply by using N-heterocyclic carbene as ligand, leading to branched products with up to three contiguous stereocentres in a (syn, anti)-mode with excellent regio and diastereoselectivities. The scope of the protocol in organic synthesis has been examined preliminarily. As a result, mechanistic studies by both experiments and density functional theory ( DFT) calculations reveal that the reaction proceeds via an inner-sphere mechanism-nucleophilic attack of enolate oxygen on Palladium followed by C-C bond-forming [3,3']-reductive elimination.

  15. Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism

    PubMed Central

    Bai, Da-Chang; Yu, Fei-Le; Wang, Wan-Ying; Chen, Di; Li, Hao; Liu, Qing-Rong; Ding, Chang-Hua; Chen, Bo; Hou, Xue-Long

    2016-01-01

    The palladium-catalysed allylic substitution reaction is one of the most important reactions in transition-metal catalysis and has been well-studied in the past decades. Most of the reactions proceed through an outer-sphere mechanism, affording linear products when monosubstituted allyl reagents are used. Here, we report an efficient Palladium-catalysed protocol for reactions of β-substituted ketones with monosubstituted allyl substrates, simply by using N-heterocyclic carbene as ligand, leading to branched products with up to three contiguous stereocentres in a (syn, anti)-mode with excellent regio and diastereoselectivities. The scope of the protocol in organic synthesis has been examined preliminarily. Mechanistic studies by both experiments and density functional theory (DFT) calculations reveal that the reaction proceeds via an inner-sphere mechanism—nucleophilic attack of enolate oxygen on Palladium followed by C–C bond-forming [3,3']-reductive elimination. PMID:27283477

  16. Experimental Study of Copper Isotope Fractionation During the Formation of Cu and Cu-Fe Sulfides in Aqueous Solutions at 40-200 °C

    NASA Astrophysics Data System (ADS)

    Pekala, M.; Asael, D.; Butler, I. B.; Matthews, A.; Rickard, D.

    2009-12-01

    Natural Cu and Cu-Fe sulfides show significant Cu fractionation. In order to interpret these data an improved understanding of the major Cu isotope fractionation processes is required. Here we report laboratory experiments aimed at elucidating processes involved in Cu isotope distribution in Cu sulfides. Progressive replacement of Fe sulfides by Cu-Fe and Cu sulfides has been widely reported from a range of magmatic, hydrothermal and sedimentary deposits, and may sometimes lead to economically relevant Cu accumulations such as in the Kupferschiefer of SW Poland [1]. This replacement sequence is commonly observed in deep sea floor hydrothermal vents where massive Cu-Fe sulfide mineralisation is found [5,6]. Experimental investigations [2,3,4] have demonstrated that this type of mineral replacement is developed during the reaction of Fe sulfides (pyrrhotite and pyrite) with Cu(II)-rich aqueous solutions. Fractionation of Cu isotopes during the reaction of Fe sulfides (natural crystals of pyrrhotite and pyrite) with Cu(II) sulfate solutions was studied under anoxic conditions. It was observed that the original Fe sulfides were replaced by Cu-Fe and Cu sulfides. The effect of temperature (40-200 °C) and reaction extent (10-100 %) were investigated. Cu isotope ratios were determined in the Cu(II) solutions and in the corresponding mineral phases by sector field multicollector inductively coupled plasma mass spectrometry. Measured Cu(II) solution-Cu sulfide fractionation factors (in excess of 2 ‰) show substantial Cu isotope fractionation accompanying the reaction of Fe sulfides with Cu(II) solutions. The data points to a kinetic fractionation process that favours the transfer of the lighter Cu isotope into the mineral phase. The extent of Cu isotope fractionation resulting from this alteration process is of a similar order to fractionation observed during direct CuS precipitation from Cu(II)aq and S(-II)aq [7]. This suggests that Cu(II)-Cu(I) reduction, that proceeds

  17. Experimental study of copper isotope fractionation during the formation of Cu and Cu-Fe sulfides in aqueous solutions at 40-200 °C.

    NASA Astrophysics Data System (ADS)

    Pekala, Marek; Asael, Dan; Butler, Ian B.; Matthews, Alan; Rickard, David

    2010-05-01

    Natural Cu and Cu-Fe sulfides show significant Cu fractionation. In order to interpret these data an improved understanding of the major Cu isotope fractionation processes is required. Here we report laboratory experiments aimed at elucidating processes involved in Cu isotope distribution in Cu sulfides. Progressive replacement of Fe sulfides by Cu-Fe and Cu sulfides has been widely reported from a range of magmatic, hydrothermal and sedimentary deposits, and may sometimes lead to economically relevant Cu accumulations such as in the Kupferschiefer of SW Poland [1]. This replacement sequence is commonly observed in deep sea floor hydrothermal vents where massive Cu-Fe sulfide mineralisation is found [2,3]. Experimental investigations [4,5,6] have demonstrated that this type of mineral replacement is developed during the reaction of Fe sulfides (pyrrhotite and pyrite) with Cu(II)-rich aqueous solutions. Fractionation of Cu isotopes during the reaction of Fe sulfides (natural crystals of pyrrhotite and pyrite) with Cu(II) sulfate solutions was studied under anoxic conditions. It was observed that the original Fe sulfides were replaced by Cu-Fe and Cu sulfides. The effect of temperature (40-200 °C) and reaction extent (10-100 %) were investigated. Cu isotope ratios were determined in the Cu(II) solutions and in the corresponding mineral phases by sector field multicollector inductively coupled plasma mass spectrometry. Measured Cu(II) solution-Cu sulfide fractionation factors (in excess of 2 permil) show substantial Cu isotope fractionation accompanying the reaction of Fe sulfides with Cu(II) solutions. The data points to a kinetic fractionation process that favours the transfer of the lighter Cu isotope into the mineral phase. The extent of Cu isotope fractionation resulting from this alteration process is of a similar order to fractionation observed during direct CuS precipitation from Cu(II)aq and S(-II)aq [7]. This suggests that Cu(II)-Cu(I) reduction, that

  18. Laboratory studies of Aedes aegypti (L.) attraction to ketones, sulfides and primary chloroalkanes tested alone and in combination with l-lactic acid

    USDA-ARS?s Scientific Manuscript database

    The attraction of female Aedes aegypti to single compounds and binary compositions comprised of L-lactic acid and an additional saturated compound from a set of ketones, sulfides, and chloroalkanes was studied using a triple-cage dual-port olfactometer. These chemical classes were studied because o...

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

    SciTech Connect

    Rajamani, S.

    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.

  20. Regio- and stereospecific rhodium-catalyzed allylic alkylation with an acyl anion equivalent: an approach to acyclic α-ternary β,γ-unsaturated aryl ketones.

    PubMed

    Turnbull, Ben W H; Chae, Jungha; Oliver, Samuel; Evans, P Andrew

    2017-05-01

    The regio- and stereospecific rhodium-catalyzed allylic alkylation of secondary allylic carbonates with cyanohydrin pronucleophiles facilitates the direct construction of acyclic α-ternary β,γ-unsaturated aryl ketones. Interestingly, this study illustrates the impact of deaggregating agents on regiocontrol and the electronic nature of the aryl component to suppress olefin isomerization. In addition, we demonstrate that the dimethylamino substituent, which modulates the pKa of the α-ternary β,γ-unsaturated aryl ketone, provides a useful synthetic handle for further functionalization via Kumada cross-coupling of the aryl trimethylammonium salt. Finally, the stereospecific alkylation of a chiral nonracemic secondary allylic carbonate affords the enantioenriched α-ternary aryl ketone, which was employed in a formal synthesis of trichostatic acid to illustrate that the allylic alkylation proceeds with net retention of configuration.

  1. Infrared reflection absorption spectroscopic studies on the adsorption structures of dimethyl sulfide and methyl ethyl sulfide on Ag(1 1 0) and Cu(1 1 0)

    NASA Astrophysics Data System (ADS)

    Kasahara, T.; Shinohara, H.; Oshima, Y.; Kadokura, K.; Uriu, Y.; Ohe, C.; Itoh, K.

    2004-06-01

    Infrared reflection absorption (IRA) spectra were measured for dimethyl sulfide (CH 3SCH 3, DMS) and methyl ethyl sulfide (CH 3SCH 2CH 3, MES) with increasing exposure to metal substrates, Ag(1 1 0) and Cu(1 1 0), at 80 K. The spectral simulations performed by using the DFT calculation at the B3LYP/6-311++G** level indicated that (i) DMS adsorbs on the substrates with the CSC plane appreciably tilted from the surface normal, the tilt angle being about 80° for the adsorbate on Ag(1 1 0) and about 60° for the adsorbate on Cu(1 1 0), (ii) MES on Ag(1 1 0) at a submonolayer coverage state takes on the trans form with the molecular plane tilted from the surface normal by about 60°, and (iii) MES on Cu(1 1 0) takes the gauche form with the CSC plane almost perpendicular to the surface. The tilting of DMS is contrasted to dimethyl ether (DME) adsorbs on Ag(1 1 0) and Cu(1 1 0), where the molecular plane is perpendicular to the substrate surfaces [J. Phys. Chem. B 106 (2002) 3469]. The adsorption structures of DMS and DME are mainly determined by the coordination of the sulfur and oxygen atoms, the sulfur atom tending to coordinate to the Ag and Cu atoms through one of the 3p lone pairs (atop coordination) and the oxygen atom to the metal atoms through both of the 2p lone pairs (bridging coordination). It has been known that methyl ethyl ether (MEE) on Ag(1 1 0) takes on the trans form with the molecular plane tilted by about 45° and MEE on Cu(1 1 0) the gauche form with the COC plane almost perpendicular to the surface [J. Phys. Chem. B 107 (2003) 5008]. These results suggest that an attractive van der Waals interaction between the ethyl group of the adsorbates and the substrate surfaces play an important role in addition to the coordination of the sulfur and oxygen atoms in determining the rotational isomerism and orientation of MES and MEE on Ag(1 1 0) and Cu(1 1 0).

  2. Cadmium sulfide membranes

    DOEpatents

    Spanhel, Lubomir; Anderson, Marc A.

    1992-07-07

    A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.

  3. Cadmium sulfide membranes

    DOEpatents

    Spanhel, Lubomir; Anderson, Marc A.

    1991-10-22

    A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.

  4. SULFIDE MINERALS IN SEDIMENTS

    EPA Science Inventory

    The formation processes of metal sulfides in sediments, especially iron sulfides, have been the subjects of intense scientific research because of linkages to the global biogeochemical cycles of iron, sulfur, carbon, and oxygen. Transition metal sulfides (e.g., NiS, CuS, ZnS, Cd...

  5. SULFIDE MINERALS IN SEDIMENTS

    EPA Science Inventory

    The formation processes of metal sulfides in sediments, especially iron sulfides, have been the subjects of intense scientific research because of linkages to the global biogeochemical cycles of iron, sulfur, carbon, and oxygen. Transition metal sulfides (e.g., NiS, CuS, ZnS, Cd...

  6. Direct, Intermolecular, Enantioselective, Iridium-Catalyzed Allylation of Carbamates to Form Carbamate-Protected, Branched Allylic Amines

    PubMed Central

    Weix, Daniel J.; Marković, Dean; Ueda, Mitsuhiro; Hartwig, John F.

    2009-01-01

    The direct reaction between carbamates and achiral allylic carbonates to form branched, conveniently protected primary allylic amines with high regioselectivity and enantioselectivity is reported. This process occurs without base or with 0.5 equiv K3PO4 in the presence of a metalacyclic iridium catalyst containing a labile ethylene ligand. The reactions of aryl, heteroaryl and alkyl-substituted allylic carbonates with BocNH2, FmocNH2, CbzNH2, TrocNH2, TeocNH2, and 2-oxazolidinone occur in good yields, with high selectivity for the branched isomer, and high enantioselectivities (98% average ee). PMID:19552468

  7. Direct, intermolecular, enantioselective, iridium-catalyzed allylation of carbamates to form carbamate-protected, branched allylic amines.

    PubMed

    Weix, Daniel J; Marković, Dean; Ueda, Mitsuhiro; Hartwig, John F

    2009-07-02

    The direct reaction between carbamates and achiral allylic carbonates to form branched, conveniently protected primary allylic amines with high regioselectivity and enantioselectivity is reported. This process occurs without base or with 0.5 equiv K(3)PO(4) in the presence of a metalacyclic iridium catalyst containing a labile ethylene ligand. The reactions of aryl-, heteroaryl-, and alkyl-substituted allylic carbonates with BocNH(2), FmocNH(2), CbzNH(2), TrocNH(2), TeocNH(2), and 2-oxazolidinone occur in good yields, with high selectivity for the branched isomer and high enantioselectivities (98% average ee).

  8. Silicon-directed rhenium-catalyzed allylic carbaminations and oxidative fragmentations of γ-silyl allylic alcohols.

    PubMed

    Chavhan, Sanjay W; Cook, Matthew J

    2014-04-22

    A highly regioselective allylic substitution of β-silyl allylic alcohols has been achieved that provides the branched isomer as a single product. This high level of regiocontrol is achieved through the use of a vinyl silane group that can perform a Hiyama coupling providing 1,3-disubstituted allylic amines. An unusual oxidative fragmentation product was also observed at elevated temperature that appears to proceed by a Fleming-Tamao-type oxidation-elimination pathway. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Chewing gum containing allyl isothiocyanate from mustard seed extract is effective in reducing volatile sulfur compounds responsible for oral malodor.

    PubMed

    Tian, Minmin; Hanley, Anthony Bryan; Dodds, Michael W J; Yaegaki, Ken

    2013-08-01

    To evaluate the in vivo effect of chewing gum containing allyl isothiocyanate alone, and in combination with zinc salts on reduction of the level of volatile sulfur compounds responsible for oral malodor. 15 healthy volunteers between the ages of 20-50 chewed either an experimental gum or a placebo gum for 12 minutes. Their mouth air was analyzed for volatile sulfur compounds by a gas chromatograph at baseline, immediately after chewing, and at 60, 120 and 180 minutes after treatment. The study revealed that allyl isothiocyanate, a constituent of mustard seed extract, can effectively reduce the concentration of volatile sulfur compounds in mouth air. Chewing gum containing 0.1% zinc lactate and 0.01% of allyl isothiocyanate eliminated 89%, 55.5%, 48% and 24% of the total VSC concentration immediately after chewing and at 1, 2, and 3 hours after chewing, respectively.

  10. Time- and frequency-resolved photoionisation of the allyl radical

    PubMed

    Schultz; Clarke; Gilbert; Deyerl; Fischer

    2000-01-01

    We report picosecond time-resolved pump-probe photoelectron spectra of the allyl radical, C3H5, and the fully deuterated allyl, C3D5, carried out in order to elucidate the primary photophysical processes upon UV excitation. It is shown that the UV bands of allyl decay in a two-step process: the first step is an internal conversion to the lower-lying A-state within 20 ps or less, while the second step is a very fast decay from the A-state to the electronic ground state through a conical intersection. In addition we report the first zero kinetic energy (ZEKE) photoelectron spectrum of allyl, yielding an ionisation energy of 65762 cm-1.

  11. The zeolite mediated isomerization of allyl phenyl ether

    NASA Astrophysics Data System (ADS)

    Pebriana, R.; Mujahidin, D.; Syah, Y. M.

    2017-04-01

    Allyl phenyl ether is an important starting material in organic synthesis that has several applications in agrochemical industry. The green transformation of allyl phenyl ether assisted by heterogeneous catalyst is an attractive topic for an industrial process. In this report, we investigated the isomerization of allyl phenyl ether by heating it in zeolite H-ZSM-5 and Na-ZSM-5. The conversion of allyl phenyl ether (neat) in H-ZSM-5 was 67% which produced 40% of 2-allylphenol, 17% of 2-methyldihydrobenzofuran, and other product (4:1.7:1), while in Na-ZSM-5 produced exclusively 2-allylphenol with 52% conversion. These results showed that zeolite properties can be tuned to give a selective transformation by substitution of metal ion into the zeolite interior.

  12. Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase.

    PubMed

    Mishanina, Tatiana V; Yadav, Pramod K; Ballou, David P; Banerjee, Ruma

    2015-10-09

    The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be -123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation.

  13. NMR studies of chiral P,S-chelate platinum, rhodium, and iridium complexes and the X-ray structure of a palladium(II) allyl derivative

    SciTech Connect

    Albinati, A.; Eckert, J.; Pregosin, P.; Ruegger, H.; Salzmann, R.; Stoessel, C.

    1997-02-18

    Several Rh(I), Ir(III), and Pt(II) complexes of the chiral P,S-bidentate ligand 2 have been prepared and characterized. Detailed two-dimensional NMR studies show that (i) the boat-type chelate ring and the stereogenic sulfur center can invert rapidly at ambient temperature and (ii) the sulfur donor may dissociate, essentially destroying the chiral pocket. The solid-state structure of [Pt({eta}{sup 3}-C{sub 3}H{sub 5})(2)]PF{sub 6} (3) has been determined and the sulfur substituent shown to have an axial orientation. The six-membered chelate ring takes up a boat-like conformation. As shown by an X-ray diffraction study for 3, and via incoherent inelastic neutron scattering (IINS) measurements for the Pd analog, 4, the OH group is remote from the metal atom. 42 refs., 11 figs., 6 tabs.

  14. Highly Stereoselective Intermolecular Haloetherification and Haloesterification of Allyl Amides

    PubMed Central

    Soltanzadeh, Bardia; Jaganathan, Arvind; Staples, Richard J.

    2016-01-01

    An organocatalytic and highly regio-, diastereo-, and enantioselective intermolecular haloetherification and haloesterification reaction of allyl amides is reported. A variety of alkene substituents and substitution patterns are compatible with this chemistry. Notably, electronically unbiased alkene substrates exhibit exquisite regio- and diastereoselectivity for the title transformation. We also demonstrate that the same catalytic system can be used in both chlorination and bromination reactions of allyl amides with a variety of nucleophiles with little or no modification. PMID:26110812

  15. Palladium-catalyzed allylic C-H fluorination.

    PubMed

    Braun, Marie-Gabrielle; Doyle, Abigail G

    2013-09-04

    The first catalytic allylic C-H fluorination reaction using a nucleophilic fluoride source is reported. Under the influence of a Pd/Cr cocatalyst system, simple olefin substrates undergo fluorination with Et3N·3HF in good yields with high branched:linear regioselectivity. The mild conditions and broad scope make this reaction a powerful alternative to established methods for the preparation of allylic fluorides from prefunctionalized substrates.

  16. A SeCSe-Pd(II) pincer complex as a highly efficient catalyst for allylation of aldehydes with allyltributyltin.

    PubMed

    Yao, Qingwei; Sheets, Matthew

    2006-07-07

    An air- and moisture-stable SeCSe-Pd(II) pincer complex was synthesized and found to catalyze the nucleophilic allylation of aldehydes with allyltributyltin. The allylation of a variety of aromatic and aliphatic aldehydes to give the corresponding homoallyl alcohols was performed at room temperature to 60 degrees C in yields ranging from 50% (for typical aliphatic aldehydes) to up to 97% (for aromatic aldehydes) using 5 x 10(-3) to 1 mol % of the Pd catalyst. NMR spectroscopic study indicated that a sigma-allylpalladium intermediate was formed and possibly functions as the nucleophilic species that undergoes addition to the aldehydes.

  17. General allylic C-H alkylation with tertiary nucleophiles.

    PubMed

    Howell, Jennifer M; Liu, Wei; Young, Andrew J; White, M Christina

    2014-04-16

    A general method for intermolecular allylic C-H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium(II)/bis(sulfoxide) catalysis. Allylic C-H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C-H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C-H reactivity are illustrated in an allylic C-H alkylation/Diels-Alder reaction cascade: a reactive diene is generated via intermolecular allylic C-H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids.

  18. Influence of extracellular calcium on allyl alcohol-induced hepatotoxicity.

    PubMed

    Strubelt, O; Younes, M; Pentz, R

    1986-07-01

    The role of calcium in allyl alcohol-induced hepatotoxicity was investigated in the isolated haemoglobin-free perfused rat liver. At a Ca++ concentration of 2.5 mmol/l in the perfusate, allyl alcohol (initial concentration 1.17 mmol/l) produced an enhanced release of GPT and SDH from the liver, an increase in the lactate/pyruvate ratio of the perfusate, a decrease in hepatic oxygen consumption and an increase of both hepatic calcium and malondialdehyde content. In the absence of Ca++ in the perfusate, no hepatic calcium accumulation occurred with allyl alcohol, but all other signs of hepatic damage were as severe as with 2.5 mmol/l Ca++. On the other hand, high extracellular Ca++ (5 mmol/l) alone led to a threefold increase of liver calcium but produced only marginal hepatotoxicity and only slightly enhanced the hepatotoxic effects of allyl alcohol. The concentrations of allyl alcohol in the perfusate were not altered at different Ca++ concentrations. In conclusion, the primary allyl alcohol-induced hepatotoxic injury does not appear to depend upon an influx of extracellular calcium.

  19. Iron(III) [bond] Salen complexes as enzyme models: mechanistic study of oxo(salen)iron complexes oxygenation of organic sulfides.

    PubMed

    Sivasubramanian, Veluchamy Kamaraj; Ganesan, Muniyandi; Rajagopal, Seenivasan; Ramaraj, Ramasamy

    2002-03-08

    The oxidation of a series of para-substituted phenyl methyl sulfides was carried out with several oxo(salen)iron (salen = N,N'-bis(salicylidine)ethylenediaminato) complexes in acetonitrile. The oxo complex [O=Fe(IV)(salen)](*+), generated from an iron(III) [bond] salen complex and iodosylbenzene, effectively oxidizes the organic sulfides to the corresponding sulfoxides. The formation of [O [double bond] Fe(IV)(salen)](*+) as the active oxidant is supported by resonance Raman studies. The kinetic data indicate that the reaction is first-order in the oxidant and fractional-order with respect to sulfide. The observed saturation kinetics of the reaction and spectral data indicate that the substrate binds to the oxidant before the rate-controlling step. The rate constant (k) values for the product formation step determined using Michaelis-Menten kinetics correlate well with Hammett sigma constants, giving reaction constant (rho) values in the range of -0.65 to -1.54 for different oxo(salen)iron complexes. The log k values observed in the oxidation of each aryl methyl sulfide by substituted oxo(salen)iron complexes also correlate with Hammett sigma constants, giving positive rho values. The substituent effect, UV-vis absorption, and EPR spectral studies indicate oxygen atom transfer from the oxidant to the substrate in the rate-determining step.

  20. (E)-4-(3-(3,5-dimethoxyphenyl)allyl)-2-methoxyphenol inhibits growth of colon tumors in mice.

    PubMed

    Zheng, Jie; Park, Mi Hee; Son, Dong Ju; Choi, Min Gi; Choi, Jeong Soon; Nam, Kyung Tak; Kim, Hae Deun; Rodriguez, Kevin; Gann, Benjamin; Ham, Young Wan; Han, Sang Bae; Hong, Jin Tae

    2015-12-08

    In our previous study, we found that (E)-2,4-bis(p-hydroxyphenyl)-2-butenal showed anti-cancer effect, but it showed lack of stability and drug likeness. We have prepared several (E)-2,4-bis(p-hydroxyphenyl)-2-butenal analogues by Heck reaction. We selected two compounds which showed significant inhibitory effect of colon cancer cell growth. Thus, we evaluated the anti-cancer effects and possible mechanisms of one compound (E)-4-(3-(3,5-dimethoxyphenyl)allyl)-2-methoxyphenol in vitro and in vivo. In this study, we found that (E)-4-(3-(3,5-dimethoxyphenyl)allyl)-2-methoxyphenol induced apoptotic cell death in a dose dependent manner (0-15 μg/ml) through activation of Fas and death receptor (DR) 3 in HCT116 and SW480 colon cancer cell lines. Moreover, the combination treatment with (E)-4-(3-(3,5-dimethoxyphenyl)allyl)-2-methoxyphenol and nuclear factor κB (NF-κB) inhibitor, phenylarsine oxide (0.1 μM) or signal transducer and activator of transcription 3 (STAT3) inhibitor, Stattic (50 μM) increased the expression of Fas and DR3 more significantly. In addition, (E)-4-(3-(3,5-dimethoxyphenyl)allyl)-2-methoxyphenol suppressed the DNA binding activity of both STAT3 and NF-κB. Knock down of STAT3 or NF-κB p50 subunit by STAT3 small interfering RNA (siRNA) or p50 siRNA magnified (E)-4-(3-(3,5-dimethoxyphenyl)allyl)-2-methoxyphenol-induced inhibitory effect on colon cancer cell growth. Besides, the expression of Fas and DR3 was increased in STAT3 siRNA or p50 siRNA transfected cells. Moreover, docking model and pull-down assay showed that (E)-4-(3-(3,5-dimethoxyphenyl)allyl)-2-methoxyphenol directly bound to STAT3 and NF-κB p50 subunit. Furthermore, (E)-4-(3-(3,5-dimethoxyphenyl)allyl)-2-methoxyphenol inhibited colon tumor growth in a dose dependent manner (2.5 mg/kg-5 mg/kg) in mice. Therefore, these findings indicated that (E)-4-(3-(3,5-dimethoxyphenyl)allyl)-2-methoxyphenol may be a promising anti-cancer agent for colon cancer with more advanced research.

  1. Effect of environmental exposure to hydrogen sulfide on central nervous system and respiratory function: a systematic review of human studies

    PubMed Central

    Lim, Eunjung; Mbowe, Omar; Lee, Angela S. W.; Davis, James

    2016-01-01

    Background Assessment of the health effects of low-level exposure to hydrogen sulfide (H2S) on humans through experiments, industrial, and community studies has shown inconsistent results. Objective To critically appraise available studies investigating the effect of H2S on the central nervous system (CNS) and on respiratory function. Methods A search was conducted in 16 databases for articles published between January 1980 and July 2014. Two researchers independently evaluated potentially relevant papers based on a set of inclusion/exclusion criteria. Results Twenty-seven articles met the inclusion criteria: 6 experimental, 12 industry-based studies, and 10 community-based studies (one article included both experimental and industry-based studies). The results of the systematic review varied by study setting and quality. Several community-based studies reported associations between day-to-day variations in H2S levels and health outcomes among patients with chronic respiratory conditions. However, evidence from the largest and better-designed community-based studies did not support that chronic, ambient H2S exposure has health effects on the CNS or respiratory function. Results from industry-based studies varied, reflecting the diversity of settings and the broad range of H2S exposures. Most studies did not have individual measurements of H2S exposure. Discussion The results across studies were inconsistent, justifying the need for further research. PMID:27128692

  2. Effect of environmental exposure to hydrogen sulfide on central nervous system and respiratory function: a systematic review of human studies.

    PubMed

    Lim, Eunjung; Mbowe, Omar; Lee, Angela S W; Davis, James

    2016-01-01

    Assessment of the health effects of low-level exposure to hydrogen sulfide (H2S) on humans through experiments, industrial, and community studies has shown inconsistent results. To critically appraise available studies investigating the effect of H2S on the central nervous system (CNS) and on respiratory function. A search was conducted in 16 databases for articles published between January 1980 and July 2014. Two researchers independently evaluated potentially relevant papers based on a set of inclusion/exclusion criteria. Twenty-seven articles met the inclusion criteria: 6 experimental, 12 industry-based studies, and 10 community-based studies (one article included both experimental and industry-based studies). The results of the systematic review varied by study setting and quality. Several community-based studies reported associations between day-to-day variations in H2S levels and health outcomes among patients with chronic respiratory conditions. However, evidence from the largest and better-designed community-based studies did not support that chronic, ambient H2S exposure has health effects on the CNS or respiratory function. Results from industry-based studies varied, reflecting the diversity of settings and the broad range of H2S exposures. Most studies did not have individual measurements of H2S exposure. The results across studies were inconsistent, justifying the need for further research.

  3. An In Situ Directing Group Strategy for Chiral Anion Phase-Transfer Fluorination of Allylic Alcohols

    PubMed Central

    2015-01-01

    An enantioselective fluorination of allylic alcohols under chiral anion phase-transfer conditions is reported. The in situ generation of a directing group proved crucial for achieving effective enantiocontrol. In the presence of such a directing group, a range of acyclic substrates underwent fluorination to afford highly enantioenriched α-fluoro homoallylic alcohols. Mechanistic studies suggest that this transformation proceeds through a concerted enantiodetermining transition state involving both C–F bond formation and C–H bond cleavage. PMID:25203796

  4. The role of hydrogen sulfide in burns.

    PubMed

    Akter, Farhana

    2016-05-01

    Hydrogen sulfide is a novel gasotransmitter that has been shown to play a major role in regulating vascular tone. However, the role of hydrogen sulfide in inflammation, sepsis and burns has only recently been studied. In animal studies, hydrogen sulfide has been shown to play a role in both promoting and inhibiting inflammation. Understanding the role of H2S in sepsis and shock is particularly important due to the high mortality associated with both conditions. In animal sepsis models, hydrogen sulfide appears to increase survival. Severe burns are associated with an inflammatory response that causes increased permeability and edema. Currently, there are few studies that have examined the exact role of hydrogen sulfide in burns. However, the role of hydrogen sulfide in inflammation enables us to hypothesize its role in burns. This review highlights the role of hydrogen sulfide in the mechanisms of action underlying inflammation, wound healing and sepsis as well as examining the potential role of hydrogen sulfide in burns. The authors of this article hope that this review will stimulate research to discover the exact role of this fascinating molecule in burns.

  5. Combined Raman-LIBS Studies on Iron Sulfides to Investigate the Effect of the LIBS Plasma on the Mineral Composition

    NASA Astrophysics Data System (ADS)

    Alsemgeest, J.; Schröder, S.; Böttger, U.; Pavlov, S. G.; Weber, I.; Greshake, A.; Knöfler, H.-R.; Altenberger, U.; Hübers, H.-W.

    2016-08-01

    Iron sulfides, analyzed under martian conditions, show alteration caused by LIBS. This means that, during robotic planetary exploration by combined LIBS-Raman, effects must be taken into account with the interpretation of post-LIBS Raman data.

  6. ESEM Studies of Colloidal Sulfur Deposition in a Natural Microbial Community from a Cold Sulfide Spring Near Ancaster, Ontario, Canada

    NASA Technical Reports Server (NTRS)

    Douglas, S.; Douglas, D.

    2000-01-01

    We have used a relatively new microscopial technique, environmental scanning electron microscopy (ESEM), together with transmission electron microscopy (TEM) and light microscopy to investigate a unique microbial community from a temperate climate, cold sulfide spring near Ancaster, Ontario, Canada.

  7. Sulfide Stability of Planetary Basalts

    NASA Technical Reports Server (NTRS)

    Caiazza, C. M.; Righter, K.; Gibson, E. K., Jr.; Chesley, J. T.; Ruiz, J.

    2004-01-01

    The isotopic system, 187Re 187Os, can be used to determine the role of crust and mantle in magma genesis. In order to apply the system to natural samples, we must understand variations in Re/Os concentrations. It is thought that low [Os] and [Re] in basalts can be attributed to sulfide (FeS) saturation, as Re behaves incompatibly to high degrees of evolution until sulfide saturation occurs [1]. Previous work has shown that lunar basalts are sulfide under-saturated, and mid-ocean ridge, ocean-island and Martian (shergottites) basalts are saturated [2,3]. However, little is known about arc basalts. In this study, basaltic rocks were analyzed across the Trans-Mexican Volcanic Belt.

  8. Sulfide bonded atomic radii

    NASA Astrophysics Data System (ADS)

    Gibbs, G. V.; Ross, N. L.; Cox, D. F.

    2017-03-01

    The bonded radius, r b(S), of the S atom, calculated for first- and second-row non-transition metal sulfide crystals and third-row transition metal sulfide molecules and crystals indicates that the radius of the sulfur atom is not fixed as traditionally assumed, but that it decreases systematically along the bond paths of the bonded atoms with decreasing bond length as observed in an earlier study of the bonded radius of the oxygen atom. When bonded to non-transition metal atoms, r b(S) decreases systematically with decreasing bond length from 1.68 Å when the S atom is bonded to the electropositive VINa atom to 1.25 Å when bonded to the more electronegative IVP atom. In the case of transition metal atoms, rb(S) likewise decreases with decreasing bond length from 1.82 Å when bonded to Cu and to 1.12 Å when bonded to Fe. As r b(S) is not fixed at a given value but varies substantially depending on the bond length and the field strength of the bonded atoms, it is apparent that sets of crystal and atomic sulfide atomic radii based on an assumed fixed radius for the sulfur atom are satisfactory in that they reproduce bond lengths, on the one hand, whereas on the other, they are unsatisfactory in that they fail to define the actual sizes of the bonded atoms determined in terms of the minima in the electron density between the atoms. As such, we urge that the crystal chemistry and the properties of sulfides be studied in terms of the bond lengths determined by adding the radii of either the atomic and crystal radii of the atoms but not in terms of existing sets of crystal and atomic radii. After all, the bond lengths were used to determine the radii that were experimentally determined, whereas the individual radii were determined on the basis of an assumed radius for the sulfur atom.

  9. Sulfide bonded atomic radii

    NASA Astrophysics Data System (ADS)

    Gibbs, G. V.; Ross, N. L.; Cox, D. F.

    2017-09-01

    The bonded radius, r b(S), of the S atom, calculated for first- and second-row non-transition metal sulfide crystals and third-row transition metal sulfide molecules and crystals indicates that the radius of the sulfur atom is not fixed as traditionally assumed, but that it decreases systematically along the bond paths of the bonded atoms with decreasing bond length as observed in an earlier study of the bonded radius of the oxygen atom. When bonded to non-transition metal atoms, r b(S) decreases systematically with decreasing bond length from 1.68 Å when the S atom is bonded to the electropositive VINa atom to 1.25 Å when bonded to the more electronegative IVP atom. In the case of transition metal atoms, rb(S) likewise decreases with decreasing bond length from 1.82 Å when bonded to Cu and to 1.12 Å when bonded to Fe. As r b(S) is not fixed at a given value but varies substantially depending on the bond length and the field strength of the bonded atoms, it is apparent that sets of crystal and atomic sulfide atomic radii based on an assumed fixed radius for the sulfur atom are satisfactory in that they reproduce bond lengths, on the one hand, whereas on the other, they are unsatisfactory in that they fail to define the actual sizes of the bonded atoms determined in terms of the minima in the electron density between the atoms. As such, we urge that the crystal chemistry and the properties of sulfides be studied in terms of the bond lengths determined by adding the radii of either the atomic and crystal radii of the atoms but not in terms of existing sets of crystal and atomic radii. After all, the bond lengths were used to determine the radii that were experimentally determined, whereas the individual radii were determined on the basis of an assumed radius for the sulfur atom.

  10. Origin of fast catalysis in allylic amination reactions catalyzed by Pd-Ti heterobimetallic complexes.

    PubMed

    Walker, Whitney K; Kay, Benjamin M; Michaelis, Scott A; Anderson, Diana L; Smith, Stacey J; Ess, Daniel H; Michaelis, David J

    2015-06-17

    Experiments and density functional calculations were used to quantify the impact of the Pd-Ti interaction in the cationic heterobimetallic Cl2Ti(N(t)BuPPh2)2Pd(η(3)-methallyl) catalyst 1 used for allylic aminations. The catalytic significance of the Pd-Ti interaction was evaluated computationally by examining the catalytic cycle for catalyst 1 with a conformation where the Pd-Ti interaction is intact versus one where the Pd-Ti interaction is severed. Studies were also performed on the relative reactivity of the cationic monometallic (CH2)2(N(t)BuPPh2)2Pd(η(3)-methallyl) catalyst 2 where the Ti from catalyst 1 was replaced by an ethylene group. These computational and experimental studies revealed that the Pd-Ti interaction lowers the activation barrier for turnover-limiting amine reductive addition and accelerates catalysis up to 10(5). The Pd-Ti distance in 1 is the result of the N(t)Bu groups enforcing a boat conformation that brings the two metals into close proximity, especially in the transition state. The turnover frequency of classic Pd π allyl complexes was compared to that of 1 to determine the impact of P-Pd-P coordination angle and ligand electronic properties on catalysis. These experiments identified that cationic (PPh3)2Pd(η(3)-CH2C(CH3)CH2) catalyst 3 performs similarly to 1 for allylic aminations with diethylamine. However, computations and experiment reveal that the apparent similarity in reactivity is due to very fast reaction kinetics. The higher reactivity of 1 versus 3 was confirmed in the reaction of methallyl chloride and 2,2,6,6-tetramethylpiperidine (TMP). Overall, experiments and calculations demonstrate that the Pd-Ti interaction induces and is responsible for significantly lower barriers and faster catalysis for allylic aminations.

  11. Association between Daily Hydrogen Sulfide Exposure and Incidence of Emergency Hospital Visits: A Population-Based Study

    PubMed Central

    Finnbjornsdottir, Ragnhildur Gudrun; Carlsen, Hanne Krage; Thorsteinsson, Throstur; Oudin, Anna; Lund, Sigrun Helga; Gislason, Thorarinn; Rafnsson, Vilhjalmur

    2016-01-01

    Background The adverse health effects of high concentrations of hydrogen sulfide (H2S) exposure are well known, though the possible effects of low concentrations have not been thoroughly studied. The aim was to study short-term associations between modelled ambient low-level concentrations of intermittent hydrogen sulfide (H2S) and emergency hospital visits with heart diseases (HD), respiratory diseases, and stroke as primary diagnosis. Methods The study is population-based, using data from patient-, and population-registers from the only acute care institution in the Reykjavik capital area, between 1 January, 2007 and 30 June, 2014. The study population was individuals (≥18yr) living in the Reykjavik capital area. The H2S emission originates from a geothermal power plant in the vicinity. A model was used to estimate H2S exposure in different sections of the area. A generalized linear model assuming Poisson distribution was used to investigate the association between emergency hospital visits and H2S exposure. Distributed lag models were adjusted for seasonality, gender, age, traffic zones, and other relevant factors. Lag days from 0 to 4 were considered. Results The total number of emergency hospital visits was 32961 with a mean age of 70 years. In fully adjusted un-stratified models, H2S concentrations exceeding 7.00μg/m3 were associated with increases in emergency hospital visits with HD as primary diagnosis at lag 0 risk ratio (RR): 1.067; 95% confidence interval (CI): 1.024–1.111, lag 2 RR: 1.049; 95%CI: 1.005–1.095, and lag 4 RR: 1.046; 95%CI: 1.004–1.089. Among males an association was found between H2S concentrations exceeding 7.00μg/m3, and HD at lag 0 RR: 1.087; 95%CI: 1.032–1.146 and lag 4 RR: 1080; 95%CI: 1.025–1.138; and among those 73 years and older at lag 0 RR: 1.075; 95%CI: 1.014–1.140 and lag 3 RR: 1.072; 95%CI: 1.009–1.139. No associations were found with other diseases. Conclusions The study showed an association between

  12. Efficient epoxidation of a terminal alkene containing allylic hydrogen atoms: trans-methylstyrene on Cu{111}.

    PubMed

    Cropley, Rachael L; Williams, Federico J; Urquhart, Andrew J; Vaughan, Owain P H; Tikhov, Mintcho S; Lambert, Richard M

    2005-04-27

    The selective oxidation of trans-methylstyrene, a phenyl-substituted propene that contains labile allylic hydrogen atoms, has been studied on Cu{111}. Mass spectrometry and synchrotron fast XPS were used to detect, respectively, desorbing gaseous products and the evolution of surface species as a function of temperature and time. Efficient partial oxidation occurs yielding principally the epoxide, and the behavior of the system is sensitive to the order in which reactants are adsorbed. The latter is understandable in terms of differences in the spatial distribution of oxygen adatoms; isolated adatoms lead to epoxidation, while islands of "oxidic" oxygen do not. NEXAFS data taken over a range of coverages and in the presence and absence of coadsorbed oxygen indicate that the adsorbed alkene lies essentially flat with the allylic hydrogen atoms close to the surface. The photoemission results and comparison with the corresponding behavior of styrene on Cu{111} strongly suggest that allylic hydrogen abstraction is indeed a critical factor that limits epoxidation selectivity. An overall mechanism consistent with the structural and reactive properties is proposed.

  13. Loss of haem in rat liver caused by the porphyrogenic agent 2-allyl-2-isopropylacetamide

    PubMed Central

    De Matteis, F.

    1971-01-01

    1. The effect of a single dose of 2-allyl-2-isopropylacetamide on the cytochrome P-450 concentration in rat liver microsomal fraction was studied. The drug caused a rapid loss of cytochrome P-450 followed by a gradual increase to above the normal concentration. 2. The loss of cytochrome P-450 was accompanied by a loss of microsomal haem and by a brown–green discoloration of the microsomal fraction suggesting that a change in the chemical constitution of the lost haem had taken place. Direct evidence for this was obtained by prelabelling the liver haems with radioactive 5-aminolaevulate: the drug caused a loss of radioactivity from the haem with an increase of radioactivity in a fraction containing certain un-identified green pigments. 3. Evidence was obtained by a dual-isotopic procedure that rapidly turning-over haem(s) may be preferentially affected. 4. The loss of cytochrome P-450 as well as the loss of microsomal haem and the discoloration of the microsomal fraction were more intense in animals pretreated with phenobarbitone and were much less evident when compound SKF 525-A (2-diethylaminoethyl 3,3-diphenylpropylacetate) was given before 2-allyl-2-isopropylacetamide, suggesting that the activity of the drug-metabolizing enzymes may be involved in these effects. 5. The relevance of the destruction of liver haem to the increased activity of 5-aminolaevulate synthetase caused by 2-allyl-2-isopropylacetamide is discussed. PMID:5131732

  14. Pendant Allyl Crosslinking as a Tunable Shape Memory Actuator for Vascular Applications

    PubMed Central

    Zachman, Angela L.; Lee, Sue Hyun; Balikov, Daniel A.; Kim, Kwangho; Bellan, Leon M.; Sung, Hak-Joon

    2015-01-01

    Thermo-responsive shape memory polymers (SMPs) can be fit into small-bore incisions and recover their functional shape upon deployment in the body. This property is of significant interest for developing the next generation of minimally-invasive medical devices. To be used in such applications, SMPs should exhibit adequate mechanical strengths that minimize adverse compliance mismatch-induced host responses (e.g. thrombosis, hyperplasia), be biodegradable, and demonstrate switch-like shape recovery near body temperature with favorable biocompatibility. Combinatorial approaches are essential in optimizing SMP material properties for a particular application. In this study, a new class of thermo-responsive SMPs with pendant, photocrosslinkable allyl groups, x%poly( -caprolactone)-co-y%( -allyl carboxylate -caprolactone) (x%PCL-y%ACPCL), are created in a robust, facile manner with readily tunable material properties. Thermomechanical and shape memory properties can be drastically altered through subtle changes in allyl composition. Molecular weight and gel content can also be altered in this combinatorial format to fine-tune material properties. Materials exhibit high elastic, switch-like shape recovery near 37 °C. Endothelial compatibility is comparable to tissue culture polystyrene (TCPS) and 100%PCL in vitro and vascular compatibility is demonstrated in vivo in a murine model of hindlimb ischemia, indicating promising suitability for vascular applications. PMID:26072363

  15. Effect of various process treatment conditions on the allyl isothiocyanate extraction rate from mustard meal.

    PubMed

    Sharma, Harish K; Ingle, Sandeep; Singh, Charanjiv; Sarkar, Bhavesh C; Upadhyay, Ashutosh

    2012-06-01

    Allyl isothiocyanate (AITC), which has the potential to be used as flavoring, antibacterial, antifungal, antifermentative and antibrowning agent in food industry, was extracted from the pretreated MM by distillation technique. The mustard meal was analyzed for the proximate composition and the metals Fe, Mg and Zn. At the optimum pretreatment conditions of temperature 60 °C, time 120 min and pH 4.5, the effect of fractional distillation, mesh size and different additives was studied. Considerable effect of mesh size was observed, as the mesh size was decreased from 1,690 to 400 μm, the allyl isothiocyanate content was increased from 99.15 to 337.11 mg/100 ml. Addition of magnesium chloride (0.05 g/l to 0.2 g/l) and L-ascorbic acid (1 g/l to 5 g/l) increased allyl isothiocyanate from 257.79 to 317.28 mg/100 ml and 316.77 to 396.60 mg/100 ml respectively whereas the addition of the magnesium chloride and L-ascorbic acid in combination did not affect the AITC extraction rate as compare to their addition in single effect.

  16. Inactivation of Salmonella on whole cantaloupe by application of an antimicrobial coating containing chitosan and allyl isothiocyanate

    USDA-ARS?s Scientific Manuscript database

    This study investigated the antimicrobial effect of a chitosan coating + allyl isothiocyanate (AIT) and nisin against Salmonella on whole fresh cantaloupes. Cantaloupes were inoculated with a cocktail of three Salmonella strains and treated with chitosan, chitosan + AIT, chitosan + nisin, and chitos...

  17. Efficient, regioselective palladium-catalyzed tandem Heck-isomerization reaction of aryl bromides and non-allylic benzyl alcohols.

    PubMed

    Crawley, Matthew L; Phipps, Kristin M; Goljer, Igor; Mehlmann, John F; Lundquist, Joseph T; Ullrich, John W; Yang, Cuijian; Mahaney, Paige E

    2009-03-05

    An efficient and mild method to couple aryl bromides and activated non-allylic alcohols in a Heck reaction with tandem isomerization to selectively afford high yields of 1,5-diarylalkan-1-ones has been developed. Mechanistic insight was gained through NMR studies of products derived from deuterium-labeled intermediates.

  18. Asymmetric Allylation/RCM-Mediated Synthesis of Fluorinated Benzo-Fused Bicyclic Homoallylic Amines As Dihydronaphthalene Derivatives.

    PubMed

    Sedgwick, Daniel M; Barrio, Pablo; Simón, Antonio; Román, Raquel; Fustero, Santos

    2016-10-07

    Enantiomerically enriched fluorinated benzo-fused bicyclic homoallylic amines have been synthesized through an asymmetric allylation/ring closing metathesis (RCM) sequence. This sequence has been carried out using α-trifluoromethylstyrene derivatives as key intermediates, synthesized by microwave radiation. The great deactivating effect exerted by such substituents has been brought to light by a comparative study.

  19. The role of diallyl sulfides and dipropyl sulfides in the in vitro antimicrobial activity of the essential oil of garlic, Allium sativum L., and leek, Allium porrum L.

    PubMed

    Casella, Sergio; Leonardi, Michele; Melai, Bernardo; Fratini, Filippo; Pistelli, Luisa

    2013-03-01

    The in vitro antibacterial activity of essential oils (EOs) obtained from fresh bulbs of garlic, Allium sativum L., and leek, Allium porrum L. ( Alliaceae), was studied. A. sativum (garlic) EO showed a good antimicrobial activity against Staphylococcus aureus (inhibition zone 14.8 mm), Pseudomonas aeruginosa (inhibition zone 21.1 mm), and Escherichia coli (inhibition zone 11.0 mm), whereas the EO of A. porrum (leek) had no antimicrobial activity. The main constituents of the garlic EO were diallyl monosulfide, diallyl disulfide (DADS), diallyl trisulfide, and diallyl tetrasulfide. The EO of A. porrum was characterized by the presence of dipropyl disulfide (DPDS), dipropyl trisulfide, and dipropyl tetrasulfide. The antimicrobial activities of the DADS and DPDS were also studied. The results obtained suggest that the presence of the allyl group is fundamental for the antimicrobial activity of these sulfide derivatives when they are present in Allium or in other species (DADS inhibition zone on S. aureus 15.9 mm, P. aeruginosa 21.9 mm, E. coli 11.4 mm).

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

    PubMed

    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.

  1. Hydrogen sulfide alleviates the aluminum-induced changes in Brassica napus as revealed by physiochemical and ultrastructural study of plant.

    PubMed

    Ali, Basharat; Qian, Ping; Sun, Rui; Farooq, Muhammad A; Gill, Rafaqat A; Wang, Jian; Azam, Muhammad; Zhou, Weijun

    2015-02-01

    In the present study, ameliorating role of hydrogen sulfide (H2S) in oilseed rape (Brassica napus L.) was studied with or without application of H2S donor sodium hydrosulfide (NaHS) (0.3 mM) in hydroponic conditions under three levels (0, 0.1 and 0.3 mM) of aluminum (Al). Results showed that addition of H2S significantly improved the plant growth, photosynthetic gas exchange, and nutrients concentration in the leaves and roots of B. napus plants under Al stress. Exogenously applied H2S significantly lowered the Al concentration in different plant parts, and reduced the production of malondialdehyde and reactive oxygen species by improving antioxidant enzyme activities in the leaves and roots under Al stress. Moreover, the present study indicated that exogenously applied H2S improved the cell structure and displayed clean mesophyll and root tip cells. The chloroplast with well-developed thylakoid membranes could be observed in the micrographs. Under the combined application of H2S and Al, a number of modifications could be observed in root tip cell, such as mitochondria, endoplasmic reticulum, and golgi bodies. Thus, it can be concluded that exogenous application of H2S under Al stress improved the plant growth, photosynthetic parameters, elements concentration, and biochemical and ultrastructural changes in leaves and roots of B. napus.

  2. Effect of Allylic Groups on SN2 Reactivity

    PubMed Central

    2015-01-01

    The activating effects of the benzyl and allyl groups on SN2 reactivity are well-known. 6-Chloromethyl-6-methylfulvene, also a primary, allylic halide, reacts 30 times faster with KI/acetone than does benzyl chloride at room temperature. The latter result, as well as new experimental observations, suggests that the fulvenyl group is a particularly activating allylic group in SN2 reactions. Computational work on identity SN2 reactions, e.g., chloride– displacing chloride– and ammonia displacing ammonia, shows that negatively charged SN2 transition states (tss) are activated by allylic groups according to the Galabov–Allen–Wu electrostatic model but with the fulvenyl group especially effective at helping to delocalize negative charge due to some cyclopentadienide character in the transition state (ts). In contrast, the triafulvenyl group is deactivating. However, the positively charged SN2 transition states of the ammonia reactions are dramatically stabilized by the triafulvenyl group, which directly conjugates with a reaction center having SN1 character in the ts. Experiments and calculations on the acidities of a variety of allylic alcohols and carboxylic acids support the special nature of the fulvenyl group in stabilizing nearby negative charge and highlight the ability of fulvene species to dramatically alter the energetics of processes even in the absence of direct conjugation. PMID:24977317

  3. Catalytic asymmetric generation of (Z)-disubstituted allylic alcohols.

    PubMed

    Salvi, Luca; Jeon, Sang-Jin; Fisher, Ethan L; Carroll, Patrick J; Walsh, Patrick J

    2007-12-26

    A one-pot method for the direct preparation of enantioenriched (Z)-disubstituted allylic alcohols is introduced. Hydroboration of 1-halo-1-alkynes with dicyclohexylborane, reaction with t-BuLi, and transmetalation with dialkylzinc reagents generate (Z)-disubstituted vinylzinc intermediates. In situ reaction of these reagents with aldehydes in the presence of a catalyst derived from (-)-MIB generates (Z)-disubstituted allylic alcohols. It was found that the resulting allylic alcohols were racemic, most likely due to a rapid addition reaction promoted by LiX (X = Br and Cl). To suppress the LiX-promoted reaction, a series of inhibitors were screened. It was found that 20-30 mol % tetraethylethylenediamine inhibited LiCl without inhibiting the chiral zinc-based Lewis acid. In this fashion, (Z)-disubstituted allylic alcohols were obtained with up to 98% ee. The asymmetric (Z)-vinylation could be coupled with tandem diastereoselective epoxidation reactions to provide epoxy alcohols and allylic epoxy alcohols with up to three contiguous stereogenic centers, enabling the rapid construction of complex building blocks with high levels of enantio- and diastereoselectivity.

  4. Scalable and Sustainable Electrochemical Allylic C–H Oxidation

    PubMed Central

    Chen, Yong; Tang, Jiaze; Chen, Ke; Eastgate, Martin D.; Baran, Phil S.

    2016-01-01

    New methods and strategies for the direct functionalization of C–H bonds are beginning to reshape the fabric of retrosynthetic analysis, impacting the synthesis of natural products, medicines, and even materials1. The oxidation of allylic systems has played a prominent role in this context as possibly the most widely applied C–H functionalization due to the utility of enones and allylic alcohols as versatile intermediates, along with their prevalence in natural and unnatural materials2. Allylic oxidations have been featured in hundreds of syntheses, including some natural product syntheses regarded as “classics”3. Despite many attempts to improve the efficiency and practicality of this powerful transformation, the vast majority of conditions still employ highly toxic reagents (based around toxic elements such as chromium, selenium, etc.) or expensive catalysts (palladium, rhodium, etc.)2. These requirements are highly problematic in industrial settings; currently, no scalable and sustainable solution to allylic oxidation exists. As such, this oxidation strategy is rarely embraced for large-scale synthetic applications, limiting the adoption of this important retrosynthetic strategy by industrial scientists. In this manuscript, we describe an electrochemical solution to this problem that exhibits broad substrate scope, operational simplicity, and high chemoselectivity. This method employs inexpensive and readily available materials, representing the first example of a scalable allylic C–H oxidation (demonstrated on 100 grams), finally opening the door for the adoption of this C–H oxidation strategy in large-scale industrial settings without significant environmental impact. PMID:27096371

  5. Cu-catalyzed enantioselective allylic alkylation with organolithium reagents.

    PubMed

    Hornillos, Valentín; Guduguntla, Sureshbabu; Fañanás-Mastral, Martín; Pérez, Manuel; Bos, Pieter H; Rudolph, Alena; Harutyunyan, Syuzanna R; Feringa, Ben L

    2017-03-01

    This protocol describes a method for the catalytic enantioselective synthesis of tertiary and quaternary carbon stereogenic centers, which are widely present in pharmaceutical and natural products. The method is based on the direct reaction between organolithium compounds, which are cheap, readily available and broadly used in chemical synthesis, and allylic electrophiles, using chiral copper catalysts. The methodology involves the asymmetric allylic alkylation (AAA) of allyl bromides, chlorides and ethers with organolithium compounds using catalyst systems based on Cu-Taniaphos and Cu-phosphoramidites. The protocol contains a complete description of the reaction setup, a method based on (1)H-NMR, gas chromatography-mass spectrometry (GC-MS) and chiral HPLC for assaying the regioselectivity and enantioselectivity of the product, and isolation, purification and characterization procedures. Six Cu-catalyzed AAA reactions between different organolithium reagents and allylic systems are detailed in the text as representative examples of these procedures. These reactions proceed within 1-10 h, depending on the nature of the allylic substrate (bromide, chloride, or ether and disubstituted or trisubstituted) or the chiral ligand used (Taniaphos or phosphoramidite). However, the entire protocol, including workup and purification, generally requires an additional 4-7 h to complete.

  6. Scalable and sustainable electrochemical allylic C-H oxidation.

    PubMed

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

    2016-05-05

    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.

  7. Catalytic Asymmetric Generation of (Z)-Disubstituted Allylic Alcohols

    PubMed Central

    Salvi, Luca; Jeon, Sang-Jin; Fisher, Ethan L.; Carroll, Patrick J.; Walsh, Patrick J.

    2008-01-01

    A one-pot method for the direct preparation of enantioenriched (Z)-disubstituted allylic alcohols is introduced. Hydroboration of 1-halo-1-alkynes with dicyclohexylborane, reaction with t-BuLi, and transmetallation with dialkylzinc reagents generates (Z)-disubstituted vinylzinc intermediates. In situ reaction of these reagents with aldehydes in the presence of a catalyst derived from (−)-MIB generates (Z)-disubstituted allylic alcohols. It was found that the resulting allylic alcohols were racemic, most likely due to a rapid addition reaction promoted by LiX (X = Br and Cl). To suppress the LiX promoted reaction, a series of inhibitors was screened. It was found that 20–30 mol % tetraethylethylene diamine (TEEDA) inhibited LiCl without inhibiting the chiral zinc-based Lewis acid. In this fashion, (Z)-disubstituted allylic alcohols were obtained with up to 98% ee. The asymmetric (Z)-vinylation could be coupled with tandem diastereoselective epoxidation reactions to provide epoxy alcohols and allylic epoxy alcohols with up to three contiguous stereogenic centers, enabling the rapid construction of complex building blocks with high levels of enantio- and diastereoselectivity. PMID:18052173

  8. Reactions of allylic radicals that impact molecular weight growth kinetics.

    PubMed

    Wang, Kun; Villano, Stephanie M; Dean, Anthony M

    2015-03-07

    The reactions of allylic radicals have the potential to play a critical role in molecular weight growth (MWG) kinetics during hydrocarbon oxidation and/or pyrolysis. Due to their stability (when compared to alkyl radicals), they can accumulate to relatively high concentrations. Thus, even though the rate coefficients for their various reactions are small, the rates of these reactions may be significant. In this work, we use electronic structure calculations to examine the recombination, addition, and abstraction reactions of allylic radicals. For the recombination reaction of allyl radicals, we assign a high pressure rate rule that is based on experimental data. Once formed, the recombination product can potentially undergo an H-atom abstraction reaction followed by unimolecular cyclization and β-scission reactions. Depending upon the conditions (e.g., higher pressures) these pathways can lead to the formation of stable MWG species. The addition of allylic radicals to olefins can also lead to MWG species formation. Once again, cyclization of the adduct followed by β-scission is an important energy accessible route. Since the recombination and addition reactions produce chemically-activated adducts, we have explored the pressure- and temperature-dependence of the overall rate constants as well as that for the multiple product channels. We describe a strategy for estimating these pressure-dependencies for systems where detailed electronic structure information is not available. We also derive generic rate rules for hydrogen abstraction reactions from olefins and diolefins by methyl and allyl radicals.

  9. Iridium-catalyzed regio- and enantioselective allylic substitution of silyl dienolates derived from dioxinones.

    PubMed

    Chen, Ming; Hartwig, John F

    2014-11-03

    Reported herein is the iridium-catalyzed regio- and enantioselective allylic substitution reactions of unstabilized silyl dienolates derived from dioxinones. Asymmetric allylic substitution of a variety of allylic trichloroethyl carbonates with these silyl dienolates gave γ-allylated products selectively in 60-84% yield and 90-98% ee. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    SciTech Connect

    Solehudin, Agus; Nurdin, Isdiriayani

    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.

  11. A gas chromatography-mass spectrometry based study on urine metabolomics in rats chronically poisoned with hydrogen sulfide.

    PubMed

    Deng, Mingjie; Zhang, Meiling; Sun, Fa; Ma, Jianshe; Hu, Lufeng; Yang, Xuezhi; Lin, Guanyang; Wang, Xianqin

    2015-01-01

    Gas chromatography-mass spectrometry (GS-MS) in combination with multivariate statistical analysis was applied to explore the metabolic variability in urine of chronically hydrogen sulfide- (H2S-) poisoned rats relative to control ones. The changes in endogenous metabolites were studied by partial least squares-discriminate analysis (PLS-DA) and independent-samples t-test. The metabolic patterns of H2S-poisoned group are separated from the control, suggesting that the metabolic profiles of H2S-poisoned rats were markedly different from the controls. Moreover, compared to the control group, the level of alanine, d-ribose, tetradecanoic acid, L-aspartic acid, pentanedioic acid, cholesterol, acetate, and oleic acid in rat urine of the poisoning group decreased, while the level of glycine, d-mannose, arabinofuranose, and propanoic acid increased. These metabolites are related to amino acid metabolism as well as energy and lipid metabolism in vivo. Studying metabolomics using GC-MS allows for a comprehensive overview of the metabolism of the living body. This technique can be employed to decipher the mechanism of chronic H2S poisoning, thus promoting the use of metabolomics in clinical toxicology.

  12. Interaction between anions and molybdenum allyl dicarbonyl complexes of 1,4,7-trithiacyclononane.

    PubMed

    Morales, Dolores; Puerto, Marcos; del Río, Ignacio; Pérez, Julio; López, Ramón

    2012-12-07

    The labile complex [MoCl(η(3)-methallyl)(CO)(2)(NCMe)(2)] reacts with the ligand 1,4,7-trithiacyclononane ([9]aneS(3)) and the salt NaBAr'(4) to afford [Mo(η(3)-methallyl)(CO)(2)([9]aneS(3))][BAr'(4)] (1⋅BAr'(4)). An analogous reaction of [MoBr(η(3)-allyl)(CO)(2)(NCMe)(2)] yields [Mo(η(3)-allyl)(CO)(2)([9]aneS(3))][BAr'(4)] (2⋅BAr'(4)). The new compounds 1⋅BAr'(4) and 2⋅BAr'(4) were characterized by IR and NMR spectroscopic analysis and X-ray diffraction studies. Both compounds feature the cyclic thioether [9]aneS(3) coordinated as a tridentate ligand to the molybdenum center. The allyl ligand in 2⋅BAr'(4) is aligned with the middle of the OC-Mo-CO angle, which is acute. Both of these features are typical of most pseudo-octahedral allyl dicarbonyl molybdenum complexes. In contrast, the allyl group is rotated in 1⋅BAr'(4), which is attributed to steric hindrance between the methyl substituent and the ligated thioether, and the OC-Mo-CO angle is obtuse. Compound 1⋅BAr'(4) undergoes rapid substitution of [9]aneS(3) by either chloride and fluoride ions in dichloromethane, and the products include the known species [{Mo(η(3)-methallyl)(CO)(2)}(2)(μ-Cl)(3)](-) and a structurally similar new anionic complex with two fluoro and one hydroxo bridging ligands, respectively. Stable supramolecular adducts were formed in the reactions of 1⋅BAr'(4) and 2⋅BAr(4) with bromide, iodide, hydrogensulfate, and methanesulfonate compounds. The binding constants of these adducts in dichloromethane were calculated from (1)H NMR spectroscopic titration data, and the solid-state structures of the 1⋅Br, 1⋅HSO(4), 1⋅I, and 2⋅I adducts were determined by X-ray diffraction studies. The surprising slightly higher stability of the iodide adduct relative to that of bromide was investigated theoretically, with the results pointing to an effect of the differential solvation of the halide ions.

  13. Redox-Neutral Rh(III)-Catalyzed Olefination of Carboxamides with Trifluoromethyl Allylic Carbonate.

    PubMed

    Park, Jihye; Han, Sangil; Jeon, Mijin; Mishra, Neeraj Kumar; Lee, Seok-Yong; Lee, Jong Suk; Kwak, Jong Hwan; Um, Sung Hee; Kim, In Su

    2016-11-18

    The rhodium(III)-catalyzed olefination of various carboxamides with α-CF3-substituted allylic carbonate is described. This reaction provides direct access to linear CF3-allyl frameworks with complete trans-selectivity. In particular, a rhodium catalyst provided Heck-type γ-CF3-allylation products via the β-O-elimination of rhodacycle intermediate and subsequent olefin migration process.

  14. 40 CFR 721.7000 - Polymer of disodium maleate, allyl ether, and ethylene oxide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 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...

  15. 40 CFR 721.7000 - Polymer of disodium maleate, allyl ether, and ethylene oxide.

    Code of Federal Regulations, 2010 CFR

    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...

  16. 40 CFR 721.7000 - Polymer of disodium maleate, allyl ether, and ethylene oxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 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 (P-91...

  17. 40 CFR 721.7000 - Polymer of disodium maleate, allyl ether, and ethylene oxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 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 (P-91...

  18. 40 CFR 721.7000 - Polymer of disodium maleate, allyl ether, and ethylene oxide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 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 (P-91...

  19. Pd-catalyzed reaction of allyl carbonate with polyols: the role of CO2 in transesterification versus etherification of glycerol.

    PubMed

    Gordillo, Alvaro; Lloyd-Jones, Guy C

    2012-02-27

    An intermolecular Pd/PPh(3)-catalyzed transesterification of diallyl carbonate with glycerol to generate glycerol carbonate has been developed. Analysis of the reaction kinetics in THF indicates a first-order dependence on Pd and diallyl carbonate, that the Pd bears two phosphines during the turnover limiting event, and that increasing the glycerol concentration inhibits reaction, possibly via change in the polarity of the medium. (13)C isotopic labeling studies demonstrate that the Pd-catalyzed transesterification requires at least one allyl carbonate moiety and that there is rapid equilibrium of the allyl carbonate with CO(2) in solution, even when present only at low concentrations. A mechanism that is consistent with these results involves oxidative addition of the allyl carbonate to Pd followed by reversible decarboxylation, with the intermediate η(1)- and η(3)-allyl Pd alkoxides mediating direct and indirect transesterification reactions with the glycerol. Using this model, successful simulations of the kinetics of reactions conducted under atmospheres of N(2) or CO(2) could be achieved, including switching in selectivity between etherification and transesterification in the early stages of reaction. Reactions with the higher polyols threitol and erythritol are also efficient, generating the terminal (1,2) monocarbonates with high selectivity. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Sulfide Mineral Surfaces

    SciTech Connect

    Rosso, Kevin M.; Vaughan, David J.

    2006-08-01

    The past twenty years or so have seen dramatic development of the experimental and theoretical tools available to study the surfaces of solids at the molecular (?atomic resolution?) scale. On the experimental side, two areas of development well illustrate these advances. The first concerns the high intensity photon sources associated with synchrotron radiation; these have both greatly improved the surface sensitivity and spatial resolution of already established surface spectroscopic and diffraction methods, and enabled the development of new methods for studying surfaces. The second centers on the scanning probe microscopy (SPM) techniques initially developed in the 1980's with the first scanning tunneling microscope (STM) and atomic force microscope (AFM) experiments. The direct 'observation' of individual atoms at surfaces made possible with these methods has truly revolutionized surface science. On the theoretical side, the availability of high performance computers coupled with advances in computational modeling has provided powerful new tools to complement the advances in experiment. Particularly important have been the quantum mechanics based computational approaches such as density functional theory (DFT), which can now be easily used to calculate the equilibrium crystal structures of solids and surfaces from first principles, and to provide insights into their electronic structure. In this chapter, we review current knowledge of sulfide mineral surfaces, beginning with an overview of the principles relevant to the study of the surfaces of all crystalline solids. This includes the thermodynamics of surfaces, the atomic structure of surfaces (surface crystallography and structural stability, adjustments of atoms at the surface through relaxation or reconstruction, surface defects) and the electronic structure of surfaces. We then discuss examples where specific crystal surfaces have been studied, with the main sulfide minerals organized by structure type

  1. Methodological approach to study energetic and structural properties of nanostructured cadmium sulfide by using ab-initio molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Burresi, E.; Celino, M.

    2012-05-01

    A single wurtzite phase of cadmium sulfide cluster is investigated by ab-initio molecular dynamics simulations at different temperatures, ranging from 100 K to 600 K. In this study we propose a possible procedure to characterize the CdS quantum dots system by means of molecular dynamics calculations using a standard Car-Parrinello scheme. In order to ensure the accuracy of the numerical approach, preliminary calculations to test pseudopotentials, cutoff and box size on both single atoms systems and Cd-Cd, S-S, Cd-S dimers have been performed. Calculated binding energies and bond lengths are obtained in good agreement with experimental data. Subsequently, an uncapped CdS cluster with size below 2 nm, 48 atoms of cadmium and 48 atoms of sulfur, in a wurtzite geometry was structurally optimized to minimize internal stresses. The CdS cluster has been carefully characterized structurally at several temperatures up to T = 600 K. At the temperature of 340 K atomic diffusion on the surface allows the onset of a new stable atomic configuration.

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

    NASA Astrophysics Data System (ADS)

    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).

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

    PubMed

    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%.

  4. Global sensitivity analysis of an in-sewer process model for the study of sulfide-induced corrosion of concrete.

    PubMed

    Donckels, B M R; Kroll, S; Van Dorpe, M; Weemaes, M

    2014-01-01

    The presence of high concentrations of hydrogen sulfide in the sewer system can result in corrosion of the concrete sewer pipes. The formation and fate of hydrogen sulfide in the sewer system is governed by a complex system of biological, chemical and physical processes. Therefore, mechanistic models have been developed to describe the underlying processes. In this work, global sensitivity analysis was applied to an in-sewer process model (aqua3S) to determine the most important model input factors with regard to sulfide formation in rising mains and the concrete corrosion rate downstream of a rising main. The results of the sensitivity analysis revealed the most influential model parameters, but also the importance of the characteristics of the organic matter, the alkalinity of the concrete and the movement of the sewer gas phase.

  5. Origins of Regioselectivity in Iridium Catalyzed Allylic Substitution.

    PubMed

    Madrahimov, Sherzod T; Li, Qian; Sharma, Ankit; Hartwig, John F

    2015-12-02

    Detailed studies on the origin of the regioselectivity for formation of branched products over linear products have been conducted with complexes containing the achiral triphenylphosphite ligand. The combination of iridium and P(OPh)3 was the first catalytic system shown to give high regioselectivity for the branched product with iridium and among the most selective for forming branched products among any combination of metal and ligand. We have shown the active catalyst to be generated from [Ir(COD)Cl]2 and P(OPh)3 by cyclometalation of the phenyl group on the ligand and have shown such species to be the resting state of the catalyst. A series of allyliridium complexes ligated by the resulting P,C ligand have been generated and shown to be competent intermediates in the catalytic system. We have assessed the potential impact of charge, metal-iridium bond length, and stability of terminal vs internal alkenes generated by attack at the branched and terminal positions of the allyl ligand, respectively. These factors do not distinguish the regioselectivity for attack on allyliridium complexes from that for attack on allylpalladium complexes. Instead, detailed computational studies suggest that a series of weak, attractive, noncovalent interactions, including interactions of H-bond acceptors with a vinyl C-H bond of the alkene ligand, favor formation of the branched product with the iridium catalyst. This conclusion underscores the importance of considering attractive interactions, as well as repulsive steric interactions, when seeking to rationalize selectivities.

  6. Allyl isothiocyanate affects the cell cycle of Arabidopsis thaliana

    PubMed Central

    Åsberg, Signe E.; Bones, Atle M.; Øverby, Anders

    2015-01-01

    Isothiocyanates (ITCs) are degradation products of glucosinolates present in members of the Brassicaceae family acting as herbivore repellents and antimicrobial compounds. Recent results indicate that allyl ITC (AITC) has a role in defense responses such as glutathione depletion, ROS generation and stomatal closure. In this study we show that exposure to non-lethal concentrations of AITC causes a shift in the cell cycle distribution of Arabidopsis thaliana leading to accumulation of cells in S-phases and a reduced number of cells in non-replicating phases. Furthermore, transcriptional analysis revealed an AITC-induced up-regulation of the gene encoding cyclin-dependent kinase A while several genes encoding mitotic proteins were down-regulated, suggesting an inhibition of mitotic processes. Interestingly, visualization of DNA synthesis indicated that exposure to AITC reduced the rate of DNA replication. Taken together, these results indicate that non-lethal concentrations of AITC induce cells of A. thaliana to enter the cell cycle and accumulate in S-phases, presumably as a part of a defensive response. Thus, this study suggests that AITC has several roles in plant defense and add evidence to the growing data supporting a multifunctional role of glucosinolates and their degradation products in plants. PMID:26042144

  7. Sulfide elimination by intermittent nitrate dosing in sewer sediments.

    PubMed

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

    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 of efficient sulfide control with lower carbon source loss. The optimal control condition is feasible for the sulfide elimination in sewer systems.

  8. Photocatalytic decomposition of hydrogen sulfide on cadmium and zinc sulfides immobilized on a cation exchange film

    SciTech Connect

    Makhmadmurodov, A.; Gruzdkov, Y.A.; Parmon, V.N.; Savinov, E.N.

    1986-08-01

    The photocatalytic decomposition of hydrogen sulfide on cadmium, zinc, and tin sulfides, immobilized on a polymer, was studied. Activation of the photocatalyst by finely divided particles of Pd and Pt was used. A quantum yield of 9.5% was achieved.

  9. Synthesis of Neoglycoconjugates by the Desulfurative Rearrangement of Allylic Disulfides

    PubMed Central

    Crich, David; Yang, Fan

    2009-01-01

    Two series of neoglucosyl donors are prepared based on connection of the allylic disulfide motif to the anomeric center via either a simple O-glycosyl linkage or N-glycosyl amide unit. Conjugation of both sets of donors to cysteine in peptides is demonstrated through classical disulfide exchange followed by the phosphine-mediated desulfurative allylic rearrangement resulting in neoglycopeptides characterized by a simple thioether spacer. The conjugation reaction functions in the absence of protecting groups on both the neoglycosyl donor and peptide in aqueous media at room temperature. PMID:18729514

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

    PubMed

    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

  11. Sulfide Mineralogy and Geochemistry

    NASA Astrophysics Data System (ADS)

    Dilles, John

    2007-02-01

    Reviews in Mineralogy and Geochemistry Series, Volume 61 David J. Vaughan, Editor Geochemical Society and Mineralogical Society of America; ISBN 0-939950-73-1 xiii + 714 pp.; 2006; $40. Sulfide minerals as a class represent important minor rock-forming minerals, but they are generally known as the chief sources of many economic metallic ores. In the past two decades, sulfide research has been extended to include important roles in environmental geology of sulfide weathering and resultant acid mine drainage, as well as in geomicrobiology in which bacteria make use of sulfides for metabolic energy sources. In the latter respect, sulfides played an important role in early evolution of life on Earth and in geochemical cycling of elements in the Earth's crust and hydrosphere.

  12. 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

    USGS Publications Warehouse

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

  13. Hydrothermal ore-forming processes in the light of studies in rock- buffered systems: I. Iron-copper-zinc-lead sulfide solubility relations

    USGS Publications Warehouse

    Hemley, J.J.; Cygan, G.L.; Fein, J.B.; Robinson, G.R.; d'Angelo, W. M.

    1992-01-01

    Experimental studies, using cold-seal and extraction vessel techniques, were conducted on Fe, Pb, Zn, and Cu sulfide solubilities in chloride soultions at temperatures from 300?? to 700??C and pressures from 0.5 to 2 kbars. The solutions were buffered in pH by quartz monzonite and the pure potassium feldspar-muscovite-quartz assemblage and in fS2-fO2 largely by the assemblage pyrite-pyrrhotite-magnetite. Solubilities increase with increasing temperature and total chloride, and decrease with increasing pressure. The effect of increasing chloride concentration on solubility reflects primarily a shift to lower pH via the silicate buffer reactions. Similarity in behaviour with respect to the temperature and pressure of Fe, Zn, and Pb sulfide solubilities points to similarity in chloride speciation, and the neutral species appear to be dominant in the high-temperature region. -from Authors

  14. SN2 reactions with allylic substrates--Trends in reactivity

    NASA Astrophysics Data System (ADS)

    Ochran, Richard A.; Uggerud, Einar

    2007-09-01

    The gas-phase identity SN2 reactions of allylic substrates has been studied by systematic altering of the nucleophile/nucleofuge X, the remote substituent Y, and the number of methyl substituents at the reaction centre: X- + YCHCHCZ2X --> YCHCHCZ2X + X- (X = H, CH3, NH2, F, Cl; Y = F, OH, H, CHO, BH2; Z = H, CH3). Key regions of the potential energy surfaces have been explored by MP2, B3LYP, G3B3 and G3 calculations; the latter two methods providing accurate estimates of the reaction barrier. The calculations show that irrespective of theoretical level, for the second row of the periodic table (X = CH3, NH2, OH, and F), the tendency is that the barrier height decreases in going from left to right in agreement with the previously observed trend for identity SN2 reactions at methyl. The barrier height decreases by introduction a [pi] electron withdrawing substituents, Y, remote 6rom the reaction centre. The barrier height increases by introducing methyl groups (Z = CH3) next to the reaction centre, but the effect is less than half of that of changing the remote substituent from Y = CHO to Y = OH. The trends cannot be explained by simplified valence bond theory and are discussed in light of a simple electrostatic bonding model of the transition structure.

  15. Allyl isothiocyanate induces stomatal closure in Vicia faba.

    PubMed

    Sobahan, Muhammad Abdus; Akter, Nasima; Okuma, Eiji; Uraji, Misugi; Ye, Wenxiu; Mori, Izumi C; Nakamura, Yoshimasa; Murata, Yoshiyuki

    2015-01-01

    Isothiocyanates are enzymatically produced from glucosinolates in plants, and allyl isothiocyanate (AITC) induces stomatal closure in Arabidopsis thaliana. In this study, we investigated stomatal responses to AITC in Vicia faba. AITC-induced stomatal closure accompanied by reactive oxygen species (ROS) and NO production, cytosolic alkalization and glutathione (GSH) depletion in V. faba. GSH monoethyl ester induced stomatal reopening and suppressed AITC-induced GSH depletion in guard cells. Exogenous catalase and a peroxidase inhibitor, salicylhydroxamic acid, inhibited AITC-induced stomatal closure, unlike an NAD(P)H oxidase inhibitor, diphenylene iodonium chloride. The peroxidase inhibitor also abolished the AITC-induced ROS production, NO production, and cytosolic alkalization. AITC-induced stomatal closure was suppressed by an NO scavenger, 2-(4-carboxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, and an agent to acidify cytosol, butyrate. These results indicate that AITC-induced stomatal closure in V. faba as well as in A. thaliana and suggest that AITC signaling in guard cells is conserved in both plants.

  16. Release of allyl isothiocyanate from mustard seed meal powder.

    PubMed

    Dai, Ruyan; Lim, Loong-Tak

    2014-01-01

    Allyl isothiocyanate (AITC) is a wide-spectrum antimicrobial compound found in mustard seeds, produced when their tissues are disrupted. The formation of AITC in mustard seed is mediated by the myrosinase enzyme which catalyzes the release of volatile AITC from a glucosinolate-sinigrin. Since water is a substrate in the reaction, humidity from the air can be used to activate the release of AITC from mustard seed. In this study, defatted and partially defatted mustard seed meals were ground into powders with particle size ranging from 5 to 300 μm. The mustard seed meal powder (MSMP) samples were enclosed within hermetically sealed glass jars wherein the headspace air was adjusted to 85% or 100% relative humidity at 5, 20, or 35 °C. Data from gas chromatography analysis showed that AITC release rate and amount increased with increasing relative humidity and temperature. Moreover, the release rate can be manipulated by particle size and lipid content of the MSMP samples. The amount of AITC released ranged from 2 to 17 mg/g MSMP within 24 h under the experimental conditions tested. In view of the antimicrobial properties of AITC, the mustard meal powder may be used as a natural antimicrobial material for extending the shelf life of food products.

  17. Oxidation of hydrogen sulfide by human liver mitochondria.

    PubMed

    Helmy, Nada; Prip-Buus, Carina; Vons, Corinne; Lenoir, Véronique; Abou-Hamdan, Abbas; Guedouari-Bounihi, Hala; Lombès, Anne; Bouillaud, Frédéric

    2014-09-15

    Hydrogen sulfide (H2S) is the third gasotransmitter discovered. Sulfide shares with the two others (NO and CO) the same inhibiting properties towards mitochondrial respiration. However, in contrast with NO or CO, sulfide at concentrations lower than the toxic (μM) level is an hydrogen donor and a substrate for mitochondrial respiration. This is due to the activity of a sulfide quinone reductase found in a large majority of mitochondria. An ongoing study of the metabolic state of liver in obese patients allowed us to evaluate the sulfide oxidation capacity with twelve preparations of human liver mitochondria. The results indicate relatively high rates of sulfide oxidation with a large variability between individuals. These observations made with isolated mitochondria appear in agreement with the main characteristics of sulfide oxidation as established before with the help of cellular models.

  18. Nanostructured lead sulfide: synthesis, structure and properties

    NASA Astrophysics Data System (ADS)

    Sadovnikov, S. I.; Gusev, A. I.; Rempel, A. A.

    2016-07-01

    The theoretical and experimental results of recent studies dealing with nanostructured lead sulfide are summarized and analyzed. The key methods for the synthesis of nanostructured lead sulfide are described. The crystal structure of PbS in nanopowders and nanofilms is discussed. The influence of the size of nanostructure elements on the optical and thermal properties of lead sulfide is considered. The dependence of the band gap of PbS on the nanoparticle (crystallite) size for powders and films is illustrated. The bibliography includes 222 references.

  19. Fluorescent probes for hydrogen sulfide (H2S) and sulfane sulfur and their applications to biological studies.

    PubMed

    Shimamoto, Kazuhito; Hanaoka, Kenjiro

    2015-04-30

    Hydrogen sulfide (H2S), a toxic gas with the smell of rotten eggs, plays key roles in many physiological processes, including relaxation of vascular smooth muscles, mediation of neurotransmission, inhibition of insulin signaling, and regulation of inflammation. The most commonly used methods or detecting H2S are the methylene blue method and the electrode method, but these methods require destructive sampling, e.g., homogenization of biological samples. On the other hand, the fluorescence detection method has been widely used in biological studies to study the physiological roles of H2S, because this technology provides real-time, easy-to-use, nondestructive detection in live cells or tissues. Many selective fluorescent probes for H2S have been reported. Sulfane sulfur compounds contain divalent sulfur atoms bonded to other sulfur atom(s), as in persulfides (R-S-SH) and polysulfides (R-S-Sn-S-R). They are currently attracting increasing interest because one of the mechanisms of activity regulation of proteins by H2S is sulfhydration of cysteine residues (RSH → RSSH). Since H2S and sulfane sulfur are redox partners, they are very likely to coexist in biological systems, and from a reactivity point-of-view, sulfane sulfur seems likely to be much more effective than H2S in S-sulfhydration. Therefore, sulfane sulfur may be involved in mediating at least some of the biological activities of H2S. In this review, we summarize recent work on fluorescent probes selective for H2S and/or sulfane sulfur, and we briefly review their applications to biological studies.

  20. Syntheses of amorphous and crystalline cupric sulfide nanoparticles and study on the specific activities on different cells.

    PubMed

    Guo, Yuming; Zhang, Jie; Yang, Lin; Wang, Huajie; Wang, Feifei; Zheng, Zhi

    2010-05-28

    Copper sulfide amorphous nanoparticles and nanocrystals were prepared successfully by a special process. These CuS nanoparticles could specifically and significantly induce the apoptosis and inhibit the proliferation of human cancer cells rather than normal cells. Moreover, the biological activities of these nanoparticles are related to their polymorphs.

  1. Quenching and radical formation in the reaction of photoexcited benzophenone with thiols and thioethers (sulfides). Nanosecond flash studies

    SciTech Connect

    Inbar, S.; Linschitz, H.; Cohen, S.G.

    1982-01-01

    Laser flash measurements have been made of rate constants and primary radical yields in the reactions of triplet benzophenone with aliphatic and aromatic thiols and with dialkyl and aryl alkyl sulfides. Reaction with n-pentylthiol in benzene leads mainly to quenching, with k/sub ir/ = 9 x 10/sup 6/ M/sup -1/ s/sup -1/ and radical yield (ketyl) = 0.14; with mesitylene-2 thiol in benzene k/sub ir/ = 7 x 10/sup 8/ M/sup -1/ s/sup -1/ and hydrogen transfer is efficient, radical yield (ketyl) approx. 1.0. In reactions with both p-chlorophenyl ethyl and diisopropyl sulfides, k/sub ir/ increases and radical yield (ketyl) decreases with increasing solvent polarity. Values of k/sub ir/ are higher and those of radical yield (ketyl) are lower for the dialkyl than for the aryl alkyl sulfide. Results are discussed in terms of rapid interaction of the triplet with S, followed by quenching and/or hydrogen transfer. Quenching without hydrogen transfer occurs to a much greater extent with sulfides and aliphatic thiols than with amines.

  2. Mechanistic study of the hydrodesulfurization of methanethiol over tungsten disulfide; a survey of rare earth sulfides for hydrodesulfurization activity

    SciTech Connect

    Dowd, D.Q.

    1985-06-01

    Hydrodesulfurization is a process whereby sulfur bound in organic compounds is removed as hydrogen sulfide, and is important to the control of sulfur dioxide emissions in the combustion of petroleum and coal fuels. It involves the cleavage of carbon sulfur bonds, and is catalyzed by layered disulfides such as molybdenum and tungsten disulfide. The simplest example is the reaction CH/sub 3/SH + H/sub 2/ ..-->.. CH/sub 4/ + H/sub 2/S. The mechanism of even this protypical reaction is unclear. In an effort to clarify it, the kinetics of methanethiol hydrodesulfurization over tungsten disulfide at low pressures was established, with partial pressures of methanethiol and hydrogen varied over a hundred fold. The kinetic order in each reactant was positive when its partial pressure was low negative when its partial pressure was high. The negative order in hydrogen had not been previously seen. The product gases, methane and hydrogen sulfide, each exhibited negative kinetic orders at high partial pressures, zero kinetic orders at low partial pressures. A dual site Langmuir-Hinshelwood type mechanism, which defines one active site as two adjacent edge sulfur vacancies and the second as a neighboring sulfur atom, describes these results quite well. Seventeen rare earth sulfides were surveyed for catalytic activity toward methanethiol hydrodesulfurization. These sulfides included both stoichiometric and nonstoichiometric compositions and four different morphologies. In general, nonconductors were inactive and conductors were active. This correlation extended to the nonstoichiometric ..gamma..-phase sesquisulfides which exhibit both insulating and conducting properties. 96 refs.

  3. Mechanistic study of the hydrodesulfurization of methanethiol over tungsten disulfide. II. A survey of rare earth sulfides for hydrodesulfurization activity

    SciTech Connect

    Dowd, D.Q.

    1985-01-01

    I. Hydrodesulfurization is a process whereby sulfur bound in organic compounds is removed as hydrogen sulfide, and is important to the control of sulfur dioxide emissions in the combustion of petroleum and coal fuels. It involves the cleavage of carbon sulfur bonds, and is catalyzed by layered disulfides such as molybdenum and tungsten disulfide. The simplest example is the reaction CH/sub 3/SH + H/sub 2/ ..-->.. CH/sub 4/ + H/sub 2/S. The mechanism of even this prototypical reaction is unclear. In an effort to clarify it, the kinetics of methanethiol hydro desulfurization over tungsten disulfide at low pressures was established, with partial pressures of methanethiol and hydrogen varied over a hundred fold. The kinetic order in each reactant was positive when its partial pressure was low, negative when its partial pressure was high. The negative order in hydrogen had not been previously seen. The product gases, methane and hydrogen sulfide, each exhibited negative kinetic orders at high partial pressures, zero kinetic orders at low partial pressures. A dual site Langmuir-Hinshelwood type mechanism, which defines one active site as two adjacent edge sulfur vacancies and the second as a neighboring sulfur atom, describes these results quite well. II. Seventeen rare earth sulfides were surveyed for catalytic activity toward methanethiol hydrodesulfurization. These sulfides included both stoichiometric and nonstoichiometric compositions and four different morphologies. In general, nonconductors were inactive and conductors were active. This correlation extended to the nonstoichiometric ..gamma..-phase sesquisulfides which exhibit both insulating and conducting properties.

  4. Metal-free metathesis reaction of C-chiral allylic sulfilimines with aryl isocyanates: construction of chiral nonracemic allylic isocyanates.

    PubMed

    Grange, Rebecca L; Evans, P Andrew

    2014-08-27

    We report the facile and efficient metal-free metathesis reaction of C-chiral allylic sulfilimines with aryl isocyanates. This process facilitates the room temperature construction of an array of chiral nonracemic allylic isocyanates, which are versatile intermediates for the construction of unsymmetrical ureas, carbamates, thiocarbamates and amides. Furthermore, the sulfilimine/isocyanate metathesis reaction with 4,4'-methylene diphenyl diisocyanate (4,4'-MDI) circumvents harsh reaction conditions and/or hazardous reagents employed with more classical methods for the preparation of this important functional group.

  5. The subchronic oral toxicity of polyphenylene sulfide.

    PubMed

    Thomas, W C; Kirwin, C J; Wazeter, F X; Jessup, D C

    1984-02-01

    Polyphenylene sulfide was offered to Charles River CD rats for 6 months in the diet at concentrations of 0.00, 0.50, 2.75 and 5.00% (w/w). In this study, animals of both sexes consumed polyphenylene sulfide for 6 months without exhibiting compound-related effects. Parameters studied were: body weight, hematology, clinical chemistry, urinalysis, organ weights, gross pathology and histopathology.

  6. Palladium-Catalyzed, Site-Selective Direct Allylation of Aryl C–H Bonds by Silver-Mediated C–H Activation: A Synthetic and Mechanistic Investigation

    PubMed Central

    Lee, Sarah Yunmi; Hartwig, John F.

    2016-01-01

    We describe a method for the site-selective construction of a C(aryl)–C(sp3) bond by the palladium-catalyzed direct allylation of arenes with allylic pivalates in the presence of AgOPiv to afford the linear (E)-allylated arene with excellent regioselectivity; this reaction occurs with arenes that have not undergone site-selective and stereoselective direct allylation previously, such as monofluorobenzenes and non-fluorinated arenes. Mechanistic studies indicate that AgOPiv ligated by a phosphine reacts with the arene to form an arylsilver(I) species, presumably through a concerted metalation–deprotonation pathway. The activated aryl moiety is then transferred to an allylpalladium(II) intermediate formed by oxidative addition of the allylic pivalate to the Pd(0) complex. Subsequent reductive elimination furnishes the allyl–aryl coupled product. The aforementioned proposed intermediates, including an arylsilver complex, have been isolated, structurally characterized, and determined to be chemically and kinetically competent to undergo the proposed elementary steps of the catalytic cycle. PMID:27797512

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

    PubMed

    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.

  8. Surface studies of the interaction of copper ions with metal sulfide minerals

    SciTech Connect

    Perry, D.L.; Tsao, L.; Taylor, J.A.

    1984-05-01

    The interaction of copper ions in aqueous solution with the surface of galena (PbS) and sphalerite (ZnS) has been studied using x-ray photoelectron spectroscopy (XPS), scanning Auger microscopy (SAM), and scanning electron microscopy (SEM). These studies were conducted with several of the experimental parameters of the chemical reaction systems being varied, the parameters including copper ion concentration, variation of the anion associated with the initial copper salt, temperature, reaction time, and pH. Scanning Auger microscopy was used for studying elemental segregation and mapping of the reacted mineral surfaces. A rigorous use of model compounds was made in the study of each mineral surface reaction system.

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

    NASA Astrophysics Data System (ADS)

    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. Sulfide Consumption in Sulfurimonas denitrificans and Heterologous Expression of Its Three Sulfide-Quinone Reductase Homologs.

    PubMed

    Han, Yuchen; Perner, Mirjam

    2016-04-01

    Sulfurimonas denitrificans is a sulfur-oxidizing epsilonproteobacterium. It has been reported to grow with sulfide and to harbor genes that encode sulfide-quinone reductases (SQRs) (catalyze sulfide oxidation). However, the actual sulfide concentrations at which S. denitrificans grows and whether its SQRs are functional remain enigmatic. Here, we illustrate the sulfide concentrations at which S. denitrificans exhibits good growth, namely, 0.18 mM to roughly 1.7 mM. Around 2.23 mM, sulfide appears to inhibit growth. S. denitrificans harbors three SQR homolog genes on its genome (Suden_2082 for type II SQR, Suden_1879 for type III SQR, and Suden_619 for type IV SQR). They are all transcribed in S. denitrificans. According to our experiments, they appear to be loosely bound to the membrane. Each individual S. denitrificans SQR was heterologously expressed in the Rhodobacter capsulatus SB1003 sqr deletion mutant, and all exhibited SQR activities individually. This suggests that all of these three genes encode functional SQRs. This study also provides the first experimental evidence of a functional bacterial type III SQR. Although the epsilonproteobacterium Sulfurimonas denitrificans has been described as using many reduced sulfur compounds as electron donors, there is little knowledge about its growth with sulfide. In many bacteria, the sulfide-quinone reductase (SQR) is responsible for catalyzing sulfide oxidation. S. denitrificans has an array of different types of sqr genes on its genome and so do several other sulfur-oxidizing Epsilonproteobacteria. However, whether these SQRs are functional has remained unknown. Here, we shed light on sulfide metabolism in S. denitrificans. Our study provides the first experimental evidence of active epsilonproteobacterial SQRs and also gives the first report of a functional bacterial type III SQR. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

  11. Cadmium sulfide/copper sulfide heterojunction cell research. Critical studies in materials and durability. Annual progress report, July 1, 1979-August 31, 1980

    SciTech Connect

    1981-01-01

    A summary of the structural and morphological features of CdS and (CdZn)S layers and their heterojunctions with Cu/sub 2/S is presented. The growth of the Cu/sub 2/S layer has been studied as a function of time for both the solution and solid state process using transmission electron microscopy. Preliminary observations have also been made on vapor and sputter deposited Cu/sub 2/S layers. The effect of oxidation and reduction heat treatments on the optical properties of Cu/sub 2/S are reported. Changes of cell performance with time for cells loaded to various points in the power quadrant are described.

  12. Is hydrogen sulfide a circulating "gasotransmitter" in vertebrate blood?

    PubMed

    Olson, Kenneth R

    2009-07-01

    Hydrogen sulfide (H(2)S) is gaining acceptance as a signaling molecule and has been shown to elicit a variety of biological effects at concentrations between 10 and 1000 micromol/l. Dissolved H(2)S is a weak acid in equilibrium with HS(-) and S(2-) and under physiological conditions these species, collectively referred to as sulfide, exist in the approximate ratio of 20% H(2)S, 80% HS(-) and 0% S(2-). Numerous analyses over the past 8 years have reported plasma or blood sulfide concentrations also in this range, typically between 30 and 300 micromol/l, thus supporting the biological studies. However, there is some question whether or not these concentrations are physiological. First, many of these values have been obtained from indirect methods using relatively harsh chemical conditions. Second, most studies conducted prior to 2000 failed to find blood sulfide in micromolar concentrations while others showed that radiolabeled (35)S-sulfide is rapidly removed from blood and that mammals have a relatively high capacity to metabolize exogenously administered sulfide. Very recent studies using H(2)S gas-sensing electrodes to directly measure sulfide in plasma or blood, or HPLC analysis of head-space gas, have also indicated that sulfide does not circulate at micromolar levels and is rapidly consumed by blood or tissues. Third, micromolar concentrations of sulfide in blood or exhaled air should be, but are not, malodorous. Fourth, estimates of dietary sulfur necessary to sustain micromolar levels of plasma sulfide greatly exceed the daily intake. Collectively, these studies imply that many of the biological effects of sulfide are only achieved at supra-physiological concentrations and they question whether circulating sulfide is a physiologically relevant signaling molecule. This review examines the blood/plasma sulfide measurements that have been reported over the past 30 years from the perspective of the analytical methods used and the potential sources of error.

  13. Activation parameters for cyclohexene oxygenation by an oxoiron(IV) porphyrin pi-cation radical complex: entropy control of an allylic hydroxylation reaction.

    PubMed

    Takahashi, Akihiro; Kurahashi, Takuya; Fujii, Hiroshi

    2007-08-06

    Activation parameters for epoxidation and allylic hydroxylation reactions of cyclohexene with FeIVO(TMP)*+Cl (1) were determined. Within the experimental temperature range, the epoxidation reaction was enthalpy-controlled (i.e., DeltaH > -TDeltaS), while the allylic hydroxylation reaction was entropy-controlled (i.e., -TDeltaS > DeltaH). An unexpectedly large contribution of the entropy term for the allylic hydroxylation reaction indicated that the free energy of activation, DeltaG, rather than the activation energy, Ea, should be used to discuss the reaction mechanism and chemoselectivity. The results of this study bring caution to previous density functional theory studies, in which the reaction mechanism and chemoselectivity are evaluated from calculated Ea.

  14. Interstellar hydrogen sulfide.

    NASA Technical Reports Server (NTRS)

    Thaddeus, P.; Kutner, M. L.; Penzias, A. A.; Wilson, R. W.; Jefferts, K. B.

    1972-01-01

    Hydrogen sulfide has been detected in seven Galactic sources by observation of a single line corresponding to the rotational transition from the 1(sub 10) to the 1(sub 01) levels at 168.7 GHz. The observations show that hydrogen sulfide is only a moderately common interstellar molecule comparable in abundance to H2CO and CS, but somewhat less abundant than HCN and much less abundant than CO.

  15. Interstellar hydrogen sulfide.

    NASA Technical Reports Server (NTRS)

    Thaddeus, P.; Kutner, M. L.; Penzias, A. A.; Wilson, R. W.; Jefferts, K. B.

    1972-01-01

    Hydrogen sulfide has been detected in seven Galactic sources by observation of a single line corresponding to the rotational transition from the 1(sub 10) to the 1(sub 01) levels at 168.7 GHz. The observations show that hydrogen sulfide is only a moderately common interstellar molecule comparable in abundance to H2CO and CS, but somewhat less abundant than HCN and much less abundant than CO.

  16. Order-disorder phase transition and dissociation of hydrogen sulfide under high pressure: Ab initio molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Wang, Liancheng; Tian, Fubo; Feng, Wanxiang; Chen, Changbo; He, Zhi; Ma, Yanming; Cui, Tian; Liu, Bingbing; Zou, Guangtian

    2010-04-01

    The structural and dynamical properties of phase IV and V of hydrogen sulfide were investigated by means of extensive ab initio molecular dynamics simulations. Starting from an experimental proposal for the structure of phase IV, an Ibca symmetry with a stable hydrogen bonding network is found at 15 GPa and 100 K. Molecular dynamics simulations at increasing temperature and at the pressure of 15 GPa suggest that phase IV will transform to a proton disordered structure at 15 GPa and 350 K. The newfound structure has a hexagonal lattice of P63/mmc symmetry, which is believed to be the remaining crystalline structure of phase V. The high mobility of protons in phase V is believed to be the key point to the dissociation and decomposition of hydrogen sulfide.

  17. An XPS study of gold deposition at low temperatures on sulfide minerals: Reducing agents

    SciTech Connect

    Hyland, M.M.; Bancroft, G.M. )

    1989-02-01

    The reduction of KAuCl{sub 4} to metallic gold by pyrite, high iron content sphalerite and galena was studied using surface analytical and solution techniques, including X-ray photoelectron spectroscopy (XPS) and atomic absorption spectroscopy (A.A.). High resolution XPS of the reacted mineral showed that the mineral surface is the Au reducing agent. On galena and high iron sphalerite, a corroded layer forms rapidly as S{sup 2 minus} is oxidized to polysulfides, S{sup 2{minus}}{sub x}, and the metals are leached from the surface. Although Au is also reduced on pyrite, the formation of surface polysulfide is not concurrent with Au reduction. Solution analysis for the pyrite and high iron sphalerite reactions shows, however, that considerable sulfate is produced due to the oxidation of S{sup 2{minus}}, S{sup 2{minus}}{sub 2} or the intermediate polysulphide.

  18. Study of the effects of gaseous environments on sulfidation attack of superalloys

    NASA Technical Reports Server (NTRS)

    Smeggil, J. G.; Bornstein, N. S.

    1977-01-01

    Studies were conducted to examine the effect of the gaseous corrodents NaCl, HCl, and NaOH on the high temperature oxidation and Na2SO4-induced corrosion behavior of the alumina former NiAl, the chromia former Ni-25 wt.% Cr, elemental Cr, and the superalloy B-1900. Experiments were conducted at 900 and 1050 C in air in the presence and absence of the gaseous corrodents. Effects involving both reaction rates and microstructural changes in oxide morphology were observed due to the presence of these corrodents at levels anticipated to be present in operating industrial and marine gas turbines. The effect of gaseous NaCl, HCl, and possibly NaOH on NiAl in simple oxidation was to remove aluminum from below the protective alumina layer and to simultaneously weaken the adherence of the protective alumina oxide scale to the substrate. The aluminum removed from below the oxide scale was redeposited on its surface as alpha-Al2O3 whiskers. With respect to the chromia formers, gaseous NaCl and HCl promoted breakaway oxidation kinetics and changes in the microstructures of the oxide scales.

  19. Ore mineralogy and sulfur isotope study of the massive sulfide deposit of Filon Norte, Tharsis Mine, Spain

    NASA Astrophysics Data System (ADS)

    Kase, K.; Yamamoto, M.; Nakamura, T.; Mitsuno, C.

    1990-10-01

    The volcanogenic massive sulfide deposit of Filon Norte at Tharsis is hosted by carbonaceous black slate and connected only partly with stockwork veins. The massive ores are usually composed of fine-grained pyrite with subordinate amounts of sphalerite, chalcopyrite, galena and arsenopyrite. Monoclinic pyrrhotite sometimes occurs in massive pyritic ores in the apparently middle and upper horizons of the orebody, and siderite-rich ores are interstratified with compact pyritic ores in the apparently lower horizons. From the occurrence of monoclinic pyrrhotite, together with the FeS contents of sphalerite mostly ranging from 11 to 16 mol %, it is inferred that the sulfide minerals of the massive orebody were precipitated in euxinic muds on the sea-floor at temperatures below 250°C. The negatively shifted, highly variable δ 34S values of the massive ores and their close similarity to those of the underlying black slates strongly suggest that the sulfide sulfur of the massive orebody and the slates is cognate and biogenic.

  20. Sulfide, the first inorganic substrate for human cells.

    PubMed

    Goubern, Marc; Andriamihaja, Mireille; Nübel, Tobias; Blachier, François; Bouillaud, Frédéric

    2007-06-01

    Hydrogen sulfide (H2S) is produced inside the intestine and is known as a poison that inhibits cellular respiration at the level of cytochrome oxidase. However, sulfide is used as an energetic substrate by many photo- and chemoautotrophic bacteria and by animals such as the lugworm Arenicola marina. The concentrations of sulfide present in their habitats are comparable with those present in the human colon. Using permeabilized colonic cells to which sulfide was added by an infusion pump we show that the maximal respiratory rate of colonocyte mitochondria in presence of sulfide compares with that obtained with succinate or L-alpha-glycerophosphate. This oxidation is accompanied by mitochondrial energization. In contrast, other cell types not naturally exposed to high concentration of sulfide showed much lower oxidation rates. Mitochondria showed a very high affinity for sulfide that permits its use as an energetic substrate at low micromolar concentrations, hence, below the toxic level. However, if the supply of sulfide exceeds the oxidation rate, poisoning renders mitochondria inefficient and our data suggest that an anaerobic mechanism involving partial reversion of Krebs cycle already known in invertebrates takes place. In conclusion, this work provides additional and compelling evidence that sulfide is not only a toxic compound. According to our study, sulfide appears to be the first inorganic substrate for mammalian cells characterized thus far.

  1. Stability studies of cadmium telluride/cadmium sulfide thin film solar cells

    NASA Astrophysics Data System (ADS)

    Tetali, Bhaskar Reddy

    CdTe/CdS solar cells have shown great potential for terrestrial solar power applications. To be commercially viable they need to operate efficiently for about 30 years. CdS/CdTe solar cells fabricated at USF have shown record efficiencies upto 16.5% [46]. This research involves the study of thermal stress (TS) and light soaking (LS) on the stability of high efficiency (>10%) solar cells. The change in key electrical parameters Voc, FF, J sc, A and Jo are quantified for more than 2000 hours of stressing. The device degradation was found to increase with stress temperature for TS. Below 100°C, the changes were due to collection and recombination losses. Above 100°C, "shunting" mechanisms were found to start affecting the device performance. A fast drop in performance within the first 500 hours was observed. It is believed to be due to an increase in deep-level Cu-related defects that increase with stress temperature. Diffusion of Cu i+ ions from the back contact along CdTe grain boundaries had been previously reported [16]. An increase in light/dark J-V crossover and bulk Rs with stress time and temperature was observed. A slow degradation component attributed to Cu-related substitutional defect [23] formation/diffusion to the junction and CdS is proposed. This should compensate the CdS over time and increase its photoconductivity/resistivity. An improvement in the current collection and FF within 100 hours of LS was observed. This is possibly due to the enhancement of Cui + diffusion into the junction and CdS during LS as previously reported [16]. A reduction in light/dark J-V crossover was observed, possibly due to an increase in CdS doping and reduction in the CdS/SnO2 front contact barrier. However, a fast decrease in Voc and increase in recombination current was also observed in the first 1000 hours of LS. This is possibly due to the existence of higher concentration of Cu-related deep level defects at the junction. A larger decrease in Voc was found for LS

  2. Terminal Olefins to Chromans, Isochromans, and Pyrans via Allylic C–H Oxidation

    PubMed Central

    2015-01-01

    The synthesis of chroman, isochroman, and pyran motifs has been accomplished via a combination of Pd(II)/bis-sulfoxide C–H activation and Lewis acid co-catalysis. A wide range of alcohols are found to be competent nucleophiles for the transformation under uniform conditions (catalyst, solvent, temperature). Mechanistic studies suggest that the reaction proceeds via initial C–H activation followed by a novel inner-sphere functionalization pathway. Consistent with this, the reaction shows reactivity trends orthogonal to those of traditional Pd(0)-catalyzed allylic substitutions. PMID:24983326

  3. [Inhibition of aflatoxin production and fungal growth on stored corn by allyl isothiocyanate vapor].

    PubMed

    Okano, Kiyoshi; Ose, Ayaka; Takai, Mitsuhiro; Kaneko, Misao; Nishioka, Chikako; Ohzu, Yuji; Odano, Masayoshi; Sekiyama, Yasushi; Mizukami, Yuichi; Nakamura, Nobuya; Ichinoe, Masakatsu

    2015-01-01

    Studies were conducted to determine the effectiveness of allyl isothiocyanate (AIT) vapor treatment with a commercial mustard seed extract (Wasaouro(®)) in controlling aflatoxin-producing fungi on stored corn. The concentration of AIT in the closed container peaked at 54.6 ng/mL on the 14th day and remained at 21.8 ng/mL on the 42nd day. AIT inhibited visible growth of aflatoxigenic molds in unsterilized corn and in sterilized corn inoculated with various aflatoxigenic fungi. However, fungi such as Aspergillus glaucus group, A. penicillioides and A. restrictus were detected by means of culture methods.

  4. Terminal olefins to chromans, isochromans, and pyrans via allylic C-H oxidation.

    PubMed

    Ammann, Stephen E; Rice, Grant T; White, M Christina

    2014-08-06

    The synthesis of chroman, isochroman, and pyran motifs has been accomplished via a combination of Pd(II)/bis-sulfoxide C-H activation and Lewis acid co-catalysis. A wide range of alcohols are found to be competent nucleophiles for the transformation under uniform conditions (catalyst, solvent, temperature). Mechanistic studies suggest that the reaction proceeds via initial C-H activation followed by a novel inner-sphere functionalization pathway. Consistent with this, the reaction shows reactivity trends orthogonal to those of traditional Pd(0)-catalyzed allylic substitutions.

  5. 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

    NASA Astrophysics Data System (ADS)

    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

  6. Enhanced reductive dechlorination of trichloroethylene by sulfidated nanoscale zerovalent iron.

    PubMed

    Rajajayavel, Sai Rajasekar C; Ghoshal, Subhasis

    2015-07-01

    Direct injection of reactive nanoscale zerovalent iron particles (NZVI) is considered to be a promising approach for remediation of aquifers contaminated by chlorinated organic pollutants. In this study we show that the extent of sulfidation of NZVI enhances the rate of dechlorination of trichloroethylene (TCE) compared to that by unamended NZVI, and the enhancement depends on the Fe/S molar ratio. Experiments where TCE was reacted with NZVI sulfidated to different extents (Fe/S molar ratios 0.62-66) showed that the surface-area normalized first-order TCE degradation rate constant increased up to 40 folds compared to non-sulfidated NZVI. Fe/S ratios in the range of 12-25 provided the highest TCE dechlorination rates, and rates decreased at both higher and lower Fe/S. In contrast, sulfidated NZVI exposed to water in the absence of TCE showed significantly lower hydrogen evolution rate (2.75 μmol L(-1) h(-1)) compared to that by an unamended NZVI (6.92 μmol L(-1) h(-1)), indicating that sulfidation of NZVI suppressed corrosion reactions with water. Sulfide (HS(-)) ions reacted rapidly with NZVI and X-ray photoelectron spectroscopy analyses showed formation of a surface layer of FeS and FeS2. We propose that more electrons are preferentially conducted from sulfidated NZVI than from unamended NZVI to TCE, likely because of greater binding of TCE on the reactive sites of the iron sulfide outer layer. Resuspending sulfidated NZVI in sulfide-free or sulfide containing solutions altered the TCE degradation rate constants because of changes in the FeS layer thickness. Sulfidated NZVI maintained its high reactivity in the presence of multiple mono and divalent ions and with polyelectrolyte coatings. Thus, sulfide ions in groundwater can significantly alter NZVI reactivity.

  7. Allyl isothiocyanate: comparative disposition in rats and mice

    SciTech Connect

    Ioannou, Y.M.; Burka, L.T.; Matthews, H.B.

    1984-09-15

    Allyl isothiocyanate (AITC), the major component of volatile oil of mustard, was recently reported to induce transitional-cell papillomas in the urinary bladder of male Fischer 344 rats, but not in the bladders of female rats or B6C3F1 mice. The present investigation of comparative disposition in both sexes of each species was designed to detect sex or species differences in disposition which might explain susceptibility to AITC toxicity. AITC was readily cleared from all rat and mouse tissues so that within 24 hrs. after administration less than 5% of the total dose was retained in tissues. The highest concentration of AITC-derived radioactivity was observed in male rat bladder. Clearance of AITC-derived radioactivity by each species was primarily in urine (70 to 80%) and in exhaled air (13 to 15%) with lesser amounts in feces (3 to 5%). Rats excreted one major and four minor metabolites in urine. The major metabolite from rat urine was identified by NMR spectroscopy to be the mercapturic acid N-acetyl-S-(N-allylthiocarbamoyl)-L-cysteine. Mice excreted in urine the same major metabolite identified in rat urine as well as three other major and two minor metabolites. Sex-related variations were observed in the relative amounts of these metabolites. Both species excreted a single metabolite in feces. Metabolism of AITC by male and female rats was similar, but female rats excreted over twice the urine volume of male rats. Results of the present study indicate that excretion of a more concentrated solution of AITC metabolite(s) in urine may account for the toxic effects of AITC on the bladder of male rats.

  8. Sulindac sulfide--induced stimulation of eryptosis.

    PubMed

    Zbidah, Mohanad; Lupescu, Adrian; Yang, Wenting; Bosc, Anastasia; Jilani, Kashif; Shaik, Nazneen; Lang, Florian

    2012-01-01

    Sulindac sulfide, a non-steroidal anti-inflammatory drug (NSAID), stimulates apoptosis of tumor cells and is thus effective against malignancy. In analogy to apoptosis of nucleated cells, erythrocytes may undergo eryptosis, an apoptosis-like suicidal erythrocyte death, characterized by cell shrinkage and cell membrane scrambling with phosphatidylserine-exposure at the cell surface. Stimulators of eryptosis include increase of cytosolic Ca(2+)-activity ([Ca(2+)](i)) and ceramide formation. The present study explored, whether sulindac sulfide stimulates eryptosis. [Ca(2+)](i) was estimated from Fluo-3 fluorescence, cell volume from forward scatter, phosphatidylserine-exposure from binding of fluorescent annexin-V, hemolysis from hemoglobin release, and ceramide abundance utilizing fluorescent antibodies. A 48 h exposure to sulindac sulfide (≤ 20 µM) was followed by significant increase of [Ca(2+)](i), enhanced ceramide abundance, decreased forward scatter and increased percentage of annexin-V-binding erythrocytes. Sulindac sulfide triggered slight but significant hemolysis. Removal of extracellular Ca(2+) significantly blunted, but did not abrogate the effect of sulindac sulfide (20 µM) on annexin-V-binding. Sulindac sulfide stimulates the suicidal death of erythrocytes or eryptosis, an effect paralleled by Ca(2+)-entry, ceramide formation, cell shrinkage and phosphatidylserine-exposure. Copyright © 2012 S. Karger AG, Basel.

  9. Hydrogen-Bond Directed Regioselective Pd-Catalyzed Asymmetric Allylic Alkylation: The Construction of Chiral α-Amino Acids with Vicinal Tertiary and Quaternary Stereocenters.

    PubMed

    Wei, Xuan; Liu, Delong; An, Qianjin; Zhang, Wanbin

    2015-12-04

    A Pd-catalyzed asymmetric allylic alkylation of azlactones with 4-arylvinyl-1,3-dioxolan-2-ones was developed, providing "branched" chiral α-amino acids with vicinal tertiary and quaternary stereocenters, in high yields and with excellent selectivities. Mechanistic studies revealed that the formation of a hydrogen bond between the Pd-allylic complex and azlactone isomer is responsible for the excellent regioselectivities. This asymmetric alkylation can be carried out on a gram scale without a loss of catalytic efficiency, and the resulting product can be further transformed to a chiral azetidine in two simple steps.

  10. Catalytic, nucleophilic allylation of aldehydes with 2-substituted allylic acetates: carbon-carbon bond formation driven by the water-gas shift reaction.

    PubMed

    Denmark, Scott E; Matesich, Zachery D

    2014-07-03

    The ruthenium-catalyzed allylation of aldehydes with allylic acetates has been expanded to incorporate substituents at the 2-position of the allylic components. Allylic acetates bearing a variety of substituents (CO2-t-Bu, COMe, Ph, CH(OEt)2, and Me) undergo high-yielding additions with aromatic, α,β-unsaturated, and aliphatic aldehydes. The conditions of the reaction were found to be mild (75 °C, 24-48 h) and only required the use of 2-3 mol % of the triruthenium dodecacarbonyl catalyst under 40-80 psi of CO. The stoichiometries of water and allylic acetate employed were found to be critical to reaction efficiency.

  11. Postharvest application of brassica meal-derived allyl-isothiocyanate to kiwifruit: effect on fruit quality, nutraceutical parameters and physiological response.

    PubMed

    Ugolini, Luisa; Righetti, Laura; Carbone, Katya; Paris, Roberta; Malaguti, Lorena; Di Francesco, Alessandra; Micheli, Laura; Paliotta, Mariano; Mari, Marta; Lazzeri, Luca

    2017-03-01

    The use of natural compounds to preserve fruit quality and develop high value functional products deserves attention especially in the growing industry of processing and packaging ready-to-eat fresh-cut fruit. In this work, potential mechanisms underlying the effects of postharvest biofumigation with brassica meal-derived allyl-isothiocyanate on the physiological responses and quality of 'Hayward' kiwifruits were studied. Fruits were treated with 0.15 mg L(-1) of allyl-isothiocyanate vapours for 5 h and then stored in controlled atmosphere (2% O2, 4.5% CO2) at 0 °C and 95% relative humidity, maintaining an ethylene concentration <0.02 μL L(-1). The short- and long-term effects of allyl-isothiocyanate on fruit quality traits, nutraceutical attributes, glutathione content, antiradical capacity and the activity of antioxidant enzymes were investigated. The treatment did not influence the overall fruit quality after 120 days of storage, but interestingly it enhanced the ascorbic acid, polyphenols and flavan-3-ol content, improving the antioxidant potential of kiwifruit. The short-term effect of allyl-isothiocyanate was evidenced by an increase of superoxide dismutase activity and of oxidative glutathione redox state, which were restored 24 h after the treatment. The expression levels of genes involved in detoxification functions, ethylene, ascorbate and phenylpropanoid biosynthesis, were also significantly affected upon allyl-isothiocyanate application. These results suggest that allyl-isothiocyanate treatment probably triggered an initial oxidative burst, followed by an induction of protective mechanisms, which finally increased the nutraceutical and technological value of treated kiwifruits.

  12. Marine diagenesis of hydrothermal sulfide

    SciTech Connect

    Moammar, M.O.

    1985-01-01

    An attempt is made to discuss the artificial and natural oxidation and hydrolysis of hydrothermal sulfide upon interaction with normal seawater. Synthetic and natural ferrosphalerite particles used in kinetic oxidation and hydrolysis studies in seawater develop dense, crystalline coatings consisting of ordered and ferrimagnetic delta-(Fe, Zn)OOH. Due to the formation of this reactive diffusion barrier, the release of Zn into solution decreases rapidly, and sulfide oxidation is reduced to a low rate determined by the diffusion of oxygen through the oxyhydroxide film. This also acts as an efficient solvent for ions such as Zn/sup 2 +/, Ca/sup 2 +/, and possibly Cd/sup 2 +/, which contribute to the stabilization of the delta-FeOOH structure. The oxidation of sulfide occurs in many seafloor spreading areas, such as 21/sup 0/N on the East Pacific Ridge. In these areas the old surface of the sulfide chimneys are found to be covered by an orange stain, and sediment near the base of nonactive vents is also found to consist of what has been referred to as amorphous iron oxide and hydroxide. This thesis also discusses the exceedingly low solubility of zinc in seawater, from delta-(Fe, Zn)OOH and the analogous phase (zinc-ferrihydroxide) and the zinc exchange minerals, 10-A manganate and montmorillonite. The concentrations of all four are of the same magnitude (16, 36.4, and 12 nM, respectively) as the zinc concentration in deep ocean water (approx. 10 nM), which suggests that manganates and montmorillonite with iron oxyhydroxides control zinc concentration in the deep ocean.

  13. Mitochondria and sulfide: a very old story of poisoning, feeding, and signaling?

    PubMed

    Bouillaud, Frédéric; Blachier, François

    2011-07-15

    Sulfide is a molecule with toxicity comparable to that of cyanide. It inhibits mitochondrial cytochrome oxidase at submicromolar concentrations. However, at even lower concentrations, sulfide is a substrate for the mitochondrial electron transport chain in mammals, and is comparable to succinate. This oxidation involves a sulfide quinone reductase. Sulfide is thus oxidized before reaching a toxic concentration, which explains why free sulfide concentrations are very low in mammals, even though sulfide is constantly released as a result of cellular metabolism. It has been suggested that sulfide has signaling properties in mammals like two other gases, NO and CO, which are also cytochrome oxidase inhibitors. The oxidation of sulfide by mitochondria creates further complexity in the description/use of sulfide signaling in mammals. In fact, in the many studies reported in the literature, the sulfide concentrations that have been used were well within the range that affects mitochondrial activity. This review focuses on the relevance of sulfide bioenergetics to sulfide biology and discusses the case of colonocytes, which are routinely exposed to higher sulfide concentrations. Finally, we offer perspectives for future studies on the relationship between the two opposing aspects of this Janus-type molecule, sulfide.

  14. ION EXCHANGE SUBSTANCES BY SAPONIFICATION OF ALLYL PHOSPHATE POLYMERS

    DOEpatents

    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.

  15. Distribution and function of the hydrogen sulfide-sensitive TRPA1 ion channel in rat urinary bladder.

    PubMed

    Streng, Tomi; Axelsson, Helena E; Hedlund, Petter; Andersson, David A; Jordt, Sven-Eric; Bevan, Stuart; Andersson, Karl-Erik; Högestätt, Edward D; Zygmunt, Peter M

    2008-02-01

    To investigate the distribution of the transient receptor potential (TRP) A1 ion channel in the rat urinary bladder, and to study the effects of hydrogen sulfide (H(2)S) and known TRPA1 activators on micturition in conscious rats and on heterologously expressed ion channels. The expression of TRPA1 in urinary bladder was studied with fluorescence immunohistochemistry and real-time PCR in female Sprague-Dawley rats. Cystometric investigations were performed in conscious animals subjected to intravesical administration of sodium hydrogen sulfide (NaHS, donor of H(2)S), allyl isothiocyanate (AI), and cinnamaldehyde (CA). Fluorometric calcium imaging was used to study the effect of NaHS on human and mouse TRPA1 expressed in CHO cells. TRPA1 immunoreactivity was found on unmyelinated nerve fibres within the urothelium, suburothelial space, and muscle layer as well as around blood vessels throughout the bladder. All TRPA1 immunoreactive nerves fibres also expressed TRPV1 immunoreactivity and vice versa. TRPA1 was also detected in urothelial cells at both transcriptional and protein levels. AI increased micturition frequency and reduced voiding volume. CA and NaHS produced similar changes in urodynamic parameters after disruption of the urothelial barrier with protamine sulfate. NaHS also induced calcium responses in TRPA1-expressing CHO cells, but not in untransfected cells. The expression of TRPA1 on C-fibre bladder afferents and urothelial cells together with the finding that intravesical TRPA1 activators initiate detrusor overactivity indicate that TRPA1 may have a role in sensory transduction in this organ. The study also highlights H(2)S as a TRPA1 activator potentially involved in inflammatory bladder disease.

  16. General, Simple, and Chemoselective Catalysts for the Isomerization of Allylic Alcohols: The Importance of the Halide Ligand.

    PubMed

    Erbing, Elis; Vázquez-Romero, Ana; Bermejo Gómez, Antonio; Platero-Prats, Ana E; Carson, Fabian; Zou, Xiaodong; Tolstoy, Päivi; Martín-Matute, Belén

    2016-10-24

    Remarkably simple Ir(III) catalysts enable the isomerization of primary and sec-allylic alcohols under very mild reaction conditions. X-ray absorption spectroscopy (XAS) and mass spectrometry (MS) studies indicate that the catalysts, with the general formula [Cp*Ir(III) ], require a halide ligand for catalytic activity, but no additives or additional ligands are needed. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Pd(Quinox)-Catalyzed Allylic Relay Suzuki Reactions of Secondary Homostyrenyl Tosylates via Alkene-Assisted Oxidative Addition.

    PubMed

    Stokes, Benjamin J; Bischoff, Amanda J; Sigman, Matthew S

    2014-06-01

    Pd-catalyzed allylic relay Suzuki cross-coupling reactions of secondary alkyl tosylates, featuring a sterically-hindered oxidative addition and precise control of β-hydride elimination, are reported. The identification of a linear free energy relationship between the relative rates of substrate consumption and the electronic nature of the substrate alkene suggests that the oxidative addition requires direct alkene involvement. A study of the effect of chain length on the reaction outcome supports a chelation-controlled oxidative addition.

  18. Low-temperature synthesis of allyl dimethylamine by selective heating under microwave irradiation used for water treatment

    NASA Astrophysics Data System (ADS)

    Tian, Binghui; Luan, Zhaokun; Li, Mingming

    2005-08-01

    Low-temperature synthesis of allyl dimethylamine (ADA) by selective heating under microwave irradiation (MI) used for water treatment is investigated. The effect of MI, ultrasound irradiation (UI) and conventional heating on yield of ADA, reaction time and the flocculation efficiency of polydiallyl dimethylammunion chloride (PDADMAC) prepared form ADA were studied. The results show that by selective heating at low temperature, MI not only increases yield of ADA and reduces reaction time, but also greatly enhances the flocculation efficiency of PDADMAC.

  19. Highly selective indium mediated allylation of unprotected pentosylamines.

    PubMed

    Behr, Jean-Bernard; Hottin, Audrey; Ndoye, Alpha

    2012-03-16

    A straightforward functionalization of D-pentoses is reported, which affords homoallylaminopolyols in two steps and uses ion exchange chromatography as the only purification operation. The key indium-mediated allylation is effected on unprotected glycosylamines and occurs with good to excellent syn stereoselection. Validation of the synthetic utility of the method was exemplified by a 3-step synthesis of an optically active 1,2,3,6-tetrahydropyridine from D-xylose.

  20. Rh2(esp)2-catalyzed allylic and benzylic oxidations.

    PubMed

    Wang, Yi; Kuang, Yi; Wang, Yuanhua

    2015-04-07

    The dirhodium(II) catalyst Rh2(esp)2 allows direct solvent-free allylic and benzylic oxidations by T-HYDRO with a remarkably low catalyst loading. This method is operationally simple and scalable at ambient temperature without the use of any additives. The high catalyst stability in these reactions may be attributed to a dirhodium(II,II) catalyst resting state, which is less prone to decomposition.

  1. Copper-catalyzed trifluoromethylation of trisubstituted allylic and homoallylic alcohols.

    PubMed

    Lei, Jian; Liu, Xiaowu; Zhang, Shaolin; Jiang, Shuang; Huang, Minhao; Wu, Xiaoxing; Zhu, Qiang

    2015-04-27

    An efficient copper-catalyzed trifluoromethylation of trisubstituted allylic and homoallylic alcohols with Togni's reagent has been developed. This strategy, accompanied by a double-bond migration, leads to various branched CF3-substituted alcohols by using readily available trisubstituted cyclic/acyclic alcohols as substrates. Moreover, for alcohols in which β-H elimination is prohibited, CF3-containing oxetanes are isolated as the sole product.

  2. Mineralogical studies of sulfide samples and volatile concentrations of basalt glasses from the southern Juan de Fuca Ridge.

    USGS Publications Warehouse

    Brett, R.; Evans, H.T.; Gibson, E.K.; Hedenquist, J.W.; Wandless, M.-V.; Sommer, M.A.

    1987-01-01

    Specifically considers unusual minerals and geothermometric relations not previously covered. Equilibrium, if attained at all, during deposition of most sulfides was a transient event over a few tens of micrometers at most and was perturbed by rapid temperature and compositional changes of the circulating fluid. Two new minerals were found: one, a hydrated Zn, Fe hydroxy-chlorosulfate, and the other, a (Mn, Mg, Fe) hydroxide or hydroxy-hydrate. Both were formed at relatively low temperatures. Lizardite, starkeyite, and anatase were found for the first time in such an environment.-from Authors

  3. Palladium-catalyzed regio- and enantioselective fluorination of acyclic allylic halides.

    PubMed

    Katcher, Matthew H; Sha, Allen; Doyle, Abigail G

    2011-10-12

    This report describes the Pd(0)-catalyzed fluorination of linear allylic chlorides and bromides, yielding branched allylic fluorides in high selectivity. Many of the significant synthetic limitations previously associated with the preparation of these products are overcome by this catalytic method. We also demonstrate that a chiral bisphosphine-ligated palladium catalyst enables highly enantioselective access to a class of branched allylic fluorides that can be readily diversified to valuable fluorinated products.

  4. Infrared spectroscopy of gas phase C{sub 3}H{sub 5}{sup +}: The allyl and 2-propenyl cations

    SciTech Connect

    Douberly, Gary E.; Ricks, Allen M.; Schleyer, Paul v. R.; Duncan, Michael A.

    2008-01-14

    C{sub 3}H{sub 5}{sup +} cations are probed with infrared photodissociation spectroscopy in the 800-3500 cm{sup -1} region using the method of rare gas tagging. The ions and their complexes with Ar or N{sub 2} are produced in a pulsed electric discharge supersonic expansion cluster source. Two structural isomers are characterized, namely, the allyl (CH{sub 2}CHCH{sub 2}{sup +}) and 2-propenyl (CH{sub 3}CCH{sub 2}{sup +}) cations. The infrared spectrum of the allyl cation confirms previous theoretical and condensed phase studies of the C{sub 2v} charge delocalized, resonance-stabilized structure. The 2-propenyl cation spectrum is consistent with a C{sub s} symmetry structure having a nearly linear CCC backbone and a hyperconjugatively stabilizing methyl group.

  5. A review of the fundamental studies of the copper activation mechanisms for selective flotation of the sulfide minerals, sphalerite and pyrite.

    PubMed

    Chandra, A P; Gerson, A R

    2009-01-30

    A review of the considerable, but often contradictory, literature examining the specific surface reactions associated with copper adsorption onto the common metal sulfide minerals sphalerite, (Zn,Fe)S, and pyrite (FeS(2)), and the effect of the co-location of the two minerals is presented. Copper "activation", involving the surface adsorption of copper species from solution onto mineral surfaces to activate the surface for hydrophobic collector attachment, is an important step in the flotation and separation of minerals in an ore. Due to the complexity of metal sulfide mineral containing systems this activation process and the emergence of activation products on the mineral surfaces are not fully understood for most sulfide minerals even after decades of research. Factors such as copper concentration, activation time, pH, surface charge, extent of pre-oxidation, water and surface contaminants, pulp potential and galvanic interactions are important factors affecting copper activation of sphalerite and pyrite. A high pH, the correct reagent concentration and activation time and a short time delay between reagent additions is favourable for separation of sphalerite from pyrite. Sufficient oxidation potential is also needed (through O(2) conditioning) to maintain effective galvanic interactions between sphalerite and pyrite. This ensures pyrite is sufficiently depressed while sphalerite floats. Good water quality with low concentrations of contaminant ions, such as Pb(2+)and Fe(2+), is also needed to limit inadvertent activation and flotation of pyrite into zinc concentrates. Selectivity can further be increased and reagent use minimised by opting for inert grinding and by carefully choosing selective pyrite depressants such as sulfoxy or cyanide reagents. Studies that approximate plant conditions are essential for the development of better separation techniques and methodologies. Improved experimental approaches and surface sensitive techniques with high spatial

  6. Direct and enantioselective α-allylation of ketones via singly occupied molecular orbital (SOMO) catalysis

    PubMed Central

    Mastracchio, Anthony; Warkentin, Alexander A.; Walji, Abbas M.; MacMillan, David W. C.

    2010-01-01

    The first enantioselective organocatalytic α-allylation of cyclic ketones has been accomplished via singly occupied molecular orbital catalysis. Geometrically constrained radical cations, forged from the one-electron oxidation of transiently generated enamines, readily undergo allylic alkylation with a variety of commercially available allyl silanes. A reasonable latitude in both the ketone and allyl silane components is readily accommodated in this new transformation. Moreover, three new oxidatively stable imidazolidinone catalysts have been developed that allow cyclic ketones to successfully participate in this transformation. The new catalyst platform has also been exploited in the first catalytic enantioselective α-enolation and α-carbooxidation of ketones. PMID:20921367

  7. Iridium-catalyzed enantioselective allylic substitution of unstabilized enolates derived from α,β-unsaturated ketones.

    PubMed

    Chen, Ming; Hartwig, John F

    2014-08-11

    We report Ir-catalyzed, enantioselective allylic substitution reactions of unstabilized silyl enolates derived from α,β-unsaturated ketones. Asymmetric allylic substitution of a variety of allylic carbonates with silyl enolates gave allylated products in 62-94% yield with 90-98% ee and >20:1 branched-to-linear selectivity. The synthetic utility of this method was illustrated by the short synthesis of an anticancer agent, TEI-9826. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. SULFIDE METHOD PLUTONIUM SEPARATION

    DOEpatents

    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.

  9. Neutron diffraction study of magnetic ordering of the manganese bismuth chloro-sulfide: MnBiS{sub 2}Cl

    SciTech Connect

    Doussier-Brochard, C.; Leone, P. Andre, G.; Moelo, Y.

    2009-04-02

    In quaternary compounds of Mn{sup 2+}PnQ{sub 2}X (Pn = Sb, Bi; Q = S, Se; X = Cl, Br, I), Mn atoms in octahedral coordination (4 Q and 2 X) form waved layers separated by Pn atoms. The magnetic structure of the manganese bismuth chloro-sulfide MnBiS{sub 2}Cl has been determined by neutron powder diffraction, revealing a magnetic ordering with an incommensurate wave-vector along b-axis (k = [0, 0.3978, 0]) at 1.6 K. Two modulation models, sinusoidal and helicoidal, give quite equivalent magnetic reliability factors (R{sub mag} = 0.0450 and 0.0481, respectively). The magnetic moment decreases with increasing temperature, to zero at T{sub N} = 32 K. The evolution of the propagation wave-vector shows an irregularity at about 28 K. It could evidence two-phase transitions in agreement with the specific heat measurements. These results are compared to those of manganese antimony chloro-sulfide MnSbS{sub 2}Cl, isotypic with MnBiS{sub 2}Cl.

  10. Laboratory Studies of Aedes aegypti Attraction to Ketones, Sulfides, and Primary Chloroalkanes Tested Alone and in Combination with L-Lactic Acid.

    PubMed

    Bernier, Ulrich R; Kline, Daniel L; Allan, Sandra A; Barnard, Donald R

    2015-03-01

    The attraction of female Aedes aegypti to single compounds and binary compositions containing L-lactic acid and an additional saturated compound from a set of ketones, sulfides, and chloroalkanes was studied using a triple-cage dual-port olfactometer. These chemical classes were studied because of their structural relation to acetone, dimethyl disulfide, and dichloromethane, which have all been reported to synergize attraction to L-lactic acid. Human odors, carbon dioxide, and the binary mixture of L-lactic acid and CO₂served as controls for comparison of attraction responses produced by the binary mixtures. All tested mixtures that contained chloroalkanes attracted mosquitoes at synergistic levels, as did L-lactic acid and CO₂. Synergism was less frequent in mixtures of L-lactic acid with sulfides and ketones; in the case of ketones, synergistic attraction was observed only for L-lactic acid combined with acetone or butanone. Suppression or inhibition of attraction response was observed for combinations that contained ketones of C7-C12 molecular chain length (optimum in the C8-C10 range). This inhibition effect is similar to that observed previously for specific ranges of carboxylic acids, aldehydes, and alcohols.

  11. Quantum Mechanics/Molecular Mechanics Studies on the Sulfoxidation of Dimethyl Sulfide by Compound I and Compound 0 of Cytochrome P450: Which Is the Better Oxidant?

    NASA Astrophysics Data System (ADS)

    Porro, Cristina S.; Sutcliffe, Michael J.; de Visser, Sam P.

    2009-06-01

    The cytochromes P450 are ubiquitous enzymes that are involved in key metabolizing processes in the body through the monoxygenation of substrates; however, their active oxidant is elusive. There have been reports that implicate that two oxidants, namely, the iron(IV)-oxo porphyrin cation radical (compound I) and the iron(III)-hydroperoxo complex (compound 0), both act as oxidants of sulfoxidation reactions, which contrasts theoretical studies on alkene epoxidation by compounds I and 0 that implicated compound 0 as a sluggish oxidant. To resolve this controversy and to establish the potency of compound I and compound 0 in sulfoxidation reactions, we have studied dimethyl sulfide sulfoxidation by both oxidants using the quantum mechanics/molecular mechanics (QM/MM) technique on cytochrome P450 enzymes and have set up a model of two P450 isozymes: P450cam and P450BM3. The calculations support earlier gas-phase density functional theory modeling and show that compound 0 is a sluggish oxidant that is unable to compete with compound I. Furthermore, compound I is shown to react with dimethyl sulfide via single-state reactivity on a dominant quartet spin state surface.

  12. Toxicological analysis of 17 autopsy cases of hydrogen sulfide poisoning resulting from the inhalation of intentionally generated hydrogen sulfide gas.

    PubMed

    Maebashi, Kyoko; Iwadate, Kimiharu; Sakai, Kentaro; Takatsu, Akihiro; Fukui, Kenji; Aoyagi, Miwako; Ochiai, Eriko; Nagai, Tomonori

    2011-04-15

    Although many cases of fatal hydrogen sulfide poisoning have been reported, in most of these cases, it resulted from the accidental inhalation of hydrogen sulfide gas. In recent years, we experienced 17 autopsy cases of fatal hydrogen sulfide poisoning due to the inhalation of intentionally generated hydrogen sulfide gas. In this study, the concentrations of sulfide and thiosulfate in blood, urine, cerebrospinal fluid and pleural effusion were examined using GC/MS. The sulfide concentrations were blood: 0.11-31.84, urine: 0.01-1.28, cerebrospinal fluid: 0.02-1.59 and pleural effusion: 2.00-8.59 (μg/ml), while the thiosulfate concentrations were blood: 0-0.648, urine: 0-2.669, cerebrospinal fluid: 0.004-0.314 and pleural effusion: 0.019-0.140 (μmol/ml). In previous reports, the blood concentration of thiosulfate was said to be higher than that of sulfide in hydrogen sulfide poisoning cases, although the latter was higher than the former in 8 of the 14 cases examined in this study. These results are believed to be strongly influenced by the atmospheric concentration of hydrogen sulfide the victims were exposed to and the time interval between exposure and death.

  13. Hydrogen recovery from hydrogen sulfide by oxidation and by decomposition

    SciTech Connect

    Yang, B.L.; Kung, H.H. . Ipatieff Lab. and Chemical Engineering Dept.)

    1994-05-01

    Selective oxidation of hydrogen sulfide to hydrogen and sulfur oxides in a two-step process and the catalytic decomposition of hydrogen sulfide were studied for the recovery of hydrogen from hydrogen sulfide. Platinum, when adequately dispersed on a silica support, was found to be effective in reacting with hydrogen sulfide to produce hydrogen and platinum sulfide at 500 C. The platinum sulfide could then be treated with oxygen at 400 C to release sulfur oxides and regenerate the platinum. However, oxidation of sulfur dioxide to trioxide, retention of oxygen by platinum, and adsorption of hydrogen sulfide by the silica support also occurred, which resulted in a minor loss in hydrogen yield. In the decomposition of hydrogen sulfide, platinum sulfide was found to be catalytically active. The equilibrium hydrogen yields were measured experimentally over the range 350--650 C and compared with the values calculated on the basis of a model that included the S, allotropes, the H[sub 2]S[sub n] sulfanes, and HS. The values agreed well at low temperatures but deviated from each other up to 20% at high temperatures.

  14. Performance of a sulfide-oxidizing, sulfur-producing membrane biofilm reactor treating sulfide-containing bioreactor effluent.

    PubMed

    Sahinkaya, Erkan; Hasar, Halil; Kaksonen, Anna H; Rittmann, Bruce E

    2011-05-01

    Sulfide-containing waste streams are generated in mining, petrochemical plants, tanneries, viscose rayon manufacture, and the gasification of coal. Colorless sulfur bacteria can oxidize sulfide to elemental sulfur (S°), which can be recovered, when oxygen is their electron acceptor. This study evaluated sulfide oxidation and S° recovery in an oxygen-based membrane biofilm reactor (MBfR) treating the effluent from a sulfidogenic anaerobic baffled reactor. Sulfide oxidation efficiency (37-99%) and S° recovery (64-89% of oxidized sulfide) could be controlled by manipulating the sulfide loading, oxygen pressure to the fibers, and hydraulic retention time (HRT). For example, too-low oxygen pressure decreased S° recovery due to decreased sulfide oxidation, but too-high oxygen pressure lowered S° recovery due to its oxidation to sulfate. Most importantly, high sulfide oxidation (>98%) and conversion to S° (>75%) could be achieved together when the sulfide loading was less than 1.7 mol/m²·d and the O₂ pressure was sufficient to give an O₂ flux of at least 1.5 mol/m²·d. However, higher sulfide loading could be compensated by a higher O₂ pressure, and the best performance occurred when the sulfide loading was high (2 molS/m²·d), the O₂ pressure was high (∼1 atm), and the HRT was short (1.9 h). Membrane fouling caused a low O₂ flux, which led to low sulfide-oxidation efficiency, but fouling could be reversed by mild acid washing.

  15. The O- Acylation of Ketone Enolates by Allyl 1H-imidazole-1-carboxylate Mediated with Boron Trifluoride Etherate---A Convenient Procedure for the Synthesis of Substituted Allyl Enol Carbonates

    PubMed Central

    Trost, Barry M.; Xu, Jiayi

    2008-01-01

    A convenient access to substituted allyl enol carbonates was established through the reaction of ketone enolates with the complex of allyl 1H-imidazole-1-carboxylates and boron trifluoride etherate. PMID:17963405

  16. Factors controlling material deposition in the CVD of nickel sulfides, selenides or phosphides from dichalcogenoimidodiphosphinato complexes: deposition, spectroscopic and computational studies.

    PubMed

    Panneerselvam, Arunkumar; Periyasamy, Ganga; Ramasamy, Karthik; Afzaal, Mohammad; Malik, Mohammad A; O'Brien, Paul; Burton, Neil A; Waters, John; van Dongen, Bart E

    2010-07-14

    The series of nickel dichalcogenoimidodiphosphinates [Ni{(i)Pr(2)P(X1)NP(X2)(i)Pr(2)}(2)]: X1 = S, X2 = Se (1), X1 = X2 = S (2), and X1 = X2 = Se (3) have been successfully used as single-source precursors (SSPs) to deposit thin films of nickel sulfide, selenide or phosphide; the material deposited depended on both temperature and method used for the deposition. Aerosol-assisted (AA) chemical vapour deposition (CVD) and low-pressure (LP) CVD were used. The as-deposited films were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). A variety of phases including: Ni(2)P, Ni(0.85)Se and NiS(1.03) were deposited under different conditions. The mechanism of decomposition to the phosphide, selenide, or sulfide was studied by pyrolysis gas chromatography mass spectrometry (Py-GC-MS) and modelled by density functional theory (DFT).

  17. Atmospheric chemistry of toxic contaminants. 5. Unsaturated halogenated aliphatics: Allyl chloride, chloroprene, hexachlorocyclopentadiene, vinylidene chloride

    SciTech Connect

    Grosjean, D. )

    1991-02-01

    Detailed mechanisms are outlined for the chemical reactions involved in the atmospheric removal of four unsaturated chlorinated aliphatic contaminants, allyl chloride, chloroprene, hexachlorocyclopentadiene and vinylidene chloride. Rate constants estimated from structure-reactivity relationships indicate rapid removal for all four compounds by reactions with OH (major), ozone, and No{sub 3}, with half-lives of 2-16 hrs for removal by reaction with OH. Reaction products of allyl chloride (formaldehyde, chloroacetaldehyde, peroxychloroacetyl nitrate) and vinylidene chloride (formaldehyde, phosgene, chloroacetyl chloride) are consistent with OH addition-initiated pathways that include Cl atom elimination. The chlorine atoms produced in the OH reaction sequence react rapidly with all four unsaturated compounds, but these reactions are of negligible importance for atmospheric removal of the four toxic contaminants studied. Analogous mechanisms are discussed for chloroprene (leading to formaldehyde, CH{sub 2} {double bond} CClCHO, and ClCOCHO) and for hexachlorocyclopentadiene (leading to oxalyl chloride and ClCOCCl{sub 2}COCl).

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

    PubMed Central

    Porter, David; Poon, Belinda M-L

    2015-01-01

    Summary Iron(II) complexes of the tetradentate amines tris(2-pyridylmethyl)amine (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(hydroxy)carbamate) 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). PMID:26734101

  19. Control of selectivity in allylic alcohol oxidation on gold surfaces: the role of oxygen adatoms and hydroxyl species.

    PubMed

    Mullen, Gregory M; Zhang, Liang; Evans, Edward J; Yan, Ting; Henkelman, Graeme; Mullins, C Buddie

    2015-02-14

    Gold catalysts display high activity and good selectivity for partial oxidation of a number of alcohol species. In this work, we discuss the effects of oxygen adatoms and surface hydroxyls on the selectivity for oxidation of allylic alcohols (allyl alcohol and crotyl alcohol) on gold surfaces. Utilizing temperature programmed desorption (TPD), reactive molecular beam scattering (RMBS), and density functional theory (DFT) techniques, we provide evidence to suggest that the selectivity displayed towards partial oxidation versus combustion pathways is dependent on the type of oxidant species present on the gold surface. TPD and RMBS results suggest that surface hydroxyls promote partial oxidation of allylic alcohols to their corresponding aldehydes with very high selectivity, while oxygen adatoms promote both partial oxidation and combustion pathways. DFT calculations indicate that oxygen adatoms can react with acrolein to promote the formation of a bidentate surface intermediate, similar to structures that have been shown to decompose to generate combustion products over other transition metal surfaces. Surface hydroxyls do not readily promote such a process. Our results help explain phenomena observed in previous studies and may prove useful in the design of future catalysts for partial oxidation of alcohols.

  20. Directed Growth of Polymer Nanorods Using Surface-Initiated Ring-Opening Polymerization of N-Allyl N-Carboxyanhydride.

    PubMed

    Lu, Lu; Lahasky, Samuel H; Zhang, Donghui; Garno, Jayne C

    2016-02-17

    A stepwise chemistry route was used to prepare arrays of polymer nanostructures of poly(N-allyl glycine) on Si(111) using particle lithography. The nanostructures were used for studying surface reactions with advanced measurements of atomic force microscopy (AFM). In the first step to fabricate the surface platform, isolated nanopores were prepared within a thin film of octadecyltrichlorosilane (OTS). The OTS served as a surface resist, and the areas of nanopores provided multiple, regularly shaped sites for further reaction. An initiator, (3-aminopropyl)triethoxysilane (APTES), was grown selectively inside the nanopores to define sites for polymerization. The initiator attached selectively to the sites of nanopores indicating OTS prevented nonspecific adsorption. Surface-initiated ring-opening polymerization of N-allyl N-carboxyanhydride with APTES produced polymer nanorods on the nanodots of APTES presenting amine functional groups. The surface changes for each step were monitored using high resolution atomic force microscopy (AFM). Slight variations in the height of the poly(N-allyl glycine) nanorods were observed which scale correspondingly to the initial dimensions of nanopores. The distance between adjacent polymer nanorods was controlled by the size of mesoparticle masks used in the experiment. This surface platform has potential application in biotechnology for smart coatings or biosensors.

  1. Palladium/N-heterocyclic carbene catalysed regio and diastereoselective reaction of ketones with allyl reagents via inner-sphere mechanism

    DOE PAGES

    Bai, Da -Chang; Yu, Fei -Le; Wang, Wan -Ying; ...

    2016-06-10

    The palladium-catalysed allylic substitution reaction is one of the most important reactions in transition-metal catalysis and has been well-studied in the past decades. Most of the reactions proceed through an outer-sphere mechanism, affording linear products when monosubstituted allyl reagents are used. Here, we report an efficient Palladium-catalysed protocol for reactions of beta-substituted ketones with monosubstituted allyl substrates, simply by using N-heterocyclic carbene as ligand, leading to branched products with up to three contiguous stereocentres in a (syn, anti)-mode with excellent regio and diastereoselectivities. The scope of the protocol in organic synthesis has been examined preliminarily. As a result, mechanistic studiesmore » by both experiments and density functional theory ( DFT) calculations reveal that the reaction proceeds via an inner-sphere mechanism-nucleophilic attack of enolate oxygen on Palladium followed by C-C bond-forming [3,3']-reductive elimination.« less

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

    NASA Technical Reports Server (NTRS)

    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.

  3. Catalyst-free synthesis of skipped dienes from phosphorus ylides, allylic carbonates, and aldehydes via a one-pot SN2' allylation-Wittig strategy.

    PubMed

    Xu, Silong; Zhu, Shaoying; Shang, Jian; Zhang, Junjie; Tang, Yuhai; Dou, Jianwei

    2014-04-18

    A catalyst-free allylic alkylation of stabilized phosphorus ylides with allylic carbonates via a regioselective SN2' process is presented. Subsequent one-pot Wittig reaction with both aliphatic and aromatic aldehydes as well as ketenes provides structurally diverse skipped dienes (1,4-dienes) in generally high yields and moderate to excellent stereoselectivity with flexible substituent patterns. This one-pot SN2' allylation-Wittig strategy constitutes a convenient and efficient synthetic method for highly functionalized skipped dienes from readily available starting materials.

  4. Zinc sulfide liquefaction catalyst

    DOEpatents

    Garg, Diwakar

    1984-01-01

    A process for the liquefaction of carbonaceous material, such as coal, is set forth wherein coal is liquefied in a catalytic solvent refining reaction wherein an activated zinc sulfide catalyst is utilized which is activated by hydrogenation in a coal derived process solvent in the absence of coal.

  5. A comprehensive study of the vibrationally resolved S 2p(-1) Auger electron spectrum of carbonyl sulfide.

    PubMed

    Sekushin, V; Püttner, R; Fink, R F; Martins, M; Jiang, Y H; Aksela, H; Aksela, S; Kaindl, G

    2012-07-28

    High-resolution normal Auger-electron spectra of carbonyl sulfide subsequent to S 2p(-1) photoionization at photon energies of 200, 220, and 240 eV are reported along with corresponding photoelectron spectra. In addition, theoretical results are presented that take the core-hole orientation of the various spin-orbit-split and molecular-field-split S 2p(-1) states into account. Auger transitions to eight metastable dicationic final states are observed and assigned on the basis of the theoretical results. From Franck-Condon analysis, assuming Morse potentials along the normal coordinates for seven of the observed quasi-stable dicationic final states, information on the potential-energy surfaces is derived and compared with theoretical results from the literature.

  6. Influence of dissolved organic matter on the complexation of mercury under sulfidic conditions.

    PubMed

    Miller, Carrie L; Mason, Robert P; Gilmour, Cynthia C; Heyes, Andrew

    2007-04-01

    The complexation of Hg under sulfidic conditions influences its bioavailability for microbial methylation. Neutral dissolved Hg-sulfide complexes are readily available to Hg-methylating bacteria in culture, and thermodynamic models predict that inorganic Hg-sulfide complexes dominate dissolved Hg speciation under natural sulfidic conditions. However, these models have not been validated in the field. To examine the complexation of Hg in natural sulfidic waters, octanol/water partitioning methods were modified for use under environmentally relevant conditions, and a centrifuge ultrafiltration technique was developed. These techniques demonstrated much lower concentrations of dissolved Hg-sulfide complexes than predicted. Furthermore, the study revealed an interaction between Hg, dissolved organic matter (DOM), and sulfide that is not captured by current thermodynamic models. Whereas Hg forms strong complexes with DOM under oxic conditions, these complexes had not been expected to form in the presence of sulfide because of the stronger affinity of Hg for sulfide relative to its affinity for DOM. The observed interaction between Hg and DOM in the presence of sulfide likely involves the formation of a DOM-Hg-sulfide complex or results from the hydrophobic partitioning of neutral Hg-sulfide complexes into the higher-molecular-weight DOM. An understanding of the mechanism of this interaction and determination of complexation coefficients for the Hg-sulfide-DOM complex are needed to adequately assess how our new finding affects Hg bioavailability, sorption, and flux.

  7. Thermodynamics of Complex Sulfide Inclusion Formation in Ca-Treated Al-Killed Structural Steel

    NASA Astrophysics Data System (ADS)

    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.

  8. [Sulfide removal from wastewater by nanoscale iron].

    PubMed

    Xi, Hong-bo; Yang, Qi; Shang, Hai-tao; Hao, Chun-bo; Li, Zhi-ling

    2008-09-01

    Influencing factors, adsorption isotherm, adsorption kinetics and preliminary discussion on the mechanism of sulfide adsorption by nanoscale iron prepared in laboratory were studied using manual simulation sulfide wastewater. Experimental results indicate that the removal efficiency of S2- increases with increasing iron dosage and decreases with increasing initial S2- concentration and pH values. The removal efficiency of S2- is 100% when initial concentration is less than 100 mg x L(-1) and are 87.34%, 65.80% and 44.61% at pH 2, 7 and 13. The temperature at 25 degrees C favors the maximum adsorption of S2- with 19.17 mg x g(-1) of equilibrium adsorption quantity and the adsorption capacity decreas at higher or lower temperature. The adsorption data fit well to the Langmuir equation and the Freundlich equation. The sulfide adsorption follows the pseudo second order equation with the maximum initial sorption rate(h) is 1.575 3 mg x (g x mg)(-1) at 25 degrees C and the adsorption rate constant increases with the increasing of temperature. The activation energy(Ea) is 8.22 kJ x mol(-1). The mechanism of sulfide removal is being sorbed onto the iron nanoparticles via formation of surface compleses, FeOSH and iron sulfides (FeS, FeS2, FeSn).

  9. Evidence supporting biologically mediated sulfide oxidation in hot spring ecosystems

    NASA Astrophysics Data System (ADS)

    Cox, A. D.; Shock, E.

    2011-12-01

    The sulfide concentration of fluids in hydrothermal ecosystems is one of several factors determining the transition to microbial photosynthesis (Cox et al., 2011, Chem. Geol. 280, 344-351). To investigate the loss of sulfide in Yellowstone hot spring systems, measurements of total dissolved sulfide with respect to time were made in incubation experiments conducted on 0.2-micron filtered (killed controls) vs. unfiltered hot spring water at locations with three different pH:sulfide combinations (pH 2.5 with 50 μM sulfide, 5.2 with 5.6 μM sulfide, and 8.3 with 86 μM sulfide). At the higher pH values, the experiments yielded similar rates of sulfide loss in filtered and unfiltered water of approximately 0.8 (pH 5.2) and 7.6 nmol sulfide L-1s-1 (pH 8.3). At the acidic spring, the unfiltered water lost sulfide at a rate 1.6 times that of the filtered water (8.2 vs. 5 nmol sulfide L-1s-1). These results suggest that the pelagic biomass at the pH 5.2 and 8.3 springs may not affect sulfide loss, whereas in the pH 2.5 spring there appears to be an effect. In addition, the incubation of filamentous biomass with unfiltered water increased the rate of sulfide loss by approximately two-fold at a pH of 2.5 (59 vs. 31 nmol L-1s-1; Cox et al., 2011), five-fold at a pH of 5.2 (3.9 vs. 0.8 nmol sulfide L-1s-1), and barely increased the rate of sulfide loss at a pH of 8.3 (9.1 vs. 8.4 nmol sulfide L-1s-1). Sulfide is predominately present as HS- at a pH of 8.3, which may not be taken up as easily by microorganisms as the H2S (aq) that dominates sulfide speciation at pH 2.5 and 5.2. That the loss of sulfide at acidic pH is due to biotic rather than abiotic factors is further supported by studies with whole mat samples that show greater sulfide consumption than killed controls (D'Imperio et al., 2008, AEM 74, 5802-5808). Taken together, the results of these experiments suggest that the majority of sulfide oxidation occurs in the filamentous biomass of hot spring ecosystems, although

  10. Oxygen Demand of Fresh and Stored Sulfide Solutions and Sulfide-Rich Constructed Wetland Effluent.

    PubMed

    Chan, Carolyn; Farahbakhsh, Khosrow

    2015-08-01

    This study investigated the contribution of hydrogen sulfide to biological oxygen demand (BOD5) and chemical oxygen demand (COD) in wastewater effluents, and documented the effect of storage times and conditions on the BOD5 and COD of pH-adjusted sodium sulfide solutions as well as graywater wetland effluent. Initial COD measurements of sulfide solutions were 84-89% of the theoretical oxygen demand (ThOD), 1.996 mg O2/mg S, whereas unseeded BOD5 measurements were 55-77%. For sulfide solutions, all storage conditions led to declines of >15% (COD, BOD5), and >31% (sulfide). For wetland effluent, storage without headspace was effective in reducing COD losses (3.7%), compared to storage with headspace (17%), and affected changes in turbidity, UVA-254 and pH. The results suggest that storage times and conditions should be controlled and reported when reporting BOD5 and COD of sulfide-rich samples. Wetland models representing sulfate reduction as a method of COD removal may need to be reconsidered.

  11. Copper-Catalyzed SN2'-Selective Allylic Substitution Reaction of gem-Diborylalkanes.

    PubMed

    Zhang, Zhen-Qi; Zhang, Ben; Lu, Xi; Liu, Jing-Hui; Lu, Xiao-Yu; Xiao, Bin; Fu, Yao

    2016-03-04

    A Cu/(NHC)-catalyzed SN2'-selective substitution reaction of allylic electrophiles with gem-diborylalkanes is reported. Different substituted gem-diborylalkanes and allylic electrophiles can be employed in this reaction, and various synthetic valuable functional groups can be tolerated. The asymmetric version of this reaction was initially researched with chiral N-heterocyclic carbene (NHC) ligands.

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

    EPA Science Inventory

    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...

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

    EPA Science Inventory

    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...

  14. Enantio- and diastereoselective asymmetric allylic alkylation catalyzed by a planar-chiral cyclopentadienyl ruthenium complex.

    PubMed

    Kanbayashi, Naoya; Hosoda, Kazuki; Kato, Masanori; Takii, Koichiro; Okamura, Taka-aki; Onitsuka, Kiyotaka

    2015-07-11

    We report asymmetric allylic alkylation of allylic chloride with β-diketones as the prochiral carbon nucleophiles using a planar-chiral Cp'Ru catalyst. The reaction proceeds under mild conditions; the resulting chiral products containing vicinal tertiary stereocenters are obtained with high regio-, diastereo-, and enantioselectivities. These chiral products can then be transformed into a chiral diol by controlling the four stereocentres.

  15. Corn oil and milk enhance the absorption of orally administered allyl isothiocyanate in rats.

    PubMed

    Ippoushi, Katsunari; Ueda, Hiroshi; Takeuchi, Atsuko

    2013-11-15

    Allyl isothiocyanate, a chief component of mustard oil, exhibits anticancer effects in both cultured cancer cells and animal models. The accumulation of the N-acetylcysteine conjugate of allyl isothiocyanate, the final metabolite of allyl isothiocyanate, in urine was evaluated in rats that were orally coadministered allyl isothiocyanate with fluids (e.g., water, green tea, milk, and 10% ethanol) or corn oil. The N-acetylcysteine conjugate of allyl isothiocyanate content in urine when allyl isothiocyanate (2 or 4μmol) was coadministered with corn oil or milk showed a greater increase (1.4±0.22 or 2.7±0.34μmol or 1.2±0.32 or 2.5±0.36μmol, 1.6- to 1.8-fold or 1.5-fold, respectively) than when allyl isothiocyanate (2 or 4μmol) was coadministered with water (0.78±0.10 or 1.7±0.17μmol). This result demonstrates that corn oil and milk enhance the absorption of allyl isothiocyanate in rats.

  16. Gold(I)-catalyzed amination of allylic alcohols with cyclic ureas and related nucleophiles.

    PubMed

    Mukherjee, Paramita; Widenhoefer, Ross A

    2010-03-19

    A 1:1 mixture of [P(t-Bu)(2)-o-biphenyl]AuCl and AgSbF(6) catalyzes the intermolecular amination of allylic alcohols with 1-methylimidazolidin-2-one and related nucleophiles that, in the case of gamma-unsubstituted or gamma-methyl-substituted allylic alcohols, occurs with high gamma-regioselectivity and syn-stereoselectivity.

  17. Palladium-Catalyzed Allylic C-H Bond Functionalization of Olefins

    NASA Astrophysics Data System (ADS)

    Liu, Guosheng; Wu, Yichen

    Transition metal-mediated carbon-hydrogen bond cleavage and functionalization is a mechanistically interesting and synthetically attractive process. One of the important cases is the removal of a allylic hydrogen from an olefin by a PdII salt to yield a π-allylpalladium complex, followed by nucleophilic attack to efficient produce allylic derivatives. In contrast to the well-known allylic acetoxylation of cyclohexene, the reaction of open-chain olefins is fairly poor until recent several years. Some palladium catalytic systems have been reported to achieve allylic C-H functionalization, including acetoxylation, amination and alkylation of terminal alkenes. In the most of cases, ligand is crucial to the success of the transformation. This review surveys the recent development of palladium-catalyzed allylic C-H functionalziation of alkenes. These results promise a significant increase in the scope of olefin transformation.

  18. Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Cyclopentanones.

    PubMed

    Craig, Robert A; Loskot, Steven A; Mohr, Justin T; Behenna, Douglas C; Harned, Andrew M; Stoltz, Brian M

    2015-11-06

    The first general method for the enantioselective construction of all-carbon quaternary centers on cyclopentanones by enantioselective palladium-catalyzed decarboxylative allylic alkylation is described. Employing the electronically modified (S)-(p-CF3)3-t-BuPHOX ligand, α-quaternary cyclopentanones were isolated in yields up to >99% with ee's up to 94%. Additionally, in order to facilitate large-scale application of this method, a low catalyst loading protocol was employed, using as little as 0.15 mol % Pd, furnishing the product without any loss in ee.

  19. Nickel-Catalyzed Allylic Substitution of Simple Alkenes

    PubMed Central

    Matsubara, Ryosuke; Jamison, Timothy F.

    2011-01-01

    This report describes a nickel-catalyzed allylic substitution process of simple alkenes whereby an important structural motif, a 1,4-diene, was prepared. A key for this success is the use of an appropriate Ni-phosphine complex and a stoichiometric amount of silyl triflate. Reactions of 1-alkyl-substituted alkenes consistently provided 1,1-disubstituted alkenes with high selectivity. Insight into the reaction mechanism as well as miscellaneous application of the developed catalytic process is also documented. PMID:21387565

  20. Sulfide detoxification in plant mitochondria.

    PubMed

    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. © 2015 Elsevier Inc. All rights reserved.

  1. Sulfide and methane production in sewer sediments.

    PubMed

    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.

  2. Acute inhalation toxicity of carbonyl sulfide

    SciTech Connect

    Benson, J.M.; Hahn, F.F.; Barr, E.B.

    1995-12-01

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

  3. Geothermal hydrogen sulfide removal

    SciTech Connect

    Urban, P.

    1981-04-01

    UOP Sulfox technology successfully removed 500 ppM hydrogen sulfide from simulated mixed phase geothermal waters. The Sulfox process involves air oxidation of hydrogen sulfide using a fixed catalyst bed. The catalyst activity remained stable throughout the life of the program. The product stream composition was selected by controlling pH; low pH favored elemental sulfur, while high pH favored water soluble sulfate and thiosulfate. Operation with liquid water present assured full catalytic activity. Dissolved salts reduced catalyst activity somewhat. Application of Sulfox technology to geothermal waters resulted in a straightforward process. There were no requirements for auxiliary processes such as a chemical plant. Application of the process to various types of geothermal waters is discussed and plans for a field test pilot plant and a schedule for commercialization are outlined.

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

    SciTech Connect

    Marking, Gregory Allen

    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 Hf10Ta3S3 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 "stuffed" 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 Kα X-radiation. The compounds ZrNbP and HfNbP formed in the space group Prima with the simple Co2Si 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.

  5. Biotreatment of refinery spent sulfidic caustics

    SciTech Connect

    Sublette, K.L.; Rajganesh, B.; Woolsey, M.; Plato, A.

    1995-12-31

    Caustics are used in petroleum refinering to remove hydrogen sulfide from various hydrocarbon streams. Spent sulfidic caustics from two Conoco refineries have been successfully biotreated on bench and pilot scale, resulting in neutralization and removal of active sulfides. Sulfides were completely oxidized to sulfate by Thiobacillus denitrificans. Microbial oxidation of sulfide produced acid, which at least partially neutralized the caustic.

  6. On the chemical biology of the nitrite/sulfide interaction.

    PubMed

    Cortese-Krott, Miriam M; Fernandez, Bernadette O; Kelm, Malte; Butler, Anthony R; Feelisch, Martin

    2015-04-30

    Sulfide (H2S/HS(-)) has been demonstrated to exert an astounding breadth of biological effects, some of which resemble those of nitric oxide (NO). While the chemistry, biochemistry and potential pathophysiology of the cross-talk between sulfide and NO have received considerable attention lately, a comparable assessment of the potential biological implications of an interaction between nitrite and sulfide is lacking. This is surprising inasmuch as nitrite is not only a known bioactive oxidation product of NO, but also efficiently converted to S-nitrosothiols in vivo; the latter have been shown to rapidly react with sulfide in vitro, leading to formation of S/N-hybrid species including thionitrite (SNO(-)) and nitrosopersulfide (SSNO(-)). Moreover, nitrite is used as a potent remedy against sulfide poisoning in the clinic. The chemistry of interaction between nitrite and sulfide or related bioactive metabolites including polysulfides and elemental sulfur has been extensively studied in the past, yet much of this information appears to have been forgotten. In this review, we focus on the potential chemical biology of the interaction between nitrite and sulfide or sulfane sulfur molecules, calling attention to the fundamental chemical properties and reactivities of either species and discuss their possible contribution to the biology, pharmacology and toxicology of both nitrite and sulfide.

  7. Suicide with hydrogen sulfide.

    PubMed

    Sams, Ralph Newton; Carver, H Wayne; Catanese, Charles; Gilson, Thomas

    2013-06-01

    This presentation will address the recent rise of suicide deaths resulting from the asphyxiation by hydrogen sulfide (H2S) gas.Hydrogen sulfide poisoning has been an infrequently encountered cause of death in medical examiner practice. Most H2S deaths that have been reported occurred in association with industrial exposure.More recently, H2S has been seen in the commission of suicide, particularly in Japan. Scattered reports of this phenomenon have also appeared in the United States.We have recently observed 2 intentional asphyxial deaths in association with H2S. In both cases, the decedents committed suicide in their automobiles. They generated H2S by combining a sulfide-containing tree spray with toilet bowl cleaner (with an active ingredient of hydrogen chloride acid). Both death scenes prompted hazardous materials team responses because of notes attached to the victims' car windows indicating the presence of toxic gas. Autopsy findings included discoloration of lividity and an accentuation of the gray matter of the brain. Toxicology testing confirmed H2S exposure with the demonstration of high levels of thiosulfate in blood.In summary, suicide with H2S appears to be increasing in the United States.

  8. Platinum-group element distribution in base-metal sulfides of the UG2 chromitite, Bushveld Complex, South Africa—a reconnaissance study

    NASA Astrophysics Data System (ADS)

    Osbahr, Inga; Oberthür, Thomas; Klemd, Reiner; Josties, Anja

    2014-08-01

    Two drill cores of the UG2 chromitite from the eastern and western Bushveld Complex were studied by whole-rock analysis, ore microscopy, SEM/Mineral Liberation Analysis (MLA), and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis. The top and base of the UG2 main seam have the highest bulk-rock Pd and Pt concentrations. Sulfides mostly occur as aggregates of pentlandite, chalcopyrite, and rare pyrrhotite and pyrite or as individual grains associated mostly with chromite grains. In situ LA-ICP-MS analyses reveal that pentlandite carries distinctly elevated platinum-group element (PGE) contents. In contrast, pyrrhotite and chalcopyrite contain very low PGE concentrations. Pentlandite shows average maximum values of 350-1,000 ppm Pd, 200 ppm Rh, 130-175 ppm Ru, 20 ppm Os, and 150 ppm Ir, and is the principal host of Pd and Rh in the studied ores of the UG2. Mass balance calculations were conducted for samples representing the UG2 main seam of the drill core DT46, eastern Bushveld. Pentlandite consistently hosts elevated contents of the whole-rock Pd (up to 55 %) and Rh (up to 46 %), and erratic contents of Os (up to 50 %), Ir (2 to 17 %), and Ru (1-39 %). Platinum-group mineral (PGM) investigations support these mass balance results; most of the PGM are Pt-dominant such as braggite/cooperite and Pt-Fe alloys or laurite (carrying elevated concentrations of Os and Ir). Palladium and Rh-bearing PGM are rare. Both PGE concentrations and their distribution in base-metal sulfides (BMS) in the UG2 largely resemble that of the Merensky Reef, as most of the Pd and Rh are incorporated in pentlandite, whereas pyrrhotite, chalcopyrite, and pyrite are almost devoid of PGE.

  9. Zirconium-mediated coupling reactions of amines and enol or allyl ethers: synthesis of allyl- and homoallylamines.

    PubMed

    Barluenga, José; Rodríguez, Félix; Alvarez-Rodrigo, Lucía; Zapico, José M; Fañanás, Francisco J

    2004-01-05

    An easy and efficient zirconium-mediated synthesis of allylamines from simple amines and enol ethers is described. This strategy also allows the synthesis of amino alcohol derivatives containing a Z double bond in their structure when 2,3-dihydrofuran is used. Simple conventional modification of these amino alcohols leads to 2-substituted piperidine derivatives. By applying this approach, a formal total synthesis of the alkaloid coniine is easily achieved from a protected butylamine. Finally, the zirconium-mediated reaction of amines and allyl phenyl ether furnishes homoallylamines or amino ethers depending on the structure of the starting amine.

  10. Experimental study on stress corrosion crack propagation rate of FV520B in carbon dioxide and hydrogen sulfide solution

    NASA Astrophysics Data System (ADS)

    Qin, Ming; Li, Jianfeng; Chen, Songying; Qu, Yanpeng

    FV520B steel is a kind of precipitation hardening Martensitic stainless steel, it has high-strength, good plasticity and good corrosion resistance. Stress corrosion cracking (SCC) is one of the main corrosion failure mode for FV520B in industrial transportation of natural gas operation. For a better understanding the effect on SCC of FV520B, the improved wedge opening loading (WOL) specimens and constant displacement loading methods were employed in experimental research in carbon dioxide and hydrogen sulfide solution. The test results showed that the crack propagation rate is 1.941 × 10-7-5.748 × 10-7 mm/s, the stress intensity factor KISCC is not more than 36.83 MPa √{ m } . The rate increases with the increasing of the crack opening displacement. Under the condition of different initial loading, KISCC generally shows a decreasing tendency with the increase in H2S concentration, and the crack propagation rate showed an increasing trend substantially. For the enrichment of sulfur ion in the crack tip induced the generation of pitting corrosion, promoting the surrounding metal formed the corrosion micro batteries, the pit defects gradually extended and connected with the adjacent pit to form a small crack, leading to further propagation till cracking happened. Fracture microscopic morphology displayed typical brittle fracture phenomena, accompanying with trans-granular cracking, river shape and sector, many second cracks on the fracture surface.

  11. Sulfidation of a Cu submonolayer at the Au(1 1 1)/electrolyte interface An in situ STM study

    NASA Astrophysics Data System (ADS)

    Friebel, Daniel; Schlaup, Christian; Broekmann, Peter; Wandelt, Klaus

    2006-07-01

    We describe the electrochemical preparation of an ultrathin copper sulfide film on Au(1 1 1) and its structural characterization by in situ STM. The first step, underpotential deposition of a Cu submonolayer from CuSO 4/H 2SO 4 solution, is followed by two electrolyte exchanges for (i) Cu-free (blank) H 2SO 4 solution and (ii) NaOH/Na 2S solution. The well-known (√3 × √3) R30° structure of the upd Cu layer is stable in the blank electrolyte for at least 2 h. After exposure to bisulfide, the Cu layer contracts and forms two-dimensional islands of two distinct ordered surface phases, i.e. a rectangular and, at higher potentials, a hexagonal phase, with Cu-free Au(1 1 1) regions between them, the latter exhibiting the characteristic (√3 × √3) R30°-S adlayer structure. Potential changes lead to a complex phase behaviour including HS - ⇆ S x oxidation/reduction and, at strongly anodic potentials, dissolution of the Cu adlayer.

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

    PubMed

    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.

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

    PubMed Central

    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

  14. Study on the mesocarbon microbeads/polyphenylene sulfide composite bipolar plates applied for proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Yang, Tao; Shi, Pengfei

    Thermoplastic/graphite composite bipolar plates based on polyphenylene sulfide (PPS) and mesocarbon microbeads (MCMB) were prepared by compression molding at a pressure of 40 MPa and 400 °C. Electrical conductivity, bulk density, flexural strength, water and ethanol absorption were determined as function of PPS content. The influences of molding time, actived carbon and carbon fiber on the properties of the composite bipolar plates were investigated, the cross section of the composite plates were analyzed by scanning electron microscope (SEM). We found that the optimized PPS content is 20 wt% and the required molding time is 30 min. In particular, the composite plates containing 20 wt% PPS demonstrated in-plane conductivity as high as 133.7 S cm -1, through-plane conductivity 21.37 S cm -1, in addition to showing the value of density, flexural strength, water and ethanol absorption as 1.98 g cm -3, 38.82 MPa, 0.0409 and 0.352 g cm -3. The addition of actived carbon degraded all the performance of the bipolar plate, while addition of carbon fiber improved almost all the performance of bipolar plate except bulk density and through-plane conductivity. The performances of fuel cell with this composite bipolar plate were tested, no distinct variation occurred after the composite plates operating in fuel cell. These data indicates the chemical and mechanical stability of the composite plates and their potential application in fuel cell.

  15. In-situ high temperature X-ray diffraction study on the phase transition process of polymetallic sulfide ore

    NASA Astrophysics Data System (ADS)

    Li, Guangshi; Cheng, Hongwei; Xiong, Xiaolu; Lu, Xionggang; Xu, Cong; Lu, Changyuan; Zou, Xingli; Xu, Qian

    2017-04-01

    The phase transformation of the polymetallic sulfide ore is quite complicated, especially the variety and diversity of the roasted intermediate. The mineralogy properties of the ore particles were characterized by XRF, ICP and SEM-EDS. The thermal stability of the complex ore was investigated using TG-DSC under different atmosphere (pure N2 and 1% O2-N2). The phase changes and intermediates were revealed by the in-situ XRD in pure N2 and 1% O2-N2 atmospheres with the temperature range from 25 to 800°C. These results indicated that the crystal transformation of the pyrrhotite from monoclinic to hexagonal at 320°C, and the pentlandite and chalcopyrite were decomposed into monosulfide solid solution in pure N2. While the pentlandite and chalcopyrite were completely oxidized into M*xFe3-xO4 (M*=Fe, Ni, Cu) and Fe2O3, which is also the final product of the ore sample oxidized under 1% O2-N2 atmosphere.

  16. Cation control of diastereoselectivity in iridium-catalyzed allylic substitutions. Formation of enantioenriched tertiary alcohols and thioethers by allylation of 5H-oxazol-4-ones and 5H-thiazol-4-ones.

    PubMed

    Chen, Wenyong; Hartwig, John F

    2014-01-08

    We report highly diastereo- and enantioselective allylations of substituted 5H-oxazol-4-ones and 5H-thiazol-4-ones catalyzed by a metallacyclic iridium complex. Enantioselective Ir-catalyzed allylation of substituted 5H-oxazol-4-ones occurs with high diastereoselectivity by employing the corresponding zinc enolates; enantioselective Ir-catalyzed allylation of substituted 5H-thiazol-4-ones occurs with the corresponding magnesium enolates with high diastereoselectivity. The allylation of substituted 5H-oxazol-4-ones provides rapid access to enantioenriched tertiary α-hydroxy acid derivatives unavailable through Mo-catalyzed allylic substitution. The allylation of substituted 5H-thiazol-4-ones provides a novel method to synthesize enantioenriched tertiary thiols and thioethers. The observed cation effect implies a novel method to control the diastereoselectivity in Ir-catalyzed allylic substitution.

  17. Cation Control of Diastereoselectivity in Iridium-Catalyzed Allylic Substitutions. Formation of Enantioenriched Tertiary Alcohols and Thioethers by Allylation of 5H-Oxazol-4-ones and 5H-Thiazol-4-ones

    PubMed Central

    Chen, Wenyong; Hartwig, John F.

    2014-01-01

    We report a highly diastereo- and enantioselective allylation of substituted 5H-oxazol-4-ones and 5H-thiazol-4-ones catalyzed by the metallacyclic iridium complex. Enantioselective Ir-catalyzed allylation of substituted 5H-oxazol-4-ones occurs with high diastereoselectivity by employing the corresponding zinc enolates; enantioselective Ir-catalyzed allylation of substituted 5H-thiazol-4-ones requires the corresponding magnesium enolates to achieve high diastereoselectivity. The allylation of substituted 5H-oxazol-4-ones provides rapid access to enantioenriched tertiary α-hydroxy acid derivatives unavailable through Mo-catalyzed allylic substitution. The allylation of substituted 5H-thiazol-4-ones provides a novel method to synthesize enantioenriched tertiary thiols and thioethers. The observed cation effect implies a novel method to control the diastereoselectivity in Ir-catalyzed allylic substitution. PMID:24295427

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

    PubMed

    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.

  19. Cross-coupling of aromatic bromides with allylic silanolate salts.

    PubMed

    Denmark, Scott E; Werner, Nathan S

    2008-12-03

    The sodium salts of allyldimethylsilanol and 2-butenyldimethylsilanol undergo palladium-catalyzed cross-coupling with a wide variety of aryl bromides to afford allylated and crotylated arenes. The coupling of both silanolates required extensive optimization to deliver the expected products in high yields. The reaction of the allyldimethylsilanolate takes place at 85 degrees C in 1,2-dimethoxyethane with allylpalladium chloride dimer (2.5 mol %) to afford 73-95% yields of the allylation products. Both electron-rich and sterically hindered bromides reacted smoothly, whereas electron-poor bromides cross-coupled in poor yield because of a secondary isomerization to the 1-propenyl isomer (and subsequent polymerization). The 2-butenyldimethylsilanolate (E/Z, 80:20) required additional optimization to maximize the formation of the branched (gamma-substitution) product. A remarkable influence of added alkenes (dibenzylideneacetone and norbornadiene) led to good selectivities for electron-rich and electron-poor bromides in 40-83% yields. However, bromides containing coordinating groups (particularly in the ortho position) gave lower, and in one case even reversed, selectivity. Configurationally homogeneous (E)-silanolates gave slightly higher gamma-selectivity than the pure (Z)-silanolates. A unified mechanistic picture involving initial gamma-transmetalation followed by direct reductive elimination or sigma-pi isomerization can rationalize all of the observed trends.

  20. Bradykinetic alcohol dehydrogenases make yeast fitter for growth in the presence of allyl alcohol.

    PubMed

    Plapp, Bryce V; Lee, Ann Ting-I; Khanna, Aditi; Pryor, John M

    2013-02-25

    Previous studies showed that fitter yeast (Saccharomyces cerevisiae) that can grow by fermenting glucose in the presence of allyl alcohol, which is oxidized by alcohol dehydrogenase I (ADH1) to toxic acrolein, had mutations in the ADH1 gene that led to decreased ADH activity. These yeast may grow more slowly due to slower reduction of acetaldehyde and a higher NADH/NAD(+) ratio, which should decrease the oxidation of allyl alcohol. We determined steady-state kinetic constants for three yeast ADHs with new site-directed substitutions and examined the correlation between catalytic efficiency and growth on selective media of yeast expressing six different ADHs. The H15R substitution (a test for electrostatic effects) is on the surface of ADH and has small effects on the kinetics. The H44R substitution (affecting interactions with the coenzyme pyrophosphate) was previously shown to decrease affinity for coenzymes 2-4-fold and turnover numbers (V/Et) by 4-6-fold. The W82R substitution is distant from the active site, but decreases turnover numbers by 5-6-fold, perhaps by effects on protein dynamics. The E67Q substitution near the catalytic zinc was shown previously to increase the Michaelis constant for acetaldehyde and to decrease turnover for ethanol oxidation. The W54R substitution, in the substrate binding site, increases kinetic constants (Ks, by >10-fold) while decreasing turnover numbers by 2-7-fold. Growth of yeast expressing the different ADHs on YPD plates (yeast extract, peptone and dextrose) plus antimycin to require fermentation, was positively correlated with the log of catalytic efficiency for the sequential bi reaction (V1/KiaKb=KeqV2/KpKiq, varying over 4 orders of magnitude, adjusted for different levels of ADH expression) in the order: WT≈H15R>H44R>W82R>E67Q>W54R. Growth on YPD plus 10mM allyl alcohol was inversely correlated with catalytic efficiency. The fitter yeast are "bradytrophs" (slow growing) because the ADHs have decreased catalytic

  1. Bradykinetic alcohol dehydrogenases make yeast fitter for growth in the presence of allyl alcohol

    PubMed Central

    Plapp, Bryce V.; Lee, Ann Ting-I.; Khanna, Aditi; Pryor, John M.

    2012-01-01

    Previous studies showed that fitter yeast (Saccharomyces cerevisiae) that can grow by fermenting glucose in the presence of allyl alcohol, which is oxidized by alcohol dehydrogenase I (ADH1) to toxic acrolein, had mutations in the ADH1 gene that led to decreased ADH activity. These yeast may grow more slowly due to slower reduction of acetaldehyde and a higher NADH/NAD+ ratio, which should decrease the oxidation of allyl alcohol. We determined steady-state kinetic constants for three yeast ADHs with new site-directed substitutions and examined the correlation between catalytic efficiency and growth on selective media of yeast expressing six different ADHs. The H15R substitution (a test for electrostatic effects) is on the surface of ADH and has small effects on the kinetics. The H44R substitution (affecting interactions with the coenzyme pyrophosphate) was previously shown to decrease affinity for coenzymes 2-4-fold and turnover numbers (V/Et) by 4-6-fold. The W82R substitution is distant from the active site, but decreases turnover numbers by 5-6-fold, perhaps by effects on protein dynamics. The E67Q substitution near the catalytic zinc was shown previously to increase the Michaelis constant for acetaldehyde and to decrease turnover for ethanol oxidation. The W54R substitution, in the substrate binding site, increases kinetic constants (K’s, by > 10-fold) while decreasing turnover numbers by 2-7-fold. Growth of yeast expressing the different ADHs on YPD plates (yeast extract, peptone and dextrose) plus antimycin to require fermentation, was positively correlated with the log of catalytic efficiency for the sequential bi reaction (V1/KiaKb = KeqV2/KpKiq, varying over 4 orders of magnitude, adjusted for different levels of ADH expression) in the order: WT H15R > H44R > W82R > E67Q > W54R. Growth on YPD plus 10 mM allyl alcohol was inversely correlated with catalytic efficiency. The fitter yeast are “bradytrophs” (slow growing) because the ADHs have decreased

  2. Method of epitaxially depositing cadmium sulfide

    NASA Technical Reports Server (NTRS)

    Hawrylo, Frank Z. (Inventor)

    1980-01-01

    A single crystal layer of either cadmium sulfide or an alloy of cadmium sulfide and indium phosphide is epitaxially deposited on a substrate of cadmium sulfide by liquid phase epitaxy using indium as the solvent.

  3. Inhibition and Promotion of Pyrolysis by Hydrogen Sulfide (H2S) and Sulfanyl Radical (SH).

    PubMed

    Zeng, Zhe; Altarawneh, Mohammednoor; Oluwoye, Ibukun; Glarborg, Peter; Dlugogorski, Bogdan Z

    2016-11-17

    This study resolves the interaction of sulfanyl radical (SH) with aliphatic (C1-C4) hydrocarbons, using CBS-QB3 based calculations. We obtained the C-H dissociation enthalpies and located the weakest link in each hydrocarbon. Subsequent computations revealed that, H abstraction by SH from the weakest C-H sites in alkenes and alkynes, except for ethylene, appears noticeably exothermic. Furthermore, abstraction of H from propene, 1-butene, and iso-butene displays pronounced spontaneity (i.e., ΔrG° < -20 kJ mol(-1) between 300-1200 K) due to the relatively weak allylic hydrogen bond. However, an alkyl radical readily abstracts H atom from H2S, with H2S acting as a potent scavenger for alkyl radicals in combustion processes. That is, these reactions proceed in the opposite direction than those involving SH and alkene or alkyne species, exhibiting shallow barriers and strong spontaneity. Our findings demonstrate that the documented inhibition effect of hydrogen sulfide (H2S) on pyrolysis of alkanes does not apply to alkenes and alkynes. During interaction with hydrocarbons, the inhibitive effect of H2S and promoting interaction of SH radical depend on the reversibility of the H abstraction processes. For the three groups of hydrocarbon, Evans-Polanyi plots display linear correlations between the bond dissociation enthalpies of the abstracted hydrogens and the relevant activation energies. In the case of methane, we demonstrated that the reactivity of SH radicals toward abstracting H atoms exceeds that of HO2 but falls below those of OH and NH2 radicals.

  4. Sulfidation of silver nanoparticle reduces its toxicity in zebrafish.

    PubMed

    Devi, G Prathinkra; Ahmed, Khan Behlol Ayaz; Varsha, M K N Sai; Shrijha, B S; Lal, K K Subin; Anbazhagan, Veerappan; Thiagarajan, R

    2015-01-01

    Chemical transformations of metal nanoparticles can be an important way to mitigate nanoparticle toxicity. Sulfidation of silver nanoparticle (AgNPs) is a natural process shown to occur in environment. Very few studies, employing microbes and embryonic stages of zebrafish, have shown reduction in AgNPs toxicity as a direct result of sulfidation. However the feasibility of reducing nanoparticle toxicity by sulfidation of AgNPs has never been studied in adult vertebrates. In this study, we have used adult zebrafish as a model to study the efficacy of sulfidation of AgNPs in reducing nanoparticle toxicity by employing a battery of biomarkers in liver and brain. While AgNPs enhanced liver oxidative stress, altered detoxification enzymes and affected brain acetylcholinesterase activity, sulfidation of AgNPs resulted in significant alleviation of changes in these parameters. Histopathological analyses of liver and sulphydryl levels also support the significance of sulfidated AgNPs in controlling the toxicity of AgNPs. Our study provides the first biochemical data on the importance of sulfidation of AgNPs in reducing biological toxicity in adult vertebrates. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Enantioselective Functionalization of Allylic C-H Bonds Following a Strategy of Functionalization and Diversification

    PubMed Central

    Sharma, Ankit; Hartwig, John F.

    2013-01-01

    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 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 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. PMID:24156776

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

    PubMed

    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.

  7. Iridium-Catalyzed Intramolecular Asymmetric Allylic Dearomatization Reaction of Pyridines, Pyrazines, Quinolines, and Isoquinolines.

    PubMed

    Yang, Ze-Peng; Wu, Qing-Feng; Shao, Wen; You, Shu-Li

    2015-12-23

    The first Ir-catalyzed intramolecular asymmetric allylic dearomatization reaction of pyridines, pyrazines, quinolines, and isoquinolines has been developed. Enabled by in situ formed chiral Ir-catalyst, the dearomatized products were isolated in high levels of yield (up to 99% yield) and enantioselectivity (up to 99% ee). It is worth noting that the Me-THQphos ligand is much more efficient than other tested ligands for the dearomatization of pyrazines and certain quinolines. Mechanistic studies of the dearomatization reaction were carried out, and the results suggest the feasibility of an alternative process which features the formation of a quinolinium as the key intermediate. The mechanistic findings render this reaction a yet unknown type in the chemistry of Reissert-type reactions. In addition, the utility of this method was showcased by a large-scale reaction and formal synthesis of (+)-gephyrotoxin.

  8. Catalytic asymmetric carbon-carbon bond formation via allylic alkylations with organolithium compounds.

    PubMed

    Pérez, Manuel; Fañanás-Mastral, Martín; Bos, Pieter H; Rudolph, Alena; Harutyunyan, Syuzanna R; Feringa, Ben L

    2011-05-01

    Carbon-carbon bond formation is the basis for the biogenesis of nature's essential molecules. Consequently, it lies at the heart of the chemical sciences. Chiral catalysts have been developed for asymmetric C-C bond formation to yield single enantiomers from several organometallic reagents. Remarkably, for extremely reactive organolithium compounds, which are among the most broadly used reagents in chemical synthesis, a general catalytic methodology for enantioselective C-C formation has proven elusive, until now. Here, we report a copper-based chiral catalytic system that allows carbon-carbon bond formation via allylic alkylation with alkyllithium reagents, with extremely high enantioselectivities and able to tolerate several functional groups. We have found that both the solvent used and the structure of the active chiral catalyst are the most critical factors in achieving successful asymmetric catalysis with alkyllithium reagents. The active form of the chiral catalyst has been identified through spectroscopic studies as a diphosphine copper monoalkyl species.

  9. High-accuracy extrapolated ab initio thermochemistry of the vinyl, allyl, and vinoxy radicals.

    PubMed

    Tabor, Daniel P; Harding, Michael E; Ichino, Takatoshi; Stanton, John F

    2012-07-26

    Enthalpies of formation at both 0 and 298 K were calculated according to the HEAT (High-accuracy Extrapolated Ab initio Thermochemistry) protocol for the title molecules, all of which play important roles in combustion chemistry. At the HEAT345-(Q) level of theory, recommended enthalpies of formation at 0 K are 301.5 ± 1.3, 180.3 ± 1.8, and 23.4 ± 1.5 kJ mol(-1) for vinyl, allyl, and vinoxy, respectively. At 298 K, the corresponding values are 297.3, 168.6, and 16.1 kJ mol(-1), with the same uncertainties. The calculated values for the three radicals are in excellent agreement with the corresponding experimental values, but the uncertainties associated with the HEAT values for vinoxy are considerably smaller than those based on experimental studies.

  10. Sensitization and desensitization to allyl isothiocyanate (mustard oil) in the nasal cavity.

    PubMed

    Brand, Gerard; Jacquot, Laurence

    2002-09-01

    The aim of this study was to investigate the response, acute effects and time-course of sensitization and desensitization to allyl isothiocyanate (mustard oil) nasal stimuli in healthy subjects. Sixty subjects participated in the experiment, which employed psychophysical (intensity ratings) and psychophysiological (skin conductance response) measurements. Nasal stimuli were delivered three times with different inter-stimulus intervals. The results showed that the psychophysical and psycho-physiological data were correlated and that the successive nasal stimuli after a short period of time (<2 min) produced increased intensity of irritation, whereas the stimuli delivered after >3 min produced a markedly decreased intensity of irritation. These findings are in agreement with those obtained with capsaicin, the most frequently used irritant molecule.

  11. Analysis of allyl diglycol carbonate by laser induced-breakdown spectroscopy

    NASA Astrophysics Data System (ADS)

    Sarfraz, Mansoor; Farooq, W. A.; Al-Eshaikh, Mohammad A.; Kadachi, Ahmed N.; Aldwayyan, A. S.; Ahmad, Kaleem

    2013-05-01

    Laser-induced breakdown spectroscopy (LIBS) has been used to identify the impurities in the allyl diglycol carbonate, which is used as a charged particle track recording material in solid-state nuclear track detectors. Impurities of magnesium, calcium, sodium and silicon are detected. Plasma parameters such as temperature and electron density are also calculated at optimized conditions in air and argon atmosphere using the silicon lines. The temperature of the LIBS plasma produced in argon atmosphere was higher than the temperature of the LIBS plasma produced in air. Variation in the emission intensity of the carbon I line (247.8561 nm) with respect to acquisition delay and laser power is also studied. It is found that the intensities of Ca and Na lines from LIBS spectra were enhanced 30-40 times in an argon atmosphere as compared to air. Hence LIBS in an argon atmosphere can be used for better identification of impurities in plastics.

  12. Catalyst-controlled C-O versus C-N allylic functionalization of terminal olefins.

    PubMed

    Strambeanu, Iulia I; White, M Christina

    2013-08-14

    The divergent synthesis of syn-1,2-aminoalcohol or syn-1,2-diamine precursors from a common terminal olefin has been accomplished using a combination of palladium(II) catalysis with Lewis acid cocatalysis. Palladium(II)/bis-sulfoxide catalysis with a silver triflate cocatalyst leads for the first time to anti-2-aminooxazolines (C-O) in good to excellent yields. Simple removal of the bis-sulfoxide ligand from this reaction results in a complete switch in reactivity to afford anti-imidazolidinone products (C-N) in good yields and excellent diastereoselectivities. Mechanistic studies suggest the divergent C-O versus C-N reactivity from a common ambident nucleophile arises due to a switch in mechanism from allylic C-H cleavage/functionalization to olefin isomerization/oxidative amination.

  13. Palladium-catalyzed asymmetric allylic amination of racemic butadiene monoxide with isatin derivatives.

    PubMed

    Li, Gen; Feng, Xiangqing; Du, Haifeng

    2015-05-28

    Isatins and their derivatives are important functional moities and building blocks in pharmaceutical and synthetic chemistry. Numerous enantioselective transformations at the C-3 carbonyl group have been well developed. However, the asymmetric substitution reaction with isatins and their derivatives as nucleophiles based on the free N-H groups has been less studied due to the relatively weaker nucleophilicity resulting from the two electron-withdrawing carbonyl groups. In this paper, a palladium-catalyzed asymmetric allylic amination of racemic butadiene monoxide with isatin derivatives using a chiral phosphoramidite olefin hybrid ligand has been successfully developed under mild conditions. A variety of chiral amino alcohols were afforded in 55-87% yields with 10/1->20/1 regioselectivity ratios and 80-97% ees.

  14. Hassle free synthesis of nanodimensional Ni, Cu and Zn sulfides for spectral sensing of Hg, Cd and Pb: A comparative study.

    PubMed

    Ansari, Zarina; Singha, Shib Shankar; Saha, Abhijit; Sen, Kamalika

    2017-04-05

    A simple room temperature synthesis method of Ni, Cu and Zn sulfide nanoparticles (NPs) in aqueous medium is reported here. The NPs stabilized in aqueous medium by the citrate ions were characterized by UV-vis, ζ potentials, TEM and Raman spectroscopic techniques. The solid NPs could be isolated from the aqueous medium when allowed to stand for a prolonged time (~20h). The solids were also characterized by IR and powder X-ray analysis. The nanoparticles were further used for the development of facile optical sensing and detection of heavy metal ions at trace scale. Alterations in the absorption spectra of the generated NPs were indicative of their interactions with heavy metal ions. Raman spectral measurements further validate the detection technique. It is found that out of the three synthesized nanoparticles, nickel sulfide NP is a specific sensor for mercury ions whereas zinc sulfide and copper sulfide NPs act as sensors for Hg(2+), Cd(2+) and Pb(2+).

  15. Hassle free synthesis of nanodimensional Ni, Cu and Zn sulfides for spectral sensing of Hg, Cd and Pb: A comparative study

    NASA Astrophysics Data System (ADS)

    Ansari, Zarina; Singha, Shib Shankar; Saha, Abhijit; Sen, Kamalika

    2017-04-01

    A simple room temperature synthesis method of Ni, Cu and Zn sulfide nanoparticles (NPs) in aqueous medium is reported here. The NPs stabilized in aqueous medium by the citrate ions were characterized by UV-vis, ζ potentials, TEM and Raman spectroscopic techniques. The solid NPs could be isolated from the aqueous medium when allowed to stand for a prolonged time ( 20 h). The solids were also characterized by IR and powder X-ray analysis. The nanoparticles were further used for the development of facile optical sensing and detection of heavy metal ions at trace scale. Alterations in the absorption spectra of the generated NPs were indicative of their interactions with heavy metal ions. Raman spectral measurements further validate the detection technique. It is found that out of the three synthesized nanoparticles, nickel sulfide NP is a specific sensor for mercury ions whereas zinc sulfide and copper sulfide NPs act as sensors for Hg2 +, Cd2 + and Pb2 +.

  16. Monitoring sulfide and sulfate-reducing bacteria

    SciTech Connect

    Tanner, R.S.

    1995-12-31

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

  17. Homogeneous Pd-catalyzed transformation of terminal alkenes into primary allylic alcohols and derivatives.

    PubMed

    Tomita, Ren; Mantani, Kohei; Hamasaki, Akiyuki; Ishida, Tamao; Tokunaga, Makoto

    2014-08-04

    Synthesis of primary alcohols from terminal alkenes is an important process in both bulk and fine chemical syntheses. Herein, a homogeneous Pd-complex-catalyzed transformation of terminal alkenes into primary allylic alcohols, by using 5 mol % [Pd(PPh3)4] as a catalyst, and H2O, CO2, and quinone derivatives as reagents, is reported. When alcohols were used instead of H2O, allylic ethers were obtained. A proposed mechanism includes the addition of oxygen nucleophiles at the less-hindered terminal position of π-allyl Pd intermediates.

  18. Highly selective allylborations of aldehydes using α,α-disubstituted allylic pinacol boronic esters.

    PubMed

    Hesse, Matthew J; Essafi, Stéphanie; Watson, Charlotte G; Harvey, Jeremy N; Hirst, David; Willis, Christine L; Aggarwal, Varinder K

    2014-06-10

    α,α-Disubstituted allylic pinacol boronic esters undergo highly selective allylborations of aldehydes to give tetrasubstituted homoallylic alcohols with exceptional levels of anti-Z-selectivity (>20:1). The scope of the reaction includes both acyclic and cyclic allylic boronic esters which lead to acyclic and exocyclic tetrasubstituted homoallylic alcohols. The use of β-borylated allylic boronic esters gave fully substituted alkenes bearing a boronic ester which underwent further cross-coupling enabling a highly modular and stereoselective approach to the synthesis of diaryl tetrasubstituted alkenes. Computational analysis revealed the origin of the remarkable selectivity observed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Hydrogen-bond-assisted activation of allylic alcohols for palladium-catalyzed coupling reactions.

    PubMed

    Gumrukcu, Yasemin; de Bruin, Bas; Reek, Joost N H

    2014-03-01

    We report direct activation of allylic alcohols using a hydrogen-bond-assisted palladium catalyst and use this for alkylation and amination reactions. The novel catalyst comprises a palladium complex based on a functionalized monodentate phosphoramidite ligand in combination with urea additives and affords linear alkylated and aminated allylic products selectively. Detailed kinetic analysis show that oxidative addition of the allyl alcohol is the rate-determining step, which is facilitated by hydrogen bonds between the alcohol, the ligand functional group, and the additional urea additive.

  20. Aqueous reactions of triplet excited states with allylic compounds

    NASA Astrophysics Data System (ADS)

    Kaur, R.; Anastasio, C.; Hudson, B. M.; Tantillo, D. J.

    2016-12-01

    Triplet excited states of dissolved organic matter react with several classes of aromatic organics such as phenols, anilines, sulfonamide antibiotics and phenylurea herbicides. Aqueous triplets appear to be among the most important oxidants for atmospheric phenols in regions with biomass burning, with phenol lifetimes on the order of a few hours to a day. However, little is known of the reactions of triplets with other classes of organic compounds. Recent work from our group shows that triplets react rapidly with several biogenic volatile organic compounds (BVOCs), such as methyl jasmonate, cis-3-hexenyl acetate, and cis-3-hexen-1-ol. However, there are only a few rate constants for aqueous reactions between alkenes such as these and triplet excited states. For our work, we refer to these and similar alkenes which have hydrogen(s) attached to a carbon adjacent to the double bond, as allylic compounds. To better assess the importance of triplets as aqueous oxidants, we measured second-order rate constants (kAC+3BP*) for a number of allylic compounds (ACs) with the triplet state of benzophenone; then established a quantitative structure-activity relationship (QSAR) between kAC+3BP* and computed oxidation potential of the ACs (R2 =0.65). Using the QSAR, we estimated the rate constants for triplets with some allylic isoprene and limonene oxidation products that have high Henry's law constants (KH>103 M atm-1). Hydroxylated limonene products and the delta-isomers of isoprene hydroxyhydroperoxides (δ4ISOPOOH) and hydroxynitrates (δ4ISONO2) were faster with predicted kAC+3BP* values ranging between (0.5-3.5) x 109 M-1-s-1 whereas the beta-isomers of ISOPOOH and ISONO2 were slower (kAC+3BP* < 0.5 x 109 M-1s-1). We scaled the predicted kAC+3BP* to represent less reactive atmospheric triplets that have been measured in fog drops, and compared to gas and aqueous hydroxyl radical and ozone, triplets in fog could account for up to 20 % of the measured loss of these compounds

  1. Interactions between delta and mu opioid agonists in assays of schedule-controlled responding, thermal nociception, drug self-administration, and drug versus food choice in rhesus monkeys: studies with SNC80 [(+)-4-[(alphaR)-alpha-((2S,5R)-4-allyl-2,5-dimethyl-1-piperazinyl)-3-methoxybenzyl]-N,N-diethylbenzamide] and heroin.

    PubMed

    Stevenson, Glenn W; Folk, John E; Rice, Kenner C; Negus, S Stevens

    2005-07-01

    Interactions between delta and mu opioid agonists in rhesus monkeys vary as a function of the behavioral endpoint. The present study compared interactions between the delta agonist SNC80 [(+)-4-[(alphaR)-alpha-((2S,5R)-4-allyl-2,5-dimethyl-1-piperazinyl)-3-methoxybenzyl]-N,N-diethylbenzamide] and the mu agonist heroin in assays of schedule-controlled responding, thermal nociception, and drug self-administration. Both SNC80 (ED50 = 0.43 mg/kg) and heroin (ED50 = 0.088 mg/kg) produced a dose-dependent and complete suppression of response rates in the assay of schedule-controlled responding. Heroin also produced thermal antinociception (ED(5 degrees C) = 0.18 mg/kg) and maintained drug self-administration under both a fixed ratio schedule [dose-effect curve peak at 0.0032 mg/kg/injection (inj)] and under a food versus heroin concurrent-choice schedule (ED50 = 0.013 mg/kg/inj), whereas SNC80 did not produce thermal antinociception or maintain self-administration. Fixed ratio mixtures of SNC80 and heroin (1.6:1, 4.7:1, and 14:1 SNC80/heroin) produced additive effects in the assay of schedule-controlled responding and superadditive effects in the assay of thermal nociception. Also, SNC80 did not enhance the reinforcing effects of heroin, indicating that mixtures of SNC80 and heroin produced additive or infra-additive reinforcing effects. These results provide additional evidence to suggest that delta/mu interactions depend on the experimental endpoint and further suggest that delta agonists may selectively enhance the antinociceptive effects of mu agonists while either not affecting or decreasing the sedative and reinforcing effects of mu agonists.

  2. Copper-Catalyzed Oxidative Dehydrogenative Carboxylation of Unactivated Alkanes to Allylic Esters via Alkenes

    PubMed Central

    2015-01-01

    We report copper-catalyzed oxidative dehydrogenative carboxylation (ODC) of unactivated alkanes with various substituted benzoic acids to produce the corresponding allylic esters. Spectroscopic studies (EPR, UV–vis) revealed that the resting state of the catalyst is [(BPI)Cu(O2CPh)] (1-O2CPh), formed from [(BPI)Cu(PPh3)2], oxidant, and benzoic acid. Catalytic and stoichiometric reactions of 1-O2CPh with alkyl radicals and radical probes imply that C–H bond cleavage occurs by a tert-butoxy radical. In addition, the deuterium kinetic isotope effect from reactions of cyclohexane and d12-cyclohexane in separate vessels showed that the turnover-limiting step for the ODC of cyclohexane is C–H bond cleavage. To understand the origin of the difference in products formed from copper-catalyzed amidation and copper-catalyzed ODC, reactions of an alkyl radical with a series of copper–carboxylate, copper–amidate, and copper–imidate complexes were performed. The results of competition experiments revealed that the relative rate of reaction of alkyl radicals with the copper complexes follows the trend Cu(II)–amidate > Cu(II)–imidate > Cu(II)–benzoate. Consistent with this trend, Cu(II)–amidates and Cu(II)–benzoates containing more electron-rich aryl groups on the benzamidate and benzoate react faster with the alkyl radical than do those with more electron-poor aryl groups on these ligands to produce the corresponding products. These data on the ODC of cyclohexane led to preliminary investigation of copper-catalyzed oxidative dehydrogenative amination of cyclohexane to generate a mixture of N-alkyl and N-allylic products. PMID:25389772

  3. Regio- and stereospecific rhodium-catalyzed allylic alkylation with an acyl anion equivalent: an approach to acyclic α-ternary β,γ-unsaturated aryl ketones† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc05705e Click here for additional data file.

    PubMed Central

    Turnbull, Ben W. H.; Chae, Jungha; Oliver, Samuel

    2017-01-01

    The regio- and stereospecific rhodium-catalyzed allylic alkylation of secondary allylic carbonates with cyanohydrin pronucleophiles facilitates the direct construction of acyclic α-ternary β,γ-unsaturated aryl ketones. Interestingly, this study illustrates the impact of deaggregating agents on regiocontrol and the electronic nature of the aryl component to suppress olefin isomerization. In addition, we demonstrate that the dimethylamino substituent, which modulates the pK a of the α-ternary β,γ-unsaturated aryl ketone, provides a useful synthetic handle for further functionalization via Kumada cross-coupling of the aryl trimethylammonium salt. Finally, the stereospecific alkylation of a chiral nonracemic secondary allylic carbonate affords the enantioenriched α-ternary aryl ketone, which was employed in a formal synthesis of trichostatic acid to illustrate that the allylic alkylation proceeds with net retention of configuration. PMID:28553542

  4. Field method for sulfide determination

    SciTech Connect

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

    1982-01-01

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

  5. Sequence-defined polymers via orthogonal allyl acrylamide building blocks.

    PubMed

    Porel, Mintu; Alabi, Christopher A

    2014-09-24

    Biological systems have long recognized the importance of macromolecular diversity and have evolved efficient processes for the rapid synthesis of sequence-defined biopolymers. However, achieving sequence control via synthetic methods has proven to be a difficult challenge. Herein we describe efforts to circumvent this difficulty via the use of orthogonal allyl acrylamide building blocks and a liquid-phase fluorous support for the de novo design and synthesis of sequence-specific polymers. We demonstrate proof-of-concept via synthesis and characterization of two sequence-isomeric 10-mer polymers. (1)H NMR and LCMS were used to confirm their chemical structure while tandem MS was used to confirm sequence identity. Further validation of this methodology was provided via the successful synthesis of a sequence-specific 16-mer polymer incorporating nine different monomers. This strategy thus shows promise as an efficient approach for the assembly of sequence-specific functional polymers.

  6. Separation of Silver from a Zinc Sulfide Concentrate by a Co-smelting Process

    NASA Astrophysics Data System (ADS)

    Yang, Jian-Guang; Zhang, Xu-Liang; Yang, Jian-Ying

    2015-02-01

    The main purpose of this study is to characterize and separate silver from a zinc sulfide concentrate through co-smelting with lead oxide dust. This article reports the optimization of process parameters, such as flux composition, co-smelting temperature, flux dosage, and charging material compositions, on the silver separation rate and resultant zinc sulfide concentrate grade. A maximum silver recovery of 97.36%, zinc sulfide concentrate grade of 43.91%, and 98.25% crude lead enriched silver are obtained under the optimized condition of temperature 900°C, smelting duration 120 min, 27.5 wt.% zinc sulfide concentrate, and 15.0 wt.% lead oxide dust, flux composition . This co-smelting process was proven effective to separate silver from zinc sulfide concentrate and produce a higher grade zinc sulfide concentrate. Especially, it was found to be effective to separate some associated impurities from zinc sulfide concentrate, such as arsenic, cadmium, fluorine, and chlorine etc.

  7. Atomic layer deposition of metal sulfide materials.

    PubMed

    Dasgupta, Neil P; Meng, Xiangbo; Elam, Jeffrey W; Martinson, Alex B F

    2015-02-17

    CONSPECTUS: The field of nanoscience is delivering increasingly intricate yet elegant geometric structures incorporating an ever-expanding palette of materials. Atomic layer deposition (ALD) is a powerful driver of this field, providing exceptionally conformal coatings spanning the periodic table and atomic-scale precision independent of substrate geometry. This versatility is intrinsic to ALD and results from sequential and self-limiting surface reactions. This characteristic facilitates digital synthesis, in which the film grows linearly with the number of reaction cycles. While the majority of ALD processes identified to date produce metal oxides, novel applications in areas such as energy storage, catalysis, and nanophotonics are motivating interest in sulfide materials. Recent progress in ALD of sulfides has expanded the diversity of accessible materials as well as a more complete understanding of the unique chalcogenide surface chemistry. ALD of sulfide materials typically uses metalorganic precursors and hydrogen sulfide (H2S). As in oxide ALD, the precursor chemistry is critical to controlling both the film growth and properties including roughness, crystallinity, and impurity levels. By modification of the precursor sequence, multicomponent sulfides have been deposited, although challenges remain because of the higher propensity for cation exchange reactions, greater diffusion rates, and unintentional annealing of this more labile class of materials. A deeper understanding of these surface chemical reactions has been achieved through a combination of in situ studies and quantum-chemical calculations. As this understanding matures, so does our ability to deterministically tailor film properties to new applications and more sophisticated devices. This Account highlights the attributes of ALD chemistry that are unique to metal sulfides and surveys recent applications of these materials in photovoltaics, energy storage, and photonics. Within each application

  8. Atomic layer deposition of metal sulfide materials

    DOE PAGES

    Dasgupta, Neil P.; Meng, Xiangbo; Elam, Jeffrey W.; ...

    2015-01-12

    The field of nanoscience is delivering increasingly intricate yet elegant geometric structures incorporating an ever-expanding palette of materials. Atomic layer deposition (ALD) is a powerful driver of this field, providing exceptionally conformal coatings spanning the periodic table and atomic-scale precision independent of substrate geometry. This versatility is intrinsic to ALD and results from sequential and self-limiting surface reactions. This characteristic facilitates digital synthesis, in which the film grows linearly with the number of reaction cycles. While the majority of ALD processes identified to date produce metal oxides, novel applications in areas such as energy storage, catalysis, and nanophotonics are motivatingmore » interest in sulfide materials. Recent progress in ALD of sulfides has expanded the diversity of accessible materials as well as a more complete understanding of the unique chalcogenide surface chemistry. ALD of sulfide materials typically uses metalorganic precursors and hydrogen sulfide (H2S). As in oxide ALD, the precursor chemistry is critical to controlling both the film growth and properties including roughness, crystallinity, and impurity levels. By modification of the precursor sequence, multicomponent sulfides have been deposited, although challenges remain because of the higher propensity for cation exchange reactions, greater diffusion rates, and unintentional annealing of this more labile class of materials. A deeper understanding of these surface chemical reactions has been achieved through a combination of in situ studies and quantum-chemical calculations. As this understanding matures, so does our ability to deterministically tailor film properties to new applications and more sophisticated devices. This Account highlights the attributes of ALD chemistry that are unique to metal sulfides and surveys recent applications of these materials in photovoltaics, energy storage, and photonics. Within each application space

  9. Tandem SN2' nucleophilic substitution/oxidative radical cyclization of aryl substituted allylic alcohols with 1,3-dicarbonyl compounds.

    PubMed

    Zhang, Zhen; Li, Cheng; Wang, Shao-Hua; Zhang, Fu-Min; Han, Xue; Tu, Yong-Qiang; Zhang, Xiao-Ming

    2017-03-23

    A novel and efficient tandem SN2' nucleophilic substitution/oxidative radical cyclization reaction of aryl substituted allylic alcohols with 1,3-dicarbonyl compounds has been developed by using Mn(OAc)3 as an oxidant, which enables the expeditious synthesis of polysubstituted dihydrofuran (DHF) derivatives in moderate to high yields. The use of weakly acidic hexafluoroisopropanol (HFIP) as the solvent rather than AcOH has successfully improved the yields and expanded the substrate scope of this type of radical cyclization reactions. Mechanistic studies confirmed the cascade reaction process involving a final radical cyclization.

  10. Catalytic Reduction of Noble Metal Salts by Sodium Hypophosphite Promoted by the Film Poly-(p-Allyl Ether Benzenesulfonic Acid)

    PubMed Central

    Costa, M. I. C. F.; Steter, J. R.; Purgato, F. L. S.; Romero, J. R.

    2011-01-01

    Glassy carbon electrodes were coated with the film poly-(p-allyl ether benzenesulfonic acid) by an anodic procedure. Nickel, platinum, and palladium ions were introduced into the film by ion exchange of H+ with the corresponding salts. These ions were catalytically reduced to their corresponding metals using the known electroless reducing agent sodium hypophosphite. Scanning electron microcopy and energy dispersive X-ray spectroscopy were carried out to demonstrate the occurrence of the catalytic process. To compare this method with another one carried out in our laboratory, the electrocatalytic reduction of H+ was studied using the same modified electrodes. A suggested mechanism for the catalysis is proposed. PMID:24052832

  11. Functional analysis of three sulfide:quinone oxidoreductase homologs in Chlorobaculum tepidum.

    PubMed

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

    2009-02-01

    Sulfide:quinone oxidoreductase (SQR) catalyzes sulfide oxidation during sulfide-dependent chemo- and phototrophic growth in bacteria. The green sulfur bacterium Chlorobaculum tepidum (formerly Chlorobium tepidum) can grow on sulfide as the sole electron donor and sulfur source. C. tepidum contains genes encoding three SQR homologs: CT0117, CT0876, and CT1087. This study examined which, if any, of the SQR homologs possess sulfide-dependent ubiquinone reduction activity and are required for growth on sulfide. In contrast to CT0117 and CT0876, transcripts of CT1087 were detected only when cells actively oxidized sulfide. Mutation of CT0117 or CT1087 in C. tepidum decreased SQR activity in membrane fractions, and the CT1087 mutant could not grow with >or=6 mM sulfide. Mutation of both CT0117 and CT1087 in C. tepidum completely abolished SQR activity, and the double mutant failed to grow with >or=4 mM sulfide. A C-terminal His(6)-tagged CT1087 protein was membrane localized, as was SQR activity. Epitope-tagged CT1087 was detected only when sulfide was actively consumed by cells. Recombinantly produced CT1087 and CT0117 proteins had SQR activity, while CT0876 did not. In summary, we conclude that, under the conditions tested, both CT0117 and CT1087 function as SQR proteins in C. tepidum. CT0876 may support the growth of C. tepidum at low sulfide concentrations, but no evidence was found for SQR activity associated with this protein.

  12. [Hydrogen sulfide and penile erection].

    PubMed

    Huang, Yi-Ming; Cheng, Yong; Jiang, Rui

    2012-09-01

    Hydrogen sulfide (H2S) is the third type of active endogenous gaseous signal molecule following nitric oxide (NO) and carbon monoxide (CO). In mammalians, H2S is mainly synthesized by two proteases, cystathionine-beta-synthase (CBS) and cystathionine-gamma-lyase (CSE). H2S plays an essential function of physiological regulation in vivo, and promotes penile erection by acting on the ATP-sensitive potassium channels to relax the vascular smooth muscle as well as by the synergistic effect with testosterone and NO to relax the corpus cavernosum smooth muscle (CCSM). At present, the selective phosphodiesterase type 5 (PDE5) inhibitor is mainly used for the treatment of erectile dysfunction (ED), but some ED patients fail to respond. Therefore, further studies on the mechanism of H2S regulating penile erection may provide a new way for the management of erectile dysfunction.

  13. Expanding the scope of Metal-Free enantioselective allylic substitutions: Anthrones

    PubMed Central

    Ceban, Victor; Tauchman, Jiří; Meazza, Marta; Gallagher, Greg; Light, Mark E.; Gergelitsová, Ivana; Veselý, Jan; Rios, Ramon

    2015-01-01

    The highly enantioselective asymmetric allylic alkylation of Morita–Baylis–Hillman carbonates with anthrones is presented. The reaction is simply catalyzed by cinchona alkaloid derivatives affording the final alkylated products in good yields and excellent enantioselectivities. PMID:26592555

  14. Palladium-catalyzed allylic amination: a powerful tool for the enantioselective synthesis of acyclic nucleoside phosphonates.

    PubMed

    Azzouz, Mariam; Soriano, Sébastien; Escudero-Casao, Margarita; Matheu, M Isabel; Castillón, Sergio; Díaz, Yolanda

    2017-08-30

    Acyclic nucleoside phosphonates have been prepared in a straightforward manner and in high yields by an enantioselective palladium-catalyzed allylic substitution involving nucleic bases as nucleophiles followed by cross-metathesis reaction with diethyl allylphosphonate.

  15. Structurally simple pyridine N-oxides as efficient organocatalysts for the enantioselective allylation of aromatic aldehydes.

    PubMed

    Pignataro, Luca; Benaglia, Maurizio; Annunziata, Rita; Cinquini, Mauro; Cozzi, Franco

    2006-02-17

    A series of structurally simple pyridine N-oxides have readily been assembled from inexpensive amino acids and tested as organocatalysts in the allylation of aldehydes with allyl(trichloro)silane to afford homoallylic alcohols. (S)-proline-based catalysts afforded the products derived from aromatic aldehydes in fair to good yields and in up to 84% enantiomeric excess (ee). The allylation of heteroaromatic, unsaturated, and aliphatic aldehydes was less satisfactory. By running the reaction in the presence of achiral and chiral additives and structurally different catalysts, we collected some insights into the relationship between the stereochemical outcome and the catalyst's structural features. Even if the ee's obtained are inferior to the best values observed with other catalysts, this work concurs to show that structurally simple pyridine N-oxides can also promote the allylation reaction with satisfactory stereocontrol.

  16. Effect of Allyl Isothiocyanate on developmental toxicity in exposed Xenopus laevis embryos

    USDA-ARS?s Scientific Manuscript database

    The pungent natural compound allyl isothiocyanate isolated from the seeds of Cruciferous (Brassica) plants such as mustard is reported to exhibit numerous beneficial health-promoting antimicrobial, antifungal, anticarcinogenic, cardioprotective, and neuroprotective properties. Because it is also re...

  17. O-allyl decoration on alpha-glucan isolated from the haloalkaliphilic Halomonas pantelleriensis bacterium.

    PubMed

    Corsaro, Maria Michela; Gambacorta, Agata; Lanzetta, Rosa; Nicolaus, Barbara; Pieretti, Giuseppina; Romano, Ida; Parrilli, Michelangelo

    2007-07-02

    An alpha-glucan containing the unprecedented peculiar O-allyl substituent was isolated from the haloalkaliphilic Gram-negative Halomonas pantelleriensis bacterium. Its dextran-like structure was deduced from chemical degradative and spectroscopic methods.

  18. Expanding the scope of Metal-Free enantioselective allylic substitutions: Anthrones

    NASA Astrophysics Data System (ADS)

    Ceban, Victor; Tauchman, Jiří; Meazza, Marta; Gallagher, Greg; Light, Mark E.; Gergelitsová, Ivana; Veselý, Jan; Rios, Ramon

    2015-11-01

    The highly enantioselective asymmetric allylic alkylation of Morita-Baylis-Hillman carbonates with anthrones is presented. The reaction is simply catalyzed by cinchona alkaloid derivatives affording the final alkylated products in good yields and excellent enantioselectivities.

  19. Conversion of allylic alcohols to stereodefined trisubstituted alkenes: a complementary process to the Claisen rearrangement.

    PubMed

    Belardi, Justin K; Micalizio, Glenn C

    2008-12-17

    A stereoselective method for the conversion of allylic alcohols to (Z)-trisubstituted alkenes is presented. Overall, the reaction sequence described is stereochemically complementary to related Claisen rearrangement reactions--processes that typically deliver the stereoisomeric trisubstituted alkene containing products.

  20. Identifying Predictors of Arsenic Bioavailability in Low-Sulfide, Quartz-Hosted Gold Deposits: Case Study at the Empire Mine State Historic Park, CA, USA

    NASA Astrophysics Data System (ADS)

    Foster, A. L.; Alpers, C. N.; Burlak Regnier, T.; Blum, A.; Petersen, E. U.; Basta, N. T.; Whitacre, S.; Casteel, S. W.; Kim, C. S.

    2016-12-01

    Introduction: This study addressed a need to identify geochemical and mineralogical parameters that are significantly correlated with arsenic bioavailability at historically-mined, low-sulfide, quartz-hosted ("lode") gold deposits. The study location was the Empire Mine State Historic Park (EMSHP), a site that is typical of many lode deposits in California in that arsenic is a primary contaminant of concern. Methods: A total of 25 large-volume sediment/mine waste samples were collected from sites in the EMSHP, homogenized, and dry sieved (< 250 micron). The following datasets were collected from the 25 samples (or a subset thereof as indicated): (1) in vivo relative As bioavailability (juvenile swine; n = 12); (2) in vitro relative As bioaccessibility (n = 25); (3) solid-phase chemistry (XRF; n = 25); (4) quantitative mineralogy (n =25); (5) Bulk As- and iron (Fe) speciation (synchrotron X-ray absorption spectroscopy, XAS, n =19); (6) point-based micron-scale composition (electron microprobe, n =12); and (7) micron-scale mineralogical and compositional mapping (QEMSCAN, n = 12). The matrix of bivariate correlations among these datasets was evaluated using a cutoff criterion for significance of p < 0.05. Results:Arsenic bioavailability was positively and significantly correlated with the abundance of Fe (hydr)oxide, the relative abundance of As-bearing hydroxide and As concentration in Fe hydroxide (datasets 4, 5, and 6, respectively). The relative abundance of As associated with Al-bearing secondary minerals (determined by As-XAS) was also positively and significantly correlated with datasets (1) and (2), but the correlation quality was lower. The relative abundance of other arsenic-bearing secondary minerals (e.g., jarosite, calcium arsenate, arseniosiderite) as determined by As XAS had positive correlations with bioaccessibility and/or bioavailability, but the correlations were not statistically significant. We ascribe this result to the fact that these phases

  1. Nuclear spin lattice relaxation and conductivity studies of the non-Arrhenius conductivity behavior in lithium fast ion conducting sulfide glasses

    NASA Astrophysics Data System (ADS)

    Meyer, Benjamin Michael

    Homogeneous xB2O3 + (1-x)B 2S3 glasses were prepared between 0 ≤ x ≤ 0.80. Raman, IR, and 11B NMR spectroscopies show that the boron oxide structures of B2O3, especially the six-membered rings, quickly diminish with increasing sulfide content, whereas the corresponding sulfide structures in B2S3 remain relatively intense as oxide content is increased. Differential scanning calorimetry (DSC) and density measurements show that physical properties of these boron oxysulfide glasses heavily favor the B2S3 properties regardless of the amount of B2O3 added to the system. It is hypothesized that the stability of the thioboroxol ring group relative to that of the BS 3/2 trigonal group is a possible source of this behavior. The formation of mixed boron oxysulfide structures of composition BSzO3-z where 0 < z < 3 is proposed. Structural studies of the ternary xLi2S + (1-x)[0.5 B2S3 + 0.5 GeS2] glasses using IR, Raman, and 11B NMR show that these glasses do not have equal sharing of the lithium atoms between GeS2 and B2S3. The IR spectra indicates that the B2S3 glass network are under-doped in comparison to corresponding compositions in the xLi 2S + (1-x)B2S3 binary system. Additionally, the Raman spectra show that the GeS2 glass network is over-modified. 11Boron static NMR gives evidence that ˜80% of the boron atoms are in tetrahedral coordinated. A super macro tetrahedron is proposed as one of the structures in these glasses in which some of them may contain boron sites substituted by germanium atoms at lower Li2S content. Nuclear Spin Lattice Relaxation and ionic conductivity measurements of Li doped Li2S + GeS2 + B2S3 glasses were performed to investigate the ion hopping dynamics and the non-Arrhenius conductivity behavior that has been observed in some fast ion conducting glasses. A distribution of activation energies model was used to fit the NSLR results and conductivity results. Comparisons are made to previously studied binary lithium thio-germanate and binary

  2. Actinide sulfides in the gas phase: experimental and theoretical studies of the thermochemistry of AnS (An = Ac, Th, Pa, U, Np, Pu, Am and Cm).

    PubMed

    Pereira, Cláudia C L; Marsden, Colin J; Marçalo, Joaquim; Gibson, John K

    2011-07-28

    The gas-phase thermochemistry of actinide monosulfides, AnS, was investigated experimentally and theoretically. Fourier transform ion cyclotron resonance mass spectrometry was employed to study the reactivity of An(+) and AnO(+) (An = Th, Pa, U, Np, Pu, Am and Cm) with CS(2) and COS, as well as the reactivity of the produced AnS(+) with oxidants (COS, CO(2), CH(2)O and NO). From these experiments, An(+)-S bond dissociation energies could be bracketed. Density functional theory studies of the energetics of neutral and monocationic AnS (An = Ac, Th, Pa, U, Np, Pu, Am and Cm) provided values for bond dissociation energies and ionization energies; the computed energetics of neutral and monocationic AnO were also obtained for comparison. The theoretical data, together with comparisons with known An(+)-O bond dissociation energies and M(+)-S and M(+)-O dissociation energies for the early transition metals, allowed for the refining of the An(+)-S bond dissociation energy ranges obtained from experiment. Examination of the reactivity of AnS(+) with dienes, coupled to comparisons with reactivities of the AnO(+) analogues, systematic considerations and the theoretical results, allowed for the estimation of the ionization energies of the AnS; the bond dissociation energies of neutral AnS were consequently derived. Estimates for the case of AcS were also made, based on correlations of the data for the other An and the electronic energetics of neutral and ionic An. The nature of the bonding in the elementary molecular actinide chalcogenides (oxides and sulfides) is discussed, based on both the experimental data and the computed electronic structures. DFT calculations of ionization energies for the actinide atoms and the diatomic sulfides and oxides are relatively reliable, but the calculation of bond dissociation energies is not uniformly satisfactory, either with DFT or CCSD(T). A key conclusion from both the experimental and theoretical results is that the 5f electrons do not

  3. Iron sulfide minerals in Black Sea sediments

    NASA Astrophysics Data System (ADS)

    Franke, C.; Robin, E.; Henkel, S.; Kasten, S.; Bleil, U.

    2009-04-01

    This study presents an integrated geochemical, environmental magnetic, and electron microscopic approach to better understand the physicochemical processes in deep sea sediments from the northwestern Black Sea. The investigated gravity core GC 214 was retrieved in 2007 during RV Meteor cruise M72/1 west of the Crimean Peninsula in a water depth of 1686 mbsf. Geochemical analyses of the pore water and solid phase indicate non-steady state sedimentation. The oxygen-depleted water column conditions, anaerobic oxidation of methane (AOM) and related microbially-driven sulfate reduction favor a highly complex iron sulfide mineral assemblage in the sediment column. The detailed magnetic susceptibility and remanence measurements indicate an irregularly stratified depth profile showing intervals of particularly high values. Further environmental magnetic analyses depict strongly elevated coercivities for those depth horizons, suggesting greigite as one of the main magnetic carrier minerals. Automated chemical classification (ACC), using electron dispersive spectrometer (EDS) attached to a JEOL840 scanning electron microscope (SEM), on dispersed particle samples permitted the identification of greigite (Fe3S4) next to pyrrhotite (Fe7S8), pyrite (FeS2) and monosulfides (FeS), but also allowed for the absolute quantification of the various mineral phases. These analyses were carried out on magnetic extracts and density separates to be able to calculate budgets between the different present iron sulfides. We obtained excellent correlations between the different iron sulfide concentrations and the magnetic signal. Additional analyses on polished sections yield inside into the details of the sulfidization pathways along the depth profile of the sediment sequence and help to develop a more general process model for this particular geochemical (paleo-)environment. Keywords: Black Sea, iron sulfides, environmental magnetism, anaerobic oxidation of methane (AOM), scanning electron

  4. Direct Palladium-Catalyzed Carbonylative Transformation of Allylic Alcohols and Related Derivatives.

    PubMed

    Wu, Fu-Peng; Peng, Jin-Bao; Fu, Lu-Yang; Qi, Xinxin; Wu, Xiao-Feng

    2017-09-18

    A direct, palladium-catalyzed, carbonylative transformation of allylic alcohols for the synthesis of β,γ-unsaturated carboxylic acids has been developed. With formic acid as the CO source, various allylic alcohols were conveniently transformed into the corresponding β,γ-unsaturated carboxylic acids with excellent linear and (E)-selectivity. The reaction was performed under mild conditions; toxic CO gas manipulation and high-pressure equipment were avoided in this procedure.

  5. A Concomitant Allylic Azide Rearrangement/Intramolecular Azide–Alkyne Cycloaddition Sequence

    PubMed Central

    2015-01-01

    An intramolecular Huisgen cycloaddition of an interconverting set of isomeric allylic azides with alkynes affords substituted triazoles in high yield. The stereoisomeric vinyl-substituted triazoloxazines formed depend on the rate of cycloaddition of the different allylic azide precursors when the reaction is carried out under thermal conditions. In contrast, dimerized macrocyclic products were obtained when the reaction was done using copper(I)-catalyzed conditions, demonstrating the ability to control the reaction products through changing conditions. PMID:24635056

  6. A concomitant allylic azide rearrangement/intramolecular azide-alkyne cycloaddition sequence.

    PubMed

    Vekariya, Rakesh H; Liu, Ruzhang; Aubé, Jeffrey

    2014-04-04

    An intramolecular Huisgen cycloaddition of an interconverting set of isomeric allylic azides with alkynes affords substituted triazoles in high yield. The stereoisomeric vinyl-substituted triazoloxazines formed depend on the rate of cycloaddition of the different allylic azide precursors when the reaction is carried out under thermal conditions. In contrast, dimerized macrocyclic products were obtained when the reaction was done using copper(I)-catalyzed conditions, demonstrating the ability to control the reaction products through changing conditions.

  7. Diene-ligated iridium catalyst for allylation reactions of ketones and imines.

    PubMed

    Barker, Timothy J; Jarvo, Elizabeth R

    2009-03-05

    [Ir(cod)Cl](2) is a highly reactive catalyst for allylation reactions of ketones using allylboronic ester. Mechanistic experiments are consistent with formation of a nucleophilic allyliridium(I) complex that is activated by the diene ligand toward attack of a ketone. Aryl and alkyl ketones react smoothly at room temperature. Aldimines also undergo allylation under these reaction conditions, requiring increased reaction times relative to the corresponding ketones.

  8. A Catalytic, Brønsted Base Strategy for Intermolecular Allylic C—H Amination

    PubMed Central

    Reed, Sean A.; Mazzotti, Anthony R.; White, M. Christina

    2009-01-01

    A Brønsted base activation mode for oxidative, Pd(II)/sulfoxide catalyzed, intermolecular C—H allylic amination is reported. N,N-diisopropylethylamine was found to promote amination of unactivated terminal olefins, forming the corresponding linear allylic amine products with high levels of stereo-, regio-, and chemoselectivity. The predictable and high selectivity of this C—H oxidation method enables late-stage incorporation of nitrogen into advanced synthetic intermediates and natural products. PMID:19645492

  9. Regio- and Stereoselective Modification of Chiral α-Amino Ketones by Pd-Catalyzed Allylic Alkylation.

    PubMed

    Huwig, Kai; Schultz, Katharina; Kazmaier, Uli

    2015-07-27

    Chiral α-amino ketones are excellent nucleophiles for stereoselective palladium-catalyzed allylic alkylations. Both chiral as well as achiral allylic substrates can be applied, while the stereochemical outcome of the reaction is controlled by the chiral ketone enolate. The substituted amino ketones formed can be reduced stereoselectively, and up to five consecutive stereogenic centers can be obtained. This approach can be used for the synthesis of highly substituted piperidine derivatives.

  10. Indole synthesis by palladium-catalyzed tandem allylic isomerization - furan Diels-Alder reaction.

    PubMed

    Xu, Jie; Wipf, Peter

    2017-08-30

    A Pd(0)-catalyzed elimination of an allylic acetate generates a π-allyl complex that is postulated to initiate a novel intramolecular Diels-Alder cycloaddition to a tethered furan (IMDAF). Under the reaction conditions, this convergent, microwave-accelerated cascade process provides substituted indoles in moderate to good yields after Pd-hydride elimination, aromatization by dehydration, and in situ N-Boc cleavage.

  11. Direct use of allylic alcohols for platinum-catalyzed monoallylation of amines.

    PubMed

    Utsunomiya, Masaru; Miyamoto, Yoshiki; Ipposhi, Junji; Ohshima, Takashi; Mashima, Kazushi

    2007-08-16

    A new direct catalytic amination of allylic alcohols promoted by the combination of platinum and a large bite-angle ligand DPEphos was developed in which the allylic alcohol was effectively converted to a pi-allylplatinum intermediate without the use of an activating reagent. The use of the DPEphos ligand was essential for obtaining high catalyst activity and high monoallylation selectivity of primary amines, allowing the formation of a variety of monoallylation products in good to excellent yield.

  12. An efficient and convenient palladium catalyst system for the synthesis of amines from allylic alcohols.

    PubMed

    Banerjee, Debasis; Jagadeesh, Rajenahally V; Junge, Kathrin; Junge, Henrik; Beller, Matthias

    2012-10-01

    A novel catalyst system for efficient amination of allylic alcohols with aryl and alkyl amines is presented. By applying a convenient combination consisting of Pd(OAc)(2)/1,10-phenanthroline, a variety of allylic alcohols reacted smoothly to give the corresponding secondary and tertiary amines in good to excellent yields with high regioselectivity. The usefulness of our protocol is demonstrated in the one-step synthesis of the antifungal drug naftifine and the calcium channel blocker flunarizine.

  13. A simple, nontoxic iron system for the allylation of zinc enolates.

    PubMed

    Jarugumilli, Gopala K; Cook, Silas P

    2011-04-15

    Diiron nonacarbonyl in combination with triphenylphosphine has been identified as a low-cost and environmentally benign catalyst system for the allylation of zinc enolates generated in situ from copper-catalyzed asymmetric conjugate addition reactions. The catalyst system provides the allylated product in modest to good yields at room temperature with unprecedented diastereoselectivity in cyclic enone systems. While triphenylphosphine was uniquely effective among the investigated ligands, the exact nature of the active catalytic species remains unknown.

  14. Diastereo- and Enantioselective Iridium Catalyzed Carbonyl (α-Cyclopropyl)allylation via Transfer Hydrogenation.

    PubMed

    Tsutsumi, Ryosuke; Hong, Suckchang; Krische, Michael J

    2015-09-07

    The first examples of diastereo- and enantioselective carbonyl α-(cyclopropyl)allylation are reported. Under the conditions of iridium catalyzed transfer hydrogenation using the chiral precatalyst (R)-Ir-I modified by SEGPHOS, carbonyl α-(cyclopropyl)allylation may be achieved with equal facility from alcohol or aldehyde oxidation levels. This methodology provides a conduit to hitherto inaccessible inaccessible enantiomerically enriched cyclopropane-containing architectures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Catalytic reduction of CO with hydrogen sulfide. 4. Temperature-programmed desorption of methanethiol on anatase, rutile, and sulfided rutile

    SciTech Connect

    Beck, D.D.; White, J.M.; Ratcliffe, C.T.

    1986-07-03

    The interaction of methanethiol with anatase, rutile, and sulfided rutile was studied by temperature-programmed desorption. Dissociative adsorption occurs on rutile but is insignificant on anatase. Decomposition products are dominated by H/sub 2/ on rutile and by CH/sub 4/ on sulfided rutile. In both cases desorption occurs between 500 and 775 K. The 5- and 4-coordinate sites on the (110) face of rutile are proposed as the active sites for decomposition. The dominance of methane on a sulfided surface is attributed to the relatively large supply of highly mobile surface hydrogen atoms.

  16. Valence and conduction band edges of selenide and sulfide-based kesterites—a study by x-ray based spectroscopy and ab initio theory

    NASA Astrophysics Data System (ADS)

    Olar, Tetiana; Manoharan, Archana; Draxl, Claudia; Calvet, Wolfram; Ümsur, Bünyamin; Parvan, Vladimir; Chacko, Binoy; Xie, Haibing; Saucedo, Edgardo; Valle-Rios, Laura Elisa; Neldner, Kai; Schorr, Susan; Lux-Steiner, Martha Ch; Lauermann, Iver

    2017-10-01

    Thin film solar cells based on the kesterite material with the general composition Cu2ZnSn(Se,S)4 can be a substitute for the more common chalcopyrites (Cu(In,Ga)(Se,S)2) with a similar band gap range. When replacing the anion sulfide with selenide, the optical band gap of kesterite changes from 1.5 to 1 eV. Here we report on a study of the valence band maximum and conduction band minimum energies of kesterites with either S or Se as the anion. Knowing these positions is crucial for the design of solar cells in order to match the bands of the absorber material with those of the subsequent functional layers like buffer or window layer. Their relative positions were studied using photoelectron spectroscopy of the valence band edge and x-ray absorption spectroscopy of the cations Cu, Zn, and Sn, respectively. The experimental results are interpreted and confirmed in terms of calculations based on density-functional theory and the GW approach of the many-body theory.

  17. Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry.

    PubMed

    Antiñolo, M; Ocaña, A J; Aranguren, J P; Lane, S I; Albaladejo, J; Jiménez, E

    2017-08-01

    Unsaturated ethers are oxygenated volatile organic compounds (OVOCs) emitted by anthropogenic sources. Potential removal processes in the troposphere are initiated by hydroxyl (OH) radicals and photochemistry. In this work, we report for the first time the rate coefficients of the gas-phase reaction with OH radicals (kOH) of 2-chloroethyl vinyl ether (2ClEVE), allyl ether (AE), and allyl ethyl ether (AEE) as a function of temperature in the 263-358 K range, measured by the pulsed laser photolysis-laser induced fluorescence technique. No pressure dependence of kOH was observed in the 50-500 Torr range in He as bath gas, while a slightly negative T-dependence was observed. The temperature dependent expressions for the rate coefficients determined in this work are: The estimated atmospheric lifetimes (τOH) assuming kOH at 288 K were 3, 2, and 4 h for 2ClEVE, AE and AEE, respectively. The kinetic results are discussed in terms of the chemical structure of the unsaturated ethers by comparison with similar compounds. We also report ultraviolet (UV) and infrared (IR) absorption cross sections (σλ and σ(ν˜), respectively). We estimate the photolysis rate coefficients in the solar UV actinic region to be less than 10(-7) s(-1), implying that these compounds are not removed from the atmosphere by this process. In addition, from σ(ν˜) and τOH, the global warming potential of each unsaturated ether was calculated to be almost zero. A discussion on the atmospheric implications of the titled compounds is presented. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block

    NASA Astrophysics Data System (ADS)

    Bayeh, Liela; Le, Phong Q.; Tambar, Uttam K.

    2017-07-01

    The stereoselective oxidation of hydrocarbons is one of the most notable advances in synthetic chemistry over the past fifty years. Inspired by nature, enantioselective dihydroxylations, epoxidations and other oxidations of unsaturated hydrocarbons have been developed. More recently, the catalytic enantioselective allylic carbon-hydrogen oxidation of alkenes has streamlined the production of pharmaceuticals, natural products, fine chemicals and other functional materials. Allylic functionalization provides a direct path to chiral building blocks with a newly formed stereocentre from petrochemical feedstocks while preserving the olefin functionality as a handle for further chemical elaboration. Various metal-based catalysts have been discovered for the enantioselective allylic carbon-hydrogen oxidation of simple alkenes with cyclic or terminal double bonds. However, a general and selective allylic oxidation using the more common internal alkenes remains elusive. Here we report the enantioselective, regioselective and E/Z-selective allylic oxidation of unactivated internal alkenes via a catalytic hetero-ene reaction with a chalcogen-based oxidant. Our method enables non-symmetric internal alkenes to be selectively converted into allylic functionalized products with high stereoselectivity and regioselectivity. Stereospecific transformations of the resulting multifunctional chiral building blocks highlight the potential for rapidly converting internal alkenes into a broad range of enantioenriched structures that can be used in the synthesis of complex target molecules.

  19. Sulfides and oxides in comets

    NASA Technical Reports Server (NTRS)

    Rietmeijer, Frans J. M.

    1988-01-01

    Metal abundances associated with Sun-grazing P/comet Ikeya-Seki 1965f, the mineralogy of chrondritic interplanetary dust particles and cosmochemical affinities of Co, V, Cr, and Ni in extraterrestrial materials and probable vaporization data for nonsilicate minerals are used to evaluate the putative dearth of nonsilicates in short-period comets. It is concluded that sulfides and oxides are common, albeit minor, constituents of these comets. Sulfides and oxides can form in situ during perihelion passage in the nucleus of active short-period comets by sulfidation of Mg, Fe-silicates.

  20. Sulfides and oxides in comets

    NASA Technical Reports Server (NTRS)

    Rietmeijer, Frans J. M.

    1988-01-01

    Metal abundances associated with Sun-grazing P/comet Ikeya-Seki 1965f, the mineralogy of chrondritic interplanetary dust particles and cosmochemical affinities of Co, V, Cr, and Ni in extraterrestrial materials and probable vaporization data for nonsilicate minerals are used to evaluate the putative dearth of nonsilicates in short-period comets. It is concluded that sulfides and oxides are common, albeit minor, constituents of these comets. Sulfides and oxides can form in situ during perihelion passage in the nucleus of active short-period comets by sulfidation of Mg, Fe-silicates.