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Sample records for benzothiophenes

  1. Benzothiophene-S-oxides-an Overview

    OpenAIRE

    Thiemann, Thies; Arima, Kazuya; Kumazoe, Kazuya; Mataka, Shuntaro

    2000-01-01

    In this review on the class of benzothiophene-S-oxides the preparation, the structural and physical properties as well as the reactivity of these molecules are presented. Moreover, their importance as intermediates into the microbial transformation of environmentally harmful benzothiophenes is highlighted. Possible technical applications are also discussed.

  2. 1-Benzothiophene-2-carbaldehyde 4-ethylthiosemicarbazone

    Directory of Open Access Journals (Sweden)

    Safa'a Fares Kayed

    2009-01-01

    Full Text Available The title compound, C13H15N3S2, crystallizes with two unique molecules, A and B, in the asymmetric unit. These differ principally in that the methyl group of the 4-ethylthiosemicarbazone moiety is ordered in molecule A but disordered over two positions with equal occupancies in molecule B. The benzothiophene group and the semicarbazone unit are inclined at dihedral angles of 11.78 (8° for molecule A and 8.18 (13° for molecule B. Weak intramolecular N—H...N interactions contribute to the planarity of the semicarbazone units in both molecules and each molecule adopts an E configuration with respect to the C=N bonds. In the crystal structure, molecules form centrosymmetric dimers as a result of N—H...S hydrogen bonds, augmented by C—H...S interactions for molecule A and C—H...S interactions for molecule B. Weak C—H...π interactions stack the dimers of both molecules into columns down the a axis.

  3. 3-Methyl-4,5,6,7-tetrahydro-1-benzothiophene-2-carboxylic Acid

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    Rajendiran Nagappan

    2010-01-01

    Full Text Available 3-Methyl-4,5,6,7-tetrahydro-1-benzothiophene-2-carboxylic acid was synthesized chemoselectively from 3-formyl-4,5,6,7-tetrahydro-1-benzothiophene-2-carboxylic acid, using Et3SiH/I2 as a reducing agent. The title compound was characterized by IR, 1H NMR, 13C NMR and LCMS.

  4. Benzothiophene inhibitors of MK2. Part 2: improvements in kinase selectivity and cell potency.

    Science.gov (United States)

    Anderson, David R; Meyers, Marvin J; Kurumbail, Ravi G; Caspers, Nicole; Poda, Gennadiy I; Long, Scott A; Pierce, Betsy S; Mahoney, Matthew W; Mourey, Robert J; Parikh, Mihir D

    2009-08-15

    Optimization of kinase selectivity for a set of benzothiophene MK2 inhibitors provided analogs with potencies of less than 500 nM in a cell based assay. The selectivity of the inhibitors can be rationalized by examination of X-ray crystal structures of inhibitors bound to MK2.

  5. Benzothiophene inhibitors of MK2. Part 2: Improvements in kinase selectivity and cell potency

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, David R.; Meyers, Marvin J.; Kurumbail, Ravi G.; Caspers, Nicole; Poda, Gennadiy I.; Long, Scott A.; Pierce, Betsy S.; Mahoney, Matthew W.; Mourey, Robert J.; Parikh, Mihir D.; Pfizer

    2010-10-01

    Optimization of kinase selectivity for a set of benzothiophene MK2 inhibitors provided analogs with potencies of less than 500 nM in a cell based assay. The selectivity of the inhibitors can be rationalized by examination of X-ray crystal structures of inhibitors bound to MK2.

  6. A46, a Benzothiophene Derived Compound, Suppresses Jak2-Mediated Pathologic Cell Growth

    OpenAIRE

    Majumder, Anurima; Magis, Andrew T.; Park, Sung O.; Figueroa, Nicholas C.; Baskin, Rebekah; Kirabo, Annet; Robert W Allan; Zhao, Zhizhuang Joe; Bisht, Kirpal S.; Keserű, György M.; Sayeski, Peter P.

    2011-01-01

    Hyperkinetic Jak2 tyrosine kinase signaling has been implicated in several hematological disorders including the myeloproliferative neoplasms (MPNs). Effective Jak2 inhibitors can thus have significant therapeutic potential. Here, using structure based virtual screening, we identified a benzothiophene derived Jak2 inhibitor named A46. We hypothesized that this compound would inhibit Jak2-V617F mediated pathologic cell growth. To test this, A46 was analyzed for its ability to i) inhibit recomb...

  7. Benzothiophene inhibitors of MK2. Part 1: structure-activity relationships, assessments of selectivity and cellular potency.

    Science.gov (United States)

    Anderson, David R; Meyers, Marvin J; Kurumbail, Ravi G; Caspers, Nicole; Poda, Gennadiy I; Long, Scott A; Pierce, Betsy S; Mahoney, Matthew W; Mourey, Robert J

    2009-08-15

    Identification of potent benzothiophene inhibitors of mitogen activated protein kinase-activated protein kinase 2 (MK2), structure-activity relationship (SAR) studies, selectivity assessments against CDK2, cellular potency and mechanism of action are presented. Crystallographic data provide a rationale for the observed MK2 potency as well as selectivity over CDK2 for this class of inhibitors.

  8. Ethyl 2-(pyridine-4-carboxamido-4,5,6,7-tetrahydro-1-benzothiophene-3-carboxylate

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    Asma Mukhtar

    2012-07-01

    Full Text Available In the title compound, C17H18N2O3S, the dihedral angles between the thiophene ring and the ethyl ester group and the pyridine-4-carboxamide unit are 7.1 (2 and 9.47 (11°, respectively. An intramolecular N—H...O hydrogen bond generates an S(6 ring. In the crystal, inversion dimers linked by pairs of C—H...O hydrogen bonds between the tetrahydro-1-benzothiophene and the pyridine-4-carboxamide residues generate R22(16 loops. There exists positional disorder in three methelene groups of the cyclohexane ring and the terminal C atom of the ethyl ester side chain in a 0.691 (14:0.309 (14 occupancy ratio.

  9. Genetic analysis of benzothiophene biodesulfurization pathway of Gordonia terrae strain C-6.

    Directory of Open Access Journals (Sweden)

    Wei Wang

    Full Text Available Sulfur can be removed from benzothiophene (BT by some bacteria without breaking carbon-carbon bonds. However, a clear mechanism for BT desulfurization and its genetic components have not been reported in literatures so far. In this study, we used comparative transcriptomics to study differential expression of genes in Gordonia terrae C-6 cultured with BT or sodium sulfate as the sole source of sulfur. We found that 135 genes were up-regulated with BT relative to sodium sulfate as the sole sulfur source. Many of these genes encode flavin-dependent monooxygenases, alkane sulfonate monooxygenases and desulfinase, which perform similar functions to those involved in the 4S pathway of dibenzothiophene (DBT biodesulfurization. Three of the genes were found to be located in the same operon, designated bdsABC. Cell extracts of pET28a-bdsABC transfected E. coli Rosetta (DE3 converted BT to a phenolic compound, identified as o-hydroxystyrene. These results advance our understanding of enzymes involved in the BT biodesulfurization pathway.

  10. Temperature Induced Wetting and Dewetting Effects of Dioctylbenzothieno-benzothiophene on Silicon Oxide Surfaces

    International Nuclear Information System (INIS)

    Full text: The excellent performance of the molecule dioctyl-benzothieno-benzothiophene (C8-BTBT) in organic thin film transistors is strongly influenced by heat treatment. Spin coating of the film at elevated temperatures (within the liquid-crystalline state), leads to an increase in charge carrier mobilities up to 3 cm2/V s. The structural properties of C8-BTBT thin films are investigated as a function of temperature in terms of crystallographic properties and morphology. Spatially resolved microscopic methods (AFM and optical microscopy) as well as integral characterisation methods (Grazing incidence x-ray scattering, x-ray reflectivity) are used. The disordered monolayer film (thickness 2.4 nm) remains unstable after the spin coating process. With increasing temperatures, dewetting of the monolayer is observed by the formation of crystalline islands with an average height of about 15 nm. Approaching the transition temperature to the smectic state, at a temperature of 900C, re-wetting is observed and a monolayer is formed on the substrate surface. This monolayer (thickness 2.9 nm) remains stable in the liquid crystalline state as well as after cooling back to room temperature. Also multilayer films show pronounced dewetting during heating by the formation of huge crystalline islands with a lateral size in the μm range. At 1050C a monolayer (thickness 2.9 nm), at 1080C a bilayer and at 1150C a triple layer has developed. Decreasing temperatures reveal the reversibility of the layer-by-layer formation. All found layered structures can be stabilized by rapid cooling. (author)

  11. A Thieno[3,2-b][1]benzothiophene Isoindigo Building Block for Additive- and Annealing-Free High-Performance Polymer Solar Cells

    KAUST Repository

    Yue, Wan

    2015-08-20

    A novel photoactive polymer with two different molecular weights is reported, based on a new building block: thieno[3,2-b][1]benzothiophene isoindigo. Due to the improved crystallinity, optimal blend morphology, and higher charge mobility, solar-cell devices of the high-molecular-weight polymer exhibit a superior performance, affording efficiencies of 9.1% without the need for additives, annealing, or additional extraction layers during device fabrication.

  12. Oxidative desulfurization of benzothiophene and thiophene with WOx/ZrO2 catalysts: effect of calcination temperature of catalysts.

    Science.gov (United States)

    Hasan, Zubair; Jeon, Jaewoo; Jhung, Sung Hwa

    2012-02-29

    Oxidative desulfurization (ODS) of model fuel containing benzothiophene (BT) or thiophene (Th) has been carried out with WO(x)/ZrO2 catalyst, which was calcined at various temperatures. Based on the conversion of BT in the model fuel, it can be shown that the optimum calcination temperature of WOx/ZrO2 catalyst is around 700 °C. The most active catalyst is composed of tetragonal zirconia (ZrO2) with well dispersed polyoxotungstate species and it is necessary to minimize the contents of the crystalline WO3 and monoclinic ZrO2 for a high BT conversion. The oxidation rate was interpreted with the first-order kinetics, and it demonstrated the importance of electron density since the kinetic constant for BT was higher than that for Th even though the BT is larger than Th in size. A WOx/ZrO2 catalyst, treated suitably, can be used as a reusable active catalyst in the ODS. PMID:22245512

  13. Effect of textural property of coconut shell-based activated carbon on desorption activation energy of benzothiophene

    Institute of Scientific and Technical Information of China (English)

    Moxin YU; Zhong LI; Hongxia XI; Qibin XIA; Shuwen WANG

    2008-01-01

    In this work,the effect of the textural property of activated carbons on desorption activation energy and adsorption capacity for benzothiophene (BT) was investi-gated.BET surface areas and the textural parameters of three kinds of the activated carbons,namely SY-6,SY-13 and SY-19,were measured with an ASAP 2010 instru-ment.The desorption activation energies of BT on the activated carbons were determined by temperature-pro-grammed desorption (TPD).Static adsorption experi-ments were carried out to determine the isotherms of BT on the activated carbons.The influence of the textural property of the activated carbons on desorption activa-tion energy and the adsorption capacity for BT was dis-cussed.Results showed that the BET surface areas of the activated carbons,SY-6,SY-13 and SY-19 were 1106,diameters were 1.96,2.58 and 2.16 nm,respectively.The TPD results indicated that the desorption activation energy of BT on the activated carbons,SY-6,SY-19 and SY-13 were 58.84,53.02 and 42.57 KJ/mol,respectively.The isotherms showed that the amount of BT adsorbed on the activated carbons followed the order of SY-6 > SY-19 > SY-13.The smaller the average pore diameter of the activated carbon,the stronger its adsorption for BT and the higher the activation energy required for BT desorp-tion on its surface.The Freundlich adsorption isotherm model can be properly used to formulate the adsorption behavior of BT on the activated carbons.

  14. Hopping and band mobilities of pentacene, rubrene, and 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) from first principle calculations

    Science.gov (United States)

    Kobayashi, Hajime; Kobayashi, Norihito; Hosoi, Shizuka; Koshitani, Naoki; Murakami, Daisuke; Shirasawa, Raku; Kudo, Yoshihiro; Hobara, Daisuke; Tokita, Yuichi; Itabashi, Masao

    2013-07-01

    Hopping and band mobilities of holes in organic semiconductors at room temperature were estimated from first principle calculations. Relaxation times of charge carriers were evaluated using the acoustic deformation potential model. It is found that van der Waals interactions play an important role in determining accurate relaxation times. The hopping mobilities of pentacene, rubrene, and 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) in bulk single crystalline structures were found to be smaller than 4 cm2/Vs, whereas the band mobilities were estimated between 36 and 58 cm2/Vs, which are close to the maximum reported experimental values. This strongly suggests that band conductivity is dominant in these materials even at room temperature.

  15. Orientation-dependent energy level alignment and film growth of 2,7-diocty[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) on HOPG

    International Nuclear Information System (INIS)

    Combining ultraviolet photoemission spectroscopy, X-ray photoemission spectroscopy, atomic force microscopy, and X-ray diffraction measurements, we performed a systematic investigation on the correlation of energy level alignment, film growth, and molecular orientation of 2,7-diocty[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) on highly oriented pyrolytic graphite. The molecules lie down in the first layer and then stand up from the second layer. The ionization potential shows a sharp decrease from the lying down region to the standing up region. When C8-BTBT molecules start standing up, unconventional energy level band-bending-like shifts are observed as the film thickness increases. These shifts are ascribed to gradual decreasing of the molecular tilt angle about the substrate normal with the increasing film thickness

  16. Orientation-dependent energy level alignment and film growth of 2,7-diocty[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) on HOPG

    Energy Technology Data Exchange (ETDEWEB)

    Lyu, Lu; Niu, Dongmei, E-mail: mayee@csu.edu.cnmailto; Xie, Haipeng; Cao, Ningtong; Zhang, Hong; Zhang, Yuhe; Liu, Peng [Institute of Super-Microstructure and Ultrafast Process in Advanced Materials, School of Physics and Electronics, Central South University, No. 605 Lushan South Road, Changsha, Hunan 410012 (China); Hunan Key Laboratory for Super-Microstructure and Ultrafast Process, School of Physics and Electronics, Central South University, Changsha, Hunan 410012 (China); Gao, Yongli [Institute of Super-Microstructure and Ultrafast Process in Advanced Materials, School of Physics and Electronics, Central South University, No. 605 Lushan South Road, Changsha, Hunan 410012 (China); Hunan Key Laboratory for Super-Microstructure and Ultrafast Process, School of Physics and Electronics, Central South University, Changsha, Hunan 410012 (China); Department of Physics and Astronomy, University of Rochester, Rochester, New York 14627 (United States)

    2016-01-21

    Combining ultraviolet photoemission spectroscopy, X-ray photoemission spectroscopy, atomic force microscopy, and X-ray diffraction measurements, we performed a systematic investigation on the correlation of energy level alignment, film growth, and molecular orientation of 2,7-diocty[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) on highly oriented pyrolytic graphite. The molecules lie down in the first layer and then stand up from the second layer. The ionization potential shows a sharp decrease from the lying down region to the standing up region. When C8-BTBT molecules start standing up, unconventional energy level band-bending-like shifts are observed as the film thickness increases. These shifts are ascribed to gradual decreasing of the molecular tilt angle about the substrate normal with the increasing film thickness.

  17. Effect of central metal ions of analogous metal-organic frameworks on the adsorptive removal of benzothiophene from a model fuel.

    Science.gov (United States)

    Khan, Nazmul Abedin; Jhung, Sung Hwa

    2013-09-15

    Liquid phase adsorption of benzothiophene (BT) has been studied over CuCl₂-loaded analogous metal-organic frameworks (MOFs), metal-benzenedicarboxylates (Me-BDCs, Me: Al, Cr and V), to understand the effect of central metal ions on the adsorptive removal of BT from a model fuel. Among the central metal ions (Al(3+), Cr(3+) and V(3+)) of the Me-BDCs only V(3+) was oxidized by the loaded CuCl₂ (or Cu(2+)) at ambient condition resulting in V(4+) and Cu(+) species. Different from the CuCl₂-loaded Al- and Cr-BDCs, the CuCl₂/V-BDC adsorbed BT remarkably well compared to the virgin V-BDCs which suggests a specific favorable interaction (π-complexation) between the obtained Cu(+) in the CuCl₂/V-BDC and BT.

  18. Oxidative desulfurization of benzothiophene and thiophene with WO{sub x}/ZrO{sub 2} catalysts: Effect of calcination temperature of catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Hasan, Zubair; Jeon, Jaewoo [Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Jhung, Sung Hwa, E-mail: sung@knu.ac.kr [Department of Chemistry and Green-Nano Materials Research Center, Kyungpook National University, Daegu 702-701 (Korea, Republic of)

    2012-02-29

    Highlights: Black-Right-Pointing-Pointer Oxidative desulfurization was studied with WO{sub x}/ZrO{sub 2} calcined at different temp. Black-Right-Pointing-Pointer The importance of the phases of zirconia and tungsten oxide was suggested. Black-Right-Pointing-Pointer The catalyst was analyzed thoroughly with Raman and XRD techniques. Black-Right-Pointing-Pointer The importance of electron density on S was confirmed with the kinetics of oxidation. - Abstract: Oxidative desulfurization (ODS) of model fuel containing benzothiophene (BT) or thiophene (Th) has been carried out with WO{sub x}/ZrO{sub 2} catalyst, which was calcined at various temperatures. Based on the conversion of BT in the model fuel, it can be shown that the optimum calcination temperature of WO{sub x}/ZrO{sub 2} catalyst is around 700 Degree-Sign C. The most active catalyst is composed of tetragonal zirconia (ZrO{sub 2}) with well dispersed polyoxotungstate species and it is necessary to minimize the contents of the crystalline WO{sub 3} and monoclinic ZrO{sub 2} for a high BT conversion. The oxidation rate was interpreted with the first-order kinetics, and it demonstrated the importance of electron density since the kinetic constant for BT was higher than that for Th even though the BT is larger than Th in size. A WO{sub x}/ZrO{sub 2} catalyst, treated suitably, can be used as a reusable active catalyst in the ODS.

  19. A theoretical study of the electronic structure and charge transport properties of thieno[2,3-b]benzothiophene based derivatives.

    Science.gov (United States)

    Wang, Lijuan; Li, Tao; Shen, Yuxin; Song, Yan

    2016-03-28

    The electronic structure and charge transport properties of thieno[2,3-b]benzothiophene (TBT) and its eight derivatives are investigated via density functional theory (DFT). The impact of different π-bridge spacers (1, the dimer of TBT; 2, vinyl; 3, phenyl; and 4, tetrafluorophenyl) and substituents (5, phenyl; 6, biphenyl; 7, naphthalenyl; and 8, benzothiophenyl) on the geometric structures, reorganization energy, absorption spectra, frontier orbitals, ionization potentials (IPs) and electron affinities (EAs) of all the compounds is explored to establish the relationship between the structure and properties. All the compounds show wide band gaps and low-lying HOMOs, and the IPs of all the TBT derivatives are higher than that of pentacene. The crystal packing interactions, transfer integrals and charge carrier mobilities of compounds 1, 2, 4 and 6 are also calculated. The calculated results demonstrated that these kinds of materials may exhibit good environmental stability and high charge mobility due to their large conjugated planar structure, close π-stacking arrangement, and multiple intermolecular interactions. For compounds 1 and 4, the predicted hole mobility is as high as 0.28 and 0.17 cm(2) V(-1) s(-1), respectively, indicating that both of them benefit hole transport, while compounds 2 and 6 exhibit balanced charge transport properties with the hole and electron mobilities of 0.012 and 0.013 cm(2) V(-1) s(-1), respectively, for compound 2. Compound 6 shows a relatively lower charge mobilities of 10(-3) order of magnitude for both holes and electrons due to the larger reorganization energy and lower transfer integrals. PMID:26931147

  20. Transition Metal Complexes of Cr, Mo, W and Mn Containing {eta}{sup 1}(S)-2,5-Dimethylthiophene, Benzothiophene and Dibenzothiophene Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Reynolds, M.

    2000-09-21

    The UV photolysis of hexanes solutions containing the complexes M(CO){sub 6} (M=Cr, Mo, W) or CpMn(CO){sub 3} (Cp={eta}{sup 5}-C{sub 5}H{sub 5}) and excess thiophene (T{sup *}) (T{sup *}=2,5-dimethylthiophene (2,5-Me{sub 2}T), benzothiophene (BT), and dibenzothiophene (DBT)) produces the {eta}{sup 1}(S)-T{sup *} complexes (CO){sub 5}M({eta}{sup 1}(S)-T{sup *}) 1-8 or Cp(CO){sub 2}Mn({eta}{sup 1}(S)-T{sup *})9-11, respectively. However, when T{sup *}=DBT, and M=Mo, a mixture of two products result which includes the {eta}{sup 1}(S)-DBT complex (CO){sub 5}Mo({eta}{sup 1}(S)-DBT) 4a and the unexpected {pi}-complex (CO){sub 3}Mo({eta}{sup 6}-DBT) 4b as detected by {sup 1}H NMR. The liability of the {eta}{sup 1}(S)-T{sup *} ligands is illustrated by the rapid displacement of DBT in the complex (CO){sub 5}W({eta}{sup 1}(S)-DBT) (1) by THF, and also in the complexes (CO){sub 5}Cr({eta}{sup 1}(S)-DBT) (5) and CpMn(CO){sub 2}({eta}{sup 1}(S)-DBT) (9) by CO (1 atm) at room temperature. Complexes 1-11 have been characterized spectroscopically ({sup 1}H NMR, IR) and when possible isolated as analytically pure solids (elemental analysis, EIMS). Single crystal, X-ray structural determinations are reported for (CO){sub 5}W({eta}{sup 1}(S)-DBT) and Cp(CO){sub 2}Mn({eta}{sup 1}(S)-DBT).

  1. Crystal structure of ethyl (2S,2'R)-1'-benzyl-3-oxo-3H-di-spiro-[1-benzo-thio-phene-2,3'-pyrrolidine-2',11''-indeno[1,2-b]quinoxaline]-4'-carboxyl-ate.

    Science.gov (United States)

    Govindaraj, J; Raja, R; Suresh, M; Raghunathan, R; SubbiahPandi, A

    2015-03-01

    In the title compound, C35H27N3O3S, the spiro-linked five-membered rings both adopt twisted conformations. The pyrrolidine ring makes dihedral angles of 80.5 (1) and 77.4 (9)° with the benzo-thio-phene ring system and the quinoxaline ring system, respectively. The S atom and C=O unit of the benzo-thio-phene ring system are disordered over two opposite orientations in a 0.768 (4):0.232 (4) ratio. The atoms of the ethyl side chain are disordered over two sets of sites in a 0.680 (16):0.320 (16) ratio. In the crystal, mol-ecules are linked by C-H⋯O, C-H⋯N and π-π inter-actions [shortest centroid-centroid distance = 3.4145 (19) Å], resulting in a three-dimensional network.

  2. Crystal structure of ethyl (2S,2′R-1′-benzyl-3-oxo-3H-dispiro[1-benzothiophene-2,3′-pyrrolidine-2′,11′′-indeno[1,2-b]quinoxaline]-4′-carboxylate

    Directory of Open Access Journals (Sweden)

    J. Govindaraj

    2015-03-01

    Full Text Available In the title compound, C35H27N3O3S, the spiro-linked five-membered rings both adopt twisted conformations. The pyrrolidine ring makes dihedral angles of 80.5 (1 and 77.4 (9° with the benzothiophene ring system and the quinoxaline ring system, respectively. The S atom and C=O unit of the benzothiophene ring system are disordered over two opposite orientations in a 0.768 (4:0.232 (4 ratio. The atoms of the ethyl side chain are disordered over two sets of sites in a 0.680 (16:0.320 (16 ratio. In the crystal, molecules are linked by C—H...O, C—H...N and π–π interactions [shortest centroid–centroid distance = 3.4145 (19 Å], resulting in a three-dimensional network.

  3. Preparation and Characterization of SiO2-WO3 Mixed Oxides and Its Catalytic Performance in Oxidative Desulfurization of Benzothiophene%复合SiO2-WO3催化剂的制备、表征及氧化脱除苯并噻吩性能

    Institute of Scientific and Technical Information of China (English)

    宋华; 穆金城; 王登; 蒋博龙

    2012-01-01

    采用溶胶凝胶法制备了SiO2-WO3催化剂,并采用XRD、FT-IR、BET、TG-DTA等方法对催化剂进行表征.以苯并噻吩(BT)为模型化合物,H2O2为氧化剂,考察了催化剂的活性元素、制备方法、n(W)/n(Si)和焙烧温度对其催化氧化脱硫活性的影响.结果表明,W的引入降低了SiO2的比表面积,SiO2-WO3催化剂中W的主物相为WO3.在以W为活性组元,且n(W)/n(Si)为0.1时,500℃焙烧得到的SiO2-0.1WO3催化剂具有最好的催化脱硫活性.在模拟油20 mL、催化剂SiO2-0.1WO3用量0.04 g、n(H2O2)/n(S)为15.9、乙腈/模拟油体积比0.3、65℃反应60 min的条件下,苯并噻吩模拟油脱硫率可达99.3%.%The SiO2 WO3 catalysts were prepared by the sol-gel method and characterized by XRD, FT-IR, BET and TG-DTA. The effects of active element, preparation method, w(W)/w(Si) and calcination temperature on the desulfurization performance of SiO2-WO3 were investigated by using H2O2 as oxidant and the benzothiophene (BT) as model compound. The results showed that the introduction of W into SiO2 sample led to the decrease of its surface area. The predominant phase of W in catalyst was WO3. The Si()2-WO3 catalyst prepared with W as active element, calcination temperature of 500°C and n CW)/n (Si) of 0.1 was found to have optimal desulfurization performance. With SiO2-0. 1WO3 as catalyst and under the conditions of model oil 20 mL, catalyst 0. 04 g, n(H2O2)/n(S) 15. 9, acetonitrile/simulant oil volume ratio 0. 3, reaction temperature 65°C and reaction time 60 min, the desulfurization ratio of BT model oil reached 99. 3%.

  4. Benzothiophen-pyrazine scaffold as a potential membrane targeting drug carrier

    Energy Technology Data Exchange (ETDEWEB)

    Mazuryk, Olga [Department of Inorganic Chemistry, Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland); Niemiec, Elżbieta [Department of Inorganic Chemistry, Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland); Institute of Organic and Analytical Chemistry, University of Orléans, UMR-CNRS 7311, rue de Chartres, 45067 Orléans Cedex 2 (France); Stochel, Grażyna [Department of Inorganic Chemistry, Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland); Gillaizeau, Isabelle, E-mail: isabelle.gillaizeau@univ-orleans.fr [Institute of Organic and Analytical Chemistry, University of Orléans, UMR-CNRS 7311, rue de Chartres, 45067 Orléans Cedex 2 (France); Brindell, Małgorzata, E-mail: brindell@chemia.uj.edu.pl [Department of Inorganic Chemistry, Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow (Poland)

    2013-08-15

    The fluorescent properties of 2,5-di(benzo[b]thiophen-2-yl)pyrazine as a potential membrane targeting drug carrier were characterized and it was shown that its fluorescence intensity was much higher in organic solvent than in water. The embedding of studied compound by liposomes leads to ca. 2 orders of magnitude increase in its fluorescence intensity, suggesting its preferential accumulation in membranes. Preliminary biological studies showed its ability to accumulate in cells, and the concentration of 10 μM was sufficient for homogeneous staining of cells. The treatment of mouse carcinoma CT26 cells with studied compound up to 200 μM resulted in decreasing of viable cells by ca. 30%. Its reactivity towards albumin was found to be moderate with an association constant of 6×10{sup 4} M{sup −1}, while no interaction with DNA was observed. Our findings encourage for further studies on functionalization of this molecule to obtain a new class of anticancer drugs targeting membrane. Highlights: ► The fluorescence of 2,5-di(benzo[b]thiophen-2-yl)pyrazine is solvent dependent. ► Weak fluorescence is found in water while high in organic solvents (DMSO, chloroform). ► Embedding of compound in liposomes remarkably increased its fluorescence. ► No interaction with DNA is observed but moderate reactivity towards albumin is found. ► Homogeneous staining of cells is feasible using nontoxic dose of compound.

  5. 2-[(2-Chlorobenzylideneamino]-4,5,6,7-tetrahydro-1-benzothiophene-3-carbonitrile

    Directory of Open Access Journals (Sweden)

    Abdullah M. Asiri

    2011-09-01

    Full Text Available In the title compound, C16H13ClN2S, the mean planes fitted through all non-H atoms of the heterocyclic five-membered and the benzene rings are oriented at a dihedral angle of 5.19 (7°. In the crystal, a weak C—H...π interaction occurs, along with weak π–π interactions [cenroid–centroid distance = 3.7698 (11 Å].

  6. Crystal structure of N-(3-benzoyl-4,5,6,7-tetrahydro-1-benzothiophen-2-ylbenzamide

    Directory of Open Access Journals (Sweden)

    Manpreet Kaur

    2014-09-01

    Full Text Available In the title compound, C22H19NO2S, the cyclohexene ring adopts a half-chair conformation. The dihedral angles between the plane of the thiophene ring and those of its amide- and carbonyl-bonded benzene rings are 7.1 (1 and 59.0 (2°, respectively. An intramolecular N—H...O hydrogen bond generates an S(6 ring. In the crystal, very weak aromatic π–π stacking interactions [centroid–centroid separation = 3.9009 (10 Å] are observed.

  7. Identification of homologous series of alkylated thiophenes, thiolanes, thianes and benzothiophenes present in pyrolysates of sulphur-rich kerogens

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Kock-van Dalen, A.C.; Leeuw, J.W. de; Schenck, P.A.

    1988-01-01

    The ability of flash pyrolysis-gas chromatography with dual flame ionization and flame photometric detection, and flash pyrolysis-gas chromatography-mass spectrometry, to afford detailed information about the organic sulphur pyrolysis products of kerogens is exemplified through analysis of five diff

  8. Novel substituted benzothiophene and thienothiophene carboxanilides and quinolones: synthesis, photochemical synthesis, DNA-binding properties, antitumor evaluation and 3D-derived QSAR analysis.

    Science.gov (United States)

    Aleksić, Maja; Bertoša, Branimir; Nhili, Raja; Uzelac, Lidija; Jarak, Ivana; Depauw, Sabine; David-Cordonnier, Marie-Hélène; Kralj, Marijeta; Tomić, Sanja; Karminski-Zamola, Grace

    2012-06-14

    A series of new N,N-dimethylaminopropyl- and 2-imidazolinyl-substituted derivatives of benzo[b]thienyl- and thieno[2,3-b]thienylcarboxanilides and benzo[b]thieno[2,3-c]- and thieno[3',2':4,5]thieno[2,3-c]quinolones were prepared. Quinolones were prepared by the reaction of photochemical dehydrohalogenation of corresponding anilides. Carboxanilides and quinolones were tested for the antiproliferative activity. 2-Imidazolinyl-substituted derivatives showed very prominent activity. By use of the experimentally obtained antitumor measurements, 3D-derived QSAR analysis was performed for the set of compounds. Highly predictive 3D-derived QSAR models were obtained, and molecular properties that have the highest impact on antitumor activity were identified. Carboxanilides 6a-c and quinolones 9a-c and 11a were evaluated for DNA binding propensities and topoisomerases I and II inhibition as part of their mechanism of action assessment. The evaluated differences in the mode of action nicely correlate with the results of the 3D-QSAR analysis. Taken together, the results indicate which modifications of the compounds from the series should further improve their anticancer properties.

  9. Crystal structure of 1,3-bis(4-hexyl-5-iodothiophen-2-yl-4,5,6,7-tetrahydro-2-benzothiophene

    Directory of Open Access Journals (Sweden)

    Julian Linshoeft

    2014-10-01

    Full Text Available In the crystal structure of the title compound, C28H36I2S3, a terthiophene monomer, the central thiophene unit is arranged anti-coplanar to the two outer thiophene rings. There are two crystallographically independent molecules in the asymmetric unit, which show different conformations. In one molecule, the dihedral angles between the inner and the two outer thiophene rings are 15.7 (3 and 3.47 (3°, whereas these values are 4.2 (3 and 11.3 (3° for the second molecule. Differences are also found in the arrangement of the hexyl chains: in one of the two molecules, both chains are nearly in plane to the central moiety, whereas in the second molecule, only one chain is in plane and the other one is nearly perpendicular to the central moiety. Some of the C atoms are disordered and were refined using a split model with occupancy ratios of 0.65:0.35 and 0.70:0.30 in the two molecules.

  10. 3′,6′-Bis(diethylamino-3H-spiro[2-benzothiophene-1,9′-xanthene]-3-thione

    Directory of Open Access Journals (Sweden)

    Bing-Yuan Su

    2008-11-01

    Full Text Available The title compound, C28H30N2OS2, was obtained by thionation of 3′,6′-bis(diethylamino-3H-spiro[isobenzofuran-1,9′-xanthene]-3-one with 2,4-bis(p-methoxyphenyl-1,3-dithiadiphosphetane disulfide (Lawesson's reagent. The planes of the two benzene rings of the xanthene system are inclined at a dihedral angle of 17.4 (1°, and the plane of the dithiophthalide group and the planes through the two benzene rings of the xanthene system make dihedral angles of 80.2 (1 and 82.8 (1°, respectively.

  11. Enantiomerically pure (1S,5R) and racemic 3-(1-benzothiophen-2-yl)-8-azoniabicyclo 3.2.1 oct-2-ene acetate

    DEFF Research Database (Denmark)

    Frostrup, B.; Peters, D.; Bond, A. D.

    2012-01-01

    The title compound, C15H16NS+center dot C2H3O2-, has been crystallized as both a pure enantiomer (1S,5R) and a racemate. The racemate crystallizes in the space group Cc, with molecules of opposite handedness related to each other by the action of the c-glide. The enantiomer is essentially isostru...

  12. Catalytic Oxidation of Benzothiophene and Dibenzothiophene in Model Light Oil Over Ti-MWW%Ti-MWW催化氧化脱除轻油中苯并噻吩和二苯并噻吩

    Institute of Scientific and Technical Information of China (English)

    程时富; 刘月明; 高金宝; 汪玲玲; 刘秀丽; 高国华; 吴鹏; 何鸣元

    2006-01-01

    以Ti-MWW为催化剂,研究了轻油中的有机硫模型化合物苯并噻吩和二苯并噻吩的氧化脱除.结果表明,在343 K和乙腈为溶剂的条件下,苯并噻吩的转化率可达100%, 二苯并噻吩的转化率可达95%以上.溶剂对苯并噻吩的氧化有很大影响,在相同的反应条件下,三种溶剂中苯并噻吩的转化率为乙腈>甲醇>水.讨论了Ti-MWW催化氧化苯并噻吩的反应历程和溶剂效应.

  13. Anilides and quinolones with nitrogen-bearing substituents from benzothiophene and thienothiophene series: synthesis, photochemical synthesis, cytostatic evaluation, 3D-derived QSAR analysis and DNA-binding properties.

    Science.gov (United States)

    Aleksić, Maja; Bertoša, Branimir; Nhili, Raja; Depauw, Sabine; Martin-Kleiner, Irena; David-Cordonnier, Marie-Hélène; Tomić, Sanja; Kralj, Marijeta; Karminski-Zamola, Grace

    2014-01-01

    A series of new anilides (2a-c, 4-7, 17a-c, 18) and quinolones (3a-b, 8a-b, 9a-b, 10-15, 19) with nitrogen-bearing substituents from benzo[b]thiophene and thieno[2,3-c]thiophene series are prepared. Benzo[b]thieno[2,3-c]- and thieno[3',2':4,5]thieno[2,3-c]quinolones (3a-b, 8a-b) are synthesized by the reaction of photochemical dehydrohalogenation from corresponding anilides. Anilides and quinolones were tested for the antiproliferative activity. Fused quinolones bearing protonated aminium group, quaternary ammonium group, N-methylated and protonated aminium group, amino and protonated amino group (8a, 9b, 10-12) showed very prominent anticancer activity, whereby the hydrochloride salt of N',N'-dimethylaminopropyl-substituted quinolone (14) was the most active one, having the IC50 concentration at submicromolar range in accordance with previous QSAR predictions. On the other hand, flexible anilides were among the less active. Chemometric analysis of investigated compounds was performed. 3D-derived QSAR analysis identified solubility, metabolitic stability and the possibility of the compound to be ionized at pH 4-8 as molecular properties that are positively correlated with anticancer activity of investigated compounds, while molecular flexibility, polarizability and sum of hydrophobic surface areas were found to be negatively correlated. Anilides 2a-b, 4-7 and quinolones 3a-b, 8a-b, 9b and 10-14 were evaluated for DNA binding propensities and topoisomerases I/II inhibition as part of their mechanism of action. Among the anilides, only compound 7 presented some DNA binding propensity whereas the quinolones 8b, 9b and 10-14 intercalate in the DNA base pairs, compounds 8b, 9b and 14 being the most efficient ones. The strongest DNA intercalators, compounds 8b, 9b and 14, were clearly distinguished from the other compounds according to their molecular descriptors by the PCA and PLS analysis.

  14. A mass-spectroscopic analysis of the sulfurous compounds in average fractions of Romashkin oils

    Energy Technology Data Exchange (ETDEWEB)

    Kubas, M.; Kubelka, V.; Mostecky, J.; Vodicka, L.

    1982-01-01

    Results are presented of an analysis of sulfurous compounds in an average fraction of Romashkin (USSR) oils, produced by the method of mass-spectrometry. Some individual properties of the benzothiophene type were determined. It is shown, that in the average distillate of Romashkin petroleum, benzothiophenes are dominant.

  15. Biodegradation of Various Aromatic Compounds by Enriched Bacterial Cultures: Part B--Nitrogen-, Sulfur-, and Oxygen-Containing Heterocyclic Aromatic Compounds.

    Science.gov (United States)

    Oberoi, Akashdeep Singh; Philip, Ligy; Bhallamudi, S Murty

    2015-07-01

    Present study focused on the biodegradation of various heterocyclic nitrogen, sulfur, and oxygen (NSO) compounds using naphthalene-enriched culture. Target compounds in the study were pyridine, quinoline, benzothiophene, and benzofuran. Screening studies were carried out using different microbial consortia enriched with specific polycyclic aromatic hydrocarbon (PAH) and NSO compounds. Among different microbial consortia, naphthalene-enriched culture was the most efficient consortium based on high substrate degradation rate. Substrate degradation rate with naphthalene-enriched culture followed the order pyridine > quinoline > benzofuran > benzothiophene. Benzothiophene and benzofuran were found to be highly recalcitrant pollutants. Benzothiophene could not be biodegraded when concentration was above 50 mg/l. It was observed that 2-(1H)-quinolinone, benzothiophene-2-one, and benzofuran-2,3-dione were formed as metabolic intermediates during biodegradation of quinoline, benzothiophene, and benzofuran, respectively. Quinoline-N and pyridine-N were transformed into free ammonium ions during the biodegradation process. Biodegradation pathways for various NSO compounds are proposed. Monod inhibition model was able to simulate single substrate biodegradation kinetics satisfactorily. Benzothiophene and benzofuran biodegradation kinetics, in presence of acetone, was simulated using a generalized multi-substrate model.

  16. FXR agonist activity of conformationally constrained analogs of GW 4064

    Energy Technology Data Exchange (ETDEWEB)

    Akwabi-Ameyaw, Adwoa; Bass, Jonathan Y.; Caldwell, Richard D.; Caravella, Justin A.; Chen, Lihong; Creech, Katrina L.; Deaton, David N.; Madauss, Kevin P.; Marr, Harry B.; McFadyen, Robert B.; Miller, Aaron B.; Navas, III, Frank; Parks, Derek J.; Spearing, Paul K.; Todd, Dan; Williams, Shawn P.; Wisely, G. Bruce; (GSKNC)

    2010-09-27

    Two series of conformationally constrained analogs of the FXR agonist GW 4064 1 were prepared. Replacement of the metabolically labile stilbene with either benzothiophene or naphthalene rings led to the identification of potent full agonists 2a and 2g.

  17. Synthesis and antimicrobial activity of some novel thienopyrimidines and triazolothienopyrimidines

    Indian Academy of Sciences (India)

    Nitinkumar S Shetty; Ravi S Lamani; Imtiyaz Ahmed M Khazi

    2009-05-01

    Novel tricyclic thienopyrimidines (3, 5, 6, 9, 11, 12) and triazole fused tetracyclic thienopyrimidines (4a-c, 10a-c) were synthesized from precursors 2-amino-6-methyl-4,5,6,7-tetrahydro-1-benzothiophene-3-carbonitrile 1 and 2-amino-7-oxo-4,5,6,7-tetrahydro-1-benzothio-phene-3-carbonitrile 7 respectively. The corresponding precursors were prepared by employing the Gewald reaction. The structures of newly synthesized compounds were characterized by spectral and analytical data. All the compounds were screened for their biological activities. Some of the compounds displayed promising antibacterial and antifungal activities.

  18. Aerobic microbial metabolism of condensed thiophenes found in petroleum

    International Nuclear Information System (INIS)

    The aerobic microbial degradation of 21 condensed thiophenes found in petroleum or synthetic fuels have been studied, motivated by recent research which showed that resistance to biodegradation increases with increasing methyl-substitution. The specific objective was to identify metabolites in pure cultures of aromatic hydrocarbon-degrading Pseudomonas spp. incubated in mineral medium in the presence of an aromatic growth substrate and a condensed thiophene. Over 80 metabolites of the condensed thiophenes were identified using gas chromatography analysis with an atomic emission detector. Among the metabolites identified were sulfoxides, sulfones, hydroxy- and carboxyl-substituted benzothiophenes, hydroxy-substituted dibenzothiophenes, substituted benzothiophene-2,3-diones, and 3-hydroxy-2-formylbenzothiophenes

  19. N1-(Benzo[b]thiophen-3-ylmethylidene-N2-(2-((2-((2-(benzo[b]thiophen-3-ylmethylideneaminoethylaminoethylaminoethylethane-1,2-diamine

    Directory of Open Access Journals (Sweden)

    Carlos Lodeiro

    2012-08-01

    Full Text Available A novel probe L has been synthesized by classical Schiff-base reaction between 1-benzothiophene-3-carbaldehyde and tetraethylenepentamine as diamine. The structure of compound L was confirmed by melting point, elemental analysis, ESI-MS spectrometry, IR and 13C-NMR and 1H-NMR spectroscopy.

  20. Biodegradation of creosote compounds: Comparison of experiments at different scales

    DEFF Research Database (Denmark)

    Broholm, K.; Arvin, Erik

    2001-01-01

    This paper compares the results of biodegradation experiments with creosote compounds performed at different scales. The experiments include field observations, field experiments, large-scale intact laboratory column experiments, model fracture experiments, and batch experiments. Most of the expe...... of the pyrroles on the biodegradation of benzene, and the biodegradation of benzothiophene occurs only in the presence of a primary substrate. The experiments show that some biodegradation processes of organic compounds may be common to different microorganisms....

  1. Effect of aromatics on the adsorption of thiophenic sulfur compounds from model diesel fuel by activated carbon cloth

    OpenAIRE

    NAVIRI FALLAH, Rahimeh; Azizian, Saeid; REGGERS, Guy; Carleer, Robert; SCHREURS, Sonja; Ahenach, Janat; Meynen, Vera; Yperman, Jan

    2014-01-01

    The effects of aromatic compound presence in real diesel fuel on the adsorption of sulfur species onto activated carbon cloth (ACC) were investigated. Equilibrium and kinetics adsorption of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (DMDBT) in the presence of naphthalene (NP) and 1-methylnaphthalene (1-MNP) from prepared model diesel fuels onto ACC and its oxidized forms were studied. The total sulfur concentration inmodel diesel fuelwas 300 ppmw. The initial...

  2. Indole/triazole conjugates are selective inhibitors and inducers of bacterial biofilms †

    OpenAIRE

    Minvielle, Marine J.; Bunders, Cynthia A.; Melander, Christian

    2013-01-01

    Herein is described a method of accessing indole/triazole and benzothiophene/triazole analogues that selectively promote or inhibit biofilm formation by Gram-positive and Gram-negative bacteria. Structure/function studies revealed that the addition of a bromine atom at the 2-position of the indole/triazole scaffold altered activity against both Gram-negative and Gram-positive bacteria and could transform a biofilm inhibitor into a biofilm inducer. Isosteric replacement of the indole core by a...

  3. Synthesis and Antimicrobial Activity of New Schiff Base Compounds Containing 2-Hydroxy-4-pentadecylbenzaldehyde Moiety

    Directory of Open Access Journals (Sweden)

    Gadada Naganagowda

    2014-01-01

    Full Text Available Various novel Schiff base compounds have been synthesized by reaction of 2-hydroxy-4-pentadecylbenzaldehyde with substituted benzothiophene-2-carboxylic acid hydrazide and different substituted aromatic or heterocyclic amines in the presence of acetic acid in ethanol. The structures of all these compounds were confirmed by elemental analysis, IR, 1H-NMR, 13C-NMR, and mass spectral data and have been screened for antibacterial and antifungal activity.

  4. Oxidation Reactivities of Organic Sulfur Compounds in Fuel Oil Using Immobilized Heteropoly Acid as Crystal

    Institute of Scientific and Technical Information of China (English)

    YAN Xuemin; LEI Jiaheng; LIU Dan; GUO Liping; WU Yangchun

    2007-01-01

    Heteropoly acid of Keggin structure phosphotungstic(HPW) and phosphomolybdic(HPMo) were chemically anchored to the modified SBA-15 channel. The materials were used as catalyst for oxidative desulfurization of organic sulfur compounds including benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethydibenzothiophene (4,6-DMDBT). The experimental results show that the catalysts are efficient and reusable, the catalytic activity is hardly reduced even in the 5th cycle of use.

  5. Determination of aromatic sulphur compounds in heavy gas oil by using (low-)flow modulated comprehensive two-dimensional gas chromatography-triple quadrupole mass spectrometry.

    Science.gov (United States)

    Franchina, Flavio Antonio; Machado, Maria Elisabete; Tranchida, Peter Quinto; Zini, Cláudia Alcaraz; Caramão, Elina Bastos; Mondello, Luigi

    2015-03-27

    The present research is focused on the development of a flow-modulated comprehensive two-dimensional gas chromatography-triple quadrupole mass spectrometry (FM GC × GC-MS/MS) method for the determination of classes of aromatic organic sulphur compounds (benzothiophenes, dibenzothiophenes, and benzonaphthothiophene) in heavy gas oil (HGO). The MS/MS instrument was used to provide both full-scan and multiple-reaction-monitoring (MRM) data. Linear retention index (LRI) ranges were used to define the MRM windows for each chemical class. Calibration solutions (internal standard: 1-fluoronaphthalene) were prepared by using an HGO sample, depleted of S compounds. Calibration information was also derived for the thiophene class (along with MRM and LRI data), even though such constituents were not present in the HGO. Linearity was satisfactory over the analyzed concentration range (1-100 mg/L); intra-day precision for the lowest calibration point was always below 17%. Accuracy was also satisfactory, with a maximum percentage error of 3.5% (absolute value) found among the S classes subjected to (semi-)quantification. The highest limit of quantification was calculated to be 299 μg/L (for the C1-benzothiophene class), while the lowest was 21 μg/L (for the C4-benzothiophene class).

  6. Crystal structures of (Z-5-[2-(benzo[b]thiophen-2-yl-1-(3,5-dimethoxyphenylethenyl]-1H-tetrazole and (Z-5-[2-(benzo[b]thiophen-3-yl-1-(3,4,5-trimethoxyphenylethenyl]-1H-tetrazole

    Directory of Open Access Journals (Sweden)

    Narsimha Reddy Penthala

    2016-05-01

    Full Text Available (Z-5-[2-(Benzo[b]thiophen-2-yl-1-(3,5-dimethoxyphenylethenyl]-1H-tetrazole methanol monosolvate, C19H16N4O2S·CH3OH, (I, was prepared by the reaction of (Z-3-(benzo[b]thiophen-2-yl-2-(3,5-dimethoxyphenylacrylonitrile with tributyltin azide via a [3 + 2]cycloaddition azide condensation reaction. The structurally related compound (Z-5-[2-(benzo[b]thiophen-3-yl-1-(3,4,5-trimethoxyphenylethenyl]-1H-tetrazole, C20H18N4O3S, (II, was prepared by the reaction of (Z-3-(benzo[b]thiophen-3-yl-2-(3,4,5-trimethoxyphenylacrylonitrile with tributyltin azide. Crystals of (I have two molecules in the asymmetric unit (Z′ = 2, whereas crystals of (II have Z′ = 1. The benzothiophene rings in (I and (II are almost planar, with r.m.s deviations from the mean plane of 0.0084 and 0.0037 Å in (I and 0.0084 Å in (II. The tetrazole rings of (I and (II make dihedral angles with the mean planes of the benzothiophene rings of 88.81 (13 and 88.92 (13° in (I, and 60.94 (6° in (II. The dimethoxyphenyl and trimethoxyphenyl rings make dihedral angles with the benzothiophene rings of 23.91 (8 and 24.99 (8° in (I and 84.47 (3° in (II. In both structures, molecules are linked into hydrogen-bonded chains. In (I, these chains involve both tetrazole and methanol, and are parallel to the b axis. In (II, molecules are linked into chains parallel to the a axis by N—H...N hydrogen bonds between adjacent tetrazole rings.

  7. Selective estrogen receptor modulator BC-1 activates antioxidant signaling pathway in vitro via formation of reactive metabolites

    Institute of Scientific and Technical Information of China (English)

    Bo-lan YU; Zi-xin MAI; Xu-xiang LIU; Zhao-feng HUANG

    2013-01-01

    Aim:Benzothiophene compounds are selective estrogen receptor modulators (SERMs),which are recently found to activate antioxidant signaling.In this study the molecular mechanisms of antioxidant signaling activation by benzothiophene compound BC-1 were investigated.Methods:HepG2 cells were stably transfected with antioxidant response element (ARE)-Iuciferase reporter (HepG2-ARE cells).The expression of nuclear factor erythroid 2-related factor 2 (Nrf2) in HepG2-ARE cells was suppressed using siRNA.The metabolites of BC-1 in rat liver microsome incubation were analyzed using LC-UV and LC-MS.Results:Addition of BC-1 (5 μmol/L) in HepG2-ARE cells resulted in a 17-fold increase of ARE-luciferase activity.Pretreatment with the estrogen receptor agonist E2 (5 μmol/L) or antagonist ICl 182,780 (5 μmol/L) did not affect BC-1-induced ARE-luciferase activity.However,transfection of the cells with anti-Nrf2 siRNA suppressed this effect by 79%.Addition of BC-1 in rat microsome incubation resulted in formation of di-quinone methides and o-quinones,followed by formation of GSH conjugates.BC-1 analogues with hydrogen (BC-2) or fluorine (BC-3) at the 4' position did not form the di-quinone methides.Both BC-2 and BC-3 showed comparable estrogenic activity with BC-1,but did not induce ARE-luciferase activity in HepG2-ARE cells.Conclusion:Benzothiophene compound BC-1 activates ARE signaling via reactive metabolite formation that is independent of estrogen receptors.

  8. Nitrosation, nitration, and autoxidation of the selective estrogen receptor modulator raloxifene by nitric oxide, peroxynitrite, and reactive nitrogen/oxygen species.

    Science.gov (United States)

    Toader, Violeta; Xu, Xudong; Nicolescu, Adrian; Yu, Linning; Bolton, Judy L; Thatcher, Gregory R J

    2003-10-01

    The regulation of estrogenic and antiestrogenic effects by selective estrogen receptor modulators (SERMs) provides the basis for use in long-term therapy in cancer chemoprevention and postmenopausal osteoporosis. However, the evidence for carcinogenic properties within this class requires study of potential pathways of toxicity. There is strong evidence for the elevation of cellular levels of NO in tissue treated with SERMs, including the benzothiophene derivative, raloxifene, in part via up-regulation of nitric oxide synthases. Therefore, the reactions of 17beta-estradiol (E(2)), raloxifene, and an isomer with NO, peroxynitrite, and reactive nitrogen/oxygen species (RNOS) generated from NO(2)(-)/H(2)O(2) systems were examined. Peroxynitrite from bolus injection or slow release from higher concentrations of 3-morpholinosydnonimine (SIN-1) reacted with the benzothiophenes and E(2) to give aromatic ring nitration, whereas peroxynitrite, produced from the slow decomposition of lower concentrations of SIN-1, was relatively unreactive toward E(2) and yielded oxidation and nitrosation products with raloxifene and its isomer. The oxidation and nitrosation products formed were characterized as a dimer and quinone oxime derivative. Interestingly, the reaction of the benzothiophenes with NO in aerobic solution efficiently generated the same oxidation products. Stable quinone oximes are not unprecedented but have not been previously reported as products of RNOS-mediated metabolism. The reaction of glutathione (GSH) with the quinone oxime gave both GSH adducts from Michael addition and reduction to the corresponding o-aminophenol. The ready autoxidation of raloxifene, observed in the presence of NO, is the first such observation on the reactivity of SERMs and is potentially a general phenomenon of significance to SERM chemical toxicology. PMID:14565768

  9. Discovery of novel (4-piperidinyl)-piperazines as potent and orally active acetyl-CoA carboxylase 1/2 non-selective inhibitors: F-Boc and triF-Boc groups are acid-stable bioisosteres for the Boc group.

    Science.gov (United States)

    Chonan, Tomomichi; Wakasugi, Daisuke; Yamamoto, Daisuke; Yashiro, Miyoko; Oi, Takahiro; Tanaka, Hiroaki; Ohoka-Sugita, Ayumi; Io, Fusayo; Koretsune, Hiroko; Hiratate, Akira

    2011-03-01

    Novel (4-piperidinyl)-piperazine derivatives were synthesized and evaluated as ACC1/2 non-selective inhibitors. Optimization of the substituents on the nitrogen of the piperidine ring led to the identification of the fluorine substituted tert-butoxycarbonyl group. Advanced analog, 1,1,1-trifluoro-2-methylpropan-2-yl 4-{4-[(2-amino-6-methyl-1-benzothiophen-3-yl)carbonyl]piperazin-1-yl}piperidine-1-carboxylate (12c) showed potent inhibitory activities in enzyme-assay and cell-based assays. Compound 12c also exhibited reduction of hepatic de novo fatty acid synthesis in rats after oral administration.

  10. Solid-phase synthesis of tetrahydro-beta-carbolines and tetrahydroisoquinolines by stereoselective intramolecular N-carbamyliminium Pictet-Spengler reactions

    DEFF Research Database (Denmark)

    Diness, Frederik; Meldal, Morten

    2006-01-01

    converts into Pictet-Spengler-type products with a variety of C-nucleophiles. Amino aldehydes masked with 3-Boc-(1,3)-oxazinane (Box) have been synthesized from amino acids, amino alcohols, or 2-nitro benzaldehydes. The amino moiety of these masked aldehydes has been converted into pentafluorophenyl...... of other aromatic C-nucleophiles, including substituted indoles, benzenes, pyrene, furan, thiophenes, and benzothiophene with comparable stereoselectivity and purity. Prolonged exposure of the benzaldehyde-derived Pictet-Spengler products to strong acid and air lead to quantitative auto-oxidation which...

  11. Oxidative desulfurization of synthetic diesel using supported catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Cedeno Caero, Luis; Jorge, F.; Navarro, A.; Gutierrez-Alejandre, Aida [UNICAT, Depto. de Ing. Quimica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Cd. Universitaria, 04510 Mexico D.F. (Mexico)

    2006-09-15

    Oxidative desulfurization (ODS) of a synthetic diesel was carried out at mild conditions (atmospheric pressure and 60{sup o}C) in presence of V{sub 2}O{sub 5}/Al{sub 2}O{sub 3} and V{sub 2}O{sub 5}/TiO{sub 2} catalysts. Two main aspects were studied: the effect of the oxidant reagent and the presence of nitrogen compounds on ODS of benzothiophenic compounds prevailing in diesel, such as benzothiophene, dibenzothiophene and alkyl substituted in positions 4 and 6. Results show that activity is improved when using hydrogen peroxide, as oxidant reagent, and V{sub 2}O{sub 5}/Al{sub 2}O{sub 3}, as catalyst. This result was attributed to the high decomposition of peroxide due to the presence of catalyst. In presence of nitrogen compounds, the ODS activity decreases in the order: quinoline>indole>carbazole. In order to explain this effect, successive chemisorption of DBT and quinoline on V{sub 2}O{sub 5}/Al{sub 2}O{sub 3} catalyst was evaluated by FT-IR, and the results show that DBT is displaced by quinoline, occupying the adsorption sites of catalyst. N-compound effect could be explained by strong adsorption of nitrogen compounds on catalytic sites. (author)

  12. Oxidative desulfurization of synthetic diesel using supported catalysts. Part 3. Support effect on vanadium-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Cedeno-Caero, Luis; Gomez-Bernal, Hilda; Fraustro-Cuevas, Adriana; Guerra-Gomez, Hector D.; Cuevas-Garcia, Rogelio [UNICAT, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Cd. Universitaria 04510, Mexico D.F. (Mexico)

    2008-04-15

    Oxidesulfurization (ODS) of benzothiophenic compounds prevailing in diesel was conducted with hydrogen peroxide in presence of various catalysts, using a model diesel and actual diesel fuel. ODS activities of dibenzothiophenes (DBTs) in hexadecane for a series of V{sub 2}O{sub 5} catalysts supported on alumina, titania, ceria, niobia and silica, were evaluated. Results show that the oxidation activity of DBTs depends on the support used. It was observed that the sulfone yield is not proportional to textural properties or V content. For all catalysts, ODS of benzothiophene (BT), dibenzothiophene (DBT), 4-methyl dibenzothiophene (4-MDBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT) decreased in the following order: DBT > 4-MDBT > 4,6-DMDBT > BT. This trend does not depend on the catalyst used or the textural properties of the catalysts and supports. In presence of indole ODS activities diminish, except with catalysts supported on alumina-titania mixed oxide, whereas with V{sub 2}O{sub 5}/TiO{sub 2} catalyst the performance is the highest. ODS of Mexican diesel fuel was carried out in presence of this catalyst and S level was diminished in about 99%. (author)

  13. A novel method for oxidative desulfurization of liquid hydrocarbon fuels based on catalytic oxidation using molecular oxygen coupled with selective adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Xiaoliang; Song, Chunshan [Clean Fuels and Catalysis Program, The Energy Institute, Department of Energy and Geo-Environmental Engineering, The Pennsylvania State University, 209 Academic Projects Building, University Park, PA 16802 (United States); Zhou, Anning [Clean Fuels and Catalysis Program, The Energy Institute, Department of Energy and Geo-Environmental Engineering, The Pennsylvania State University, 209 Academic Projects Building, University Park, PA 16802 (United States); Department of Chemistry and Chemical Engineering, Xian University of Science and Technology, Xian 710054 (China)

    2007-05-30

    The present study explored a novel oxidative desulfurization (ODS) method of liquid hydrocarbon fuels, which combines a catalytic oxidation step of the sulfur compounds directly in the presence of molecular oxygen and an adsorption step of the oxidation-treated fuel over activated carbon. The ODS of a model jet fuel and a real jet fuel (JP-8) was conducted in a batch system at ambient conditions. It was found that the oxidation in the presence of molecular oxygen with Fe(III) salts was able to convert the thiophenic compounds in the fuel to the corresponding sulfone and/or sulfoxide compounds at 25 C. The oxidation reactivity of the sulfur compounds decreases in the order of 2-methylbenzothiophene > 5-methylbenzothiophene > benzothiophene >> dibenzothiophene. The alkyl benzothiophenes with more alkyl substituents have higher oxidation reactivity. In real JP-8 fuel, 2,3-dimethylbenzothiophene was found to be the most refractory sulfur compound to be oxidized. The catalytic oxidation of the sulfur compounds to form the corresponding sulfones and/or sulfoxides improved significantly the adsorptivity of the sulfur compounds on activated carbon, because the activated carbon has higher adsorptive affinity for the sulfones and sulfoxides than thiophenic compounds due to the higher polarity of the former. The remarkable advantages of the developed ODS method are that the ODS can be run in the presence of O{sub 2} at ambient condition without using peroxides and aqueous solvent and thus without involving the biphasic oil-aqueous-solution system. (author)

  14. Synthesis and anti-tubercular activity of 3-substituted benzo[b]thiophene-1,1-dioxides

    Directory of Open Access Journals (Sweden)

    N. Susantha Chandrasekera

    2014-10-01

    Full Text Available We demonstrated that the 3-substituted benzothiophene-1,1-dioxide class of compounds are effective inhibitors of Mycobacterium tuberculosis growth under aerobic conditions. We examined substitution at the C-3 position of the benzothiophene-1,1-dioxide series systematically to delineate structure–activity relationships influencing potency and cytotoxicity. Compounds were tested for inhibitory activity against virulent M. tuberculosis and eukaryotic cells. The tetrazole substituent was most potent, with a minimum inhibitory concentration (MIC of 2.6 µM. However, cytotoxicity was noted with even more potency (Vero cell TC50 = 0.1 µM. Oxadiazoles had good anti-tubercular activity (MICs of 3–8 µM, but imidazoles, thiadiazoles and thiazoles had little activity. Cytotoxicity did not track with anti-tubercular activity, suggesting different targets or mode of action between bacterial and eukaryotic cells. However, we were unable to derive analogs without cytotoxicity; all compounds synthesized were cytotoxic (TC50 of 0.1–5 µM. We conclude that cytotoxicity is a liability in this series precluding it from further development. However, the series has potent anti-tubercular activity and future efforts towards identifying the mode of action could result in the identification of novel drug targets.

  15. Efficient oxidative desulfurization (ODS) of model fuel with H{sub 2}O{sub 2} catalyzed by MoO{sub 3}/{gamma}-Al{sub 2}O{sub 3} under mild and solvent free conditions

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Yuhua; Li, Gang; Ning, Guiling [State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology (China)

    2011-01-15

    An efficient process to remove organic sulfur compounds from model fuel has been explored. Dibenzothiophene (DBT) and 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) can be completely oxidized into their corresponding sulfones by H{sub 2}O{sub 2} over 14 wt.% MoO{sub 3}/{gamma}-Al{sub 2}O{sub 3} catalyst under mild conditions in 15 min. The effects of solvent, initial sulfide concentration, loading of MoO{sub 3} and amount of catalyst on oxidative removal of DBT were studied. The employments of solvents have decreased the reaction rate of DBT, which can be attributed to the competitive adsorption between the sulfide and solvent. The oxidative reactivity increases in the order of thiophene (Th) < benzothiophene (BT) < DBT < 4, 6-DMDBT. The catalyst can be regenerated by methanol washing at 333 K. (author)

  16. Oxidative desulfurization of model diesel via dual activation by a protic ionic liquid.

    Science.gov (United States)

    Lü, Hongying; Wang, Shunan; Deng, Changliang; Ren, Wanzhong; Guo, Baocun

    2014-08-30

    A novel and green carboxylate-anion-based protic ionic liquid (PIL), [Hnmp]HCOO, was prepared through a simple and atom economic neutralization reaction between N-methyl-2-pyrrolidonium (NMP) and formic acids. Both FT-IR spectra and (1)H NMR confirmed its simple salt structure. [Hnmp]HCOO exhibited so high catalytic activity that the dibenzothiophene (DBT) removal reached 99% at 50°C in 3h under conditions of VPIL/Vmodel oil=1:10 and H2O2/DBT (O/S, molar ratio)=5. The catalytic oxidation reactivity of S-compounds was found to be in the order of DBT>4,6-dimethyldibenzothiophene (4,6-DMDBT)>benzothiophene (BT). The investigation on mechanism showed that oxidative desulfurization was realized through dual activation of PIL. Moreover, [Hnmp]HCOO can be recycled for five times with an unnoticeable decrease in desulfurization activity. PMID:25064259

  17. Oxidative Desulfurization of Diesel Fuel with Hydrogen Peroxide Using Na2WO4 s Catalyst

    Institute of Scientific and Technical Information of China (English)

    Sun Xin; Long Jun; Xu Benjing; Xie Chaogang

    2009-01-01

    Oxidative desulfurization was performed on Na2WO4 catalyst in the presence of hydrogen peroxide and acetic acid under mild reaction conditions (atmospheric pressure and temperature range of 293-343 K). Different organic com-pounds including benzothiophene (BT), dibenzothiophene (DBT), 4, 6-dimethyl dibenzothiophene (4, 6-DMDBT) were used to investigate the reactivity of this catalyst, and the effect of various parameters, such as temperature, solvents and the amount of oxidant reagent used in oxidative desulfurization reaction, was also examined. The results showed that the Na2WO4-H2O2 system was very effective for oxidative desulfurization, and the oxidation of BT, DBT and 4, 6-DMDBT was influ-enced by different parameters.

  18. Influence of Molecular Sieve Supported Metal Oxides on the Desulfurization in Catalytic Cracking of Sulfur-containing Model Compounds and Hydrocarbons

    Institute of Scientific and Technical Information of China (English)

    申宝剑; 李海丽; 李会峰; 鲍晓军; 周小虹

    2003-01-01

    Zn, La, Zr, Sn and Ti loaded molecular sieves were prepared by impregnation method. Conversions of benzothiophene and dibenzothiophene over the metal oxides modified ultra stable zeolite Y(USY), ZSM-5, β and MSU-2 molecular sieve catalysts were investigated by means of micro-activity test (MAT) experiments. The results showed that Zn and La loaded catalysts were better than the other metals, and ZSM-5 with lower SiO2/Al2O3 mole ratio showed better results than those with higher SiO2/Al2O3 as far as desulfurization reaction is considered. A comparison of the desulfurization activities of the La/Zn-USY catalyst with USY catalyst indicated that the bimetal loaded USY catalyst gave good products selectivity when sulfur containing heavy oil was used as the feedstock. The sulfur content in gasoline fraction was decreased by 25%, and there was no loss in the Research Octane Number.

  19. Influence of Molecular Sieve Supported Metal Oxides on the Desulfurization in Catalytic Cracking of Sulfur-containing Model Compounds and Hydrocarbons%金属担载分子筛对含硫模型化合物和含硫烃的催化裂化脱硫反应的影响

    Institute of Scientific and Technical Information of China (English)

    申宝剑; 李海丽; 李会峰; 鲍晓军; 周小虹

    2003-01-01

    Zn, La, Zr, Sn and Ti loaded molecular sieves were prepared by impregnation method. Conversions of benzothiophene and dibenzothiophene over the metal oxides modified ultra stable zeolite Y(USY), ZSM-5, β and MSU-2 molecular sieve catalysts were investigated by means of micro-activity test (MAT) experiments. The results showed that Zn and La loaded catalysts were better than the other metals, and ZSM-5 with lower SiO2/Al2O3 mole ratio showed better results than those with higher SiO2/Al2O3 as far as desulfurization reaction is considered. A comparison of the desulfurization activities of the La/Zn-USY catalyst with USY catalyst indicated that the bimetal loaded USY catalyst gave good products selectivity when sulfur containing heavy oil was used as the feedstock. The sulfur content in gasoline fraction was decreased by 25%, and there was no loss in the Research Octane Number.

  20. Accurate on-chip measurement of the Seebeck coefficient of high mobility small molecule organic semiconductors

    Directory of Open Access Journals (Sweden)

    C. N. Warwick

    2015-09-01

    Full Text Available We present measurements of the Seebeck coefficient in two high mobility organic small molecules, 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT and 2,9-didecyl-dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (C10-DNTT. The measurements are performed in a field effect transistor structure with high field effect mobilities of approximately 3 cm2/V s. This allows us to observe both the charge concentration and temperature dependence of the Seebeck coefficient. We find a strong logarithmic dependence upon charge concentration and a temperature dependence within the measurement uncertainty. Despite performing the measurements on highly polycrystalline evaporated films, we see an agreement in the Seebeck coefficient with modelled values from Shi et al. [Chem. Mater. 26, 2669 (2014] at high charge concentrations. We attribute deviations from the model at lower charge concentrations to charge trapping.

  1. The polymer-like organic material in the Orgueil meteorite

    Science.gov (United States)

    Bandurski, E. L.; Nagy, B.

    1976-01-01

    Results are reported for analysis of polymeric organic material contained in powder from the Orgueil chondrite, using a stepwise high-vacuum pyrolysis-gas chromatography-mass spectrometry technique. Pyrolysis products obtained include a series of alkanes and alkenes to C8, an extensive series of alkylbenzene isomers, thiophene, alkylthiophenes, benzothiophene, acetonitrile, acrylonitrile, benzonitrile, acetone, and phenol. Most of these products are shown to be similar both qualitatively and quantitatively to those previously obtained from solvent-extracted Allende powder, indicating a basically aromatic and heteroaromatic polymer matrix with short aliphatic bridges or side chains. The production of acrylonitrile, acetonitrile, and benzonitrile (common breakdown products of amino acids) from the insoluble organic material is taken to suggest that amino acids exist in an insoluble form, perhaps as peptides, in the meteorite's polymeric component. Similarities between the structure of the Orgueil polymeric material and terrestrial kerogen are discussed which raise the possibility that both might have been produced in part by similar reactions.

  2. Fluid Catalytic Cracking Feed Hydrotreatment and its Impact on Distribution of Sulfur and Nitrogen Compounds in FCC Diesel

    Institute of Scientific and Technical Information of China (English)

    Bai Rui; Chai Yongming; Zhang Chengtao; Liu Chenguang

    2015-01-01

    The sulfides and nitrogen compounds in FCC diesel were analyzed by gas chromatography equipped with a pulsed lfame photometric detector (GC-PFPD) and gas chromatography coupled with nitrogen chemiluminescence detection (GC-NCD). And the variation of sulifdes and nitrogen compounds in FCC diesel produced from gas oil feed hydrotreated at different temperatures was investigated. The test results showed that two main types of sulfur compounds, i.e. benzothio-phenes (BTs) and dibenzothiophenes (DBTs) were found in diesel. Nitrogen compounds are mainly composed of non-basic nitrogen compounds, and indoles and carbazoles account for about 98% of the total nitrogen contents. The sulifdes in FCC diesel obtained from hydrotreated feed are mainly BTs with a small amount of 4-MDBT and 4,6-DMDBT. With the increase in FCC feed hydrotreating temperature, indoles content in FCC diesel increases, while carbazoles content decreases.

  3. Theoretical Study on Interactions between N-Butylpyridinium Nitrate and Thiophenic Compounds

    International Nuclear Information System (INIS)

    By using density functional theory calculations, we have performed a systemic study on the electronic structures and topological properties of interactions between N-butylpyridinium nitrate ([BPY]+[NO3]-) and thiophene (TS), benzothiophene (BT), dibenzothiophene (DBT), naphthalene (NAP). The most stable structure of [BPY]+[NO3]- ion pair indicates that hydrogen bonding interactions between oxygen atoms on [NO3]- anion and C2-H2 on pyridinium ring play a dominating role in the formation of ion pair. The occurrence of hydrogen bonding, π···H-C, and π···π interactions between [BPY]+[NO3]- and TS, BT, DBT, NAP has been corroborated at the molecular level. But hydrogen bonding and π···π interactions between [BPY]+[NO3]- and NAP are weak in terms of structural properties and NBO, AIM analyses. DBT is prior to adsorption on N-butylpyridinium nitrate ionic liquid

  4. Transient phases during fast crystallization of organic thin films from solution

    Directory of Open Access Journals (Sweden)

    Jing Wan

    2016-01-01

    Full Text Available We report an in situ microbeam grazing incidence X-ray scattering study of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT organic semiconductor thin film deposition by hollow pen writing. Multiple transient phases are observed during the crystallization for substrate temperatures up to ≈93 °C. The layered smectic liquid-crystalline phase of C8-BTBT initially forms and preceedes inter-layer ordering, followed by a transient crystalline phase for temperature >60 °C, and ultimately the stable phase. Based on these results, we demonstrate a method to produce extremely large grain size and high carrier mobility during high-speed processing. For high writing speed (25 mm/s, mobility up to 3.0 cm2/V-s has been observed.

  5. Low-Temperature Band Transport and Impact of Contact Resistance in Organic Field-Effect Transistors Based on Single-Crystal Films of Ph-BTBT-C10

    Science.gov (United States)

    Cho, Joung-min; Mori, Takehiko

    2016-06-01

    Transistors based on single-crystal films of 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10) fabricated using the blade-coating method are investigated by the four-probe method down to low temperatures. The four-probe mobility is as large as 18 cm2/V s at room temperature, and increases to 45 cm2/V s at 80 K. At 60 K the two-probe mobility drops abruptly by about 50%, but the mobility drop is mostly attributed to the increase of the source resistance. The carrier transport in the present single-crystal film is regarded as essentially bandlike down to 30 K.

  6. Sulfoxide-Directed Metal-Free ortho-Propargylation of Aromatics and Heteroaromatics.

    Science.gov (United States)

    Eberhart, Andrew J; Shrives, Harry J; Álvarez, Estela; Carrër, Amandine; Zhang, Yuntong; Procter, David J

    2015-05-11

    A sulfoxide-directed, metal-free ortho-propargylation of aromatics and heteroaromatics exploits intermolecular delivery of a propargyl nucleophile to sulfur followed by an intramolecular relay to carbon. The operationally simple cross-coupling procedure is general, regiospecific with regard to the propargyl nucleophile, and shows complete selectivity for products of ortho-propargylation over allenylation. The use of secondary propargyl silanes allows metal-free ortho-coupling to form carbon-carbon bonds between aromatic and heteroaromatic rings and secondary propargylic centres. The 'safety-catch' nature of the sulfoxide directing group is illustrated in a selective, iterative double cross-coupling process. The products of propargylation are versatile intermediates and they have been readily converted into substituted benzothiophenes.

  7. Phonon-electron coupling and tunneling effect on charge transport in organic semi-conductor crystals of Cn-BTBT.

    Science.gov (United States)

    Zhou, Yecheng; Deng, Wei-Qiao; Zhang, Hao-Li

    2016-09-14

    Cn-[1]benzothieno[3,2-b][1]-benzothiophene (BTBT) crystals show very high hole mobilities in experiments. These high mobilities are beyond existing theory prediction. Here, we employed different quantum chemistry methods to investigate charge transfer in Cn-BTBT crystals and tried to find out the reasons for the underestimation in the theory. It was found that the hopping rate estimated by the Fermi Golden Rule is higher than that of the Marcus theory due to the high temperature approximation and failure at the classic limit. More importantly, molecular dynamics simulations revealed that the phonon induced fluctuation of electronic transfer integral is much larger than the average of the electronic transfer integral itself. Mobilities become higher if simulations implement the phonon-electron coupling. This conclusion indicates that the phonon-electron coupling promotes charge transfer in organic semi-conductors at room temperature. PMID:27634252

  8. Study on Reduction of Sulfur Content in FCC Gasoline

    Institute of Scientific and Technical Information of China (English)

    Hou Dianguo

    2003-01-01

    Reduction of sulfur content in FCC gasoline was studied in a fixed fluid bed (FFB) unit by using metal-modified LV-23 FCC catalyst. The results showed that the sulfur content in FCC gasoline could be reduced with LV-23 catalyst modified with zinc, palladium, zinc-palladium, zinc-cobalt, and zinc-nickel. Among these metals or metal combinations, palladium-containing catalyst was the most effective. Desulfurization of the heavy fraction of FCC gasoline was more effective than full-range gasoline under the same conditions with palladium-containing catalysts. A high reaction temperature was favorable to desulfurization, but it would reduce the yield of liquid product. After desulfurization reaction, the olefin content of product gasoline decreased while the aromatic and iso-alkane contents increased. Removal of thiophene and benzothiophene is higher.

  9. Oxidative desulfurization of Gas oil by polyoxometalates catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Trakarnpruk, W. [Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330 (Thailand); Center of Excellence for Petroleum, Petrochemicals, and Advanced Materials, Chulalongkorn University, Bangkok 10330 (Thailand); Rujiraworawut, K. [Program of Petrochemistry and Polymer Science, Faculty of Science, Chulalongkorn University, Bangkok 10330 (Thailand)

    2009-03-15

    Several polyoxometalates: Na{sub 2}HPM{sub 12}O{sub 40}, H{sub 3}PM{sub 12}O{sub 40}, Na{sub 2}HPM{sub 12}O{sub 40}, (VO)H[PM{sub 12}O{sub 40}] and (n-Bu{sub 4}N){sub 3}[PM{sub 12}O{sub 40}] (M = Mo and W) as well as (n-Bu{sub 4}N){sub 3} {sub +} {sub x}[PW{sub 12-x}V{sub x}O{sub 40}] (x = 0-3) were synthesized and characterized. Benzothiophene, dibenzothiophene and 4,6-dimethyl-dibenzothiophene were used as model sulfur compounds in gas oil. The oxidation reaction was performed using different polyoxometalates as catalyst and H{sub 2}O{sub 2}/acetic acid. The experimental results show that the W-based polyoxometalate catalysts are more active than the Mo catalysts. The oxidation reactivity of the catalysts depends on the type of countercation: Na{sup +} > H{sup +} > (VO){sup +} > (n-Bu{sub 4}N){sup +}. In a series of (n-Bu{sub 4}N){sub 3} {sub +} {sub x} [PW{sub 12-x}V{sub x}O{sub 40}] (x 0-3) the order of catalytic activity is V{sub 3} > V{sub 2} > V{sub 1} > V{sub 0}. The reactivity order of the sulfur compounds is: dibenzothiophene > 4,6-dimethyldibenzo-thiophene > benzothiophene. The catalytic system in this work was used for the oxidation of gas oil combined with solvent extraction to remove sulfur content in gas oil. Under mild reaction condition, high sulfur removal up to 98% can be achieved with high oil recovery (90%). (author)

  10. Structural features underlying raloxifene's biophysical interaction with bone matrix.

    Science.gov (United States)

    Bivi, Nicoletta; Hu, Haitao; Chavali, Balagopalakrishna; Chalmers, Michael J; Reutter, Christopher T; Durst, Gregory L; Riley, Anna; Sato, Masahiko; Allen, Matthew R; Burr, David D; Dodge, Jeffrey A

    2016-02-15

    Raloxifene, a selective estrogen receptor modulator (SERM), reduces fracture risk at least in part by improving the mechanical properties of bone in a cell- and estrogen receptor-independent manner. In this study, we determined that raloxifene directly interacts with the bone tissue. Through the use of multiple and complementary biophysical techniques including nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR), we show that raloxifene interacts specifically with the organic component or the organic/mineral composite, and not with hydroxyapatite. Structure-activity studies reveal that the basic side chain of raloxifene is an instrumental determinant in the interaction with bone. Thus, truncation of portions of the side chain reduces bone binding and also diminishes the increase in mechanical properties. Our results support a model wherein the piperidine interacts with bone matrix through electrostatic interactions with the piperidine nitrogen and through hydrophobic interactions (van der Waals) with the aliphatic groups in the side chain and the benzothiophene core. Furthermore, in silico prediction of the potential binding sites on the surface of collagen revealed the presence of a groove with sufficient space to accommodate raloxifene analogs. The hydroxyl groups on the benzothiophene nucleus, which are necessary for binding of SERMs to the estrogen receptor, are not required for binding to the bone surface, but mediate a more robust binding of the compound to the bone powder. In conclusion, we report herein a novel property of raloxifene analogs that allows them to interact with the bone tissue through potential contacts with the organic matrix and in particular collagen. PMID:26795112

  11. Thiophenic Sulfur Compounds Released During Coal Pyrolysis.

    Science.gov (United States)

    Xing, Mengwen; Kong, Jiao; Dong, Jie; Jiao, Haili; Li, Fan

    2013-06-01

    Thiophenic sulfur compounds are released during coal gasification, carbonization, and combustion. Previous studies indicate that thiophenic sulfur compounds degrade very slowly in the environment, and are more carcinogenic than polycyclic aromatic hydrocarbons and nitrogenous compounds. Therefore, it is very important to study the principle of thiophenic sulfur compounds during coal conversion, in order to control their emission and promote clean coal utilization. To realize this goal and understand the formation mechanism of thiophenic sulfur compounds, this study focused on the release behavior of thiophenic sulfur compounds during coal pyrolysis, which is an important phase for all coal thermal conversion processes. The pyrolyzer (CDS-5250) and gas chromatography-mass spectrometry (Focus GC-DSQII) were used to analyze thiophenic sulfur compounds in situ. Several coals with different coal ranks and sulfur contents were chosen as experimental samples, and thiophenic sulfur compounds of the gas produced during pyrolysis under different temperatures and heating rates were investigated. Levels of benzothiophene and dibenzothiophene were obtained during pyrolysis at temperatures ranging from 200°C to 1300°C, and heating rates ranging from 6°C/ms to 14°C/ms and 6°C/s to 14°C/s. Moreover, the relationship between the total amount of benzothiophene and dibenzothiophene released during coal pyrolysis and the organic sulfur content in coal was also discussed. This study is beneficial for understanding the formation and control of thiophenic sulfur compounds, since it provides a series of significant results that show the impact that operation conditions and organic sulfur content in coal have on the amount and species of thiophenic sulfur compounds produced during coal pyrolysis. PMID:23781126

  12. Transport and biodegradation of creosote compounds in clayey till, a field experiment

    Science.gov (United States)

    Broholm, Kim; Nilsson, Bertel; Sidle, Roy C.; Arvin, Erik

    2000-02-01

    The transport and biodegradation of 12 organic compounds (toluene, phenol, o-cresol, 2,6-, 3,5-dimethylphenol, naphthalene, 1-methylnaphthalene, benzothiophene, dibenzofuran, indole, acridine, and quinoline) were studied at a field site located on the island of Funen, Denmark, where a clayey till 10-15 m deep overlies a sandy aquifer. The upper 4.8 m of till is highly fractured and the upper 2.5 m contains numerous root and worm holes. A 1.5-2 m thick sand lens is encountered within the till at a depth of 4.8 m. Sampling points were installed at depths of 2.5 m, 4 m, and in the sand lens (5.5 m) to monitor the downward migration of a chloride tracer and the organic compounds. Water containing organic compounds and chloride was infiltrated into a 4 m×4.8 m basin at a rate of 8.8 m 3 day -1 for 7 days. The mass of naphthalene relative to chloride was 0.39-0.98 for the sampling points located at a depth of 2.5 m, 0.11-0.61 for the sampling points located at a depth of 4 m, and 0-0.02 for the sampling points located in the sand lens. A similar pattern was observed for eight organic compounds for which reliable results were obtained (toluene, phenol, o-cresol, 2,6-, 3,5-dimethylphenol, 1-methylnaphthalene, benzothiophene, and quinoline). This shows that the organic compounds were attenuated during the downward migration through the till despite the high infiltration rate. The attenuation process may be attributed to biodegradation.

  13. Selective Human Estrogen Receptor Partial Agonists (ShERPAs) for Tamoxifen-Resistant Breast Cancer.

    Science.gov (United States)

    Xiong, Rui; Patel, Hitisha K; Gutgesell, Lauren M; Zhao, Jiong; Delgado-Rivera, Loruhama; Pham, Thao N D; Zhao, Huiping; Carlson, Kathryn; Martin, Teresa; Katzenellenbogen, John A; Moore, Terry W; Tonetti, Debra A; Thatcher, Gregory R J

    2016-01-14

    Almost 70% of breast cancers are estrogen receptor α (ERα) positive. Tamoxifen, a selective estrogen receptor modulator (SERM), represents the standard of care for many patients; however, 30-50% develop resistance, underlining the need for alternative therapeutics. Paradoxically, agonists at ERα such as estradiol (E2) have demonstrated clinical efficacy in patients with heavily treated breast cancer, although side effects in gynecological tissues are unacceptable. A drug that selectively mimics the actions of E2 in breast cancer therapy but minimizes estrogenic effects in other tissues is a novel, therapeutic alternative. We hypothesized that a selective human estrogen receptor partial agonist (ShERPA) at ERα would provide such an agent. Novel benzothiophene derivatives with nanomolar potency in breast cancer cell cultures were designed. Several showed partial agonist activity, with potency of 0.8-76 nM, mimicking E2 in inhibiting growth of tamoxifen-resistant breast cancer cell lines. Three ShERPAs were tested and validated in xenograft models of endocrine-independent and tamoxifen-resistant breast cancer, and in contrast to E2, ShERPAs did not cause significant uterine growth.

  14. Deep oxidative desulfurization of dibenzothiophene in simulated oil and real diesel using heteropolyanion-substituted hydrotalcite-like compounds as catalysts.

    Science.gov (United States)

    Yu, Fengli; Wang, Rui

    2013-01-01

    Three heteropolyanion substituted hydrotalcite-like compounds (HPA-HTLcs) including Mg₉Al₃(OH)₂₄[PW₁₂O₄₀](MgAl-PW₁₂), Mg₉Al₃(OH)₂₄[PMo₁₂O₄₀] (MgAl-PMo₁₂) and Mg₁₂Al₄(OH)₃₂[SiW₁₂O₄₀] (MgAl-SiW₁₂), were synthesized, characterized and used as catalysts for the oxidative desulfurization of simulated oil (dibenzothiophene, DBT, in n-octane). MgAl-PMo₁₂ was identified as an effective catalyst for the oxidative removal of DBT under very mild conditions of atmospheric pressure and 60 °C in a biphasic system using hydrogen peroxide as oxidant and acetonitrile as extractant. The conversion of DBT was nearly 100%. As a result, because of the influence of the electron density and the space steric hindrance, the oxidation reactivity of the different sulfur compounds in simulated oil followed the order DBT > 4,6-dimethyldibenzothiophene (4,6-DMDBT) > benzothiophene (BT) > thiophene (TH). When the reaction is finished, the catalysts can be recovered from the acetonitrile phase by filtration. The recovered MgAl-PMo₁₂ retains nearly the same catalytic activity as the fresh material. Moreover, MgAl-PMo₁₂ was found to exhibit an ideal catalytic activity in the oxidative desulfurization of real diesel resulting in a total remaining sulfur content of 9.12 ppm(w). PMID:24284486

  15. Oxidative desulfurization of diesel fuel using amphiphilic quaternary ammonium phosphomolybdate catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, Jianghua; Wang, Guanghui; Zeng, Danlin; Tang, Yan [College of Chemical Engineering and Technology, Wuhan University of Science and Technology, Wuhan 430081 (China); Wang, Meng; Li, Yanjun [College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072 (China)

    2009-12-15

    Phosphomolybdic acid (HPMo) modified respectively with tetramethyl ammonium chloride (TMAC), dodecyl trimethyl ammonium chloride (DTAC) and hexadecyl trimethyl ammonium chloride (HTAC) as the catalysts were prepared and characterized by FT-IR, XRD and SEM. The catalysts were evaluated for the oxidative desulfurization of benzothiophene (BT), dibenzothiophene (DBT) and straight-run diesel using hydrogen peroxide as an oxidant. Results show that all of the catalysts keep the Keggin structures and are finely dispersed with mixing of quaternary ammonium salts. Hexadecyl chains are more favorable to wrap up DBT to the catalytic center and form stable emulsion system with higher conversion rates of DBT. The shorter dodecyl chains can wrap up BT more suitably and bring smaller steric hindrance, which display higher conversion rates of BT. The oxidative reactions fit apparent first-order kinetics, and the apparent activation energies of DBT are much lower than those of BT. The desulfurization rate of straight-run diesel can be up to 84.4% with the recovery rate of 98.1% catalyzed by [HPMo][HTAC]{sub 2} in 2 h. When increasing the extraction times, the desulfurization rates increase, but the recovery rates of diesel decrease significantly. (author)

  16. Oxidative desulfurization of model diesel via dual activation by a protic ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Lü, Hongying, E-mail: hylv@ytu.edu.cn; Wang, Shunan; Deng, Changliang; Ren, Wanzhong; Guo, Baocun

    2014-08-30

    Highlights: • A protic ionic liquid, [Hnmp]HCOO, was used as in ODS. • The mechanism of ODS was involved in dual activation by the PIL. • The [Hnmp]HCOO exhibited high catalytic activity in ODS. • The amounts of PILs and oxidant dosage play vital roles in desulfurization system. • This system can be recycled five times with an unnoticeable decrease in activity. - Abstract: A novel and green carboxylate-anion-based protic ionic liquid (PIL), [Hnmp]HCOO, was prepared through a simple and atom economic neutralization reaction between N-methyl-2-pyrrolidonium (NMP) and formic acids. Both FT-IR spectra and {sup 1}H NMR confirmed its simple salt structure. [Hnmp]HCOO exhibited so high catalytic activity that the dibenzothiophene (DBT) removal reached 99% at 50 °C in 3 h under conditions of V{sub PIL}/V{sub model} {sub oil} = 1:10 and H{sub 2}O{sub 2}/DBT (O/S, molar ratio) = 5. The catalytic oxidation reactivity of S-compounds was found to be in the order of DBT > 4,6-dimethyldibenzothiophene (4,6-DMDBT) > benzothiophene (BT). The investigation on mechanism showed that oxidative desulfurization was realized through dual activation of PIL. Moreover, [Hnmp]HCOO can be recycled for five times with an unnoticeable decrease in desulfurization activity.

  17. Oxidative desulfurization of fuel oil. Part I. Oxidation of dibenzothiophenes using tert-butyl hydroperoxide

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Danhong; Qian, Eika Weihua; Amano, Hiroshi; Okata, Kazuhiro; Ishihara, Atsushi; Kabe, Toshiaki [Department of Chemical Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Nakacho, Koganei, Tokyo 184-8588 (Japan)

    2003-10-20

    The oxidation of sulfur compounds in kerosene was conducted with tert-butyl hydroperoxide (t-BuOOH) in the presence of various catalysts. The oxidation activities of dibenzothiophene (DBT) in kerosene for a series of Mo catalysts supported on Al{sub 2}O{sub 3} with various Mo contents were estimated. The results show that the oxidation activity of DBT increased with increasing Mo content up to about 16wt.% and decreased when Mo content was beyond this value. The oxidation of benzothiophene (BT), dibenzothiophene (DBT), 4-methyl dibenzothiophene (4-MDBT), and 4,6-dimethyl dibenzothiophene (4,6-DMDBT) dissolved in decalin was also carried out on 16wt.% Mo/Al{sub 2}O{sub 3} catalyst with t-BuOOH to investigate the oxidation reactivities of these sulfur compounds. The results indicated that the oxidation reactivities of these sulfur compounds decreased in the order of DBT>4-MDBT>4,6-DMDBT>>BT. Analyses of the oxidative reactions of the sulfur compounds suggested that the oxidative reaction of each sulfur compound can be treated as a first-order reaction. The oxidation mechanism is then discussed.

  18. Deep Oxidative Desulfurization of Dibenzothiophene in Simulated Oil and Real Diesel Using Heteropolyanion-Substituted Hydrotalcite-Like Compounds as Catalysts

    Directory of Open Access Journals (Sweden)

    Rui Wang

    2013-11-01

    Full Text Available Three heteropolyanion substituted hydrotalcite-like compounds (HPA-HTLcs including Mg9Al3(OH24[PW12O40](MgAl-PW12, Mg9Al3(OH24[PMo12O40] (MgAl-PMo12 and Mg12Al4(OH32[SiW12O40] (MgAl-SiW12, were synthesized, characterized and used as catalysts for the oxidative desulfurization of simulated oil (dibenzothiophene, DBT, in n-octane. MgAl-PMo12 was identified as an effective catalyst for the oxidative removal of DBT under very mild conditions of atmospheric pressure and 60 °C in a biphasic system using hydrogen peroxide as oxidant and acetonitrile as extractant. The conversion of DBT was nearly 100%. As a result, because of the influence of the electron density and the space steric hindrance, the oxidation reactivity of the different sulfur compounds in simulated oil followed the order DBT > 4,6-dimethyldibenzothiophene (4,6-DMDBT > benzothiophene (BT > thiophene (TH. When the reaction is finished, the catalysts can be recovered from the acetonitrile phase by filtration. The recovered MgAl-PMo12 retains nearly the same catalytic activity as the fresh material. Moreover, MgAl-PMo12 was found to exhibit an ideal catalytic activity in the oxidative desulfurization of real diesel resulting in a total remaining sulfur content of 9.12 ppm(w.

  19. Oxidative desulfurization of simulated light fuel oil and untreated kerosene

    Energy Technology Data Exchange (ETDEWEB)

    Dehkordi, Asghar Molaei; Kiaei, Zahra; Sobati, Mohammad Amin [Department of Chemical and Petroleum Engineering, Sharif University of Technology, P.O. Box: 11155-9465, Tehran (Iran)

    2009-03-15

    An experimental investigation was conducted on the oxidative desulfurization of model sulfur compounds such as dibenzothiophene and benzothiophene in toluene as a simulated light fuel oil with a mixture of hydrogen peroxide as the oxidant and various acids as the catalyst. The influences of various parameters including reaction temperature (T), acid to sulfur molar ratio (Acid/S), oxidant to sulfur molar ratio (O/S), type of acid, and the presence of sodium tungstate and commercial activated carbon as a co-catalyst on the fractional conversion of the model sulfur compounds were investigated. The experimental data obtained were used to determine the reaction rate constant of the model sulfur compounds and the corresponding activation energy. Moreover, the adsorption of model sulfur compounds on the commercial activated carbons supplied by Jacobi Co. (Sweden, AquaSorb 101) was studied and the effects of different parameters such as temperature, and various chemical treatments on the adsorption of the sulfur compounds were investigated. Furthermore, the oxidative desulfurization of untreated kerosene with the total sulfur content of 1700 ppmw produced by an Iranian refining company (Isfahan refinery) was successfully investigated. These experiments were performed using formic acid as the catalyst and hydrogen peroxide as the oxidant at the mild operating conditions of T = 50 C, O/S 5, and the Acid/S = 10. It was realized that about 87% of the total sulfur content of untreated kerosene could be removed after 30 min oxidation followed by liquid-liquid extraction. (author)

  20. Highly efficient extraction and oxidative desulfurization system using Na7H2LaW10O36⋅32 H2O in [bmim]BF4 at room temperature.

    Science.gov (United States)

    Xu, Junhua; Zhao, Shen; Chen, Wei; Wang, Miao; Song, Yu-Fei

    2012-04-10

    Highly efficient, deep desulfurization of model oil containing dibenzothiophene (DBT), benzothiophene (BT), or 4,6-dimethyldibenzothiophene (4,6-DMDBT) has been achieved under mild conditions by using an extraction and catalytic oxidative desulfurization system (ECODS) in which a lanthanide-containing polyoxometalate Na(7)H(2)LnW(10)O(36)⋅32 H(2)O (LnW(10); Ln = Eu, La) acts as catalyst, [bmim]BF(4) (bmim = 1-butyl-3-methylimidazolium) as extractant, and H(2)O(2) as oxidant. Sulfur removal follows the order DBT>4,6-DMDBT>BT at 30 °C. DBT can be completely oxidized to the corresponding sulfone in 25 min under mild conditions, and the LaW(10)/[bmim]BF(4) system could be recycled for ten times with only slight decrease in activity. Thus, LaW(10) in [bmim]BF(4) is one of the most efficient systems for desulfurization using ionic liquids as extractant reported so far. PMID:22374858

  1. Identification of genetic and chemical modulators of zebrafish mechanosensory hair cell death.

    Directory of Open Access Journals (Sweden)

    Kelly N Owens

    2008-02-01

    Full Text Available Inner ear sensory hair cell death is observed in the majority of hearing and balance disorders, affecting the health of more than 600 million people worldwide. While normal aging is the single greatest contributor, exposure to environmental toxins and therapeutic drugs such as aminoglycoside antibiotics and antineoplastic agents are significant contributors. Genetic variation contributes markedly to differences in normal disease progression during aging and in susceptibility to ototoxic agents. Using the lateral line system of larval zebrafish, we developed an in vivo drug toxicity interaction screen to uncover genetic modulators of antibiotic-induced hair cell death and to identify compounds that confer protection. We have identified 5 mutations that modulate aminoglycoside susceptibility. Further characterization and identification of one protective mutant, sentinel (snl, revealed a novel conserved vertebrate gene. A similar screen identified a new class of drug-like small molecules, benzothiophene carboxamides, that prevent aminoglycoside-induced hair cell death in zebrafish and in mammals. Testing for interaction with the sentinel mutation suggests that the gene and compounds may operate in different pathways. The combination of chemical screening with traditional genetic approaches is a new strategy for identifying drugs and drug targets to attenuate hearing and balance disorders.

  2. Adsorptive desulfurization over hierarchical beta zeolite by alkaline treatment

    Institute of Scientific and Technical Information of China (English)

    Fuping Tian; Xiaojian Yang; Yanchun Shi; Cuiying Jia; Yongying Chen

    2012-01-01

    Hierarchical beta zeolites with SiO2/Al2O3 molar ratios of 16 to 25 were obtained by alkaline treatment in NaOH solution.The effects of treatment temperature on crystallinity,textural properties and chemical composites were studied by XRD,N2 sorption,FT-IR and XRF techniques.The desulfurization performance of parent and alkaline-treated beta zeolites was investigated by static absorption in four model fuels,containing four sulfur compounds of different molecular sizes like thiophene (TP),3-methylthiophene (3-MT),benzothiophene (BT) and dibenzothiophene (DBT),respectively.The crystallinity was observed to be successfully maintained when the treatment temperature was below 50℃.Mesoporosity of beta zeolite was evidently developed with alkaline treatment.The formation of mesopore remarkably improved the desulfurization performance for TP,3-MT,BT and DBT,especially for DBT with larger molecular diameter.Though the addition of toluene in the model fuels resulted in a significant drop of the desulfurization performance of mesoporous beta zeolite,the introduction of cerium ions to some extent mitigated the effect of toluene,which means that both the adsorbents porous structure and the adsorption mode are responsible for the desulfurization performance.The adsorbent of cerium ion-exchanged mesoporous beta showed about 80% recovery of desulfurization after the first regeneration.

  3. Thiophene-bithiazole based metal-free dye as DSSC sensitizer: Effect of co-adsorbents on photovoltaic efficiency

    Indian Academy of Sciences (India)

    Jayanthy S Panicker; Bijitha Balan; Suraj Soman; Tanwistha Ghosh; Vijayakumar C Nair

    2016-01-01

    A new molecule consisting of a bithiazole chromophore sandwiched between two thiophenes, functionalized with benzothiophene unit at one end and cyanoacrylic acid at the other end (BT1) was synthesized, photophysical properties were studied and employed as a photosensitizer in dye-sensitized solar cells (DSSCs). The molecule exhibited an intense absorption in the UV-visible region with absorption extending up to 500 nm. The ground and excited state potentials of BT1 were calculated to be 1.29 and -0.65 V, respectively vs. NHE using cyclic voltammetry. The ground state energy level is more positive than the triiodide electrolyte and excited state energy level is considerably more negative than the TiO2 satisfying the energetic requirements for a photosensitizer in DSSC. The solar cells fabricated from BT1 exhibited an efficiency of 1.13%. The effect of various co-adsorbents (CDCA, TP1 and TP2) on the DSSC performance was investigated in detail. In the presence of CDCA, the photovoltaic efficiency was enhanced to 1.25%, whereas, in the presence of TP1 and TP2, the efficiency lowered to 0.20% and 0.59%, respectively. The increased efficiency in the presence of CDCA could be attributed to the prevention of the aggregation of dye molecules induced by CDCA. On the other hand, TP1 and TP2 were found to be not as effective as CDCA to prevent aggregation leading to the lowering of photoconversion efficiency.

  4. Reducing dynamic disorder in small-molecule organic semiconductors by suppressing large-amplitude thermal motions

    Science.gov (United States)

    Illig, Steffen; Eggeman, Alexander S.; Troisi, Alessandro; Jiang, Lang; Warwick, Chris; Nikolka, Mark; Schweicher, Guillaume; Yeates, Stephen G.; Henri Geerts, Yves; Anthony, John E.; Sirringhaus, Henning

    2016-02-01

    Thermal vibrations and the dynamic disorder they create can detrimentally affect the transport properties of van der Waals bonded molecular semiconductors. The low-energy nature of these vibrations makes it difficult to access them experimentally, which is why we still lack clear molecular design rules to control and reduce dynamic disorder. In this study we discuss the promising organic semiconductors rubrene, 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothio-phene and 2,9-di-decyl-dinaphtho-[2,3-b:20,30-f]-thieno-[3,2-b]-thiophene in terms of an exceptionally low degree of dynamic disorder. In particular, we analyse diffuse scattering in transmission electron microscopy, to show that small molecules that have their side chains attached along the long axis of their conjugated core are better encapsulated in their crystal structure, which helps reduce large-amplitude thermal motions. Our work provides a general strategy for the design of new classes of very high mobility organic semiconductors with a low degree of dynamic disorder.

  5. Oxidative desulfurization of synthetic diesel using supported catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Caero, Luis Cedeno; Hernandez, Emiliano [UNICAT, Departamento de Ingenieria Quimica, Facultad de Quimica, UNAM. Cd. Universitaria, 04510 Mexico D.F. (Mexico); Pedraza, Francisco; Murrieta, Florentino [Programa de Tratamiento en Crudo Maya, Instituto Mexicano del Petroleo, Eje Central 152, 07730 Mexico D.F. (Mexico)

    2005-10-30

    In this work, an experimental study was carried out to obtain the reactivity of different organic sulfur compounds and to examine the effect of various parameters, such as temperature, solvent and the amount of oxidant reagent in oxidative desulfurization (ODS) reaction. The oxidation was performed through a vanadium based catalyst in the presence of hydrogen peroxide under mild reaction conditions, atmospheric pressure and temperature range of 303-343K. The sulfur compounds studied were: 2-methylthiophene (2-MT), 2,5-dimethylthiophene (2,5-DMT), benzothiophene (BT), dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT). All of them are typical thiophenic sulfur compounds present in diesel fuels. A synthetic diesel was prepared with these compounds in hexadecane. The experimental results showed that oxidation reactivities decreased according to the following order: DBT>BT>4-MDBT>2-MT>2,5-DMT>4,6-DMDBT. A fraction of the S compounds removed from the diesel phase, was not transformed to its corresponding sulfone, under these experimental conditions. It is only removed as sulfur compound by extraction, without ODS reaction. The surplus amount of oxidant promoted the equilibrium reaction, but the thermal decomposition of oxidant and oxidation reactions produces water, which inhibits the ODS reactions. Therefore, the controlled addition of H{sub 2}O{sub 2} improves ODS reactivity of sulfur compounds.

  6. Biocatalytic desulfurization capabilities of a mixed culture during non-destructive utilization of recalcitrant organosulfur compounds

    Directory of Open Access Journals (Sweden)

    Wael eIsmail

    2016-03-01

    Full Text Available We investigated the biodesulfurization potential of a mixed culture AK6 enriched from petroleum hydrocarbons-polluted soil with dibenzothiophene (DBT as a sulfur source. In addition to DBT, AK6 utilized the following compounds as sulfur sources: 4-methyldibenzothiophene (4-MDBT, benzothiophene (BT, and 4,6- dimethyldibenzothiophene (4,6-DM-DBT. None of these compounds supported the growth of AK6 as the sole carbon and sulfur source. AK6 could not grow on dibenzylsulfide (DBS as a sulfur source. The AK6 community structure changed according to the provided sulfur source. The major DGGE bands represented members of the genera Sphingobacterium, Klebsiella, Pseudomonas, Stenotrophomonas, Arthrobacter, Mycobacterium and Rhodococcus. Sphingobacterium sp. and Pseudomonas sp. were abundant across all cultures utilizing any of the tested thiophenic S-compounds. Mycobacterium/Rhodococcus spp. were restricted to the 4-MDBT culture. The 4-MDBT culture had the highest species richness and diversity. Biodesulfurization of DBT by resting cells of AK6 produced 2-hydroxybiphenyl (2-HBP in addition to trace amounts of phenylacetate. AK6 transformed DBT to 2-hydroxybiphenyl with a specific activity of 9 ± 0.6 µM 2-HBP g dry cell weight-1 h-1. PCR confirmed the presence in the AK6 community of the sulfur-specific (4S pathway genes dszB and dszC. Mixed cultures hold a better potential than axenic ones for the development of a biodesulfurization technology.

  7. Biocatalytic Desulfurization Capabilities of a Mixed Culture during Non-Destructive Utilization of Recalcitrant Organosulfur Compounds.

    Science.gov (United States)

    Ismail, Wael; El-Sayed, Wael S; Abdul Raheem, Abdul Salam; Mohamed, Magdy E; El Nayal, Ashraf M

    2016-01-01

    We investigated the biodesulfurization potential of a mixed culture AK6 enriched from petroleum hydrocarbons-polluted soil with dibenzothiophene (DBT) as a sulfur source. In addition to DBT, AK6 utilized the following compounds as sulfur sources: 4-methyldibenzothiophene (4-MDBT), benzothiophene (BT), and 4,6- dimethyldibenzothiophene (4,6-DM-DBT). None of these compounds supported the growth of AK6 as the sole carbon and sulfur source. AK6 could not grow on dibenzylsulfide (DBS) as a sulfur source. The AK6 community structure changed according to the provided sulfur source. The major DGGE bands represented members of the genera Sphingobacterium, Klebsiella, Pseudomonas, Stenotrophomonas, Arthrobacter, Mycobacterium, and Rhodococcus. Sphingobacterium sp. and Pseudomonas sp. were abundant across all cultures utilizing any of the tested thiophenic S-compounds. Mycobacterium/Rhodococcus spp. were restricted to the 4-MDBT culture. The 4-MDBT culture had the highest species richness and diversity. Biodesulfurization of DBT by resting cells of AK6 produced 2-hydroxybiphenyl (2-HBP) in addition to trace amounts of phenylacetate. AK6 transformed DBT to 2-hydroxybiphenyl with a specific activity of 9 ± 0.6 μM 2-HBP g dry cell weight(-1) h(-1). PCR confirmed the presence in the AK6 community of the sulfur-specific (4S) pathway genes dszB and dszC. Mixed cultures hold a better potential than axenic ones for the development of a biodesulfurization technology. PMID:26973637

  8. Ultra-high mobility transparent organic thin film transistors grown by an off-centre spin-coating method

    Science.gov (United States)

    Yuan, Yongbo; Giri, Gaurav; Ayzner, Alexander L.; Zoombelt, Arjan P.; Mannsfeld, Stefan C. B.; Chen, Jihua; Nordlund, Dennis; Toney, Michael F.; Huang, Jinsong; Bao, Zhenan

    2014-01-01

    Organic semiconductors with higher carrier mobility and better transparency have been actively pursued for numerous applications, such as flat-panel display backplane and sensor arrays. The carrier mobility is an important figure of merit and is sensitively influenced by the crystallinity and the molecular arrangement in a crystal lattice. Here we describe the growth of a highly aligned meta-stable structure of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) from a blended solution of C8-BTBT and polystyrene by using a novel off-centre spin-coating method. Combined with a vertical phase separation of the blend, the highly aligned, meta-stable C8-BTBT films provide a significantly increased thin film transistor hole mobility up to 43 cm2 Vs-1 (25 cm2 Vs-1 on average), which is the highest value reported to date for all organic molecules. The resulting transistors show high transparency of >90% over the visible spectrum, indicating their potential for transparent, high-performance organic electronics.

  9. Thermochemical sulfate reduction in deep petroleum reservoirs: a molecular approach; Thermoreduction des sulfates dans les reservoirs petroliers: approche moleculaire

    Energy Technology Data Exchange (ETDEWEB)

    Hanin, S.

    2002-11-01

    The thermochemical sulfate reduction (TSR) is a set of chemical reactions leading to hydrocarbon oxidation and production of carbon dioxide and sour gas (H{sub 2}S) which is observed in deep petroleum reservoirs enriched in anhydrites (calcium sulfate). Molecular and isotopic studies have been conducted on several crude oil samples to determine which types of compounds could have been produced during TSR. Actually, we have shown that the main molecules formed by TSR were organo-sulfur compounds. Indeed, sulfur isotopic measurements. of alkyl-di-benzothiophenes, di-aryl-disulfides and thia-diamondoids (identified by NMR or synthesis of standards) shows that they are formed during TSR as their value approach that of the sulfur of the anhydrite. Moreover, thia-diamondoids are apparently exclusively formed during this phenomenon and can thus be considered as true molecular markers of TSR. In a second part, we have investigated with laboratory experiments the formation mechanism of the molecules produced during TSR. A first model has shown that sulfur incorporation into the organic matter occurred with mineral sulfur species of low oxidation degree. The use of {sup 34}S allowed to show that the sulfates reduction occurred during these simulations. At least, some experiments on polycyclic hydrocarbons, sulfurized or not, allowed to establish that thia-diamondoids could be formed by acid-catalysed rearrangements at high temperatures in a similar way as the diamondoids. (author)

  10. SULFUR REDUCTION IN GASOLINE AND DIESEL FUELS BY EXTRACTION/ADSORPTION OF REFRACTORY DIBENZOTHIOPHENES

    Energy Technology Data Exchange (ETDEWEB)

    Scott G. McKinley; Celedonio M. Alvarez

    2003-03-01

    The purpose of this study was to remove thiophene, benzothiophene and dibenzothiophene from a simulated gasoline feedstock. We found that Ru(NH{sub 3}){sub 5}(H{sub 2}O){sup 2+} reacts with a variety of thiophenes (Th*), affording Ru(NH{sub 3}){sub 5}(Th*){sup 2+}. We used this reactivity to design a biphasic extraction process that removes more than 50% of the dibenzothiophene in the simulated feedstock. This extraction system consists of a hydrocarbon phase (simulated petroleum feedstock) and extractant Ru(NH{sub 3}){sub 5}(H{sub 2}O){sup 2+} in an aqueous phase (70% dimethylformamide, 30% H{sub 2}O). The DBT is removed in situ from the newly formed Ru(NH{sub 3}){sub 5}(DBT){sup 2+} by either an oxidation process or addition of H{sub 2}O, to regenerate Ru(NH{sub 3}){sub 5}(H{sub 2}O){sup 2+}.

  11. Scandium-Triflate/Metal-Organic Frameworks: Remarkable Adsorbents for Desulfurization and Denitrogenation.

    Science.gov (United States)

    Khan, Nazmul Abedin; Jhung, Sung Hwa

    2015-12-01

    Scandium-triflate (Sc(OTf)3) was introduced for the first time on metal-organic frameworks (MOFs), to utilize acidic Sc(OTf)3 for adsorptive desulfurization and denitrogenation of fuel containing benzothiophene (BT), dibenzothiophene (DBT), quinoline (QUI), and indole (IND). A remarkable improvement in the adsorption capacity (about 65% based on the weight of adsorbents; 90% based on the surface area of the adsorbents) was observed with the Sc(OTf)3/MOFs as compared to the virgin MOFs for the adsorption of BT from liquid fuel. The basic QUI was also adsorbed preferentially onto the acidic Sc(OTf)3/MOFs. However, nonsupported Sc(OTf)3 showed negligible adsorption capacities. The improved adsorptive performance for BT, DBT, and QUI might be derived from acid-base interactions between the acidic Sc(OTf)3 and basic adsorbates. On the other hand, the Sc(OTf)3, loaded on MOFs, reduced the adsorption capacity for neutral IND due to lack of interaction between the neutral adsorbate and acidic adsorbent and the reduced porosities of the modified adsorbents. The reusability of the adsorbents was found satisfactory up to the fourth run. On the basis of the result, it is suggested that metal-triflates, such as Sc(OTf)3, can be prospective materials for adsorptive desulfurization/denitrogenation of fuels when supported on porous materials such as MOFs. PMID:26575418

  12. Selective Human Estrogen Receptor Partial Agonists (ShERPAs) for Tamoxifen-Resistant Breast Cancer.

    Science.gov (United States)

    Xiong, Rui; Patel, Hitisha K; Gutgesell, Lauren M; Zhao, Jiong; Delgado-Rivera, Loruhama; Pham, Thao N D; Zhao, Huiping; Carlson, Kathryn; Martin, Teresa; Katzenellenbogen, John A; Moore, Terry W; Tonetti, Debra A; Thatcher, Gregory R J

    2016-01-14

    Almost 70% of breast cancers are estrogen receptor α (ERα) positive. Tamoxifen, a selective estrogen receptor modulator (SERM), represents the standard of care for many patients; however, 30-50% develop resistance, underlining the need for alternative therapeutics. Paradoxically, agonists at ERα such as estradiol (E2) have demonstrated clinical efficacy in patients with heavily treated breast cancer, although side effects in gynecological tissues are unacceptable. A drug that selectively mimics the actions of E2 in breast cancer therapy but minimizes estrogenic effects in other tissues is a novel, therapeutic alternative. We hypothesized that a selective human estrogen receptor partial agonist (ShERPA) at ERα would provide such an agent. Novel benzothiophene derivatives with nanomolar potency in breast cancer cell cultures were designed. Several showed partial agonist activity, with potency of 0.8-76 nM, mimicking E2 in inhibiting growth of tamoxifen-resistant breast cancer cell lines. Three ShERPAs were tested and validated in xenograft models of endocrine-independent and tamoxifen-resistant breast cancer, and in contrast to E2, ShERPAs did not cause significant uterine growth. PMID:26681208

  13. NiMo/γ-Al2O3 Catalysts from Ni Heteropolyoxomolybdate and Effect of Alumina Modification by B, Co, or Ni%NiMo/γ-Al2O3Catalysts from Ni Heteropolyoxomolybdate and Effect of Alumina Modification by B,Co,or Ni

    Institute of Scientific and Technical Information of China (English)

    Radostina PALCHEVA; Luděk KALU(Z)A; Alla SPOJAKINA; Květuse JIR(A)TOV(A); Georgi TYULIEV

    2012-01-01

    A hydrotreating NiMo/γ-Al2O3 catalyst (12 wt% Mo and 1,1 wt% Ni) was prepared by impregnation of the support with the Anderson-type heteropolyoxomolybdate (NH4)4 Ni(OH)6 Mo6O18.Before impregnation of the support,it was modified with an aqueous solution of H3BO3,Co(NO3)2,or Ni(NO3)2.The catalysts were investigated using N2 adsorption,O2 chemisorption,X-ray diffraction,UV-Vis spectroscopy,Fourier transform infrared spectroscopy,temperature-programmed reduction,temperature-programmed desorption,and X-ray photoelectron spectroscopy.The addition of Co,Ni,or B influenced the A12O3 phase composition and gave increased catalytic activity for 1-benzothiophene hydrodesulfurization (HDS).X-ray photoelectron spectroscopy confirmed that the prior loading of Ni,Co or B increased the degree of sulfidation of the NiMo/γ-A12O3 catalysts.The highest HDS activity was observed with the NiMo/γ-Al2O3 catalyst with prior loaded Ni.

  14. Self-Aligned Growth of Organic Semiconductor Single Crystals by Electric Field.

    Science.gov (United States)

    Kotsuki, Kenji; Obata, Seiji; Saiki, Koichiro

    2016-01-19

    We proposed a novel but facile method for growing organic semiconductor single-crystals via solvent vapor annealing (SVA) under electric field. In the conventional SVA growth process, nuclei of crystals appeared anywhere on the substrate and their crystallographic axes were randomly distributed. We applied electric field during the SVA growth of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) on the SiO2/Si substrate on which a pair of electrodes had been deposited beforehand. Real-time observation of the SVA process revealed that rodlike single crystals grew with their long axes parallel to the electric field and bridged the prepatterned electrodes. As a result, C8-BTBT crystals automatically formed a field effect transistor (FET) structure and the mobility reached 1.9 cm(2)/(V s). Electric-field-assisted SVA proved a promising method for constructing high-mobility single-crystal FETs at the desired position by a low-cost solution process. PMID:26695105

  15. Pyrolysis comprehensive two-dimensional gas chromatography study of petroleum source rock.

    Science.gov (United States)

    Wang, Frank Cheng-Yu; Walters, Clifford C

    2007-08-01

    Detailed compositional analyses of sedimentary organic matter can provide information on its biotic input, environment of deposition, and level of thermal maturation. Pyrolysis-gas chromatography (py-GC), often coupled with a mass spectrometer (py-GC/MS), is one technique used to provide this information. New developments in comprehensive two-dimensional gas chromatography (GC x GC or 2D-GC), coupled with pyrolysis (py-GC x GC), offer the prospect of providing more complete and quantitative compositional information of complex organic solids, such as kerogen and coals. This study will describe applications of pyrolysis-GC x GC to the characterization of petroleum source rocks using flame ionization detector (FID) and sulfur chemiluminescence detector (SCD). In the hydrocarbon analysis by FID, paraffins, naphthenes, and aromatics form distinct two-dimensional separated groups. In the analysis with SCD, sulfur-containing compounds can be distinguished as different classes, such as mercaptans, sulfides, thiophenes, benzothiophenes, and dibenzothiophenes. Single components or summed bands of homologous components can be analyzed qualitatively and quantitatively. With these detailed molecular fingerprints, the relations between kerogen composition and its biotic input, environment of deposition, and thermal maturation may be better understood. PMID:17585835

  16. Effect of Olefins on Formation of Sulfur Compounds in FCC Gasoline

    Institute of Scientific and Technical Information of China (English)

    Tang Jinlian; Xu Youhao; Gong Jianhong; Wang Xieqing

    2008-01-01

    The effect of olefins on formation of sulfur compounds in FCC gasoline was studied in a small-scale fixed fluidized bed (FFB) unit at temperatures ranging from 400℃ to 500℃, a weight hourly space velocity (WHSV) of 10 h-1, and a catalyst/oil ratio of 6. The results showed that C4-C6 olefins contained in the FCC gasoline could react with H2S to form predominantly thiophenes, alkyl-thiophenes as well as a fractional amount of thiols, while large molecular olefins such as heptene could react with hydrogen sulfide to form benzothiophenes. The amount of sulfur compounds formed at different tem-peratures over different catalysts were in proportion to the mass fractions of olefins in the feedstock,with the amount of sulfur compounds formed over REUSY catalyst exceeding those formed over the shape selective zeolite catalyst owing to the effect of catalyst performance and the impact of catalyst on the degree of olefin conversion. The amount of sulfur compounds generated and their increase reached a maximum at 450℃ and a minimum at 400℃ because of the influence of temperature on the thermody-namic and kinetic constants for formation of sulfur compound as well as on the olefin conversion degree.Based on the above-mentioned study, a reaction network and a model for prediction of sulfur com-pounds generated upon reaction of olefins in FCC gasoline with H2S were established.

  17. Desulfurization of dibenzothiophene (DBT) by a novel strain Lysinibacillus sphaericus DMT-7 isolated from diesel contaminated soil.

    Science.gov (United States)

    Bahuguna, Ashutosh; Lily, Madhuri K; Munjal, Ashok; Singh, Ravindra N; Dangwal, Koushalya

    2011-01-01

    A new bacterial strain DMT-7 capable of selectively desulfurizing dibenzothiophene (DBT) was isolated from diesel contaminated soil. The DMT-7 was characterized and identified as Lysinibacillus sphaericus DMT-7 (NCBI GenBank Accession No. GQ496620) using 16S rDNA gene sequence analysis. The desulfurized product of DBT, 2-hydroxybiphenyl (2HBP), was identified and confirmed by high performance liquid chromatography analysis and gas chromatography-mass spectroscopy analysis respectively. The desulfurization kinetics revealed that DMT-7 started desulfurization of DBT into 2HBP after the lag phase of 24 hr, exponentially increasing the accumulation of 2HBP up to 15 days leading to approximately 60% desulfurization of the DBT. However, further growth resulted into DBT degradation. The induced culture of DMT-7 showed shorter lag phase of 6 hr and early onset of stationary phase within 10 days for desulfurization as compared to that of non-induced culture clearly indicating the inducibility of the desulfurization pathway of DMT-7. In addition, Lysinibacillus sphaericus DMT-7 also possess the ability to utilize broad range of substrates as sole source of sulfur such as benzothiophene, 3,4-benzo DBT, 4,6-dimethyl DBT, and 4,6-dibutyl DBT. Therefore, Lysinibacillus sphaericus DMT-7 could serve as model system for efficient biodesulfurization of diesel and petrol.

  18. Desulfurization of dibenzothiophene (DBT) by a novel strain Lysinibacillus sphaericus DMT-7 isolated from diesel contaminated soil

    Institute of Scientific and Technical Information of China (English)

    Ashutosh Bahuguna; Madhuri K. Lily; Ashok Munjal; Ravindra N. Singh; Koushalya Dangwal

    2011-01-01

    A new bacterial strain DMT-7 capable of selectively desulfurizing dibenzothiophene (DBT) was isolated from diesel contaminated soil.The DMT-7 was characterized and identified as Lysinibacillus sphaericus DMT-7 (NCBI GenBank Accession No.GQ496620) using 16S rDNA gene sequence analysis.The desulfurized product of DBT, 2-hydroxybiphenyl (2HBP), was identified and confirmed by high performance liquid chromatography analysis and gas chromatography-mass spectroscopy analysis respectively.The desulfurization kinetics revealed that DMT-7 started desulfurization of DBT into 2HBP after the lag phase of 24 hr, exponentially increasing the accumulation of 2HBP up to 15 days leading to approximately 60% desulfurization of the DBT.However, further growth resulted into DBT degradation.The induced culture of DMT-7 showed shorter lag phase of 6 hr and early onset of stationary phase within 10 days for desulfurization as compared to that of non-induced culture clearly indicating the inducibility of the desulfurization pathway of DMT-7.In addition, Lysinibacillus sphaericus DMT-7 also possess the ability to utilize broad range of substrates as sole source of sulfur such as benzothiophene, 3,4-benzo DBT, 4,6-dimethyl DBT, and 4,6-dibutyl DBT.Therefore, Lysinibacillus sphaericus DMT-7 could serve as model system for efficient biodesulfurization of diesel and petrol.

  19. Mesoporous Phosphate Heterostructures: Synthesis and Application on Adsorption and Catalysis

    Science.gov (United States)

    Moreno-Tost, Ramón; Jiménez-Jiménez, José; Infantes-Molina, Antonia; Cavalcante, Celio L.; Azevedo, Diana C. S.; Soriano, María Dolores; López Nieto, José Manuel; Jiménez-López, Antonio; Rodríguez-Castellón, Enrique

    Porous phosphate heterostructures (PPHs) are solids formed by a layered metal(IV) phosphate expanded with silica galleries obtained by combining the two main strategies for obtaining mesoporous materials [pillared layered structures (PLS') and MCM-41]. The different synthetic pathways for obtaining mesoporous phosphate structures with silica galleries with Zr- or Ti-doped silica, the study of their structural, textural and acid properties, its functionalisation with different organic substances such as propionitrile, 3-aminopropyl triethoxysilane, (3-mercaptopropyl)trimethoxysilane, vinyltrimethoxysilane, phenyltriethoxysilane and 3-(triethoxysilyl)propionitrile are discussed. The preparation of metal-supported catalysts and their application in gas separation, adsorption and catalysis are reviewed. Specifically, the use of Cu- and Fe-exchanged PPH for the adsorption of benzothiophene and the separation of propane/propene is the main application as adsorbent. The hydrotreating of aromatic hydrocarbons using ruthenium-impregnated catalysts via hydrogenation and hydrogenolysis/hydrocracking for the production of clean diesel fuels, the selective catalytic reduction of NO from stationary and mobile sources by using Cu-PPH with 1, 3 and 7 wt% of Cu and the selective oxidation of hydrogen sulphide to sulphur with vanadium-containing PPH are the three catalytic reactions of environmental interest studied.

  20. Hydroxylation activity of P450 BM-3 mutant F87V towards aromatic compounds and its application to the synthesis of hydroquinone derivatives from phenolic compounds.

    Science.gov (United States)

    Sulistyaningdyah, Woro Triarsi; Ogawa, Jun; Li, Qing-Shan; Maeda, Chiharu; Yano, Yuki; Schmid, Rolf D; Shimizu, Sakayu

    2005-06-01

    Cytochrome P450 BM-3 from Bacillus megaterium is a fatty acid hydroxylase exhibiting selectivity for long-chain substrates (12-20 carbons). Replacement of Phe87 in P450 BM-3 by Val (F87V) greatly increased its activity towards a variety of aromatic and phenolic compounds. The apparent initial reaction rates of F87V as to benzothiophene, indan, 2,6-dichlorophenol, and 2-(benzyloxy)phenol were 227, 204, 129, and 385 nmol min(-1) nmol(-1) P450, which are 220-, 66-, 99-, and 963-fold those of the wild type, respectively. These results indicate that Phe87 plays a critical role in the control of the substrate specificity of P450 BM-3. Furthermore, F87V catalyzed regioselective hydroxylation at the para position of various phenolic compounds. In particular, F87V showed high activity as to the hydroxylation of 2-(benzyloxy)phenol to 2-(benzyloxy)hydroquinone. With F87V as the catalyst, 0.71 mg ml(-1) 2-(benzyloxy)hydroquinone was produced from 1.0 mg ml(-1) 2-(benzyloxy)phenol in 4 h, with a molar yield of 66%.

  1. Heterogeneous photocatalytic reactions of sulfur aromatic compounds.

    Science.gov (United States)

    Samokhvalov, Alexander

    2011-11-18

    Sulfur aromatic compounds, such as mono-, di-, tri-, and tetraalkyl-substituted thiophene, benzothiophenes, dibenzothiophenes, are the molecular components of many fossils (petroleum, oil shale, tar sands, bitumen). Structural units of natural, cross-linked heteroaromatic polymers present in brown coals, turf, and soil are similar to those of sulfur aromatic compounds. Many sulfur aromatic compounds are found in the streams of petroleum refining and upgrading (naphthas, gas oils) and in the consumer products (gasoline, diesel, jet fuels, heating fuels). Besides fossils, the structural fragments of sulfur aromatic compounds are present in molecules of certain organic semiconductors, pesticides, small molecule drugs, and in certain biomolecules present in human body (pheomelanin pigments). Photocatalysis is the frontier area of physical chemistry that studies chemical reactions initiated by absorption of photons by photocatalysts, that is, upon electronic rather than thermal activation, under "green" ambient conditions. This review provides systematization and critical review of the fundamental chemical and physicochemical information on heterogeneous photocatalysis of sulfur aromatic compounds accumulated in the last 20-30 years. Specifically, the following topics are covered: physicochemical properties of sulfur aromatic compounds, major classes of heterogeneous photocatalysts, mechanisms and reactive intermediates of photocatalytic reactions of sulfur aromatic compounds, and the selectivity of these reactions. Quantum chemical calculations of properties and structures of sulfur aromatic compounds, their reactive intermediates, and the structure of adsorption complexes formed on the surface of the photocatalysts are also discussed.

  2. Carotenoids play a positive role in the degradation of heterocycles by Sphingobium yanoikuyae.

    Directory of Open Access Journals (Sweden)

    Xiaorui Liu

    Full Text Available BACKGROUND: Microbial oxidative degradation is a potential way of removing pollutants such as heterocycles from the environment. During this process, reactive oxygen species or other oxidants are inevitably produced, and may cause damage to DNA, proteins, and membranes, thereby decreasing the degradation rate. Carotenoids can serve as membrane-integrated antioxidants, protecting cells from oxidative stress. FINDINGS: Several genes involved in the carotenoid biosynthetic pathway were cloned and characterized from a carbazole-degrading bacterium Sphingobium yanoikuyae XLDN2-5. In addition, a yellow-pigmented carotenoid synthesized by strain XLDN2-5 was identified as zeaxanthin that was synthesized from β-carotene through β-cryptoxanthin. The amounts of zeaxanthin and hydrogen peroxide produced were significantly and simultaneously enhanced during the biodegradation of heterocycles (carbazole < carbazole + benzothiophene < carbazole + dibenzothiophene. These higher production levels were consistent with the transcriptional increase of the gene encoding phytoene desaturase, one of the key enzymes for carotenoid biosynthesis. CONCLUSIONS/SIGNIFICANCE: Sphingobium yanoikuyae XLDN2-5 can enhance the synthesis of zeaxanthin, one of the carotenoids, which may modulate membrane fluidity and defense against intracellular oxidative stress. To our knowledge, this is the first report on the positive role of carotenoids in the biodegradation of heterocycles, while elucidating the carotenoid biosynthetic pathway in the Sphingobium genus.

  3. Atmospheric pressure chemical ionization Fourier transform ion cyclotron resonance mass spectrometry for complex thiophenic mixture analysis

    KAUST Repository

    Hourani, Nadim

    2013-10-01

    Rationale Polycyclic aromatic sulfur heterocycles (PASHs) are detrimental species for refining processes in petroleum industry. Current mass spectrometric Methods that determine their composition are often preceded by derivatization and dopant addition approaches. Different ionization Methods have different impact on the molecular assignment of complex PASHs. The analysis of such species under atmospheric pressure chemical ionization (APCI) is still considered limited due to uncontrolled ion generation with low- and high-mass PASHs. Methods The ionization behavior of a model mixture of five selected PASH standards was investigated using an APCI source with nitrogen as the reagent gas. A complex thiophenic fraction was separated from a vacuum gas oil (VGO) and injected using the same method. The samples were analyzed using Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS). RESULTS PASH model analytes were successfully ionized and mainly [M + H]+ ions were produced. The same ionization pattern was observed for the real thiophenic sample. It was found that S1 class species were the major sulfur-containing species found in the VGO sample. These species indicated the presence of alkylated benzothiophenic (BT), dibenzothiophenic (DBT) and benzonaphthothiophenic (BNT) series that were detected by APCI-FTICR MS. CONCLUSIONS This study provides an established APCI-FTICR MS method for the analysis of complex PASHs. PASHs were detected without using any derivatization and without fragmentation. The method can be used for the analysis of S-containing crude oil samples. © 2013 John Wiley & Sons, Ltd.

  4. Chemistry and morphology of coal liquefaction. Quarterly report, January 1, 1984-March 31, 1984

    Energy Technology Data Exchange (ETDEWEB)

    Heinemann, H.

    1984-04-01

    In task 1, selective synthesis of gasoline-range components from synthesis gas, rate expressions were developed for four different iron catalysts (promoted and unpromoted). Data for all four catalysts can be correlated by a semi-empirical expression. In task 2 catalyzed low temperature reactions of carbon and water, the catalytic activity for the production of hydrocarbons from graphite and water over KOH plus a co-catalyst was investigated for several first row transition metals. NiO showed the greatest activity. Several samples of /sup 13/CO, /sup 13/CO/sub 2/ and H/sub 2/O adsorbed on graphite and on catalyst-graphite systems after reaction with steam were prepared for NMR investigation. In task 3 chemistry of coal solubilization and liquefaction, rate studies of quinoline reduction to tetrahydroquinoline in the presence of the homogeneous catalysts (phi/sub 3/P)/sub 3/RhCl have provided definitive evidence that benzothiophene, indole, pyrrole, carbazole, thiophene, p-cresol and dibenzothiophene enhance the initial rate of hydrogenation of quinoline by a factor greater than 1.5. P-cresol was found to enhance the initial rate of hydrogenation of quinoline (1.6 to 2 fold) in a model coal liquid with polymer-supported (2% cross-linked) (phi/sub 3/P)/sub 3/ RhCl. 2 references, 6 figures.

  5. Flash pyrolysis of coal, coal maceral, and coal-derived pyrite with on-line characterization of volatile sulfur compounds

    Science.gov (United States)

    Chou, I.-Ming; Lake, M.A.; Griffin, R.A.

    1988-01-01

    A Pyroprobe flash pyrolysis-gas chromatograph equipped with a flame photometric detector was used to study volatile sulfur compounds produced during the thermal decomposition of Illinois coal, coal macerals and coal-derived pyrite. Maximum evolution of volatile organic sulfur compounds from all coal samples occurred at a temperature of approximately 700??C. At this temperature, the evolution of thiophene, its alkyl isomers, and short-chain dialkyl sulfide compounds relative to the evolution of benzothiophene and dibenzothiophene compounds was greater from coal high in organic sulfur than from coal low in organic sulfur. The variation in the evolution of sulfur compounds observed for three separate coal macerals (exinite, vitrinite, and inertinite) was similar to that observed for whole coal samples. However, the variation trend for the macerals was much more pronounced. Decomposition of coal-derived pyrite with the evolution of elemental sulfur was detected at a temperature greater than 700??C. The results of this study indicated that the gas chromotographic profile of the volatile sulfur compounds produced during flash pyrolysis of coals and coal macerals varied as a function of the amount of organic sulfur that occurred in the samples. Characterization of these volatile sulfur compounds provides a better understanding of the behavior of sulfur in coal during the thermolysis process, which could be incorporated in the design for coal cleaning using flash pyrolysis techniques. ?? 1988.

  6. Study of thermochemical sulfate reduction mechanism using compound specific sulfur isotope analysis

    Science.gov (United States)

    Alexander Meshoulam,; Ellis, Geoffrey S.; Ward Said Ahmad,; Andrei Deev,; Alex L. Sessions,; Yongchun Tang,; Jess Adkins,; Liu Jinzhong,; William P. Gilhooly III,; Zeev Aizenshtat,; Alon Amrani,

    2016-01-01

    The sulfur isotopic fractionation associated with the formation of organic sulfur compounds (OSCs) during thermochemical sulfate reduction (TSR) was studied using gold-tube pyrolysis experiments to simulate TSR. The reactants used included n-hexadecane (n-C16) as a model organic compound with sulfate, sulfite, or elemental sulfur as the sulfur source. At the end of each experiment, the S-isotopic composition and concentration of remaining sulfate, H2S, benzothiophene, dibenzothiophene, and 2-phenylthiophene (PT) were measured. The observed S-isotopic fractionations between sulfate and BT, DBT, and H2S in experimental simulations of TSR correlate well with a multi-stage model of the overall TSR process. Large kinetic isotope fractionations occur during the first, uncatalyzed stage of TSR, 12.4‰ for H2S and as much as 22.2‰ for BT. The fractionations decrease as the H2S concentration increases and the reaction enters the second, catalyzed stage. Once all of the oxidizable hydrocarbons have been consumed, sulfate reduction ceases and equilibrium partitioning then dictates the fractionation between H2S and sulfate (∼17‰).

  7. 氧化-萃取脱除柴油中噻吩类硫化物研究进展%Progresses on Oxidation-Extraction Desulfurization of Thiophenic Sulfur Compounds in Diesel Oil

    Institute of Scientific and Technical Information of China (English)

    王广建; 张晋; 郭娜娜

    2012-01-01

    近年来针对柴油中噻吩类硫化物的脱除问题国内外进行了多种非加氢脱硫技术研究,其中氧化脱硫、萃取脱硫、氧化-萃取脱硫技术是研究较多、具有应用前景的脱硫方法。本文从柴油氧化-萃取脱除噻吩类硫化物的反应机理出发,重点概述了有机酸、酸酐催化体系、离子液体催化体系及分子筛催化体系氧化-萃取脱除噻吩类硫化物获得低硫柴油的最新研究成果,并提出了目前存在的问题及该领域未来的研究方向。%In recent years, various non-hydrodesulfurization techniques, including oxidation desulfurization (ODS) , extraction desulfurization (EDS) and oxidation-extraction desulfurization (ODS-EDS) , have been studied to eliminate thiophenic sulfur compounds from diesel fuels, of which oxidation-extraction desulfurization (ODS-EDS) is the most promising method. The reaction mechanism of ODS-EDS processing of thiophenes, consisting of thiophene (TH), benzothiophene (BT), dibenzothiophene (DBT), as well as the progresses of ODS-EDS in organic acid, anhydride catalytic system, ionic liquid catalytic system and molecular sieve catalytic system were elaborated in this paper. Besides, the shortcomings and the prospects of future development of the ODS-EDS technique were discussed.

  8. Oxidative desulfurization of fuels catalyzed by Fenton-like ionic liquids at room temperature.

    Science.gov (United States)

    Jiang, Yunqing; Zhu, Wenshuai; Li, Huaming; Yin, Sheng; Liu, Hua; Xie, Qingjie

    2011-03-21

    Oxidation of the sulfur-containing compounds benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT) has been studied in a desulfurization system composed of model oil, hydrogen peroxide, and different types of ionic liquids [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3), [(C(8)H(17))(3)CH(3)N]Cl/CuCl(2), [(C(8)H(17))(3)CH(3)N]Cl/ZnCl(2), [(C(8)H(17))(3)CH(3)N]Cl/SnCl(2), [(C(4)H(9))(3)CH(3)N]Cl/FeCl(3), [C(10)H(21)(CH(3))(3)N]Cl/FeCl(3), [(C(10)H(21))(2)(CH(3))(2)N]Cl/FeCl(3). Deep desulfurization is achieved in the Fenton-like ionic liquid [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) at 25 °C for 1 h. The desulfurization of DBT reaches 97.9%, in consuming very low amount of [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) (only 0.702 mmol). The reaction conditions, for example, the amount of [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) or H(2)O(2), the temperature, and the molar ratio of FeCl(3) to [(C(8)H(17))(3)CH(3)N]Cl, are investigated for this system. The oxidation reactivity of the different sulfur-containing compounds is found to decrease in the order of DBT>BT>4,6-DMDBT. The desulfurization system can be recycled six times without significant decrease in activity. The sulfur level of FCC gasoline could be reduced from 360 ppm to 110 ppm. PMID:21394927

  9. Synthesis and application of different phthalocyanine molecular sieve catalyst for oxidative desulfurization

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Na; Li, Siwen; Wang, Jinyi; Zhang, Ronglan [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry & Material Science, Northwest University, Xi’an 710069, Shaanxi (China); Composites Research Institute, Weinan Normal University, Weinan 714000 (China); Gao, Ruimin [Research Institute of Shaanxi Yanchang Petroleum Group Corp. Ltd., Xi’an 710075 (China); Composites Research Institute, Weinan Normal University, Weinan 714000 (China); Zhao, Jianshe, E-mail: jszhao@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry & Material Science, Northwest University, Xi’an 710069, Shaanxi (China); Composites Research Institute, Weinan Normal University, Weinan 714000 (China); Wang, Junlong [Research Institute of Shaanxi Yanchang Petroleum Group Corp. Ltd., Xi’an 710075 (China); Composites Research Institute, Weinan Normal University, Weinan 714000 (China)

    2015-05-15

    M{sub 2}(PcAN){sub 2} (M=Fe, Co, Ni, Cu, Zn and Mn) anchored onto W-HZSM-5 (M{sub 2}(PcAN){sub 2}–W-HZSM-5) or the M{sub 2}(PcTN){sub 2} doping W-HZSM-5 (M{sub 2}(PcTN){sub 2}/W-HZSM-5) were prepared and their catalytic performances were tested for oxidative desulfurization in the presence of oxygen. Thiophene (T), benzothiophene (BT), and dibenzothiophene (DBT) were considered as sulfur compounds. Among zeolite-based catalysts, the Cu{sub 2}(PcAN){sub 2}–W-HZSM-5 and Cu{sub 2}(PcTN){sub 2}/W-HZSM-5 showed superior desulfurization performance and the activity of selectivity followed the order: T>BT>DBT. The effects of phthalocyanine concentration were studied by UV–Vis and calcination temperature was obtained by TG-DSC for Cu{sub 2}(PcTN){sub 2}/W-HZSM-5. Catalysts were characterized by EA, IR, XRD, SEM, TEM, ICP, and N{sub 2} adsorption. Reaction time, temperature and the amount of catalyst were investigated as the important parameters for optimization of the reaction. Furthermore, a possible process of oxidative desulfurization and the reaction products were proposed. - Graphical abstract: The ODS reaction schematic shows the reaction mechanism of ultra-deep desulfurization. The sulfur compounds are oxidized to their corresponding sulfoxides or sulfones through the use of oxygen and catalysts. The reaction process of ultra-deep desulfurization. - Highlights: • A kind of novel catalyst for deep desulfurization was synthesized. • Cu{sub 2}(PcAN){sub 2}–W-HZSM-5 exhibits excellent catalytic performance for desulfurization. • The reaction conditions that affect desulfurization efficiency are investigated. • The reaction process of model sulfur compounds is proposed.

  10. Going Beyond Common Drug Metabolizing Enzymes: Case Studies of Biotransformation Involving Aldehyde Oxidase, γ-Glutamyl Transpeptidase, Cathepsin B, Flavin-Containing Monooxygenase, and ADP-Ribosyltransferase.

    Science.gov (United States)

    Fan, Peter W; Zhang, Donglu; Halladay, Jason S; Driscoll, James P; Khojasteh, S Cyrus

    2016-08-01

    The significant roles that cytochrome P450 (P450) and UDP-glucuronosyl transferase (UGT) enzymes play in drug discovery cannot be ignored, and these enzyme systems are commonly examined during drug optimization using liver microsomes or hepatocytes. At the same time, other drug-metabolizing enzymes have a role in the metabolism of drugs and can lead to challenges in drug optimization that could be mitigated if the contributions of these enzymes were better understood. We present examples (mostly from Genentech) of five different non-P450 and non-UGT enzymes that contribute to the metabolic clearance or bioactivation of drugs and drug candidates. Aldehyde oxidase mediates a unique amide hydrolysis of GDC-0834 (N-[3-[6-[4-[(2R)-1,4-dimethyl-3-oxopiperazin-2-yl]anilino]-4-methyl-5-oxopyrazin-2-yl]-2-methylphenyl]-4,5,6,7-tetrahydro-1-benzothiophene-2-carboxamide), leading to high clearance of the drug. Likewise, the rodent-specific ribose conjugation by ADP-ribosyltransferase leads to high clearance of an interleukin-2-inducible T-cell kinase inhibitor. Metabolic reactions by flavin-containing monooxygenases (FMO) are easily mistaken for P450-mediated metabolism such as oxidative defluorination of 4-fluoro-N-methylaniline by FMO. Gamma-glutamyl transpeptidase is involved in the initial hydrolysis of glutathione metabolites, leading to formation of proximate toxins and nephrotoxicity, as is observed with cisplatin in the clinic, or renal toxicity, as is observed with efavirenz in rodents. Finally, cathepsin B is a lysosomal enzyme that is highly expressed in human tumors and has been targeted to release potent cytotoxins, as in the case of brentuximab vedotin. These examples of non-P450- and non-UGT-mediated metabolism show that a more complete understanding of drug metabolizing enzymes allows for better insight into the fate of drugs and improved design strategies of molecules in drug discovery. PMID:27117704

  11. Study on ionizing radiation effects in diesel and crude oil: organic compounds, hydrocarbon, sulfur and nitrogen; Estudo do efeito da radiacao ionizante em compostos organicos do diesel e do petroleo: hidrocarbonetos, sulfurados e nitrogenados

    Energy Technology Data Exchange (ETDEWEB)

    Andrade, Luana dos Santos

    2014-07-01

    Petroleum is the most important energy and pollution source in the world, nowadays. New technologies in petrochemical industry aim to minimize energy spending at the process and to reduce pollution products. Sulfur and nitrogen compounds generate environmental problems; the most relevant is air pollution that affects the population health directly. The nuclear technology has been used in environmental protection through pollutants removal by free radicals produced at action of the radiation in water molecule. The objective of this study is to evaluate the radiation effects on oil and diesel, mainly in the hydrocarbons, organic sulfur, and nitrogen compounds. It was studied a molecule model of sulfur, named benzothiophene, diesel and crude oil samples. The samples were irradiated using a Co-60 source, Gammacell type. The total sulfur concentration in the samples was determined by X-ray fluorescence spectrometry, and organic compounds were analyzed by gas chromatography coupled to mass spectrometry (GC-MS). The study of molecular model showed that 95% was degraded at 20 kGy dose rate. Irradiation at 15 kGy of absorbed dose showed some cracking in petrol hydrocarbons, however with higher doses it was observed polymerization and low efficiency of cracking. It was observed that the sulfur compounds from diesel and petroleum was efficiently reduced. The applied doses of 15 kGy and 30 kGy were the most efficient on desulfurization of petroleum, and for diesel the highest variation was observed with 30 kGy and 50 kGy of absorbed dose. The distillation and chromatographic separation using an open column with palladium chloride as stationary phase showed a preferential separation of organic sulfur compounds in petroleum. (author)

  12. Applications of Ferrate(VI) to Wastewater Reclamation and Water Treatment

    Science.gov (United States)

    Kim, H.; Choi, H.; Lee, K.; Nam, J.; Kim, I.

    2010-12-01

    The estimated amount of water resources is about 63 billion cubic meters in Korea. However, due to the lack of precipitation during the dry season, natural flows are not enough for the water supply. In addition, since the lack of water affects water quality, environmental problems are occurred in natural and social systems. In this study, we investigated the application feasibility of ferrate(VI) systems to water and wastewater treatment. And we'd like to suggest an alternative solution for conservation and efficient reuse of the limited water resources. In the research area of environmental applications, a primary interest has been focused to the power of ferrate(VI) systems in the decomposition of pollutants in wastewater and industrial effluents due to its potential use as a strong, relatively non-toxic, and oxidizing agent for diverse environmental contaminants. Also ferrate(VI) has additional advantages as a very efficient coagulant and a sorbent of pollutants. We have analysed and compared several ferrate(VI) manufacturing processes, especially focused on the electro chemical methods(Fig. 1). And we have investigated the applications of the manufactured ferrate(VI) in our own laboratory and the commercial ferrate(VI) to decomposition of persistent organic pollutants in water. Under optimal conditions, the removal efficiencies of 2-chlorophenol and benzothiophene were above 90%(Fig. 2). The ferrate system(VI) is promising and can be one of the most efficient alternatives among the advanced oxidation processes(AOPs) for degradation of persistent organic pollutants, and is an innovative technology for the wastewater reclamation, water reusing systems, and water treatment systems. Fig 1. Comparison of Electro-Chemical Ferrate(VI) manufacturing Processes Fig 2. Degradation of 2-Chlorophenol and Bezothiophene by Ferrate. (Experimental Conditions : 2-CP = 3ppm, BT = 5ppm, NaClO4 = 0.05M)

  13. The enhanced adsorption of sulfur compounds onto mesoporous Ni-AlKIT-6 sorbent, equilibrium and kinetic analysis

    Energy Technology Data Exchange (ETDEWEB)

    Subhan, Fazle, E-mail: fazle@awkum.edu.pk [Department of Chemistry, Abdul Wali Khan University, Mardan, K.P.K (Pakistan); State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580 (China); Yan, Zifeng, E-mail: zfyancat@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580 (China); Peng, Peng [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580 (China); Ikram, Muhammad [Department of Chemistry, Abdul Wali Khan University, Mardan, K.P.K (Pakistan); Rehman, Sadia [Department of Chemistry, Sarhad University of Science and Information Technology, Peshawar, K.P.K (Pakistan)

    2014-04-01

    Highlights: • High stable and regenerable 20%Ni-AlKIT-6(15) were synthesized. • High dispersion of nickel correlated with ultrasonic dispersion and three-dimensional pore network of AlKIT-6(15). • Sulfur adsorption capacity increases with increasing Lewis acid sites. • The kinetic pseudo second-order model and Langmuir isotherm fit the adsorption of sulfur compounds. - Abstract: High performance nickel supported on mesoporous AlKIT-6 (Si/Al = 15, 25, 50, 100) sorbents were prepared by incipient wetness impregnation (IWI) with ultrasonic aid for adsorptive desulfurization of commercial diesel and simulated fuels. The sorbents were characterized by N{sub 2} adsorption–desorption, XRD, NH{sub 3}-TPD, Py-FT-IR, HRTEM, SEM and atomic absorption spectroscopy techniques. The analysis results confirmed that Aluminum atoms entered the framework and 20%Ni-AlKIT-6(15) can still retain three dimensional structure of AlKIT-6(15) and Ni is highly dispersed in the support. The kinetic pseudo second-order model and Langmuir isotherm are shown to exhibits the best fits of experimental data for the adsorption of thiophene (T), benzothiophene (BT) and dibenzothiophene (DBT) over AlKIT-6 and 5–30%Ni-AlKIT-6. Intraparticle diffusion and steric hindrance were the rate controlling step of the adsorption of T and DBT over AlKIT-6(15) and 20%Ni-AlKIT-6(15) as verified through the intraparticle diffusion model. The characterization of regenerated 20%Ni-AlKIT-6(15) revealed that three-dimensional cubic Ia3d symmetric structure was maintained in the sorbent after 6 successive desulfurization–regeneration cycles.

  14. SULFUR REDUCTION IN GASOLINE AND DIESEL FUELS BY EXTRACTION/ADSORPTION OF REFRACTORY DIBENZOTHIOPHENES

    Energy Technology Data Exchange (ETDEWEB)

    Robert J. Angelici

    2003-06-01

    Refractory 4,6-dimethyldibenzothiophene, which is difficult to remove from petroleum feedstocks, binds to the Ru in Ru(NH{sub 3}){sub 5}(H{sub 2}O){sup 2+} by displacing the H{sub 2}O ligand. Thiophene, benzothiophene and dibenzothiophene (DBT) also react with Ru(NH{sub 3}){sub 5}(H{sub 2}O){sup 2+} similarly. This binding ability of Ru(NH{sub 3}){sub 5}(H{sub 2}O){sup 2+} has been used to remove over 50% of the DBT in simulated petroleum feedstocks by a biphasic extraction process. The extraction phase is readily regenerated by air-oxidation thereby completing a cyclic process that removes DBT from petroleum feedstocks. Solid phase extractants consisting of Ru(NH{sub 3}){sub 5}(H{sub 2}O){sup 2+}, CpRu(CO){sub 2}(BF{sub 4}), CpFe(CO){sub 2}(C{sub 4}H{sub 8}){sup +} and AgX (where X = BF{sub 4}{sup -}, PF{sub 6}{sup -} or NO{sub 3}{sup -}) adsorbed on silica have also been used to remove DBT and 4,6-Me{sub 2}DBT from simulated petroleum feedstocks. The AgX/silica adsorbents remove 90% of the DBT and 4,6-Me{sub 2}DBT and can be regenerated and re-used for multiple extractions, which makes these adsorbents of potential industrial use for the removal of refractory dibenzothiophenes from petroleum feedstocks.

  15. Analysis of the reactivity of sulphur compounds in petroleum cuts: kinetics and modelling of hydro-treating; Analyse de la reactivite des composes soufres dans les coupes petrolieres: cinetique et modelisation de l'hydrotraitement

    Energy Technology Data Exchange (ETDEWEB)

    Lopez Garcia, C.

    2000-12-01

    The study of the hydro-treating of middle distillates comprised the following steps: - Identification and reactivity study of the sulphur compounds present in these petroleum cuts; - Modelling of the process by a chemical kinetic approach. The hydro-treating of middle distillates is a refining process that allows elimination of organic compounds containing sulphur, nitrogen, oxygen and metals. The process also hydrogenates the aromatic compounds providing improved cetane index gas-oils while respecting the regulations that severely limit the content of sulphur compounds. The extension and the improvement of a kinetic model for the hydro-treating of LCO gas-oils (light cycle oil gas-oils) are presented in this work. In order to improve the hydro-desulfurization model predictions, a detailed identification of the sulphur compounds contained in LCO gas-oils was carried out using gas chromatography with a sulphur chemiluminescence detector (GC-SCD). The most refractory sulphur compounds (alkyl-di-benzothiophenes) were identified and lumped into different families. Based on a lumped reaction scheme with a Langmuir-Hinshelwood representation, the model takes into account the influence of temperature, total pressure and hydrogen sulphide partial pressure on the reaction rates for hydro-desulfurization, hydro-denitrogenation and hydro-de-aromatization. The model parameter estimation was based on experiments that were carried out on a micro-pilot unit using an industrial sulfided NiMo/Al{sub 2}O{sub 3} catalyst and LCO feedstocks. The analytical study of the sulphur compounds was also extended to the case of straight run gas-oils (SR). For these feedstocks, a method using high-resolution mass spectrometry coupled with gas chromatography (GC-HRMS) was developed. In this way, the kinetic model can now be extended for the SR gas-oil hydro-treating or for LCO-SR mixtures. (author)

  16. Microwave-assisted syntheses of N-heterocycles using alkenone-, alkynone- and aryl-carbonyl O-phenyl oximes: formal synthesis of neocryptolepine.

    Science.gov (United States)

    Portela-Cubillo, Fernando; Scott, Jackie S; Walton, John C

    2008-07-18

    This research aimed to provide a new and "clean" synthetic method that would enable both known and novel N-heterocycles to be prepared efficiently. O-Phenyl oximes were found to be excellent precursors for iminyl radicals with a variety of acceptor side chains. Dihyropyrroles were made in good yields from O-phenyl oximes containing pent-4-ene acceptors. The analogous process with a hex-5-enyl acceptor did not yield a dihydropyridine, probably because the 6-exo-trig ring closure of the iminyl radical was too slow to compete with H-atom abstraction. The iminyl radical from a precursor with a pent-4-yne type side chain underwent ring closure followed by rearrangement to afford a pyrrole derivative. Suitably substituted iminyl radicals ring closed readily onto aromatic acceptors, thus enabling several polycyclic systems to be accessed. Quinolines were made from 3-phenylpropanones via their O-phenyl oximes. Syntheses of phenanthridines starting from 2-formylbiphenyls were particularly efficient, and this approach enabled the natural product trisphaeridine to be made. Starting from 2-phenylnicotinaldehyde derivatives, ring closures of the derived iminyl radicals onto the phenyl rings yielded benzo[h][1,6]naphthyridines. Similarly, ring closure onto a phenyl ring from a benzothiophene-based iminyl yielded a benzo[b]thieno[2,3-c]quinoline. By way of contrast, iminyl radical ring closure onto pyridine rings was not observed. However, iminyl radicals did cyclize onto indoles, enabling indolopyridines to be prepared. The latter route was exploited in a short formal synthesis of neocryptolepine starting from 2-((1H-indol-3-yl)methyl)cyclohexanone.

  17. Study on ionizing radiation effects in diesel and crude oil: organic compounds, hydrocarbon, sulfur and nitrogen

    International Nuclear Information System (INIS)

    Petroleum is the most important energy and pollution source in the world, nowadays. New technologies in petrochemical industry aim to minimize energy spending at the process and to reduce pollution products. Sulfur and nitrogen compounds generate environmental problems; the most relevant is air pollution that affects the population health directly. The nuclear technology has been used in environmental protection through pollutants removal by free radicals produced at action of the radiation in water molecule. The objective of this study is to evaluate the radiation effects on oil and diesel, mainly in the hydrocarbons, organic sulfur, and nitrogen compounds. It was studied a molecule model of sulfur, named benzothiophene, diesel and crude oil samples. The samples were irradiated using a Co-60 source, Gammacell type. The total sulfur concentration in the samples was determined by X-ray fluorescence spectrometry, and organic compounds were analyzed by gas chromatography coupled to mass spectrometry (GC-MS). The study of molecular model showed that 95% was degraded at 20 kGy dose rate. Irradiation at 15 kGy of absorbed dose showed some cracking in petrol hydrocarbons, however with higher doses it was observed polymerization and low efficiency of cracking. It was observed that the sulfur compounds from diesel and petroleum was efficiently reduced. The applied doses of 15 kGy and 30 kGy were the most efficient on desulfurization of petroleum, and for diesel the highest variation was observed with 30 kGy and 50 kGy of absorbed dose. The distillation and chromatographic separation using an open column with palladium chloride as stationary phase showed a preferential separation of organic sulfur compounds in petroleum. (author)

  18. Hydrodesulfurization catalyst prepared by urea-matrix combustion method

    Institute of Scientific and Technical Information of China (English)

    Dongmei Jiao; Yeyong Ma; Fahai Cao

    2012-01-01

    Co-Mo/γ-Al2O3-TiO2 hydrodesulfurization (HDS) catalyst samples prepared by a urea matrix combustion (UMxC) method,were evaluated in a stainless tubular fixed-bed reactor,with thiophene,benzothiophene and dibenzothiophene in xylene as model feedstocks.The samples were pre-sulfurized using a cyclohexane solution of 3% CS2 and then tested for the HDS reaction.The test results were compared with catalysts prepared by conventional methods involving sequential impregnation (SI) and co-impregnation (CI).The catalysts were characterized using X-ray diffraction (XRD),laser Raman spectroscopy (LRS),high resolution transmission electron microscopy (HRTEM) and N2 physisorption,showing that the UMxC catalyst had higher pore volume and surface area than those prepared by the CI and SI methods.The UMxC method increased metal loading and avoided formation of inert phase,e.g.,β-CoMoO4,for the HDS reaction,suggesting that UMxC method is superior to the conventional impregnation techniques.TiO2 promoter made particles on the catalyst surface closer and alleviated the interaction between molybdenum oxide and the support,and facilitated the formation of well-dispersed Co- and Mo-oxo species on catalyst surface,thus resulting in higher HDS catalytic activity than pure -γ-Al2O3 support without modifiers.Consequently,the addition of TiO2 obviously improved the HDS conversion of dibenzothiophene.

  19. Genotoxicity of heterocyclic PAHs in the micronucleus assay with the fish liver cell line RTL-W1.

    Directory of Open Access Journals (Sweden)

    Markus Brinkmann

    Full Text Available Heterocyclic aromatic hydrocarbons are, together with their un-substituted analogues, widely distributed throughout all environmental compartments. While fate and effects of homocyclic PAHs are well-understood, there are still data gaps concerning the ecotoxicology of heterocyclic PAHs: Only few publications are available investigating these substances using in vitro bioassays. Here, we present a study focusing on the identification and quantification of clastogenic and aneugenic effects in the micronucleus assay with the fish liver cell line RTL-W1 that was originally derived from rainbow trout (Oncorhynchus mykiss. Real concentrations of the test items after incubation without cells were determined to assess chemical losses due to, e.g., sorption or volatilization, by means of gas chromatography-mass spectrometry. We were able to show genotoxic effects for six compounds that have not been reported in vertebrate systems before. Out of the tested substances, 2,3-dimethylbenzofuran, benzothiophene, quinoline and 6-methylquinoline did not cause substantial induction of micronuclei in the cell line. Acridine caused the highest absolute induction. Carbazole, acridine and dibenzothiophene were the most potent substances compared with 4-nitroquinoline oxide, a well characterized genotoxicant with high potency used as standard. Dibenzofuran was positive in our investigation and tested negative before in a mammalian system. Chemical losses during incubation ranged from 29.3% (acridine to 91.7% (benzofuran and may be a confounding factor in studies without chemical analyses, leading to an underestimation of the real potency. The relative potency of the investigated substances was high compared with their un-substituted PAH analogues, only the latter being typically monitored as priority or indicator pollutants. Hetero-PAHs are widely distributed in the environment and even more mobile, e.g. in ground water, than homocyclic PAHs due to the higher water

  20. Photophysical properties of heteroaromatic ring-fused (di)benzosiloles

    Institute of Scientific and Technical Information of China (English)

    SHIMIZU Masaki; MOCHIDA Kenji; KATOH Masaki; HIYAMA Tamejiro

    2012-01-01

    Benzosiloles fused to heterocycles such as thiophene,benzothiophene,and benzofuran,and indole- and benzosilole-fused dibenzosiloles were prepared by palladium-catalyzed intramolecular coupling of the corresponding 2-(arylsilyl)aryl triflates in good to high yields.Molecular and crystal structures of 5,7-dihydro-5,5,7,7-tetrakis(1- methylethyl)bis[1]benzosilolo-[2,3-b:3',2'-d]thiophene,6-methyl- 12,12-diisopropyl- 12H-indololo[3,2-b][ 1 ]silafluorene,and 5,5,11,11-tetraisopropyl-5,11H-benzosi lolo[3,2-c]silafluorene were determined by X-ray diffraction analysis.The UV absorption spectra of the (di)benzosilole derivatives in cyclohexane red-shifted when compared to 1,1-diisopropyldibenzosilole,indicating that replacing a benzene ring of dibenzosilole by the heterocycles as well as fusion of indole and benzosilole moieties onto dibenzosilole narrowed the HOMO-LUMO gaps of the π-conjugation system.The thiophene-fused benzosiloles were faintly fluorescent in solution and in the solid state,whereas the dibenzosiloles exhibited luminescence with moderate and high quantum yields in cyclohexane and in microcrystals,respectively.In other words,aggregation-induced emission was observed for the dibenzosiloles.Notably,5,5,11,11- tetraisopropyl-5,11 H-benzosilolo[3,2-c]silafluorene in microcrystals exhibited violet fluorescence (λmax =396 nm) with a quantum yield of 0.70.Density functional theory (DFT) calculations of the prepared (di)benzosiloles were also performed.

  1. Infrared and Raman spectra of bicyclic molecules using scaled noncorrelated and correlated {ital ab initio} force fields

    Energy Technology Data Exchange (ETDEWEB)

    Collier, W.B. [Department of Chemistry, Oral Roberts University, Tulsa, Oklahoma 74171 (United States); Magdo, I. [Gedeon Richter Ltd., Molecular Design Unit, P.O. Box 27, H-1475, Budapest (Hungary); Klots, T.D. [Bartlesville Thermodynamic Group, BDM Petroleum Technologies, P.O. Box 2543, Bartlesville, Oklahoma 74005 (United States)

    1999-03-01

    This paper reports the application of a scaled {ital ab initio} calculated harmonic force field to predict the frequencies, infrared intensities, Raman intensities, and depolarization ratios of benzofuran, benzothiophene, indole, benzothiazole, and benzoxazole. The theoretical calculations were made using the Hartree{endash}Fock HF/3-21G{sup {asterisk}} and HF/6-31G{sup {asterisk}} basis sets and density-functional theory (DFT)B3-LYP/6-31G{sup {asterisk}} levels. The equilibrium calculated force constants are scaled according to the method of Pulay and compared with the experimentally determined frequencies, intensities, and depolarization ratios to assess the accuracy and fit of the theoretical calculation. Methods for quantitative comparison of intensities were developed. The double numerical differentiation algorithm of Komornicki and McIver was analyzed and used to calculate the Raman intensities for the (DFT)B3-LYP/6-31G{sup {asterisk}} model. The (DFT)B3-LYP/6-31G{sup {asterisk}} model is approaching the harmonic limit in the planar and nonplanar refinement of these bicyclics with wave number fits of 5 and 4 cm{sup {minus}1}, respectively. It reduces the need for scale factors and increases their transfer accuracy, largely because the scale factors values cluster near unity. The Komornicki and McIver algorithm is still a viable method for calculating Raman intensity information for methods that do not have analytic routines programmed. The main shortcoming to this method may lie in the tighter self-consistent field (SCF) convergence criterion possibly needed to calculate Raman intensities for the totally symmetric modes of large molecules. The (DFT)B3-LYP/6-31G{sup {asterisk}} model was superior for calculating the planar intensities, but equal to the HF methods for predicting the nonplanar intensities. {copyright} {ital 1999 American Institute of Physics.}

  2. C-H and N-H bond dissociation energies of small aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Barckholtz, C.; Barckholtz, T.A.; Hadad, C.M.

    1999-01-27

    A survey of computational methods was undertaken to calculate the homolytic bond dissociation energies (BDEs) of the C-H and N-H bonds in monocyclic aromatic molecules that are representative of the functionalities present in coal. These include six-membered rings (benzene, pyridine, pyridazine, pyrimidine, pyrazine) and five-membered rings (furan, thiophene, pyrrole, oxazole). By comparison of the calculated C-H BDEs with the available experimental values for these aromatic molecules, the B3LYP/6-31G(d) level of theory was selected to calculate the BDEs of polycyclic aromatic hydrocarbons (PAHs), including carbonaceous PAHs (naphthalene, anthracene, pyrene, coronene) and heteroatomic PAHs (benzofuran, benzothiophene, indole, benzoxazole, quinoline, isoquinoline, dibenzofuran, carbazole). The cleavage of a C-H or a N-H bond generates a {sigma} radical that is, in general, localized at the site from which the hydrogen atom was removed. However, delocalization of the unpaired electron results in {approximately} 7 kcal {center{underscore}dot} mol{sup {minus}1} stabilization of the radical with respect to the formation of phenyl when the C-H bond is adjacent to a nitrogen atom in the azabenzenes. Radicals from five-membered rings are {approximately} 6 kcal {center{underscore}dot} mol{sup {minus}1} less stable than those formed from six-membered rings due to both localization of the spin density and geometric factors. The location of the heteroatoms in the aromatic ring affects the C-H bond strengths more significantly than does the size of the aromatic network. Therefore, in general, the monocyclic aromatic molecules can be used to predict the C-H BDE of the large PAHs within 1 kcal {center{underscore}dot} mol{sup {minus}1}.

  3. Discovery and Evaluation of Thiazinoquinones as Anti-Protozoal Agents

    Directory of Open Access Journals (Sweden)

    Marcel Kaiser

    2013-09-01

    Full Text Available Pure compound screening has identified the dioxothiazino-quinoline-quinone ascidian metabolite ascidiathiazone A (2 to be a moderate growth inhibitor of Trypanosoma brucei rhodesiense (IC50 3.1 μM and Plasmodium falciparum (K1 dual drug resistant strain (IC50 3.3 μM while exhibiting low levels of cytotoxicity (L6, IC50 167 μM. A series of C-7 amide and Δ2(3 analogues were prepared that explored the influence of lipophilicity and oxidation state on observed anti-protozoal activity and selectivity. Little variation in anti-malarial potency was observed (IC50 0.62–6.5 μM, and no correlation was apparent between anti-malarial and anti-T. brucei activity. Phenethylamide 7e and Δ2(3-glycine analogue 8k exhibited similar anti-Pf activity to 2 but with slightly enhanced selectivity (SI 72 and 93, respectively, while Δ2(3-phenethylamide 8e (IC50 0.67 μM, SI 78 exhibited improved potency and selectivity towards T. brucei rhodesiense compared to the natural product hit. A second series of analogues were prepared that replaced the quinoline ring of 2 with benzofuran or benzothiophene moieties. While esters 10a/10b and 15 were once again found to exhibit cytotoxicity, carboxylic acid analogues exhibited potent anti-Pf activity (IC50 0.34–0.035 μM combined with excellent selectivity (SI 560–4000. In vivo evaluation of a furan carboxylic acid analogue against P. berghei was undertaken, demonstrating 85.7% and 47% reductions in parasitaemia with ip or oral dosing respectively.

  4. Growth directions of C8-BTBT thin films during drop-casting

    Science.gov (United States)

    Iizuka, Naoki; Zanka, Tomohiko; Onishi, Yosuke; Fujieda, Ichiro

    2016-02-01

    Because charge transport in a single crystal is anisotropic, control of its orientation is important for enhancing electrical characteristics and reducing variations among devices. For growing an organic thin film, a solution process such as inkjet printing offers advantages in throughput. We have proposed to apply an external temperature gradient during drop-casting and to control the direction of solvent evaporation. In experiment, a temperature gradient was generated in a bare Si substrate by placing it on a Si plate bridging two heat stages. When a solution containing 2,7-dioctyl [1]benzothieno[3,2-b]benzothiophene (C8-BTBT) was dropped on the substrate, evaporation started at the hotter side of the droplet and proceeded toward the colder side. The front line of the liquid was not pinned and the solution extended toward the colder region. As a result, a thin film was formed in a 7mm-long region. The peripheral region of the film was significantly thicker due to the coffee ring effect. The surface of the rest of the film was mostly smooth and terrace structures with 2.6nm steps were observed. The step roughly corresponds to the length of the C8-BTBT molecule. The film thickness varied from 20nm to 50nm over the distance of 3mm. Another film was grown on a glass substrate under a similar condition. Observation of the film with a polarizing microscope revealed that fan-shaped domains were formed in the film and that their optical axes were mostly along the directions of the solvent evaporation.

  5. Polymer-bound oxidovanadium(IV) and dioxidovanadium(V) complexes as catalysts for the oxidative desulfurization of model fuel diesel.

    Science.gov (United States)

    Maurya, Mannar R; Arya, Aarti; Kumar, Amit; Kuznetsov, Maxim L; Avecilla, Fernando; Costa Pessoa, João

    2010-07-19

    The Schiff base (Hfsal-dmen) derived from 3-formylsalicylic acid and N,N-dimethyl ethylenediamine has been covalently bonded to chloromethylated polystyrene to give the polymer-bound ligand, PS-Hfsal-dmen (I). Treatment of PS-Hfsal-dmen with [V(IV)O(acac)(2)] in the presence of MeOH gave the oxidovanadium(IV) complex PS-[V(IV)O(fsal-dmen)(MeO)] (1). On aerial oxidation in methanol, complex 1 was oxidized to PS-[V(V)O(2)(fsal-dmen)] (2). The corresponding neat complexes, [V(IV)O(sal-dmen)(acac)] (3) and [V(V)O(2)(sal-dmen)] (4) were similarly prepared. All these complexes are characterized by various spectroscopic techniques (IR, electronic, NMR, and electron paramagnetic resonance (EPR)) and thermal as well as field-emission scanning electron micrographs (FE-SEM) studies, and the molecular structures of 3 and 4 were determined by single crystal X-ray diffraction. The EPR spectrum of the polymer supported V(IV)O-complex 1 is characteristic of magnetically diluted V(IV)O-complexes, the resolved EPR pattern indicating that the V(IV)O-centers are well dispersed in the polymer matrix. A good (51)V NMR spectrum could also be measured with 4 suspended in dimethyl sulfoxide (DMSO), the chemical shift (-503 ppm) being compatible with a VO(2)(+)-center and a N,O binding set. The catalytic oxidative desulfurization of organosulfur compounds thiophene, dibenzothiophene, benzothiophene, and 2-methyl thiophene (model of fuel diesel) was carried out using complexes 1 and 2. The sulfur in model organosulfur compounds oxidizes to the corresponding sulfone in the presence of H(2)O(2). The systems 1 and 2 do not loose efficiency for sulfoxidation at least up to the third cycle of reaction, this indicating that they preserve their integrity under the conditions used. Plausible intermediates involved in these catalytic processes are established by UV-vis, EPR, (51)V NMR, and density functional theory (DFT) studies, and an outline of the mechanism is proposed. The (51)V NMR spectra

  6. Catalytic Oxidative Desulfurization of Model Oil by MoO3/Mesoporous Al2O3%MoO3/介孔Al2O3催化氧化脱除模拟油中的硫

    Institute of Scientific and Technical Information of China (English)

    李宇慧; 冯丽娟; 王景刚; 周旋; 程斌斌; 王晓燕; 李春虎

    2011-01-01

    In the MoO3/mesoporous Al203-H2O2 system, a simulated oil consisting of model sulfur compounds, such as benzothiophene (BT), dibenzothiophene (DBT), 4,6-dimethyldibenzothiophene (4,6-DMDBT) and thiophene(Th) and cyclohexane as solvent was employed in the oxidative desulfurization study. The effects of catalyst, dosage of oxidation agent and reaction condition on desulfurization activity were investigated. It was shown that the removal efficiency of DBT at 60 ℃ was as high as 99.4% when the content of MoO3, dosage of catalyst and the molar ratio of H202 to sulfur were 20% ,1.5% and 4, respectively. Under the optimum conditions, the oxidative activity of the model sulfur compounds follows the order of DBT >4,6-DMDBT > BT > Th.%以环己烷为溶剂,二苯并噻吩(DBT)、苯并噻吩(BT)、4,6-二甲基二苯并噻吩(4,6-DMDBT)和噻吩(Th)为模型含硫化合物,配制成模拟油,在MoO3/介孔Al2O3-H2O2体系中对模拟油催化氧化脱硫进行了研究.考察了MoO3负载量、氧化剂用量、催化剂用量、氧化反应温度及反应时间对DBT脱除效果的影响.实验结果表明,在MoO3负载量为20%,催化剂用量为1.5%,氧化剂H2O3与模拟油中硫的摩尔比为4,反应温度为60℃,反应时间为40 min时,DBT脱除率最高(达99.4%),几乎可以被完全脱除;在此条件下模型化合物的氧化反应活性顺序为:DBT>4,6-DMDBT>BT>Th.

  7. Study of thermochemical sulfate reduction mechanism using compound specific sulfur isotope analysis

    Science.gov (United States)

    Meshoulam, Alexander; Ellis, Geoffrey S.; Said Ahmad, Ward; Deev, Andrei; Sessions, Alex L.; Tang, Yongchun; Adkins, Jess F.; Liu, Jinzhong; Gilhooly, William P.; Aizenshtat, Zeev; Amrani, Alon

    2016-09-01

    The sulfur isotopic fractionation associated with the formation of organic sulfur compounds (OSCs) during thermochemical sulfate reduction (TSR) was studied using gold-tube pyrolysis experiments to simulate TSR. The reactants used included n-hexadecane (n-C16) as a model organic compound with sulfate, sulfite, or elemental sulfur as the sulfur source. At the end of each experiment, the S-isotopic composition and concentration of remaining sulfate, H2S, benzothiophene, dibenzothiophene, and 2-phenylthiophene (PT) were measured. The observed S-isotopic fractionations between sulfate and BT, DBT, and H2S in experimental simulations of TSR correlate well with a multi-stage model of the overall TSR process. Large kinetic isotope fractionations occur during the first, uncatalyzed stage of TSR, 12.4‰ for H2S and as much as 22.2‰ for BT. The fractionations decrease as the H2S concentration increases and the reaction enters the second, catalyzed stage. Once all of the oxidizable hydrocarbons have been consumed, sulfate reduction ceases and equilibrium partitioning then dictates the fractionation between H2S and sulfate (∼17‰). Experiments involving sparingly soluble CaSO4 show that during the second catalytic phase of TSR the rate of sulfate reduction exceeds that of sulfate dissolution. In this case, there is no apparent isotopic fractionation between source sulfate and generated H2S, as all of the available sulfate is effectively reduced at all reaction times. When CaSO4 is replaced with fully soluble Na2SO4, sulfate dissolution is no longer rate limiting and significant S-isotopic fractionation is observed. This supports the notion that CaSO4 dissolution can lead to the apparent lack of fractionation between H2S and sulfate produced by TSR in nature. The S-isotopic composition of individual OSCs record information related to geochemical reactions that cannot be discerned from the δ34S values obtained from bulk phases such as H2S, oil, and sulfate minerals, and

  8. STUDY ON THE TRANSFORMATION OF DIBENZOTHIOPHENE IN FCC PROCESS%二苯并噻吩在催化裂化过程中的转化规律研究

    Institute of Scientific and Technical Information of China (English)

    崔琰; 高永灿; 姜楠

    2011-01-01

    The transformation mechanism of dibenzothiophene (DBT) in FCC process was studied on a fixed fluidized bed unit in laboratory using DBT containing hexadecane as feed. Test results showed that under the conditions of a reaction temperature of 500 ℃ ,a catalyst to oil mass ratio of 6 and a space velocity of 10 h-1 ,the conversion of DBT was about 45%. Alkylation reactions were the main reactions in which DBT took place. The main product was methtyl-benzothiophene and followed by C2-C5 alkylDBT. Nearly 90 percentage of the sulfur in the DBT-hexadecane reaction system was distributed in the liquid products,only a small portion was converted to H2S and coke. The presence of DBT reduced the conversion of hexadecane,the yield of gasoline fractions decreased, the yields of dry gas, diesel fractions and coke increased.%在小型固定流化床(FFB)装置上以二苯并噻吩(DBT)十六烷体系为原料,研究DBT在催化裂化过程中的转化规律.结果表明,在反应温度500℃、剂油质量比6、空速10 h-1的条件下,DBT的转化率为45%左右.在DBT参与的反应中,烷基化反应占主要地位.DBT转化为甲基苯并噻吩的比例最高,其次为C2~C5的烷基二苯并噻吩.DBT-十六烷反应体系的硫90%左右分布在催化裂化液体产品中,少量反应生成硫化氢,少量进入焦炭中.DBT的加入降低了十六烷的转化率,促使千气生成,汽油产率减少,柴油产率增加,焦炭产率显著增加.

  9. THE BIOCATALYTIC DESULFURIZATION PROJECT

    Energy Technology Data Exchange (ETDEWEB)

    Scott Collins; David Nunn

    2003-10-01

    The analysis of Petro Star diesel sulfur species is complete and a report is attached. Further analytical efforts will concentrate on characterization of diesel fuel, hydrodesulfurized to varying degrees, in order to determine sulfur species that may be problematic to hydrogen treatment and represent potential target substrates for biodesulfurization in a combined HDS-BDS process. Quotes have been received and are being considered for the partial treatment of Petro Star Inc. marine diesel fuel. Direction of research is changing slightly; economic analysis of the hyphenated--BDSHDS, BDS-CED--has shown the highest probability of success to be with a BDS-HDS process where the biodesulfurization precedes hydrodesulfurization. Thus, the microorganisms will be tailored to focus on those compounds that tend to be recalcitrant to hydrodesulfurization and decrease the severity of the hydrodesulfurization step. A separate, detailed justification for this change is being prepared. Research activities have continued in the characterization of the desulfurization enzymes from multiple sources. Genes for all DszA, -B, -C and -D enzymes (and homologs) have been cloned and expressed. Activity determinations, on a variety of substituted benzothiophene and dibenzothiophene substrates, have been carried out and continue. In addition, chemical synthesis efforts have been carried out to generate additional substrates for analytical standards and activity determinations. The generation of a GSSM mutant library of the ''Rhodococcus IGTS8 dszA'' gene has been completed and development of protocols for a high throughput screen to expand substrate specificity are nearing completion. In an effort to obtain improved hosts as biocatalyst, one hundred-thirty ''Rhodococcus'' and related strains are being evaluated for growth characteristics and other criteria deemed important for an optimal biocatalyst strain. We have also begun an effort to generate

  10. Effect of Polymer Binders on UV-Responsive Organic Thin-Film Phototransistors with Benzothienobenzothiophene Semiconductor.

    Science.gov (United States)

    Ljubic, Darko; Smithson, Chad S; Wu, Yiliang; Zhu, Shiping

    2016-02-17

    The influence of polymer binders on the UV response of organic thin-film phototransistors (OTF-PTs) is reported. The active channel of the OTF-PTs was fabricated by blending a UV responsive 2,7-dipenty-[1]benzothieno[2,3-b][1]benzothiophene (C5-BTBT) as small molecule semiconductor and a branched unsaturated polyester (B-upe) as dielectric binder (ratio 1:1). To understand the influence of the polymer composition on the photoelectrical properties and UV response of C5-BTBT, control blends were prepared using common dielectric polymers, namely, poly(vinyl acetate) (PVAc), polycarbonate (PC), and polystyrene (PS), for comparison. Thin-film morphology and nanostructure of the C5-BTBT/polymer blends were investigated by means of optical and atomic force microscopy, and powder X-ray diffraction, respectively. Electrical and photoelectrical characteristics of the studied OTF-PTs were evaluated in the dark and under UV illumination with a constant light intensity (P = 3 mW cm(-2), λ = 365 nm), respectively, using two- and three-terminal I-V measurements. Results revealed that the purposely chosen B-upe polymer binder strongly affected the UV response of OTF-PTs. A photocurrent increase of more than 5 orders of magnitude in the subthreshold region was observed with a responsivity as high as 9.7 AW(-1), at VG = 0 V. The photocurrent increase and dramatic shift of VTh,average (∼86 V) were justified by the high number of photogenerated charge carriers upon the high trap density in bulk 8.0 × 10(12) cm(-2) eV(-1) generated by highly dispersed C5-BTBT in B-upe binder. Compared with other devices, the B-upe OTF-PTs had the fastest UV response times (τr1/τr2 = 0.5/6.0) reaching the highest saturated photocurrent (>10(6)), at VG = -5 V and VSD = -60 V. The enhanced UV sensing properties of B-upe based OTF-PTs were attributed to a self-induced thin-film morphology. The enlarged interface facilitated the electron withdrawing/donating functional groups in the polymer chains in

  11. Gasoline Biodesulfurization DE-FC07-97ID13570 FINAL REPORT; FINAL

    International Nuclear Information System (INIS)

    Nine strains were identified to grow with gasoline as sole sulfur source. Two different genes were cloned from Gordonia terrae KGB1 and tested for the ability to support gasoline BDS. The first of these, fmoA, was cloned by screening a KGB1 gene library for the ability to convert indole to indigo (a sulfur-regulated capability in KGB1). The fmoA gene was overexpressed in a gasoline tolerant strain of Pseudomonas putida PpG1 and the recombinant strain was shown to convert thiophene to a dimer of thiophene sulfoxide at rates nearly two orders of magnitude higher than KGB1 could catalyze the reaction. Despite this high activity the recombinant PpG1 was unable to demonstrate any activity against gasoline either in shake flask or in bench-scale gasoline BDS bioreactor. A second gene (toeA) was cloned from KGB1 and shown to support growth of Rhodococcus erythropolis JB55 on gasoline. The toeA gene was also identified in another gasoline strain T. wratislaviensis EMT4, and was identified as a homolog of dszA from R. erythropolis IGTS8. Expression of this gene in JB55 supported conversion of DBTO2 (the natural substrate for DszA) to HPBS, but activity against gasoline was low and BDS results were inconsistent. It appeared that activity was directed against C2- and C3-thiophenes. Efforts to increase gene expression by plasmid manipulation, by addition of flavin reductase genes, or by expression in PpG1 were unsuccessful. The DszC protein (DBT monooxygenase) from IGTS8 has very little activity against the sulfur compounds in gasoline, but a mutant enzyme with a substitution of phenylalanine for valine at position 261 was shown to have an altered substrate range. This alteration resulted in increased activity against gasoline, with activity towards mainly C3- and C4-thiophenes and benzothiophene. A mutant library of dszB was constructed by RACHITT (W. C. Coco et al., DNA shuffling method for generating highly recombined genes and evolved enzymes. 2001. Nature Biotech. 19

  12. Simulations of charge transport in organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Vehoff, Thorsten

    2010-05-05

    We study the charge transport properties of organic liquid crystals, i.e. hexabenzocoronene and carbazole macrocycle, and single crystals, i.e. rubrene, indolocarbazole and benzothiophene derivatives (BTBT, BBBT). The aim is to find structure-property relationships linking the chemical structure as well as the morphology with the bulk charge carrier mobility of the compounds. To this end, molecular dynamics (MD) simulations are performed yielding realistic equilibrated morphologies. Partial charges and molecular orbitals are calculated based on single molecules in vacuum using quantum chemical methods. The molecular orbitals are then mapped onto the molecular positions and orientations, which allows calculation of the transfer integrals between nearest neighbors using the molecular orbital overlap method. Thus we obtain realistic transfer integral distributions and their autocorrelations. In case of organic crystals the differences between two descriptions of charge transport, namely semi-classical dynamics (SCD) in the small polaron limit and kinetic Monte Carlo (KMC) based on Marcus rates, are studied. The liquid crystals are investigated solely in the hopping limit. To simulate the charge dynamics using KMC, the centers of mass of the molecules are mapped onto lattice sites and the transfer integrals are used to compute the hopping rates. In the small polaron limit, where the electronic wave function is spread over a limited number of neighboring molecules, the Schroedinger equation is solved numerically using a semi-classical approach. The carbazole macrocycles form columnar structures arranged on a hexagonal lattice with side chains facing inwards, so columns can closely approach each other allowing inter-columnar and thus three-dimensional transport. We are able to show that, on the time-scales of charge transport, static disorder due to slow side chain motions is the main factor determining the mobility. The high mobility of rubrene is explained by two main

  13. Gasoline Biodesulfurization DE-FC07-97ID13570 FINAL REPORT

    Energy Technology Data Exchange (ETDEWEB)

    Pienkos, Philip T.

    2002-01-15

    Nine strains were identified to grow with gasoline as sole sulfur source. Two different genes were cloned from Gordonia terrae KGB1 and tested for the ability to support gasoline BDS. The first of these, fmoA, was cloned by screening a KGB1 gene library for the ability to convert indole to indigo (a sulfur-regulated capability in KGB1). The fmoA gene was overexpressed in a gasoline tolerant strain of Pseudomonas putida PpG1 and the recombinant strain was shown to convert thiophene to a dimer of thiophene sulfoxide at rates nearly two orders of magnitude higher than KGB1 could catalyze the reaction. Despite this high activity the recombinant PpG1 was unable to demonstrate any activity against gasoline either in shake flask or in bench-scale gasoline BDS bioreactor. A second gene (toeA) was cloned from KGB1 and shown to support growth of Rhodococcus erythropolis JB55 on gasoline. The toeA gene was also identified in another gasoline strain T. wratislaviensis EMT4, and was identified as a homolog of dszA from R. erythropolis IGTS8. Expression of this gene in JB55 supported conversion of DBTO2 (the natural substrate for DszA) to HPBS, but activity against gasoline was low and BDS results were inconsistent. It appeared that activity was directed against C2- and C3-thiophenes. Efforts to increase gene expression by plasmid manipulation, by addition of flavin reductase genes, or by expression in PpG1 were unsuccessful. The DszC protein (DBT monooxygenase) from IGTS8 has very little activity against the sulfur compounds in gasoline, but a mutant enzyme with a substitution of phenylalanine for valine at position 261 was shown to have an altered substrate range. This alteration resulted in increased activity against gasoline, with activity towards mainly C3- and C4-thiophenes and benzothiophene. A mutant library of dszB was constructed by RACHITT (W. C. Coco et al., DNA shuffling method for generating highly recombined genes and evolved enzymes. 2001. Nature Biotech. 19

  14. Oxidative desulfurization of diesel oil over Ti-MWW catalyst with TBHP as oxidant%Ti-MWW分子筛催化叔丁基过氧化氢氧化脱硫

    Institute of Scientific and Technical Information of China (English)

    程时富; 安莹; 司晓娟; 付贤磊; 高国华

    2011-01-01

    以Ti-MWW为催化剂,考察了不同氧化剂对分别含有苯并噻吩、二苯并噻吩和4,6-二甲基二苯并噻吩等有机硫化物模拟油品氧化反应的影响,结果表明,叔丁基过氧化氢对有机含硫化合物的氧化活性明显高于过氧化氢水溶液.以叔丁基过氧化氢为氧化剂,三种噻吩类含硫化合物氧化的难易顺序为二苯并噻吩>4,6-二甲基二苯并噻吩>苯并噻吩,其氧化活性顺序与含硫化合物中硫原子的电子云密度和空间位阻有关.考察了Ti-MWW/叔丁基过氧化氢催化氧化体系对成品柴油的催化氧化脱硫,结果表明,成品柴油中的含硫化合物可被有效地氧化脱除,在优化的反应条件下,经过两次氧化、萃取后,成品柴油中的总硫含量从1 015 μg/mL降低至11 μg/mL,总脱硫率达到99%.%Oxidative desulfurization (ODS) of benzothiophene (BT), dibenzothiophene (DBT) and 4, 6-dimethyl dibenzothiophene (DMDBT) in model light oil was investigated with different oxidants over Ti-MWW catalyst. The results indicated that te/t-butyl hydroperoxide (TBHP) exhibits higher reactivity with these organic sulfur-containing compounds than hydogen peroxide. In the presence of TBHP, the reactivity of these sulfur-containing compounds over Ti-MWW catalyst is in the order of DBT > DMDBT > BT, which is determined by the electron density of sulfur atom in thiophene ring as well as the steric hindrance of sulfur compounds. ODS of a commercial diesel oil was also investigated over the Ti-MWW/TBHP system. The sulfur compounds in the commercial diesel oil can be efficiently oxidized to corresponding sulfone under mild reaction conditions; by oxidation and extraction twice, the sulfur content in the commercial diesel oil is decreased from 1 015 μg/mL to 11 μg/ mL and the sulfur removal reaches 99%.

  15. STUDY ON OXIDATIVE DESULFURIZATION OF SIMULATED OIL USING PHOSPHOTUNGSTIC ACID?SEMI-COKE AS CATALYST%以磷钨酸/半焦为催化剂对模拟油氧化脱硫的研究

    Institute of Scientific and Technical Information of China (English)

    王亮; 贾腾飞; 李春虎; 冯丽娟

    2015-01-01

    Oxidative desulfurization of benzothiophene(BT,DBT and 4,6-DMDBT)in simulated oil was investigated using hydrogen peroxide as oxidant,Span60 as emulsifier,N-methyl pyrrolidone as ex-tractant and phosphotungstic acid?semi-coke (HPW?Sc)as catalyst.The HPW?Sc catalysts were charac-terized by FT-IR.The effect of HPW loading amount,reaction temperature,reaction time,and aromat-ics,olefins and nitrogen compounds on desulfurization rate was studied.The results show that the sul-fur removal efficiency of DBT reaches above 99% using the catalyst with 30% HPW loading at the con-ditions of temperature of 60 ℃,reaction time of 60 min,amount of catalyst 1.0%,n(H2O2)?n(S)=3, amount of Span60 emulsifier 0.36%,and the oxidative activity of the model sulfur compounds follows the order of DBT>4,6-DMDBT>BT. The benzene in the test oil can promote DBT desulfurization, while quinoline and cyclohexene inhibit the removal of DBT.%以双氧水为氧化剂、磷钨酸?半焦(HPW?Sc)为催化剂、N-甲基吡咯烷酮为萃取剂、Span60为乳化剂,对以苯并噻吩(BT)、二苯并噻吩(DBT)、4,6-二甲基二苯并噻吩(4,6-DMDBT)为模型含硫化合物的模拟油进行氧化脱硫研究,考察磷钨酸负载量、氧化温度、氧化反应时间和模拟油中烯烃、芳烃和含氮化合物对含硫化合物脱除效果的影响。结果表明:催化剂的最佳磷钨酸负载量(w)为30%;在反应时间为60 min、反应温度为60℃、HPW?Sc2用量(w)为1.0%、Span60用量(w)为0.36%、n(H2 O2)?n(S)=3的条件下,DBT脱除率可达到99%,含硫化合物的氧化活性由大到小的顺序为 DBT>4,6-DMDBT>BT;模拟油中的苯可促进 DBT的脱除,而喹啉和环己烯则抑制DBT的脱除。

  16. Benzene and ethylene in Bio-SNG production. Nuisance, fuel or valuable products?

    Energy Technology Data Exchange (ETDEWEB)

    Rabou, L.P.L.M. Rabou; Van der Drift, A. [ECN Biomass and Energy Efficiency, Petten (Netherlands)

    2011-11-15

    , it has no use for benzene as an additional heat source. That is why ECN research focuses on solving problems associated with the conversion of benzene and ethylene to methane. One of the problems is removal of organic sulphur compounds, especially thiophene and its derivatives like benzo-thiophene. The main route pursued by ECN is conversion of thiophenes by a hydrodesulphurization (HDS) catalyst, followed by adsorption of the hydrogensulphide produced. Benzene removed from producer gas by liquid scrubbing or adsorption to a solid sorbent can also be recovered for use as fuel in a separate boiler. An advantage of that approach would be that benzene can be stored more easily than producer gas to match heat production with demand by e.g. a district heat system or to provide heat during gasifier maintenance. In fact, that would copy the approach followed in Harbooere with tar. Another promising option is cryogenic separation of producer gas. In principle, that would make it possible to separate and recover not only benzene but also ethylene. Even without purification, these may have more value as chemical base materials than when used as fuel. The cryogenic treatment would probably also capture sulphur compounds, thus considerably simplifying the gas cleaning needed for protection of the methanation catalyst. Advantages and disadvantages of the above options will be discussed. Experimental results of ECN research on hydrodesulphurization and adsorbents will be presented. Further research questions will be addressed.

  17. Selective Estrogen Receptor Modulators – an Updatebr (Joint Statement by the German Society for Gynecological Endocrinology and Reproductive Medicine [DGGEF] and the German Professional Association of Gynecologists [BVF

    Directory of Open Access Journals (Sweden)

    Rabe T

    2015-01-01

    (with at least 12 months since the last menses for whom treatment with progestin-containing therapy is not appropriate.br Clomifene (Triphenylethylene derivative: Treatment of ovarian dysfunction (infertility. Ospemifene: FDA registration for treatment of moderate or severe dyspareunia, a symptom of vulvar and vaginal atrophy, due to menopause; EU-registration for moderate or severe symptoms of vulvo-vaginal atrophy.br Ormeloxifene used in India for contraception and treatment of dysfunctional uterine bleeding. Raloxifene (Benzothiophene derivative used for treatment and prevention of osteoporosis in postmenopausal women and in some countries (including the USA for breast cancer prevention in high risk women. Raloxifene has no marketing authorization for this indication in Europe. The VTE risk is increased, similar to HRT. Death due to stroke was increased in the RUTH study (secondary prevention study, but not in the MORE or CORE studies (osteoporosis treatment and extension studies.br Tamoxifene (triphenylethylene derivative is licensed for adjuvant use in women with primary or metastasized breast cancer and in some countries for the primary prevention of breast cancer. Tamoxifene is an antiestrogen, used (20 mg/day in women who have estrogen receptor-positive (ER+ breast cancer. Unfortunately, resistance to tamoxifene is common in women with metastatic disease. Possible side effects include an increased risk of endometrial cancer and, like with all SERMs, an increased risk of VTE. An increased risk of stroke has been observed in the NSABP-1 study (RR1.42, but this was not statistically significant. Some antidepressants (SSRIs abolish the effect of tamoxifene.br Toremifene (citrate (also a triphenylethylene derivative has EU marketing authorization for first line endocrine treatment of hormone-dependent meta static breast cancer in postmenopausal patients. Fareston is not recommended for patients with estrogen receptor negative tumors. According to the US license