Sample records for benzothiophenes

  1. Regioselective synthesis of C3 alkylated and arylated benzothiophenes (United States)

    Shrives, Harry J.; Fernández-Salas, José A.; Hedtke, Christin; Pulis, Alexander P.; Procter, David J.


    Benzothiophenes are heterocyclic constituents of important molecules relevant to society, including those with the potential to meet modern medical challenges. The construction of molecules would be vastly more efficient if carbon-hydrogen bonds, found in all organic molecules, can be directly converted into carbon-carbon bonds. In the case of elaborating benzothiophenes, functionalization of carbon-hydrogen bonds at carbon-number 3 (C3) is markedly more demanding than at C2 due to issues of regioselectivity (C3 versus C2), and the requirement of high temperatures, precious metals and the installation of superfluous directing groups. Herein, we demonstrate that synthetically unexplored but readily accessible benzothiophene S-oxides serve as novel precursors for C3-functionalized benzothiophenes. Employing an interrupted Pummerer reaction to capture and then deliver phenol and silane coupling partners, we have discovered a directing group-free method that delivers C3-arylated and -alkylated benzothiophenes with complete regioselectivity, under metal-free and mild conditions.

  2. Desulfurization of petroleum induced by ionization radiation: benzothiophene behavior

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    Andrade, Luana S.; Calvo, Wilson A.P.; Duarte, Celina L., E-mail:, E-mail:, E-mail: [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)


    Hydrodesulfurization (HDS) is currently the most common method used by refineries; this removes significantly sulfur compounds from petroleum fractions, however, is not highly effective for removing thiophene compounds such as benzothiophene, and generates high costs for the oil industry. Another factor, are the environmental laws, which over the years has become increasingly strict, especially regarding the sulfur content. This compound cause incalculable damage both to the industry and to the environment. Therefore new methods for petroleum desulfurization should be studied in order to minimize the impacts that these compounds cause. In the present study it was used ionizing radiation, a promising method of advanced oxidation in reducing sulfur compounds. The analysis were performed after purge and trap concentration of samples, followed by gas chromatography-mass spectrometry (GC-MS). Then benzothiophene samples with the same concentration from 27 mg.L{sup -1} to 139 mg.L{sup -1} were irradiated with different absorbed doses of radiation ranging from 1 kGy to 20 kGy in gamma irradiator Cobalt-60, Gammacell. These samples were analyzed by the same procedure used for the calibration curve, and the removals of benzothiophene after ionizing radiation treatment were calculated. It was observed that at higher doses there was a greater degradation of this compound and the formation of fragments, such as 1,2-dimethylbenzene and toluene, which may be removed by simple processes. (author)

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

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    Rajendiran Nagappan


    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. Catalytic Desulfurization of Benzothiophene Using Keggin Type Polyoxometalates as Catalyst

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    Aldes Lesbani


    Full Text Available Performance of catalytic desulfurization of benzothiophen (BT was studied using polyoxometalates as catalyst. Polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40], have different heteroatom in Keggin structure and catalytic activities. Polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40] have high crystallinity with homogeneous distribution particles. Desulfurization of BT using polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40] resulted % conversion up to 99% for 3 h reaction time and at temperature 40 oC. Application of polyoxometalates H3[a-PW12O40] and H4[a-SiW12O40] for crude oil desulfurization showed % conversion of 4-88%. The main functional groups of polyoxometalates still retained after catalytic desulfurization indicated the stability of polyoxometalate compounds

  5. Photocatalytic degradation of benzothiophene and dibenzothiophene using supported gold nanoparticle

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    Suzan Khayyat


    Full Text Available Photocatalytic oxidation of benzothiophene (BT and dibenzothiophene (DBT was studied over Au nanoparticles (NPs incorporated titania (Au/TiO2 catalyst under UV radiation using H2O2 as oxidant. The reaction parameters such as, catalyst weight, Au loading, calcination of Au/TiO2 catalysts and [H2O2]:[DBT] mole ratio are studied. The Au/TiO2 catalyst was synthesised by deposition–precipitation method. The catalysts were characterized by ICPAES, XRD and TEM analysis. ICP-AES analysis demonstrate that with a nominal amount of 1, 1.5, 2, 2.5 and 3 at.% of Au in a solution at pH 7, the amount of gold deposited on the TiO2 was 0.78, 1.42, 1.92, 2.45 and 2.87 at.% respectively. The average particle size of Au in the 2 at.% Au/TiO2 sample after drying was 3 nm and in the sample after calcination at 573 K was 5 nm. The XPS spectra of Au/TiO2 sample demonstrate that the sample dried at 373 K contains Au0 and Au3+ and the sample after calcination at 573 K contains Au0 and negligible amount of Au3+. The photocatalysis studies show that the Au nanoparticles (NPs incorporated titania showed higher activity for the removal of DBT compared to pure titania. The optimum Au loading in Au/TiO2 for the photocatalytic removal of DBT was found to be 1.5 at.% Au. The Au NPs act as electron sink to enhance e/h+ charge separation and produce number of oxidizing species, thereby increase the reaction rate. The calcined catalyst sample showed higher activity toward DBT removal compared to the uncalcined sample. This is due to the presence of metallic gold in the calcined sample, which can effectively involve in the charge separation. The optimum catalyst weight for DBT removal was found to be 0.3 g of Au/TiO2 for 200 ml of DBT in isooctane (200 ppm S. The optimum [H2O2]:[DBT] molar ratio was found to be 3. Comparison of photocatalytic removal of DBT and BT showed that the removal of DBT is faster than the BT.

  6. (+-(S-N-[(1-Benzothiophen-2-ylmethylidene]-1-(naphthalen-1-ylethylamine

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    Guadalupe Hernández-Téllez


    Full Text Available In the title compound, C21H17NS, the C=N double bond shows an E conformation. The dihedral angle between the mean planes of the naphthyl residue and the benzothiophene residue is 89.14 (6°. The crystal packing is stabilized by intermolecular C—H...π interactions, building a ribbon structure along the a axis.

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


    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.

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

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    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


    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.

  9. Synthesis and evaluation of benzothiophene derivatives as ligands for imaging {beta}-amyloid plaques in Alzheimer's disease

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    Chang, Young Soo [Department of Nuclear Medicine, Seoul National University College of Medicine, Seoul 110-744 (Korea, Republic of); Cancer Research Institute, Seoul National University College of Medicine, Seoul 110-744 (Korea, Republic of)]|[Institute of Radiation Medicine, Medical Research Center, Seoul National University, Seoul 110-744 (Korea, Republic of); Jeong, Jae Min [Department of Nuclear Medicine, Seoul National University College of Medicine, Seoul 110-744 (Korea, Republic of)]|[Cancer Research Institute, Seoul National University College of Medicine, Seoul 110-744 (Korea, Republic of) and Institute of Radiation Medicine, Medical Research Center, Seoul National University, Seoul 110-744 (Korea, Republic of)]. E-mail:; Lee, Yun-Sang [Department of Nuclear Medicine, Seoul National University College of Medicine, Seoul 110-744 (Korea, Republic of)]|[Institute of Radiation Medicine, Medical Research Center, Seoul National University, Seoul 110-744 (Korea, Republic of); Kim, Hyung Woo [Department of Nuclear Medicine, Seoul National University College of Medicine, Seoul 110-744 (Korea, Republic of)]|[Institute of Radiation Medicine, Medical Research Center, Seoul National University, Seoul 110-744 (Korea, Republic of); Ganesha, Rai B.; Kim, Young Ju; Lee, Dong Soo [Department of Nuclear Medicine, Seoul National University College of Medicine, Seoul 110-744 (Korea, Republic of); Chung, June-Key [Department of Nuclear Medicine, Seoul National University College of Medicine, Seoul 110-744 (Korea, Republic of)]|[Cancer Research Institute, Seoul National University College of Medicine, Seoul 110-744 (Korea, Republic of); Lee, Myung Chul [Department of Nuclear Medicine, Seoul National University College of Medicine, Seoul 110-744 (Korea, Republic of)


    The imaging of the distribution of {beta}-amyloid (A{beta}) plaques in the brain is becoming an important diagnostic modality in Alzheimer's disease (AD). Here, we synthesized novel benzothiophene derivatives and labeled them with {sup 18}F for the potential diagnostic imaging of AD patients using positron emission tomography. The K {sub i} values of benzothiophene derivatives were evaluated by competitive binding assay using 2-(3'-[{sup 125}I]iodo-4'-N-methylaminophenyl)benzothiazole as a radioligand and A{beta}(1-40) or A{beta}(1-42) aggregates as receptors. All synthesized benzothiophene derivatives showed high binding affinities (K {sub i}=0.28-6.50 nM) to both A{beta}(1-40) and A{beta}(1-42) aggregates. Binding affinities were increased by O-alkylation or N-alkylation of 2-(4'-hydroxyphenyl)benzothiophene or 2-(4'-aminophenyl)benzothiophene. Biodistribution studies of 2-(4'-O-(2''-[{sup 18}F]fluoroethyl)hydroxyphenyl)benzothiophene ([{sup 18}F]) and 2-(4'-O-(3''-[{sup 18}F]fluoropropyl)hydroxyphenyl)benzothiophene ([{sup 18}F]) in normal mice were performed after intravenous injection through the tail vein. In biodistribution data, [{sup 18}F] and [{sup 18}F] showed high initial brain uptakes at 2 min (5.2{+-}0.4% and 3.3{+-}0.2% ID/g, respectively), and brain activities washed out to 2.0{+-}0.2% and 0.5{+-}0.1% ID/g at 4 h, respectively. In conclusion, benzothiophene derivatives showed excellent binding affinities for A{beta} aggregates and high initial brain uptakes in normal mice.

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


    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.

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

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    Asma Mukhtar


    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.

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

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    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.

  13. Preparation of Ag/TiO2-zeolite adsorbents, their desulfurization performance, and benzothiophene adsorption isotherms (United States)

    Song, Hua; Yang, Gang; Song, Hua-Lin; Wang, Deng; Wang, Xue-Qin


    A series of Ag/TiO2-NaY (TY) composite adsorbents were successfully prepared and characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, BET, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) techniques. The effects of TiO2 and Ag contents on the structure and desulfurization performance of NaY zeolite were studied. The results show that anatase phase is the main form of TiO2 in AgTY adsorbent, and the Y-zeolite framework remained unchanged. AgTY with 6 wt % of Ag and 50 wt % of TiO2 exhibited the best desulfurization performance with the effluent volume of 63.2 mL/g at 10 mg/L sulfur breakthrough level (desulfurization rate of 95%). The benzothiophene (BT) removal performance of the various adsorbents follows the order: NaY < TiO2 < TY-50 < AgTY-50-6. The equilibrium data were modeled by Langmuir and Freundlich equations. The Langmuir model can describe well the adsorption isotherms of BT over AgTY.

  14. Selective adsorption of thiophene and 1-benzothiophene on metal-ion-exchanged zeolites in organic medium. (United States)

    Xue, Mei; Chitrakar, Ramesh; Sakane, Kohji; Hirotsu, Takahiro; Ooi, Kenta; Yoshimura, Yuji; Feng, Qi; Sumida, Naoto


    Adsorption of the organic sulfur compounds thiophene (TP) and 1-benzothiophene (1-BTP) in an organic model solution of hydrodesulfurizated gasoline (heptane with 1 wt% toluene and 0.156 mM (5 ppmw as sulfur) TP or 1-BTP) was studied by a batch method at 80 degrees C using metal-ion-exchanged Y-zeolites. Although NaY-zeolite or its acid-treated material rarely adsorbed the organic sulfur compounds, NaY-zeolites exchanged with Ag+, Cu2+, and Ce3+ ions and NH(4)Y-zeolites exchanged with Ce3+ ions showed markedly high adsorptive capacities for TP and 1-BTP. The sulfur uptake increased in the order CuY-zeolite(Na)

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

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    Yue, Wan


    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.

  16. Macrophage inducible nitric oxide synthase gene expression is blocked by a benzothiophene derivative with anti-HIV properties. (United States)

    Carballo, M; Conde, M; Tejedo, J; Gualberto, A; Jimenez, J; Monteseirín, J; Santa María, C; Bedoya, F J; Hunt, S W; Pintado, E; Baldwin, A S; Sobrino, F


    Nitric oxide (NO) has been shown to mediate multiple physiological and toxicological functions. The inducible nitric oxide synthase (iNOS) is responsible for the high output generation of NO by macrophages following their stimulation by cytokines or bacterial antigens. The inhibition of TNF alpha-stimulated HIV expression and the anti-inflammatory property of PD144795, a new benzothiophene derivative, have been recently described. We have now analyzed whether some of these properties could be mediated by an effect of PD144795 on NO-dependent inflammatory events. We show that PD144795 suppresses the lipopolysaccharide-elicited production of nitrite (NO(-)(2)) by primary peritoneal mouse macrophages and by a macrophage-derived cell line, RAW 264.7. This effect was dependent on the dose and timing of addition of PD144795 to the cells. Suppression of NO(-)(2) production was associated with a decrease in the amount of iNOS protein, iNOS enzyme activity and mRNA expression. The effect of PD144795 was partially abolished by coincubation of the cells with LPS and IFN gamma. However, the inhibitory effect of PD144795 was not abrogated by the simultaneous addition of LPS and TNF alpha, which indirectly suggests that the effect of PD144795 was not due to the inhibition of TNF alpha synthesis. Additionally, PD144795 did not block NF-kappa B nuclear translocation induced by LPS. Inhibition of iNOS gene expression represents a novel mechanism of PD144795 action that underlines the anti-inflammatory effects of this immunosuppressive drug.

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

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


    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.

  18. Modifying the Chemical Structure of a Porphyrin Small Molecule with Benzothiophene Groups for the Reproducible Fabrication of High Performance Solar Cells. (United States)

    Liang, Tianxiang; Xiao, Liangang; Gao, Ke; Xu, Wenzhan; Peng, Xiaobin; Cao, Yong


    A porphyrin-based molecule DPPEZnP-BzTBO with bulky benzothiophene groups was designed and synthesized as an electron donor material for bulk heterojunction (BHJ) solar cells. The optimized devices under thermal annealing (TA) and then chloroform solvent vapor anneanling (SVA) for 80 s exhibited an outstanding power conversion efficiencie (PCE) of 9.08%. Contrasted with the smaller thienyl substituted analogues we reported previously, DPPEZnP-BzTBO-based BHJ solar cells exhibited a higher open circuit voltage due to the lower highest occupied molecular orbital energy level. The TA post-treatment of the active layers induced the formation of more crystallized components, and the subsequent SVA provided a driving force for the domain growth, resulting in more obvious phase segregation between the donor and the acceptor in nanoscale. Furthermore, the PCEs kept above 95% upon the further SVA treatment within the time range of 60 to 95 s probably because the bulky benzothiophene groups retard the too quick change of crystallinity, providing a wide processing window for the reproducible device fabrication.

  19. Effect of central metal ions of analogous metal-organic frameworks on the adsorptive removal of benzothiophene from a model fuel. (United States)

    Khan, Nazmul Abedin; Jhung, Sung Hwa


    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.

  20. 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. (United States)

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


    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.

  1. 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

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    J. Govindaraj


    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.

  2. N-((1S)-1-{[4-((2S)-2-{[(2,4-dichlorophenyl)sulfonyl]amino}-3-hydroxypropanoyl)-1-piperazinyl]carbonyl}-3-methylbutyl)-1-benzothiophene-2-carboxamide (GSK1016790A), a novel and potent transient receptor potential vanilloid 4 channel agonist induces urinary bladder contraction and hyperactivity: Part I. (United States)

    Thorneloe, Kevin S; Sulpizio, Anthony C; Lin, Zuojun; Figueroa, David J; Clouse, Angela K; McCafferty, Gerald P; Chendrimada, Tim P; Lashinger, Erin S R; Gordon, Earl; Evans, Louise; Misajet, Blake A; Demarini, Douglas J; Nation, Josephine H; Casillas, Linda N; Marquis, Robert W; Votta, Bartholomew J; Sheardown, Steven A; Xu, Xiaoping; Brooks, David P; Laping, Nicholas J; Westfall, Timothy D


    The transient receptor potential (TRP) vanilloid 4 (TRPV4) member of the TRP superfamily has recently been implicated in numerous physiological processes. In this study, we describe a small molecule TRPV4 channel activator, (N-((1S)-1-{[4-((2S)-2-{[(2,4-dichlorophenyl)sulfonyl]amino}-3-hydroxypropanoyl)-1-piperazinyl]carbonyl}-3-methylbutyl)-1-benzothiophene-2-carboxamide (GSK1016790A), which we have used as a valuable tool in investigating the role of TRPV4 in the urinary bladder. GSK1016790A elicited Ca2+ influx in mouse and human TRPV4-expressing human embryonic kidney (HEK) cells (EC50 values of 18 and 2.1 nM, respectively), and it evoked a dose-dependent activation of TRPV4 whole-cell currents at concentrations above 1 nM. In contrast, the TRPV4 activator 4alpha-phorbol 12,13-didecanoate (4alpha-PDD) was 300-fold less potent than GSK1016790A in activating TRPV4 currents. TRPV4 mRNA was detected in urinary bladder smooth muscle (UBSM) and urothelium of TRPV4+/+ mouse bladders. Western blotting and immunohistochemistry demonstrated protein expression in both the UBSM and urothelium that was absent in TRPV4-/- bladders. TRPV4 activation with GSK1016790A contracted TRPV4+/+ mouse bladders in vitro, both in the presence and absence of the urothelium, an effect that was undetected in TRPV4-/- bladders. Consistent with the effects on TRPV4 HEK whole-cell currents, 4alpha-PDD demonstrated a weak ability to contract bladder strips compared with GSK1016790A. In vivo, urodynamics in TRPV4+/+ and TRPV4-/- mice revealed an enhanced bladder capacity in the TRPV4-/- mice. Infusion of GSK1016790A into the bladders of TRPV4+/+ mice induced bladder overactivity with no effect in TRPV4-/- mice. Overall TRPV4 plays an important role in urinary bladder function that includes an ability to contract the bladder as a result of the expression of TRPV4 in the UBSM.

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

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    Abdullah M. Asiri


    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].

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


    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.

  5. 3′,6′-Bis(diethylamino-3H-spiro[2-benzothiophene-1,9′-xanthene]-3-thione

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    Bing-Yuan Su


    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.

  6. 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


    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.

  7. 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.


    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...... isostructural with the racemate, except that the glide symmetry is violated by interchange of CH and CH2 groups within the seven-membered ring. The space-group symmetry is reduced to P1 with two molecules in the asymmetric unit. The enantiomer structure shows disorder of the thiophene ring for one...... of the molecules in the asymmetric unit. The major component of the disorder has the thiophene ring in the same position as in the racemate, but generates a higher-energy molecular conformation. The minor disorder component has different intermolecular interactions but retains a more stable molecular conformation....

  8. 过氧化叔戊醇对苯并噻吩类衍生物的氧化%Oxidation of benzothiophenes using tert-amyl hydroperoxide

    Institute of Scientific and Technical Information of China (English)

    周新锐; 盖洪涛; 王静; 张珊珊; 杨锦宗; 张淑芬


    Homogeneous oxidation using an oil-soluble oxidant,tert-amyl hydroperoxide(TAHP).for ultra-deep desulfurizmion was performed under mild conditions in the presence of molybdenum oxide catalysts.Dibenzothio phene(DBT),benzothiophcne(BT)and 4,6-dimethyl-dibenzothiophene(DMDBT),which are the refractory sulfur compounds for hydrodesulfurization(HDS),were employed as model substrates for a simulated diesel fuel.Activ ity of molybdenum oxide supported on a macroporous weak acidic resin was investigated.The mass conversion of DBT reached near 100%at 90°C and a TAHP,DBT molar ratio of 3 with 1% of molybdenum oxide supported on Amberlite IRC-748 resin for l h.It was further found that the activities of the model Substrates decreasca rin the order of DMDBT>DBT>B T.In the flow oxidation using TAHP as the oxidant,mass conversion of DBT increased remarkably from 61.3%to 98.5%when dropping the weight hourly space velocity(WHSV)from 40 h1 to 10 h-1.A series of experiments dealt with selectivity of this oxidation using TAHP revealed that the model unsaturated compounds,i.e.4,6,8-trimethyl-2-nonylene,and 2-methylnaphthaIene did not affect the oxidation of DBT.Carbazole had nearly no effect on the conversion of DBT using TAHP.but had some influence on the one using tert-butyl hydroperoxide(TBHP).The mass conversion of DBT decreased remarkably from 75.2%to 3.6%when the content of carbazole increased from 0 to 500 ug.g-1.In the flow oxidation using TAHP as the oxidant.the concentration of.DBT in model fuels was reduced from 500 ug.g-1 to 7.2 ug.g-1 at WHSV of 10 h-1,and then reduced to 3.8 ug.g-1 by adsorption of Al2O3.

  9. Modified ibogaine fragments: synthesis and preliminary pharmacological characterization of 3-ethyl-5-phenyl-1,2,3,4,5, 6-hexahydroazepino[4,5-b]benzothiophenes. (United States)

    Efange, S M; Mash, D C; Khare, A B; Ouyang, Q


    Five phenyl-substituted derivatives and analogues of 1,2,3,4,5, 6-hexahydroazepino[4,5-b]indole, 5, a major fragment of ibogaine (1), were synthesized and tested for binding to monoamine transporters, the NMDA receptor-coupled cation channel, and dopamine and opioid receptors. All five derivatives, 9 and 17a-d, displayed 8-10-fold higher affinity at the DA transporter than ibogaine and noribogaine (4). At the serotonin transporter, two compounds (9 and 17a) exhibited higher potency than ibogaine, while the rest had weaker binding affinities than the lead compound. In keeping with their structural similarity to ibogaine, all five compounds displayed weak to poor affinity for dopamine D1 and D2 receptors. However, two compounds, 17a,c, demonstrated moderate binding affinities at dopamine D3 receptors. All five compounds displayed weak to poor affinities for mu and kappa opioid receptors and for the NMDA receptor-coupled cation channel. Despite the qualitative differences, derivatives and analogues of 5may serve as useful substitutes for ibogaine.


    Institute of Scientific and Technical Information of China (English)

    张进; 朴香兰; 朱慎林


    合成了5种新型离子液体[bmim]AlCl1,[bmin]DBP,[bmim]BeS,[bmim]PF6,[bmim]BF4,并将它们用于萃取模拟油品中的苯并噻吩(BT)、二笨并噻吩(DBT).比较了5种离子液体的萃取性能,结合分子间作用力的理论和价键理论阐述了离子液体萃取脱硫的机理.结果表明,离子液体的萃取性能与其阴离子结构有关,其中[bmim]DBP适宜作萃取脱硫溶剂.BT、DBT在模拟油品中的初始含量分别为1 000μg/g左右时,[bmim]DBP经4级错流萃取和5级逆流萃取,BT、DBT含量均能降至50μg/g以下.

  11. 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. (United States)

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


    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.

  12. 5-n-Butyl-4-[2-(2-ethyl-1-benzothiophen-3-yl-3,3,4,4,5,5-hexafluorocyclopent-1-en-1-yl]thiophene-2-carbaldehyde

    Directory of Open Access Journals (Sweden)

    Seik Weng Ng


    Full Text Available The title compound, C24H20F6OS2, exhibiting photochromic behaviour, has thienyl and benzothienyl substituents attached to the double-bond C atoms of the envelope-shaped cyclopentene ring. The mean planes of aromatic systems form dihedral angles of 43.0 (1 (thienyl and 73.8 (1° (benzothienyl with the mean plane of the C—C=C—C portion of the cyclopentene ring. This conformation avoids steric hindrance between the n-butyl and ethyl substituents. The formyl substituent of the thienyl group, as well as the ethyl substituent of the benzothienyl group, are disordered [occupancies of 0.788 (17:0.212 (17 and 0.64 (5:0.36 (5, respectively].

  13. 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.


    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.

  14. Biodegradation of Various Aromatic Compounds by Enriched Bacterial Cultures: Part B--Nitrogen-, Sulfur-, and Oxygen-Containing Heterocyclic Aromatic Compounds. (United States)

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


    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.

  15. Modelling of the Kinetics of Sulfure Compounds in Desulfurisation Processes Based on Industry Data of Plant

    Directory of Open Access Journals (Sweden)

    Krivtcova Nadezhda


    Full Text Available Modelling of sulfur compounds kinetics was performed, including kinetics of benzothiophene and dibenzothiophene homologues. Modelling is based on experimental data obtained from monitoring of industrial hydrotreating set. Obtained results include kinetic parameters of reactions.

  16. Tellurium-Containing Conjugated Materials for Solar Cells: From Sulfur to Tellurium

    Energy Technology Data Exchange (ETDEWEB)

    Park Y. S.; Kale, T.; Wu, Q.; Ocko, B.M.; Black, C.T., Grubbs, R.B.


    A series of diketopyrrolopyrrole(DPP)-based small molecules have been synthesized by palladium-catalyzed coupling reactions. Electron-donating moieties (benzothiophene, benzoselenophene, and benzotellurophene) are bridged by an electron-withdrawing DPP unit to generate donor-acceptor-donor (D-A-D) type molecules. We observe red-shifts in absorption spectra of these compounds by varying heteroatoms from sulfur to tellurium. In bulk heterojunction solar cells with [6,6]phenyl-C61-butyric acid methyl ester (PC61BM) as acceptor, we obtain power conversion efficiencies of 2.4% (benzothiophene), 4.1% (benzoselenophene), and 3.0% (benzotellurophene), respectively.

  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


    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. Session 4: HDS, HDN and HYD assisted by ultrasound using formic acid as hydrogen precursor

    Energy Technology Data Exchange (ETDEWEB)

    Scott Carlos, E.; Bolivar, C.; Grobas, J. [Universidad Central de Venezuela, Centro de Catalisis Petroleo y Petroquimica, Escuela de Quimica, Facultad de Ciencias, Caracas (Venezuela)


    The study of chemical effects of ultrasound is a rapidly growing research area, and its use in heavy crude oil upgrading has been explored. In this work, hydrogenation of cyclohexene and biphenyl, hydrodesulfurization of benzothiophene and hydro-denitrogenation of quinoline, in the presence of a hydrogen precursor, a Pd/C catalyst and ultrasound irradiation was studied. It was found, that the use of formic acid as hydrogen precursor in presence of ultrasonic irradiation was an effective system to promote hydrogenation of cyclohexene (98%) and biphenyl (21%), desulfurization of benzothiophene (18%) and hydrogenation of quinoline (19%), at very mild conditions, i.e. ambient temperature and pressure. (authors)

  19. Rhodium(I)-Catalyzed Benzannulation of Heteroaryl Propargylic Esters: Synthesis of Indoles and Related Heterocycles. (United States)

    Li, Xiaoxun; Xie, Haibo; Fu, Xiaoning; Liu, Ji-Tian; Wang, Hao-Yuan; Xi, Bao-Min; Liu, Peng; Xu, Xiufang; Tang, Weiping


    A de novo synthesis of a benzene ring allows for the preparation of a diverse range of heterocycles including indoles, benzofurans, benzothiophenes, carbazoles, and dibenzofurans from simple heteroaryl propargylic esters using a unified carbonylative benzannulation strategy. Multiple substituents can be easily introduced to the C4-C7 positions of indoles and related heterocycles.

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

    Directory of Open Access Journals (Sweden)

    Gadada Naganagowda


    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.

  1. Adsorption of N/S heterocycles in the flexible metal-organic framework MIL-53(Fe(III)) studied by in situ energy dispersive X-ray diffraction. (United States)

    Van de Voorde, Ben; Munn, Alexis S; Guillou, Nathalie; Millange, Franck; De Vos, Dirk E; Walton, Richard I


    The adsorption of N/S-containing heterocyclic organic molecules in the flexible iron(III) terephthalate MIL-53, Fe(III)(OH)(0.6)F(0.4)(O2C-C6H4-CO2)·(H2O), from the liquid phase was studied with in situ energy dispersive X-ray diffraction (EDXRD), in order to follow the adsorption-induced expansion of the structure. For comparison with the diffraction data, liquid phase adsorption isotherms were recorded for uptake of benzothiophene, benzothiazole and indole in isopropanol and in heptane. The solvent not only influences pore opening but is also a competing guest. The in situ EDXRD experiments allow the kinetics of guest uptake and the competition with solvent to be monitored directly. Indole uptake is limited; this adsorbate is barely capable of opening the closed, either hydrated or dehydrated, MIL-53(Fe) structure, or of penetrating the isopropanol-containing material in the concentration range under study. When isopropanol is used as a solvent, the guest molecules benzothiophene and benzothiazole must be present at a certain threshold concentration before substantial adsorption into the metal-organic framework takes place, eventually resulting in full opening of the structure. The fully expanded structures of benzothiophene or benzothiazole loaded MIL-53(Fe) materials have Imcm symmetry and a unit cell volume of ca. 1600 Å(3), and upon uptake of the guest molecules by the closed form (unit cell volume ~1000 Å(3)) no intermediate crystalline phases are seen. Successful uptake by MIL-53(Fe) requires that the adsorbate is primarily a good hydrogen bond acceptor; additionally, based on UV-visible spectroscopy, a charge-transfer interaction between the S atoms of benzothiophene and the aromatic rings in the MOF pore wall is proposed.

  2. 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


    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.

  3. Crystal structure of 6-(p-tolylbenzo[b]naphtho[2,3-d]thiophene and of an orthorhombic polymorph of 7-phenylanthra[2,3-b]benzo[d]thiophene

    Directory of Open Access Journals (Sweden)

    S. Gopinath


    Full Text Available The title compounds, C23H16S, (I, and C26H16S, (II, are benzothiophene derivatives in which the benzothiophene moiety is fused with a naphthalene ring system in (I, and with an anthracene ring system in (II. In (I, the mean plane of the benzothiophene ring system makes a dihedral angle of 2.28 (6° with the naphthalene ring system, and a dihedral angle of 1.28 (6° with the anthracene ring system in (II, showing that the fused units are essentially planar. In (I, the 4-methylbenzene ring substituent makes a dihedral angle of 71.40 (9° with the naphthalene ring system, while the phenyl ring substituent in (II makes a dihedral angle of 67.08 (12° with the anthracene ring system. In the crystals of both compounds, molecules are linked by C—H...π interactions, leading to the formation of slabs parallel to (001 in (I and to zigzag chains along [001] in (II. There are also offset π–π interactions present within the slabs in (I. In the crystal of (II, they link the chains, forming sheets parallel to (010. The triclinic polymorph of compound (II has been reported [Sivasakthikumaran et al., (2012. J. Org. Chem. 77, 9053–9071].

  4. Variation in toxicity during the biodegradation of various heterocyclic and homocyclic aromatic hydrocarbons in single and multi-substrate systems. (United States)

    Oberoi, Akashdeep Singh; Philip, Ligy


    In the present study, an attempt was made to understand the variation in the toxicity during the biodegradation of aromatic hydrocarbons in single and multi-substrate system. The bacterial bioassay based on the inhibition of dehydrogenase enzyme activity of two different bacterial sp. E.coli and Pseudomonas fluorescens was used for toxicity assessment. Amongst the chosen pollutants, the highest acute toxicity was observed for benzothiophene followed by benzofuran having EC50 value of 16.60mg/L and 19.30mg/L respectively. Maximum residual toxicity of 30.8% was observed at the end during the degradation of benzothiophene. Due to the accumulation of transitory metabolites in both single and multisubstrate systems, reduction in toxicity was not proportional to the decrease in pollutant concentration. In multi-substrate system involving mixture of heterocyclic hydrocarbons, maximum residual toxicity of 39.5% was observed at the end of biodegradation. Enhanced degradation of benzofuran, benzothiophene and their metabolic intermediates were observed in the presence of naphthalene resulting in significant reduction in residual toxicity. 2 (1H) - quinolinone, an intermediate metabolite of quinoline was observed having significant eco-toxicity amongst all other intermediates investigated.

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

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


    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. 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


    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.

  7. Matrix-Isolation Spectroscopy and Computational Studies of Reactive Organic Molecules of Relevance to Interstellar Space (United States)

    Kopff, Laura A.; Kreifels, Terese A.; Schaffer, Christopher J.; Haenni, Benjamin C.; Esselman, Brian J.; McMahon, Robert J.


    Matrix isolation, the process of trapping a molecule in an inert gas at low temperature, provides a means for studying highly reactive intermediates, such as carbenes or radicals. Reactive species can be characterized by IR, UV-vis and/or EPR spectroscopy. Comparison of experimental and computed spectral data, as well as chemical reactivity, is used for structural assignment. Highly-unsaturated carbon chains are well known compounds in the interstellar medium (ISM). Detection of these molecules relies mostly on radioastronomy, making the detection of the linear HC2nH series difficult. The electronic structure changes from even carbon chain lengths (HC2nH) to odd chain lengths (HC2n+1H), changing from closed shell to open shell species. The odd series further alternate from a diradical character (HC3H) to a localized carbene (HC5H). This poster will present the synthesis and spectroscopy of the HC3H and HC7H species and derivatives. The study of arylcarbenes is vital to understanding the chemistry of carbon-rich environments, such as discharges, interstellar clouds, and circumstellar envelopes. The identification of small, sulfur containing molecules, and the identification of aromatics in the ISM make future thiophene and benzothiophene detections a real possibility. Studies on 2- and 3- diazomethyl substituted benzothiophenes are underway to assess their photochemical reactivity and potential for forming benzothiophene carbenes. Macrocylic polyynes are proposed to be involved in carbon condensation via the ring coalescence and annealing model to produce graphitic sheets or fullerenes. To simplify a complex system we are computationally studying the series of ethynyl-substituted cyclobutadienes and their possible involvement in the build-up of larger carbon containing molecules in the ISM.

  8. 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. (United States)

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


    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.

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

    DEFF Research Database (Denmark)

    Broholm, Kim; Nilsson, B.; Sidle, Roy C.


    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......-methylnaphthalene, benzothio- phene, 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. q2000 Elsevier Science B.V. All rights reserved....

  10. Carboxylated Photoswitchable Diarylethenes for Biolabeling and Super-Resolution RESOLFT Microscopy. (United States)

    Roubinet, Benoît; Bossi, Mariano L; Alt, Philipp; Leutenegger, Marcel; Shojaei, Heydar; Schnorrenberg, Sebastian; Nizamov, Shamil; Irie, Masahiro; Belov, Vladimir N; Hell, Stefan W


    Reversibly photoswitchable 1,2-bis(2-ethyl-6-phenyl-1-benzothiophene-1,1-dioxide-3-yl)perfluorocyclopentenes (EBT) having fluorescent "closed" forms were decorated with four or eight carboxylic groups and attached to antibodies. Low aggregation, efficient photoswitching in aqueous buffers, specific staining of cellular structures, and good photophysical properties were demonstrated. Alternating light pulses of UV and blue light induce numerous reversible photochemical transformations between two stables states with distinct structures. Using relatively low light intensities, EBTs were applied in biology-related super-resolution microscopy based on the reversible saturable (switchable) optical linear fluorescence transitions (RESOLFT) and demonstrated optical resolution of 75 nm.

  11. Mathematical modeling of diesel fuel hydrotreating (United States)

    Tataurshikov, A.; Ivanchina, E.; Krivtcova, N.; Krivtsov, E.; Syskina, A.


    Hydrotreating of the diesel fraction with the high initial sulfur content of 1,4 mass% is carried out in the flow-through laboratory setup with the industrial GKD-202 catalyst at various process temperature. On the basis of the experimental data the regularities of the hydrogenation reactions are revealed, and the formalized scheme of sulfur-containing components (sulfides, benzothiophenes, and dibenzothiophenes) transformations is made. The mathematical model of hydrotreating process is developed, the constant values for the reaction rate of hydrodesulfurization of the specified components are calculated.

  12. Changing the composition of the group hydrocarbons of diesel fractions in the process of hydrotreating (United States)

    Krivtcova, N.; Baklashkina, К; Sabiev, Sh; Krivtsov, E.; Syskina, A.


    Change in group composition of sulfur compounds and structural group composition of the diesel fractions in the course of hydrotreating is presented in the paper. The removal degree of sulfur compounds is shown to comprise 95.8% rel. The homologs of benzothiophenes are removed for 93.9% rel., ones of the dibenzothiophenes are for 90.7% rel. A considerable change in group composition of diesel fraction is established in the course of hydrotreating. Hydrogenation degree of aromatic hydrocarbons is 24.4% wt., the amount of saturated hydrocarbons has increased by 20.4% wt.

  13. 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


    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...

  14. Reactivity of silicon and germanium doped CNTs toward aromatic sulfur compounds: A theoretical approach

    Energy Technology Data Exchange (ETDEWEB)

    Galano, Annia [Departamento de Quimica, Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Col. Vicentina. Iztapalapa, C.P. 09340 Mexico D.F. (Mexico); Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, 07730 Mexico D.F. (Mexico)], E-mail:; Francisco-Marquez, Misaela [Departamento de Quimica, Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Col. Vicentina. Iztapalapa, C.P. 09340 Mexico D.F. (Mexico); Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, 07730 Mexico D.F. (Mexico)


    Adsorption processes of thiophene and benzothiophene on pristine carbon nanotubes (CNTs), and on CNTs doped with Si or Ge, have been modeled with Density Functional. This is the first study on the chemical reactivity of such doped tubes. The calculated data suggest that the presence of silicon or germanium atoms in CNTs increases their reactivity toward thiophene, and benzothiophene. The adsorption of these species on pristine CNTs seems very unlikely to occur, while the addition products involving doped CNTs were found to be very stable, with respect to the isolated reactants, in terms of Gibbs free energy. Several of these adsorption processes were found to be significantly exergonic ({delta}G < 0) in non-polar liquid phase. The results reported in this work suggest that Si and Ge defects on CNTs increase their reactivity toward unsaturated species, and could make them useful in the removal processes of aromatic sulfur compounds from oil-hydrocarbons. However, according to our results, CNTs doped with Si atoms are expected to be more efficient as aromatic sulfur compounds scavengers than those doped with Ge. These results also suggest that the presence of silicon and germanium atoms in the CNTs structures enhances their reactivity toward nucleophilic molecules, compared to pristine carbon nanotubes.

  15. Zinc-aluminates for an in situ sulfur reduction in cracked gasoline

    Energy Technology Data Exchange (ETDEWEB)

    Quintana-Solorzano, R.; Valente, J.S.; Hernandez-Beltran, F.J.; Castillo-Araiza, C.O. [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas Norte 152 C.P., 07730 Mexico, D.F. (Mexico)


    Using additives remains as an attractive alternative for an in situ sulfur reduction in cracked gasoline since it is a practical, flexible and economical option. Zinc-aluminates prepared by the sol-gel method are used as additives for reducing sulfur in gasoline from the cracking of a high-sulfur feed in a fixed-bed bench reactor. Products distribution and feed conversion are not dramatically altered after incorporating the additive to the base catalyst with some effect on gasoline and its octane number and coke. A decrease in the gasoline sulfur content of up to 35 wt% including benzothiophene, and up to 50% excluding benzothiophene, is observed when blending the zinc-aluminates to the base catalyst, which is caused by lowering the C{sub 1} to C{sub 4} alkyl-thiophenes content. The zinc content of the zinc-aluminates has a positive effect on the gasoline sulfur reduction. It is suggested that together with the direct cracking of adsorbed thiophenic species on the additive, a further gasoline sulfur decrease is possible through cracking of saturated thiophenic species formed by hydrogenation of adsorbed thiophenic species with hydrogen produced in situ in the additive. The obtained results also demonstrate that solids with higher Lewis acidity are not unfailingly the most effective for gasoline sulfur reduction. (author)

  16. Application of solid-phase microextraction to the determination of polycyclic aromatic sulfur heterocycles in Bohai Sea crude oils. (United States)

    Yang, Baijuan; Hou, Wei; Zhang, Kuiying; Wang, Xiaoru


    A simple and rapid solid-phase microextraction approach for the isolation of polycyclic aromatic sulfur heterocycles from the aromatic fraction of crude oil is described. 8-Hydroxyquinoline silica gel impregnated with palladium chloride was used as a sorbent material for extraction. Operational parameters of the extraction solvents have been evaluated and optimized. Benzothiophene, dibenzothiophene, and benzo[b]naphtho[1,2-d]thiophene and their C1-C4 alkyl derivatives were identified and quantified by GC-MS. Under optimum conditions, the limits of detection for benzothiophene, dibenzothiophene, and benzo[b]naphtho[1,2-d]thiophene were 0.277, 0.193, and 0.597 μg/g oil, respectively. The recoveries for the polycyclic aromatic sulfur heterocycles ranged from 81.5 to 92.1%, and the linear dynamic range was from 10 to 1000 ng/mL. The developed methodology was tested in the characterization of crude oil samples collected at the DY, SZ, ZH, and HC petroleum oil fields of the Bohai Sea. The results proved that SPE coupled with GC-MS is a promising tool for the quantitative analysis of polycyclic aromatic sulfur heterocycles in crude oils, especially for oil samples with low concentrations of polycyclic aromatic sulfur heterocycles.

  17. Studies in coal liquefaction with application to the SRC and related processes. Quarterly report, August 1981-October 1981. [Using model compounds

    Energy Technology Data Exchange (ETDEWEB)

    Tarrer, A. R.; Guin, J. A.; Curtis, C. W.


    Model compound reactions were studied to evaluate the effects of mass transfer, solvent type, solvent blending, hydrogen partial pressure, temperature, reactant concentration, additive loading and its preparation, etc. Naphthalene hydrogenation and benzothiophene hydrodesulfurization were investigated under the conditions comparable to commercial coal liquefaction and related processes. Both of these reaction systems were observed to be surface reaction controlled under the reaction conditions used in this work. Certain aromatic compounds were observed to cause a reduction in the reaction rates of naphthalene and benzothiophene. Single stage coal dissolution was investigated using tetralin as a hydrogen donor solvent and a commercial cobalt-molybdate catalyst. A spinning basket system was developed to allow injection of the catalyst at a desired time in the reaction cycle. This catalyst injection technique proved to be reliable for the exploratory work done here. The degree of catalyst deactivation was rated by comparing the activities of the spent catalyst for model compound (naphthalene and cumene) reactivities relative to those of the fresh catalyst. No substantial reduction in deactivation was observed to result with delayed contacting of the catalyst with the coal-tetralin reaction mixture. The effect of reaction temperature on the initial rate of catalyst deactivation was also studied.

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

    Directory of Open Access Journals (Sweden)

    N. Susantha Chandrasekera


    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.

  19. Matrix-Isolation Spectroscopy of Reactive Organic Molecules of Relevance to Interstellar Space (United States)

    Kopff, Laura A.; Nolan, Alex M.; Kreifels, Terese A.; Draxler, Thomas W.; Esselman, Brian J.; Burrmann, Nicola J.; McMahon, Robert J.


    Matrix isolation, the process of trapping a molecule in an inert gas at low temperature, provides a means for studying highly reactive intermediates, such as carbenes or radicals. Reactive species can be characterized by IR, UV-vis and/or EPR spectroscopy. Comparison of experimental and computed spectral data, as well as chemical reactivity, is used for structural assignment Triplet propynylidene is proposed to exist in the interstellar medium (ISM), due to the detection of a higher-energy isomers via rotational spectroscopy. Currently, we are exploring the structural and photochemical effects of varying substituents on the propynylidne system. A diazo precursor has been synthesized and photolyzed to produce dimethylpropynylidene in an argon matrix. A photochemical hydrogen shift to produce 1-penten-3-yne has been observed through infrared spectroscopy. Cyanocarbons are known to be abundant in the ISM and the atmosphere of Titan, however matrixisolation studies have not yet been carried out for a significant number of these compounds. Photolysis of 3-cyano-3-methyldiazirine should yield methylcyanocarbene, one of the simplest species in this family. Another molecule of interest is l-HC4N, which has been detected in the ISM, but has not yet been matrix-isolated and characterized. The study of arylcarbenes is vital to understanding the chemistry of carbon-rich environments, such as discharges, interstellar clouds, and circumstellar envelopes. The identification of small, sulfur containing molecules, and the identification of aromatics in the ISM make future thiophene and benzothiophene detections a real possibility. Studies on 2- and 3-diazomethyl substituted benzothiophenes are underway to assess their photochemical reactivity and potential for forming benzothiophene carbenes. Macrocylic polyynes are proposed to be involved in carbon condensation via the ring coalescence and annealing model to produce graphitic sheets or fullerenes. To simplify a complex system we

  20. Crystal structures of (Z)-5-[2-(benzo[b]thio-phen-2-yl)-1-(3,5-di-meth-oxy-phen-yl)ethen-yl]-1H-tetra-zole and (Z)-5-[2-(benzo[b]thio-phen-3-yl)-1-(3,4,5-tri-meth-oxy-phen-yl)ethen-yl]-1H-tetra-zole. (United States)

    Penthala, Narsimha Reddy; Yadlapalli, Jaishankar K B; Parkin, Sean; Crooks, Peter A


    (Z)-5-[2-(Benzo[b]thio-phen-2-yl)-1-(3,5-di-meth-oxy-phen-yl)ethen-yl]-1H-tetrazole methanol monosolvate, C19H16N4O2S·CH3OH, (I), was prepared by the reaction of (Z)-3-(benzo[b]thio-phen-2-yl)-2-(3,5-di-meth-oxy-phen-yl)acrylo-nitrile with tri-butyl-tin azide via a [3 + 2]cyclo-addition azide condensation reaction. The structurally related compound (Z)-5-[2-(benzo[b]thio-phen-3-yl)-1-(3,4,5-tri-meth-oxy-phen-yl)ethen-yl]-1H-tetra-zole, C20H18N4O3S, (II), was prepared by the reaction of (Z)-3-(benzo[b]thio-phen-3-yl)-2-(3,4,5-tri-meth-oxy-phen-yl)acrylo-nitrile with tri-butyl-tin azide. Crystals of (I) have two mol-ecules in the asymmetric unit (Z' = 2), whereas crystals of (II) have Z' = 1. The benzo-thio-phene 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 tetra-zole rings of (I) and (II) make dihedral angles with the mean planes of the benzo-thio-phene rings of 88.81 (13) and 88.92 (13)° in (I), and 60.94 (6)° in (II). The di-meth-oxy-phenyl and tri-meth-oxy-phenyl rings make dihedral angles with the benzo-thio-phene rings of 23.91 (8) and 24.99 (8)° in (I) and 84.47 (3)° in (II). In both structures, mol-ecules are linked into hydrogen-bonded chains. In (I), these chains involve both tetra-zole and methanol, and are parallel to the b axis. In (II), mol-ecules are linked into chains parallel to the a axis by N-H⋯N hydrogen bonds between adjacent tetra-zole rings.

  1. Methacrylate-bonded covalent-organic framework monolithic columns for high performance liquid chromatography. (United States)

    Liu, Li-Hua; Yang, Cheng-Xiong; Yan, Xiu-Ping


    Covalent-organic frameworks (COFs) are a newfangled class of intriguing microporous materials. Considering their unique properties, COFs should be promising as packing materials for high performance liquid chromatography (HPLC). However, the irregular shape and sub-micrometer size of COFs synthesized via the traditional methods render the main obstacles for the application of COFs in HPLC. Herein, we report the preparation of methacrylate-bonded COF monolithic columns for HPLC to overcome the above obstacles. The prepared COF bonded monolithic columns not only show good homogeneity and permeability, but also give high column efficiency, good resolution and precision for HPLC separation of small molecules including polycyclic aromatic hydrocarbons, phenols, anilines, nonsteroidal anti-inflammatory drugs and benzothiophenes. Compared with the bare polymer monolithic column, the COF bonded monolithic columns show enhanced hydrophobic, π-π and hydrogen bond interactions in reverse phase HPLC. The results reveal the great potential of COF bonded monoliths for HPLC and COFs in separation sciences.

  2. Cinchona Alkaloid Derivative-Catalyzed Enantioselective Synthesis via a Mannich-Type Reaction and Antifungal Activity of β-Amino Esters Bearing Benzoheterocycle Moieties

    Directory of Open Access Journals (Sweden)

    Han Xiao


    Full Text Available An efficient synthesis of highly functionalized chiral β-amino ester derivatives containing benzothiophene and benzothiazole moieties is developed by a Mannich-type reaction using a cinchona alkaloid-derived thiourea catalyst. The desired products were obtained in good yields and high enantioselectivities (~86% yield, >99% ee using to the optimized reaction conditions. The synthesized compounds were characterized by 1H-NMR, 13C-NMR, IR, and HREI-MS analyses. The bioassays identified that compound 5dr has excellent antifungal activity, with a 60.53% inhibition rate against F. oxysporum, higher than that of the commercial agricultural fungicide hymexazol, whose inhibition rate was 56.12%.

  3. Structurally Diverse π-Extended Conjugated Polycarbo- and Heterocycles through Pd-Catalyzed Autotandem Cascades. (United States)

    Barroso, Raquel; Cabal, María-Paz; Badía-Laiño, Rosana; Valdés, Carlos


    The Pd-catalyzed reaction between 2,2'-dibromobiphenyls and related systems with tosylhydrazones gives rise to new π-extended conjugated polycarbo- and heterocycles through an autotandem process involving a cross-coupling reaction followed by an intramolecular Heck cyclization. The reaction shows wide scope regarding both coupling partners. Cyclic and acyclic tosylhydrazones can participate in the process. Additionally, a variety of aromatic and heteroaromatic dibromoderivatives have been employed, leading to an array of diverse scaffolds featuring a fluorene or acridine central nucleus, and containing binaphthyl, thiophene, benzothiophene and indole moieties. The application to appropriate tetrabrominated systems led to greater structural complexity through two consecutive autotandem cascades. The photophysical properties of selected compounds were studied through their absorption and emission spectra. Fluorescence molecules featuring very high quantum yields were identified, showing the potential of this methodology in the development of molecules with interesting optoelectronic properties.

  4. Single crystalline growth of a soluble organic semiconductor in a parallel aligned liquid crystal solvent using rubbing-treated polyimide films (United States)

    Matsuzaki, Tomoya; Shibata, Yosei; Takeda, Risa; Ishinabe, Takahiro; Fujikake, Hideo


    For directional control of organic single crystals, we propose a crystal growth method using liquid crystal as the solvent. In this study, we examined the formation of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) single crystals using a parallel aligned liquid crystal (LC) cell and rubbing-treated polyimide films in order to clarify the effects of LC alignment on anisotropic C8-BTBT crystal growth. Based on the results, we found that the crystal growth direction of C8-BTBT single crystals was related to the direction of the aligned LC molecules because of rubbing treatment. Moreover, by optical evaluation, we found that the C8-BTBT single crystals have a aligned molecular structure.

  5. Preparation of AAO-CeO2 nanotubes and their application in electrochemical oxidation desulfurization of diesel (United States)

    Du, Xiaoqing; Yang, Yumeng; Yi, Chenxi; Chen, Yu; Cai, Chao; Zhang, Zhao


    The coaxial arrays of AAO-CeO2 NTs have been successfully galvanostatically deposited on an anode, characterized and adopted as a catalyst for removing organic sulfurs from diesel. The influence of the main electrochemical oxidation factors on the efficiency of desulfurization have also been investigated. The results show that the fabrication process of AAO-CeO2 NTs is accompanied by the formation of a new phase, namely Al3Ce, and the main oxidation products of the diesel are soluble inorganic sulphides, especially Ce2(SO4)3. When compared with dibenzothiophene and 4, 6-dimethyldibenzothiophene, benzothiophene is much more easily removed, with a removal efficiency that reaches 87.2%. Finally, a possible electrochemical oxidation desulfurization pathway for diesel is proposed.

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

    Directory of Open Access Journals (Sweden)

    C. N. Warwick


    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.

  7. Characterization and deposit-forming tendency of polar compounds in cracked components of gasoline. Identification of phenols and aromatic sulfur compounds

    Energy Technology Data Exchange (ETDEWEB)

    Martin, P.; McCarty, F.; Ehrmann, U.; Lima, L. de; Carvajal, N.; Rojas, A. (INTEVEP S.A., Caracas (Venezuela))


    Acidic compounds in cracked components of gasoline, isolated by extraction with aqueous solutions of sodium bicarbonate and sodium hydroxide, were identified as phenol and its mono-, di-, tri- and tetramethyl- derivatives. Aromatic sulfur compounds separated as the hexane and benzene fractions by chromatography on an alumina column were identified as thiophene, its mono-, di- and trimethyl- derivatives, ethylthiophene, benzothiophene and methylbenzothiophene. The identification of the phenolic compounds was achieved by IR, hydrogen-1 and carbon-13 NMR spectroscopy and GC-MS. Additionally, for complete identification of sulfur compounds a GC equipped with a selective sulfur detector was used. ISD Induction System Deposit (ISD) tests showed a decreased deposit-forming tendency for phenol compounds and no significant deposit formation for aromatic sulfur compounds or other fractions isolated. 10 refs., 6 figs., 4 tabs.

  8. Study on Reduction of Sulfur Content in FCC Gasoline

    Institute of Scientific and Technical Information of China (English)

    Hou Dianguo


    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. Accepting the Invitation to Open Innovation in Malaria Drug Discovery: Synthesis, Biological Evaluation, and Investigation on the Structure-Activity Relationships of Benzo[b]thiophene-2-carboxamides as Antimalarial Agents. (United States)

    Pieroni, Marco; Azzali, Elisa; Basilico, Nicoletta; Parapini, Silvia; Zolkiewski, Michal; Beato, Claudia; Annunziato, Giannamaria; Bruno, Agostino; Vacondio, Federica; Costantino, Gabriele


    Malaria eradication is a global health priority, but current therapies are not always suitable for providing a radical cure. Artemisinin has paved the way for the current malaria treatment, the so-called Artemisinin-based Combination Therapy (ACT). However, with the detection of resistance to ACT, innovative compounds active against multiple parasite species and at multiple life stages are needed. GlaxoSmithKline has recently disclosed the results of a phenotypic screening of an internal library, publishing a collection of 400 antimalarial chemotypes, termed the "Malaria Box". After analysis of the data set, we have carried out a medicinal chemistry campaign in order to define the structure-activity relationships for one of the released compounds, which embodies a benzothiophene-2-carboxamide core. Thirty-five compounds were prepared, and a description of the structural features responsible for the in vitro activity against different strains of P. falciparum, the toxicity, and the metabolic stability is herein reported.

  10. 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


    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.

  11. Sulfoxide-Directed Metal-Free ortho-Propargylation of Aromatics and Heteroaromatics. (United States)

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


    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.

  12. 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


    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.

  13. Electron spectra of radical cations of heteroanalogs

    Energy Technology Data Exchange (ETDEWEB)

    Petrushenko, K.B.; Turchaninov, V.K.; Vokin, A.I.; Ermikov, A.F.; Frolov, Yu.L.


    Radical cation spectra of indazole and benzothiophene in the visible region were obtained by laser photolysis during the reaction of photoexcited quinones with these compounds in acetonitrile. The charge transfer bands of the complexes of the test compounds with p-chloranil and 7,7,8,8-tetracyanoquinodimethane in dioxane were recorded on a Specord M-40. Photoelectron spectra were obtained on a ES-3201 electron spectrometer. The He(I) resonance band (21.21 eV) was used for excitation. Measurements were carried out in the 60-120/sup 0/C range. The energy scale was calibrated form the first ionization potentials of Ar (15.76 eV) and chlorobenzene (9.06 eV). The error in the determination of the ionization potentials for the first four photoelectron bands was 0.05 eV.

  14. A DFT study of the extractive desulfurization mechanism by [BMIM](+)[AlCl4](-) ionic liquid. (United States)

    Li, Hongping; Chang, Yonghui; Zhu, Wenshuai; Jiang, Wei; Zhang, Ming; Xia, Jiexiang; Yin, Sheng; Li, Huaming


    In this work, the interaction nature between [BMIM](+)[AlCl4](-) ionic liquid (IL) and aromatic sulfur compounds (thiophene, benzothiophene, and dibenzothiophene) has been studied by means of density functional theory (M06-2X functional) combined with an implicit solvation model. Although [BMIM](+)[AlCl4](-) is a metal-containing IL, its extractive desulfurization mechanism is different from other metal-containing ILs but similar to non-metal-containing ILs. Important reactions involved in extractive desulfurization (EDS) were systematically studied. Our results have demonstrated that both the cation and the anion play important roles in EDS. On the basis of the structure analysis, reduced density gradient analaysis (RDG), and energy decomposition analysis, [BMIM](+) cation affords a π-π interaction while [AlCl4](-) anion provides a hydrogen bonding interaction. Electrostatic potential analysis implies the dominant π-π interaction and hydrogen bonding interaction are driven by electrostatic interaction between IL and aromatic sulfur compounds. Interaction energy between [BMIM](+)[AlCl4](-) and thiophene (TH), benzothiophene (BT), and dibenzothiophene (DBT) follows the order TH < BT < DBT. Moreover, Al-containing IL with a high molar ratio of AlCl3 ([BMIMCl]/2[AlCl3]) has also been studied. Results show that [Al2Cl7](-) species will be formed with excess AlCl3. However, the [Al2Cl7](-)-based IL cannot improve the EDS performance. Improvement of EDS performance with a high molar ratio of AlCl3 is credited to the Lewis acidity of AlCl3. Charge analysis reveals that there is no obvious charge transfer during the reaction, which is different from Fe-containing ILs as well as solid sorbents. In addition, CH-π interaction is not important for the current system.

  15. Identification of organic sulfur compounds in coal bitumen obtained by different extraction techniques using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometric detection. (United States)

    Machado, Maria Elisabete; Fontanive, Fernando Cappelli; de Oliveira, José Vladimir; Caramão, Elina Bastos; Zini, Cláudia Alcaraz


    The determination of organic sulfur compounds (OSC) in coal is of great interest. Technically and operationally these compounds are not easily removed and promote corrosion of equipment. Environmentally, the burning of sulfur compounds leads to the emission of SO(x) gases, which are major contributors to acid rain. Health-wise, it is well known that these compounds have mutagenic and carcinogenic properties. Bitumen can be extracted from coal by different techniques, and use of gas chromatography coupled to mass spectrometric detection enables identification of compounds present in coal extracts. The OSC from three different bitumens were tentatively identified by use of three different extraction techniques: accelerated solvent extraction (ASE), ultrasonic extraction (UE), and supercritical-fluid extraction (SFE). Results obtained from one-dimensional gas chromatography (1D GC) coupled to quadrupole mass spectrometric detection (GC-qMS) and from two-dimensional gas chromatography with time-of-flight mass spectrometric detection (GC × GC-TOFMS) were compared. By use of 2D GC, a greater number of OSC were found in ASE bitumen than in SFE and UE bitumens. No OSC were identified with 1D GC-qMS, although some benzothiophenes and dibenzothiophenes were detected by use of EIM and SIM modes. GC × GC-TOFMS applied to investigation of OSC in bitumens resulted in analytical improvement, as more OSC classes and compounds were identified (thiols, sulfides, thiophenes, naphthothiophenes, benzothiophenes, and benzonaphthothiophenes). The roof-tile effect was observed for OSC and PAH in all bitumens. Several co-elutions among analytes and with matrix interferents were solved by use of GC × GC.

  16. Transport and biodegradation of creosote compounds in clayey till, a field experiment (United States)

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


    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.

  17. Facile C-S, S-H, and S-S bond cleavage using a nickel(0) NHC complex. (United States)

    Schaub, Thomas; Backes, Marc; Plietzsch, Oliver; Radius, Udo


    [Ni2(iPr2Im)4(COD)] 1 (iPr2Im = 1,3-di(isopropyl)-imidazol-2-ylidene) reacts at room temperature with the thioethers methyl para-tolyl sulfide, ethyl phenyl sulfide, benzothiophene and dibenzothiophene to afford the C-S bond cleavage products [Ni(iPr2Im)2(4-CH3-C6H4)(SMe)] 2, [Ni(iPr2Im)2(C6H5)(SEt)] 3, [Ni(iPr2Im)2(1,8-benzothiophenylato)] 4 and [Ni(iPr2Im)2(C,S-dibenzothiophenylato)] 5. In contrast to the reaction of thioethers or sulfoxides (reported earlier), no C-S bond cleavage was observed for the reaction of 1 with the sulfones bezothiophene-1,1-dioxide and methyl phenyl sulfone. In those cases the stable compounds [Ni(iPr2Im)2(eta2-2,3-benzothiophene-1,1-dioxide)] 6 and [Ni(iPr2Im)2(eta2-MeSO2C6H5)] 7 with a eta2-coordinated sulfone ligand have been isolated. Compound 6 has been structurally characterized. S-H bond cleavage was observed using 2-methyl-2-propanthiol to afford [Ni(iPr2Im)2(H)(StBu)] 8. The reaction of 1 with disulfides led to the dithiolato complexes [Ni(iPr2Im)2(SR)2] (R = tBu 9, Me 10, Ph 11) by S-S bond scission.

  18. Design and prediction of new anticoagulants as a selective Factor IXa inhibitor via three-dimensional quantitative structure-property relationships of amidinobenzothiophene derivatives

    Directory of Open Access Journals (Sweden)

    Gao JS


    Full Text Available Jia-Suo Gao,1* Xu-Peng Tong,2* Yi-Qun Chang,1 Yu-Xuan He,1 Yu-Dan Mei,1 Pei-Hong Tan,1 Jia-Liang Guo,1 Guo-Chao Liao,3 Gao-Keng Xiao,1 Wei-Min Chen,1 Shu-Feng Zhou,4 Ping-Hua Sun1 1Guangdong Province Key Laboratory of Pharmacodynamic Constituents of Traditional Chinese Medicine and New Drugs Research, College of Pharmacy, Jinan University, Guangzhou, People’s Republic of China; 2College of Pharmacy, China Pharmaceutical University, Nanjing, People’s Republic of China; 3Department of Chemistry, Wayne State University, Detroit, Michigan, USA; 4College of Pharmacy, University of South Florida, Tampa, FL, USA *These authors contributed equally to this work Abstract: Factor IXa (FIXa, a blood coagulation factor, is specifically inhibited at the initiation stage of the coagulation cascade, promising an excellent approach for developing selective and safe anticoagulants. Eighty-four amidinobenzothiophene antithrombotic derivatives targeting FIXa were selected to establish three-dimensional quantitative structure–activity relationship (3D-QSAR and three-dimensional quantitative structure–selectivity relationship (3D-QSSR models using comparative molecular field analysis and comparative similarity indices analysis methods. Internal and external cross-validation techniques were investigated as well as region focusing and bootstrapping. The satisfactory q2 values of 0.753 and 0.770, and r2 values of 0.940 and 0.965 for 3D-QSAR and 3D-QSSR, respectively, indicated that the models are available to predict both the inhibitory activity and selectivity on FIXa against Factor Xa, the activated status of Factor X. This work revealed that the steric, hydrophobic, and H-bond factors should appropriately be taken into account in future rational design, especially the modifications at the 2'-position of the benzene and the 6-position of the benzothiophene in the R group, providing helpful clues to design more active and selective FIXa inhibitors for the


    Institute of Scientific and Technical Information of China (English)

    山红红; 李春义; 赵辉; 杨朝合; 张建芳


    Online pulsereaction chromatography and MS transient response technique were used to investigate the cracking de sulfurization of thiophene over a USY zeolite The products of thiophene cracki ng contain hydrocarbons (propylene, butane, and butene, etc) and sulfides (H 2S,2methylthiophene, 3 methylthiophene, dimethylthiophene, trimethy lthiophene and benzothiophene)During the reaction, cracking and hydrogen tr ansfer are two important elementary steps Thermodynamically, the former favors higher temperature while the latter does lower The contradiction leads to abo ut 400℃ to be the optimal temperature for thiophene conversion Based on the experimental results, the desulfurization mechanism of thiophene over the USY z eolite is proposed sufurization of thiophene over a USY zeolite The products of thiophene cracki ng contain hydrocarbons (propylene, butane, and butene, etc) and sulfides (H 2S,2methylthiophene, 3methylthiophene, dimethylthiophene, trimethy lthiophene and benzothiophene) During the reaction, cracking and hydrogen tr ansfer are two important elementary steps Thermodynamically, the former favors higher temperature while the latter does lower The contradiction leads to abo ut 400?℃ to be the optimal temperature for thiophene conversion Based on the experimental results, the desulfurization mechanism of thiophene over the USY z eolite is proposed%采用在线脉冲反应色谱和质谱瞬变响应技术,对噻吩在USY沸石上的裂化脱硫反应行为进行了研究.结果表明,噻吩在USY沸石上发生反应,除生成烃和H2S外,还可以生烷基噻吩和苯并噻吩等硫化物;但噻吩的裂化脱硫是主要反应.噻吩在USY沸石上裂化脱硫反应中,裂化和氢转移是两个重要的反应步骤.热力学上高温有利于前者而低温有利于后者,这对矛盾使得400?℃左右最有利于噻吩的裂化脱硫.本文在实验结果的基础上,提出了

  20. Study of pyrolysis performance of sulfur compounds in residual oil by pyrolysis-gas chromatography%PY-GC法研究渣油中硫化物的热裂解性能

    Institute of Scientific and Technical Information of China (English)

    马少华; 孙宾宾


    High temperature pyrolysis gas chromatography ( PY- GO has been used to investigate the pyrolysis performance of sulfur compounds in residual oil. On the basis of optimization of a series of (PY-GC) experiment conditions, the pyrolysis chromatograms which could reflect the composition and structure of sulfides in residue were obtained. Then the pyrolysates were characterized by comparing to a series of standard sulfur compounds and referring to literature. It was found that the sulfur compounds in pyrolysates mainly consisted of H2S, thiophene, benzothiophene and dibenzothiophene species of compounds. According to the (PY-GC) analysis result of model compounds, it was estimated that H2S was not only from the sulfide structure, but also from thiophene, benzothiophene and dibenzothiophene structures. In addition, thiophene, BT and DBT series of compounds in the pyrolysates were mainly from the large molecules of thiophene, BT and DBT compounds of the heavy oil.%采用裂解气相色谱(PY-GC)方法研究渣油中的大分子硫化物的裂解性能.首先对(PY-GC)的实验条件进行优化,在此基础上,得到了可以反应渣油样品中硫化物组成和结构的裂解色谱图;通过标准物对比并结合文献对渣油裂解产物中硫化物的组成进行定性.研究发现,渣油高温裂解产物中的硫化物主要有:H2S、噻吩类、苯并噻吩类和二苯并噻吩类系列的化合物.根据模型化合物的裂锯色谱分析结果,推测出渣油裂解产物中的H2S不仅来源于重油分子中硫醚类结构的裂解,而且与重油分子中噻吩、苯并噻吩和二苯并噻吩类结构的裂解有关,而渣油裂解产物中的噻吩、BT和DBT系列化合物主要来白于重油中的大分子噻吩、BT和DBT类化合物的裂解.

  1. 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.

  2. Design and prediction of new anticoagulants as a selective Factor IXa inhibitor via three-dimensional quantitative structure-property relationships of amidinobenzothiophene derivatives. (United States)

    Gao, Jia-Suo; Tong, Xu-Peng; Chang, Yi-Qun; He, Yu-Xuan; Mei, Yu-Dan; Tan, Pei-Hong; Guo, Jia-Liang; Liao, Guo-Chao; Xiao, Gao-Keng; Chen, Wei-Min; Zhou, Shu-Feng; Sun, Ping-Hua


    Factor IXa (FIXa), a blood coagulation factor, is specifically inhibited at the initiation stage of the coagulation cascade, promising an excellent approach for developing selective and safe anticoagulants. Eighty-four amidinobenzothiophene antithrombotic derivatives targeting FIXa were selected to establish three-dimensional quantitative structure-activity relationship (3D-QSAR) and three-dimensional quantitative structure-selectivity relationship (3D-QSSR) models using comparative molecular field analysis and comparative similarity indices analysis methods. Internal and external cross-validation techniques were investigated as well as region focusing and bootstrapping. The satisfactory q (2) values of 0.753 and 0.770, and r (2) values of 0.940 and 0.965 for 3D-QSAR and 3D-QSSR, respectively, indicated that the models are available to predict both the inhibitory activity and selectivity on FIXa against Factor Xa, the activated status of Factor X. This work revealed that the steric, hydrophobic, and H-bond factors should appropriately be taken into account in future rational design, especially the modifications at the 2'-position of the benzene and the 6-position of the benzothiophene in the R group, providing helpful clues to design more active and selective FIXa inhibitors for the treatment of thrombosis. On the basis of the three-dimensional quantitative structure-property relationships, 16 new potent molecules have been designed and are predicted to be more active and selective than Compound 33, which has the best activity as reported in the literature.

  3. Design of α7 nicotinic acetylcholine receptor ligands using the (het)Aryl-1,2,3-triazole core: Synthesis, in vitro evaluation and SAR studies. (United States)

    Ouach, Aziz; Pin, Frederic; Bertrand, Emilie; Vercouillie, Johnny; Gulhan, Zuhal; Mothes, Céline; Deloye, Jean-Bernard; Guilloteau, Denis; Suzenet, Franck; Chalon, Sylvie; Routier, Sylvain


    We report here the synthesis of a large library of 1,2,3-triazole derivatives which were in vitro tested as α7 nAchR ligands. The SAR study revealed that several crucial factors are involved in the affinity of these compounds for α7 nAchR such as a (R) quinuclidine configuration and a mono C-3 quinuclidine substitution. The triazole ring was substituted by a phenyl ring bearing small OMe/CH2F groups or fluorine atom and by several heterocycles such as thiophenes, furanes, benzothiophenes or benzofuranes. Among the 30 derivatives tested, the two derivatives 10 and 39 with Ki in the nanomolar range were identified (2.3 and 3 nM respectively). They exhibited a strict selectivity toward the α4β2 nicotinic receptor (up to 1 μM) but interacted with the 5HT3 receptors with Ki around 3 nM. Synthesis, SAR studies and a full description of the derivatives are reported.

  4. Hybrid complementary circuits based on p-channel organic and n-channel metal oxide transistors with balanced carrier mobilities of up to 10 cm2/Vs

    KAUST Repository

    Isakov, Ivan


    We report the development of hybrid complementary inverters based on p-channel organic and n-channel metal oxide thin-film transistors (TFTs) both processed from solution at <200 °C. For the organic TFTs, a ternary blend consisting of the small-molecule 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene, the polymer indacenodithiophene-benzothiadiazole (CIDT-BT) and the p-type dopant CF was employed, whereas the isotype InO/ZnO heterojunction was used for the n-channel TFTs. When integrated on the same substrate, p- and n-channel devices exhibited balanced carrier mobilities up to 10 cm/Vs. Hybrid complementary inverters based on these devices show high signal gain (>30 V/V) and wide noise margins (70%). The moderate processing temperatures employed and the achieved level of device performance highlight the tremendous potential of the technology for application in the emerging sector of large-area microelectronics.

  5. Photocatalytic oxidative desulfurization of dibenzothiophene catalyzed by amorphous TiO{sub 2} in ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Wenshuai; Xu, Yehai; Li, Huaming; Dai, Bilian; Xu, Hui; Wang, Chao; Chao, Yanhong; Liu, Hui [Jiangsu University, Zhenjiang (China)


    Three types of TiO{sub 2} were synthesized by a hydrolysis and calcination method. The catalysts were characterized by X-ray powder diffraction (XRD), diffuse reflectance spectrum (DRS), Raman spectra, and X-ray photoelectron spectroscopy (XPS). The XRD and Raman spectra indicated that amorphous TiO{sub 2} was successfully obtained at 100 .deg. C. The results indicated that amorphous TiO{sub 2} achieved the highest efficiency of desulfurization. The photocatalytic oxidation of dibenzothiophene (DBT), benzothiophene (BT), 4,6-dimethyldibenzothiophene (4,6-DMDBT) and dodecanethiol (RSH) in model oil was studied at room temperature (30 .deg. C) with three catalysts. The system contained amorphous TiO{sub 2}, H{sub 2}O{sub 2}, and [Bmim]BF{sub 4} ionic liquid, ultraviolet (UV), which played vitally important roles in the photocatalytic oxidative desulfurization. Especially, the molar ratio of H{sub 2}O{sub 2} and sulfur (O/S) was only 2 : 1, which corresponded to the stoichiometric reaction. The sulfur removal of DBT-containing model oil with amorphous TiO{sub 2} could reach 96.6%, which was apparently superior to a system with anatase TiO{sub 2} (23.6%) or with anatase - rutile TiO{sub 2} (18.2%). The system could be recycled seven times without a signicant decrease in photocatalytic activity.

  6. Highly efficient extraction and oxidative desulfurization system using Na7H2LaW10O36⋅32 H2O in [bmim]BF4 at room temperature. (United States)

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


    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.

  7. 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


    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.

  8. 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


    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.

  9. Deep oxidative desulfurization of dibenzothiophene in simulated oil and real diesel using heteropolyanion-substituted hydrotalcite-like compounds as catalysts. (United States)

    Yu, Fengli; Wang, Rui


    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).

  10. Enhancing the Pharmacokinetic Properties of Botulinum Neurotoxin Serotype A Protease Inhibitors Through Rational Design. (United States)

    Capek, Petr; Zhang, Yan; Barlow, Deborah J; Houseknecht, Karen L; Smith, Garry R; Dickerson, Tobin J


    Botulinum neurotoxin (BoNT), the etiological agent that causes the neuroparalytic disease botulism, has become a highly studied drug target in light of the potential abuse of this toxin as a weapon of bioterrorism. In particular, small molecule inhibitors of the light chain metalloprotease of BoNT serotype A have received significant attention and a number of small molecule and biologic inhibitors have been reported. However, all small molecules reported have been identified from either primary screens or medicinal chemistry follow-up studies, and the pharmacokinetic profiles of these compounds have not been addressed. In this study, we have removed the pharmacologic liabilities of one of the best compounds reported to date, 2,4-dichlorocinnamate hydroxamic acid, and in the process, uncovered a related class of benzothiophene hydroxamic acids that are significantly more potent inhibitors of the BoNT/A light chain, while also possessing greatly improved ADME properties, with the best compound showing the most potent inhibition of BoNT/A light chain reported (K(i) = 77 nM). Using a strategy of incorporating traditional drug development filters early into the discovery process, potential liabilities in BoNT/A lead compounds have been illuminated and removed, clearing the path for advancement into further pharmacologic optimization and in vivo efficacy testing.

  11. 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


    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.

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

    KAUST Repository

    Hourani, Nadim


    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.

  13. 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


    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.

  14. 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.


    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)

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


    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.


    Institute of Scientific and Technical Information of China (English)

    罗斌杰; 李新宇


    Crude oils from different basins in China ,Australia and New Zealand were analyzed to character-ize aromatic hydrocarbons produced in different environments by means of GC/MS .The distributions of some common compounds such as naphthalene, phenanthrene, chrysene,pyrene, fluoranthene, fluorine,dibenzothiophene and dibenzofuran were found to be related to sedimentary environments.Especially the relative contents of fluorenes ,dibenzofurans and dibenzothiophenes can be used to di-vide the oils into three types(1) saline or marine carbonate environment;(2) fresh-brackish water lake;(3) swamp and coal-bearing sequence.A romatic biomarkers (e.g.retene, nor-abietene,derivatives of lupeol and β-amyrin)represent higher plant inpults with respect to the precursors of crude oils. High contents of sulphur-containing compounds like benzothiophene and dibenzothiophene series indicate a reducing sulphur-abundant diagenetic condition .The benzohopane series (C32-C35) was identified both in hypersaline and coal-bearing basins, and it is postulated to be the result of strong bacteria activity.In all the sam-ples, a complete series of alkyl benzenes was analyzed .The similarity of its carbon-number distrbu-tion with that of n-alkanes probably suggests their genetic relationship. The distribution of the methylphenanthrene series reflects the evolution degree of crude oils,MPI holding a positive correlation with C29-sterane 20S/(20S+20R).

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

    DEFF Research Database (Denmark)

    Broholm, K.; Arvin, Erik


    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......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 experiments were conducted with till or ground water from the field site at Ringe on the island of Funen. Although the experiments were conducted on different scales, they revealed that some phenomena-e.g., an extensive biodegradation potential of several of the creosote compounds, the inhibitory influence...... 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....

  18. Adsorptive desulfurization on a heteroatoms Y zeolite prepared by secondary synthesis

    Institute of Scientific and Technical Information of China (English)


    Gallium atoms have been introduced into the framework of Y zeolite by treating the zeolite with an aqueous solution of ammonium hexafluoro gallate.Desulfurization of various model fuels containing about 500 μg/g sulfur has been studied over the synthesized Y zeolite(GaAlY).The sulfur adsorption capacity is 7.0,17.4,14.5,16.9,6.9 and 5.8 mg(S)/g adsorbent for thiophene,tetrahydrothiophene(THT),4,6-dimethyldibenzothiophene(4,6-DMDBT),dibenzophiophene(DBT),benzothiophene(BT) and 4-methyldibenzothiophene(4-MDBT),respectively.The charges on the S atom in thiophene,THT,4,6DMDBT,DBT,BT and 4-MDBT,calculated using the density functional theory(DFT),are-0.159,-0.298,-0.214,-0.211,-0.193 and-0.188,respectively,implying that the S-M bond between the adsorption sites and thiophene is much weaker than that between the adsorption sites and THT,4,6-DMDBT or DBT.The sulfur removal of FCC gasoline on GaAlY is 68%.

  19. 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


    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.

  20. Intermolecular band dispersion of quasi-single crystalline organic semiconductor monolayer measured by angle-resolved photoemission spectroscopy (United States)

    Ohtomo, Manabu; Shimada, Toshihiro; Hasegawa, Tetsuya


    Band structure of organic semiconductors is important knowledge to improve the molecular design. Angle-Resolved Photoemission Spectroscopy (ARPES) studies using highly conductive single domain samples grown in-situ is the most direct technique. In this study, we developed a novel method to grow quasi-single crystalline monolayer on conductive substrate and electronic structure was investigated. As a template for orientation control, we used a step-bunched Si(111) substrate with dangling bond termination. In case of pentacene, it was confirmed that the crystal is quasi-single crystal with 2.2^o rotated twins. The band dispersion was identical to that of thin-film phase. The effective mass and transfer integrals are evaluated using two-dimensional tight binding fit and compared with band calculations [1]. We also report the growth of 2,7-Dipheny[1]benzothieno[3,2-b]benzothiophene (DPh-BTBT) [2] on Bi-Si substrate and compare discuss its band structure. [4pt] [1] M.Ohtomo et al., APL 95, 123308 (2009).[0pt] [2] K.Takimiya, JACS 128, 3044 (2006).

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

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


    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.

  2. Hydroxylation activity of P450 BM-3 mutant F87V towards aromatic compounds and its application to the synthesis of hydroquinone derivatives from phenolic compounds. (United States)

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


    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%.

  3. Heterogeneous photocatalytic reactions of sulfur aromatic compounds. (United States)

    Samokhvalov, Alexander


    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.

  4. Adsorption of Thiophenic Compounds from Model Diesel Fuel Using Copper and Nickel Impregnated Activated Carbons

    Directory of Open Access Journals (Sweden)

    Ramin Karimzadeh


    Full Text Available Adsorption of sulfur compoundsby porous materials is an effective way to produce cleaner diesel fuel.In this study, adsorption of refractory thiophenic sulfur compounds, i.e., benzothiophene (BT, dibenzothiophene (DBT, and 4,6-dimethyldibenzothiophene (4,6-DMDBT in single-solute systems from n-hexane solutions onto metal-impregnated activated carbons was investigated. A hydrogen-treated activated carbon fiber was selectively loaded with Ni, NiO, Cu, Cu2O, and CuO species to systematically assess the impact of each metal species on the adsorption of thiophenic compounds (TC. Metal-loaded adsorbents had the same total metal contents and similar microporosities, but contained different types of copper or nickel species. All metal-loaded adsorbents showed enhanced adsorption of tested TC. Cu2O- or NiO-loaded adsorbents exhibited the highest uptakes, due to more specific interactions between Cu+ or Ni2+ species and TC molecules. The theoretical monolyer coverage of TC on the exposed Cu+ sites was estimated and compared with that calculated from the experimental data. Results suggested catalytic conversion of TC molecules to other compounds on the Cu+ sites, followed by adsorption of reaction products onto the carbon surface or multilayer accumulation of TC molecules on the Cu+sites. TC adsorption uptake of the majority of adsorbents followed the order of: 4,6-DMDBT > DBT > BT due to higher intensity of specific and non-specific interactions of larger TC molecules with adsorbents.

  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)


    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. Sulfur removal and release behaviors of sulfur-containing model compounds during pyrolysis under inert atmosphere by TG-MS connected with Py-GC%TG-MS与Py-GC相结合法研究惰性气氛下含硫模型化合物热解过程中硫的脱除及释放行为研究

    Institute of Scientific and Technical Information of China (English)

    郭慧卿; 谢丽丽; 王鑫龙; 刘粉荣; 王美君; 胡瑞生


    Sulfur containing model compounds, tetradecyl mercaptan, dibutyl sulfide, phenyl sulfide, 2-methyl thiophene, benzothiophene and dibenzothiophene, were selected to investigate their sulfur removal and release behaviors during pyrolysis under inert atmosphere by thermo-gravimetric analyzer with mass spectrometer (TG-MS) and pyrolysis connected with gas chromatogram (Py-GC). It was found that the order of sulfur removal was tetradecyl mercaptan > dibutyl sulfide > 2-methyl thiophene > benzo thiophene > phenyl sulfide > dibenzothiophene. Except for phenylsulfide, this rule is contrary to the decomposition temperature order of the sulfur functional groups. SO 2 evolution was detected by MS and GC for all those model compounds and COS evolution was also found except for phenylsulfide and dibenzothiophene; while H2 S evolution was measured only for tetradecyl mercaptan, dibutyl sulfide and 2-methyl thiophene. However, SO2 content was much higher than H2 S and COS in pyrolysis gas for each model compound, which may be caused by that indigenous hydrogen was much less than indigenous oxygen under inert atmosphere, when actived carbon was used as carrier. Thus, most of sulfur radicals can connect with indigenous oxygen and release in the form of SO . For phenyl sulfide, benzothiophene and dibenzothiophene, as their indigenous hydrogen was not enough to react with sulfur radicals, no H2 S was detected during pyrolysis under inert atmosphere, while SO2 was found and its content was very high in pyrolysis gas.%采用热重-质谱法( TG-MS)和热解-气相色谱法( Py-MS)相结合的方法对模型化合物(十四硫醇、二丁基硫醚、苯硫醚、二甲基噻吩、苯并噻吩和二苯并噻吩等)在惰性气氛下硫的脱除及释放行为进行研究。惰性气氛下硫的脱除顺序为:十四硫醇>二丁基硫醚>二甲基噻吩>苯并噻吩>苯硫醚>二苯并噻吩,苯硫醚除外,该顺序与含硫官能团的热分解顺序一致。在热解过程中,所有

  7. Importance of heterocylic aromatic compounds in monitored natural attenuation for coal tar contaminated aquifers: A review (United States)

    Blum, Philipp; Sagner, Anne; Tiehm, Andreas; Martus, Peter; Wendel, Thomas; Grathwohl, Peter


    NSO heterocycles (HET) are typical constituents of coal tars. However, HET are not yet routinely monitored, although HET are relatively toxic coal tar constituents. The main objectives of the study is therefore to review previous studies and to analyse HET at coal tar polluted sites in order to assess the relevance of HET as part of monitored natural attenuation (MNA) or any other long-term monitoring programme. Hence, natural attenuation of typical HET (indole, quinoline, carbazole, acridine, methylquinolines, thiophene, benzothiophene, dibenzothiophene, benzofuran, dibenzofuran, methylbenzofurans, dimethylbenzofurans and xanthene) were studied at three different field sites in Germany. Compound-specific plume lengths were determined for all main contaminant groups (BTEX, PAH and HET). The results show that the observed plume lengths are site-specific and are above 250 m, but less than 1000 m. The latter, i.e. the upper limit, however mainly depends on the level of investigation, the considered compound, the lowest measured concentration and/or the achieved compound-specific detection limit and therefore cannot be unequivocally defined. All downstream contaminant plumes exhibited HET concentrations above typical PAH concentrations indicating that some HET are generally persistent towards biodegradation compared to other coal tar constituents, which results in comparatively increased field-derived half-lives of HET. Additionally, this study provides a review on physicochemical and toxicological parameters of HET. For three well investigated sites in Germany, the biodegradation of HET is quantified using the centre line method (CLM) for the evaluation of bulk attenuation rate constants. The results of the present and previous studies suggest that implementation of a comprehensive monitoring programme for heterocyclic aromatic compounds is relevant at sites, if MNA is considered in risk assessment and for remediation.

  8. 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.


    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)

  9. Ultra-Deep Adsorptive Desulfurization of Light-Irradiated Diesel Fuel over Supported TiO2-CeO2 Adsorbents

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Jing; Wang, Xiaoxing; Chen, Yongsheng; Fujii, Mamoru; Song, Chunshan [SCUT-China; (Penn)


    This study investigates ultra-deep adsorptive desulfurization (ADS) from light-irradiated diesel fuel over supported TiO2–CeO2 adsorbents. A 30-fold higher desulfurization capacity of 95 mL of fuel per gram of adsorbent (mL-F/g-sorb) or 1.143 mg of sulfur per gram of adsorbent (mg-S/g-sorb) was achieved from light-irradiated fuel over the original low-sulfur fuel containing about 15 ppm by weight (ppmw) of sulfur. The sulfur species on spent TiO2–CeO2/MCM-48 adsorbent was identified by sulfur K-edge XANES as sulfones and the adsorption selectivity to different compounds tested in a model fuel decreases in the order of indole > dibenzothiophenesulfone → dibenzothiophene > 4-methyldibenzothiophene > benzothiophene > 4,6-dimethyldibenzothiophene > phenanthrene > 2-methylnaphthalene ~ fluorene > naphthalene. The results suggest that during ADS of light-irradiated fuel, the original sulfur species were chemically transformed to sulfones, resulting in the significant increase in desulfurization capacity. For different supports for TiO2–CeO2 oxides, the ADS capacity increases with a decrease in the point of zero charge (PZC) value; for silica-supported TiO2–CeO2 oxides (the lowest PZC value of 2–4) with different surface areas, the ADS capacity increases monotonically with increasing surface area. The supported TiO2–CeO2/MCM-48 adsorbent can be regenerated using oxidative air treatment. The present study provides an attractive new path to achieve ultraclean fuel more effectively.

  10. 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


    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)

  11. 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: [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: [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)


    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.

  12. Microwave-assisted syntheses of N-heterocycles using alkenone-, alkynone- and aryl-carbonyl O-phenyl oximes: formal synthesis of neocryptolepine. (United States)

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


    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.

  13. 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: [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)


    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.

  14. Identification and in vitro evaluation of new leads as selective and competitive glycogen synthase kinase-3β inhibitors through ligand and structure based drug design. (United States)

    Darshit, B S; Balaji, B; Rani, P; Ramanathan, M


    Glycogen synthase kinase-3β elicits multi-functional effects on intracellular signaling pathways, thereby making the kinase a therapeutic target in multiple pathologies. Hence, it is important to selectively inhibit GSK-3β over structurally and biologically similar targets, such as CDK5. The current study was designed to identify and evaluate novel ATP-competitive GSK-3β inhibitors. The study was designed to identify new leads by ligand based drug design, structure based drug design and in vitro evaluation. The best validated pharmacophore model (AADRRR) identified using LBDD was derived from a dataset of 135 molecules. There were 357 primary hits within the SPECS database using this pharmacophore model. A SBDD approach to the GSK-3β and CDK5 proteins was applied to all primary hits, and 5 selective inhibitors were identified for GSK-3β. GSK-3β and CDK5 in vitro kinase inhibition assays were performed with these molecules to confirm their selectivity for GSK-3β. The molecules showed IC50 values ranging from 0.825μM to 1.116μM and were 23- to 57-fold selective for GSK-3β. Of all the molecules, molecule 3 had the lowest IC50 value of 0.825μM. Our research identified molecules possessing benzothiophene, isoquinoline, thiazolidinedione imidazo-isoquinoline and quinazolinone scaffolds. Potency of these molecules may be due to H-bond interaction with backbone residues of Val135, Asp133 and side chain interaction with Tyr134. Selectivity over CDK5 may be due to side chain interactions with Asp200, backbone of Val61, ionic interaction with Lys60 and π-cationic interaction with Arg141. These selective molecules were also exhibited small atom hydrophobicity and H-bond interaction with water molecule.

  15. Hydrodesulfurization catalyst prepared by urea-matrix combustion method

    Institute of Scientific and Technical Information of China (English)

    Dongmei Jiao; Yeyong Ma; Fahai Cao


    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.

  16. Applications of Ferrate(VI) to Wastewater Reclamation and Water Treatment (United States)

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


    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)

  17. 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

  18. GABA(A) receptor subtype selective cognition enhancers. (United States)

    Maubach, Karen


    Currently the treatment of Alzheimer's disease (AD) and Mild Cognitive Impairment (MCI) is largely unrealised, with no preventive or curative therapies. The marketed acetylcholinesterase inhibitors (eg. donepezil, Aricept) are directed toward temporary symptomatic relief from impaired cognition, but have prominent adverse effects with minimal efficacy. In pursuit of novel cognition enhancers, the observation that classical benzodiazepines (BZ, eg. diazepam) are amnesic, coupled with the preservation of GABA(A) receptors in brain areas most affected by AD, highlighted the GABA(A) receptor as a potential therapeutic target. In contrast to the amnesic BZ agonists, the BZ inverse agonists (eg. DMCM) which attenuate GABA(A) receptor function, have been shown to improve performance in animal models of learning and memory. Unfortunately, such non-selective ligands also induce anxiety and convulsions. More recently, novel ligands have been developed (eg. 6,6-dimethyl-3-(2-hydroxyethyl)thio-1-(thiazol-2-yl)-6,7-dihydro-2-benzothiophen-4(5H)-one) that demonstrate binding selectivity and high inverse agonism for the alpha5 GABA(A) receptor subtype, which is preferentially located in the hippocampus, a region of the brain associated with learning and memory. Pre-clinical results are encouraging, since these alpha5 selective inverse agonists enhance memory in animal models, such as spatial learning in the Morris water-maze, but are devoid of the adverse effects associated with activity at other GABA(A) receptor subtypes in other brain regions. If the efficacy and safety profiles of alpha5 inverse agonists in humans prove to be similar to those seen in pre-clinical studies, these compounds would offer significant benefit to AD and MCI patients.

  19. 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)


    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.}

  20. 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.


    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}.

  1. Detailed compositional characterization of plastic waste pyrolysis oil by comprehensive two-dimensional gas-chromatography coupled to multiple detectors. (United States)

    Toraman, Hilal E; Dijkmans, Thomas; Djokic, Marko R; Van Geem, Kevin M; Marin, Guy B


    The detailed compositional characterization of plastic waste pyrolysis oil was performed with comprehensive two-dimensional GC (GC×GC) coupled to four different detectors: a flame ionization detector (FID), a sulfur chemiluminescence detector (SCD), a nitrogen chemiluminescence detector (NCD) and a time of flight mass spectrometer (TOF-MS). The performances of different column combinations were assessed in normal i.e. apolar/mid-polar and reversed configurations for the GC×GC-NCD and GC×GC-SCD analyses. The information obtained from the four detectors and the use of internal standards, i.e. 3-chlorothiophene for the FID and the SCD and 2-chloropyridine for the NCD analysis, enabled the identification and quantification of the pyrolysis oil in terms of both group type and carbon number: hydrocarbon groups (n-paraffins, iso-paraffins, olefins and naphthenes, monoaromatics, naphthenoaromatics, diaromatics, naphthenodiaromatics, triaromatics, naphthenotriaromatics and tetra-aromatics), nitrogen (nitriles, pyridines, quinolines, indole, caprolactam, etc.), sulfur (thiols/sulfides, thiophenes/disulfides, benzothiophenes, dibenzothiophenes, etc.) and oxygen containing compounds (ketones, phenols, aldehydes, ethers, etc.). Quantification of trace impurities is illustrated for indole and caprolactam. The analyzed pyrolysis oil included a significant amount of nitrogen containing compounds (6.4wt%) and to a lesser extent sulfur containing compounds (0.6wt%). These nitrogen and sulfur containing compounds described approximately 80% of the total peak volume for respectively the NCD and SCD analysis. TOF-MS indicated the presence of the oxygen containing compounds. However only a part of the oxygen containing compounds (2.5wt%) was identified because of their low concentrations and possible overlap with the complex hydrocarbon matrix as no selective detector or preparative separation for oxygen compounds was used.

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

    Directory of Open Access Journals (Sweden)

    Marcel Kaiser


    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.

  3. Inkjet printing of single-crystal films (United States)

    Minemawari, Hiromi; Yamada, Toshikazu; Matsui, Hiroyuki; Tsutsumi, Jun'ya; Haas, Simon; Chiba, Ryosuke; Kumai, Reiji; Hasegawa, Tatsuo


    The use of single crystals has been fundamental to the development of semiconductor microelectronics and solid-state science. Whether based on inorganic or organic materials, the devices that show the highest performance rely on single-crystal interfaces, with their nearly perfect translational symmetry and exceptionally high chemical purity. Attention has recently been focused on developing simple ways of producing electronic devices by means of printing technologies. `Printed electronics' is being explored for the manufacture of large-area and flexible electronic devices by the patterned application of functional inks containing soluble or dispersed semiconducting materials. However, because of the strong self-organizing tendency of the deposited materials, the production of semiconducting thin films of high crystallinity (indispensable for realizing high carrier mobility) may be incompatible with conventional printing processes. Here we develop a method that combines the technique of antisolvent crystallization with inkjet printing to produce organic semiconducting thin films of high crystallinity. Specifically, we show that mixing fine droplets of an antisolvent and a solution of an active semiconducting component within a confined area on an amorphous substrate can trigger the controlled formation of exceptionally uniform single-crystal or polycrystalline thin films that grow at the liquid-air interfaces. Using this approach, we have printed single crystals of the organic semiconductor 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) (ref. 15), yielding thin-film transistors with average carrier mobilities as high as 16.4cm2V-1s-1. This printing technique constitutes a major step towards the use of high-performance single-crystal semiconductor devices for large-area and flexible electronics applications.

  4. Biocatalytic desulfurization of thiophenic compounds and crude oil by newly isolated bacteria

    Directory of Open Access Journals (Sweden)

    Magdy El-Said Mohamed


    Full Text Available Microorganisms possess enormous highly specific metabolic activities, which enable them to utilize and transform nearly every known chemical class present in crude oil. In this context, one of the most studied biocatalytic processes is the biodesulfurization (BDS of thiophenic sulfur-containing compounds such as benzothiophene (BT and dibenzothiophene (DBT in crude oils and refinery streams. Three newly isolated bacterial strains, which were affiliated as Rhodococcus sp. strain SA11, Stenotrophomonas sp. strain SA21, and Rhodococcus sp. strain SA31, were enriched from oil contaminated soil in the presence of DBT as the sole S source. GC-FID analysis of DBT-grown cultures showed consumption of DBT, transient formation of DBT sulfone (DBTO2 and accumulation of 2-hydroxybiphenyl (2-HBP. Molecular detection of the plasmid-borne dsz operon, which codes for the DBT desulfurization activity, revealed the presence of dszA, dszB, and dszC genes. These results point to the operation of the known 4S pathway in the BDS of DBT. The maximum consumption rate of DBT was 11 µmol/g Dry Cell Weight (DCW/h and the maximum formation rate of 2-HBP formation was 4 µmol/g DCW/h. Inhibition of both cell growth and DBT consumption by 2-HBP was observed for all isolates but SA11 isolate was the least affected. The isolated biocatalysts desulfurized other model DBT alkylated homologs. SA11 isolate was capable of desulfurizing BT as well. Resting cells of SA11 exhibited 10% reduction in total sulfur present in heavy crude oil and 18% reduction in total sulfur present in the hexane-soluble fraction of the heavy crude oil. The capabilities of the isolated bacteria to survive and desulfurize a wide range of S compounds present in crude oil are desirable traits for the development of a robust BDS biocatalyst to upgrade crude oils and refinery streams.


    Energy Technology Data Exchange (ETDEWEB)

    Robert J. Angelici


    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.

  6. Simulations of charge transport in organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Vehoff, Thorsten


    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


    Energy Technology Data Exchange (ETDEWEB)

    Scott Collins; David Nunn


    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

  8. New insight-guided approaches to detect, cure, prevent and eliminate malaria. (United States)

    Kumar, Sushil; Kumari, Renu; Pandey, Richa


    scaffold structure several of the desired properties of malaria cure and control are exemplified by OZ439, NITD609, ELQ300 and tafenoquine that are already undergoing clinical trials, and decoquinate, usnic acid, torin-2, ferroquine, WEHI-916, MMV396749 and benzothiophene-type N-myristoyltransferase (NMT) inhibitors, which are candidates for future clinical usage. Among these, NITD609, ELQ300, decoquinate, usnic acid, torin-2 and NMT inhibitors not only cure simple malaria and are prophylactic against simple malaria, but they also cure relapsing malaria.

  9. Effects of thermal maturation and thermochemical sulfate reduction on compound-specific sulfur isotopic compositions of organosulfur compounds in Phosphoria oils from the Bighorn Basin, USA (United States)

    Ellis, Geoffrey S.; Said-Ahamed, Ward; Lillis, Paul G.; Shawar, Lubna; Amrani, Alon


    Compound-specific sulfur isotope analysis was applied to a suite of 18 crude oils generated from the Permian Phosphoria Formation in the Bighorn Basin, western USA. These oils were generated at various levels of thermal maturity and some experienced thermochemical sulfate reduction (TSR). This is the first study to examine the effects of thermal maturation on stable sulfur isotopic compositions of individual organosulfur compounds (OSCs) in crude oil. A general trend of 34S enrichment in all of the studied compounds with increasing thermal maturity was observed, with the δ34S values of alkyl-benzothiophenes (BTs) tending to be enriched in 34S relative to those of the alkyl-dibenzothiophenes (DBTs) in lower-maturity oils. As thermal maturity increases, δ34S values of both BTs and DBTs become progressively heavier, but the difference in the average δ34S value of the BTs and DBTs (Δ34S BT-DBT) decreases. Differences in the isotopic response to thermal stress exhibited by these two compound classes are considered to be the result of relative differences in their thermal stabilities. TSR-altered Bighorn Basin oils have OSCs that are generally enriched in 34S relative to non-TSR-altered oils, with the BTs being enriched in 34S relative to the DBTs, similar to the findings of previous studies. However, several oils that were previously interpreted to have been exposed to minor TSR have Δ34S BT-DBT values that do not support this interpretation. The δ34S values of the BTs and DBTs in some of these oils suggest that they did not experience TSR, but were derived from a more thermally mature source. The heaviest δ34S values observed in the OSCs are enriched in 34S by up to 10‰ relative to that of Permian anhydrite in the Bighorn Basin, suggesting that there may be an alternate or additional source of sulfate in some parts of the basin. These results indicate that the sulfur isotopic composition of OSCs in oil provides a sensitive indicator for the extent of TSR

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


    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Pienkos, Philip T.


    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. TiO 2-MCM-41的制备表征及选择性吸附脱硫研究%Preparation and Characterization of TiO 2-MCM-41 and Its Performance on the Desulfurization

    Institute of Scientific and Technical Information of China (English)

    尹锋; 秦玉才; 于文宇; 王红; 裴婷婷; 吕莉; 宋丽娟


    TiO 2-MCM-41 mesoporous molecular sieve(n (Si)/n (Ti)= 5 )was synthesized by heating reflux method,using titanium tetrabutoxide as the Ti source,MCM-41 as the carrier.The samples were investigated by means of XRD,FT-IR and N2 adsorption/desorption.The static and dynamic desulfurization experiment was carried out using fluid catalytic cracking (FCC)fuel oils.Properties of selective adsorptive desulfurization of FCC gasoline on the adsorbents have been investigated in this paper by a fixed-bed adsorption experiment and a GC-SCD technique.It was indicated thatthe titania homodisperses in the modified MCM-41,titania connected with the pendant OH groups of MCM-41 via Si—O—Ti bonds.After the load of TiO 2 ,the properties of adsorptive desulfurization on the adsorbents weresignificantly improved.The removal selectivities of the sulfur compounds in the gasoline changed slightly before and after the load of TiO 2 ,while the poor removal selectivities of benzothiophene,2/3-methylthiophene,2,3-dimethylthiophene,2,4-dimethylthiophene and 2,5-dimethylthiophene on MCM-41 and TiO 2-MCM-41 were the same.%以钛酸正丁酯作为钛源,MCM-41为载体,采用加热回流法合成了 TiO 2-MCM-41介孔分子筛(n (Si)/n (Ti)=5),并借助 XRD、FT-IR、N2吸附-脱附等表征手段研究了吸附剂的结构特性。以催化裂化汽油为油品进行静态脱硫和动态脱硫实验,结合使用固定床技术和色谱-硫化学发光检测(GC-SCD)偶联技术系统考查了吸附剂的选择性吸附脱硫性能及其对不同硫化物的选择性规律。结果表明,TiO 2在介孔分子筛 MCM-41的内孔壁能均匀分散;TiO 2与 MCM-41孔道表面的 SiO 2以 Si—O—Ti 键连接;MCM-41经负载 TiO 2后,吸附脱硫性能明显提高;TiO 2-MCM-41对 FCC 汽油中各种硫化物的选择性顺序为:四氢噻吩>2-甲基四氢噻吩≈C5硫醚>3,4-二甲基噻吩>2/3-乙基噻吩>2-乙基-5-甲基噻吩>噻吩>2,5-二甲基噻吩>C1-C3硫醇>2-甲基噻吩>2,3-

  13. Investigation of extractable organic compounds in deep-sea hydrothermal vent fluids along the Mid-Atlantic Ridge (United States)

    McCollom, Thomas M.; Seewald, Jeffrey S.; German, Christopher R.


    phenanthrenes and benzothiophene were the only compounds that could be identified as indigenous components of these fluids. Although hydrocarbons and fatty acids were observed in some samples, those compounds were likely derived from particulate matter or biomass entrained during fluid collection. In addition, extracts of some fluid samples from the Rainbow field were found to contain an unresolved complex mixture (UCM) of organic compounds. This UCM shared some characteristics with organic matter extracted from bottom seawater, suggesting that the organic matter observed in these samples might represent seawater-derived compounds that had persisted, albeit with partial alteration, during circulation through the hydrothermal system. While there is considerable evidence that Rainbow and Lost City vent fluids contain methane and other light hydrocarbons produced through abiotic reduction of inorganic carbon, we found no evidence for more complex organic compounds with an abiotic origin in the same fluids.

  14. 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


    (with at least 12 months since the last menses for whom treatment with progestin-containing therapy is not 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 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 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 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

  15. 低品质煤大规模提质利用的基础研究%Basic Research of Large-scale Quality Improvement and Utilization of Low-quality Coal

    Institute of Scientific and Technical Information of China (English)

    刘炯天; 朱书全; 张明旭; 赵跃民; 王智化


    Since the project was officially launched, the team conduct a large number of studies, combine with expert advice, thus further clarify the research focus, adjust and improve the scheme. As the project goes, constantly and timely adjusting experimental scheme; refine the research process. After the first year of the project construction, improve the research content, form clear research objectives and laid a solid foundation for the project to conduct smoothly and orderly.(1)The team completes the basic indicator analysis of typical low-quality coal, preliminarily discover how the principal forming-ash minerals/sulfur/moisture of the typical low-quality coal exist and clarify surface oxygen functional groups and pore structure.(2)The team establishes a lignite-dewatering system under pressure and high temperature, lignite-upgrading unit through hot water,CO2 supercritical extractor, and lignite-drying in hot flue gas (nitrogen) lab facilities. Taiyuan University of Technology establishes lignite-upgrading relapse experimental platform. we build calculating simulation platform of lignite dehydration based on high performance servers like dawn 5000A, IBMPOWER755、DELL、BAODE etc. and calculation software like GAUSSIAN09、ADF、MS5.5、VASP,SIESTA.(3)The team establishes a platform for testing electromagnetic characteristics. Through its wholly-component separation, Soxhlet extraction, XPS, GC / MS and other methods, we discover the surface structure and distribution of organic sulfur of the coking coal. Obtain the complex permittivity of coking coal samples from Xinyu at different frequencies using electromagnetic characteristics-testing system. Preliminarily discover optimal microwave band for desulfurization, research theoretically the structure and properties of benzothiophene and four- six two methylbenzothiophene using the DMol3 module in Materials Studio 6.0 software. In summary, from January 1, 2012 to October 31, 2012, 83 people participate the project, 1

  16. Desulfurization of oil products by extractive distillation:simulation and optimization%萃取蒸馏脱除油品中硫的过程模拟与优化

    Institute of Scientific and Technical Information of China (English)

    张清珍; 代成娜; 韩敬莉; 雷志刚


    ,recovery ratio was 70% and the mass flow ratio of solvent to feed was 1. The method of extractive distillation could remove benzothiophene,thioether and thiophenes effectively,and the content of these sulfides could be decreased from 1581μg/g to 5.37μg/g in model gasoline,desulfurization efficiency was 98.1%,the distillate could reach up to mass yield 70% and volume yield 75%. Moreover,the prediction accuracy of COSMO-RS model in thermodynamics of IL,UNIFAC model in vapor-liquid equilibrium of organic sulfur compounds -hydrocarbon system and the reliability of simulation process were tested by comparing calculated value and experimental value in literature.

  17. Vieillissement du polyamide 11 utilisé dans les conduites flexibles : influence de la composition du fluide transporté Influence of the Chemical Nature of the Environment on the Aging of Polyamide 11 Used for Offshore Flexible Pipes

    Directory of Open Access Journals (Sweden)

    Ubrich E.


    hydrocarbons absorbed preferentially, and having a pasticating role, was determined. These are two-cycle aromatics (alkylnaphthalenes, acenaphthenes, diphenyls, acenaphthylenes, fluorenes and sulfur-containing aromatics (benzothiophenes and dibenzothiophenes. The different results led to the conclusion that the principal phenomenon involved in aging is a hydrolysis caused by the presence of absorbed water in the material, which leads to the cutting of the macromolecular chains and embrittlement of the polymer. Lastly, the model created with gas-oil cuts was applied to a case of aging of a crude oil, and this led to the satisfactory prediction of how the mechanical and physicochernical properties of the polymer evolve in such an environment.