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Sample records for model supported olefin

  1. Supported organometallic catalysts for hydrogenation and Olefin Polymerization

    Science.gov (United States)

    Marks, Tobin J.; Ahn, Hongsang

    2001-01-01

    Novel heterogeneous catalysts for the which hydrogenation of olefins and arenes with high conversion rates under ambient conditions and the polymerization of olefins have been developed. The catalysts are synthesized from Ziegler-type precatalysts by supporting them on sulfate-modified zirconia.

  2. Nature of active centers and mechanism of metathesis of olefines on supported oxidic catalysts of molybdenum, tungsten and rhenium

    International Nuclear Information System (INIS)

    Kadushin, A.A.; Aliev, R.K.; Krylov, O.V.; Andreev, A.A.; Edreva-Kardzhieva, R.M.; Shopov, D.M.; Bylgarska Akademiya na Naukite, Sofia. Inst. za Obshta i Organichna Khimiya)

    1982-01-01

    A unified model of active centre in metathesis of olefines for oxide catalysts of molybdenum, tungsten and rhenium, supported on aluminium oxide and silica gel, is suggested. A supposition is made that electron transfer from the nearest electron donor through ion of higher valency transition metal to the olefine adsorbed is the main stage of activation process of surface olefine complex. The model is justified by quantum-chemical calculation

  3. Mesoporous molecular sieves as advanced supports for olefin metathesis catalysts

    Czech Academy of Sciences Publication Activity Database

    Balcar, Hynek; Čejka, Jiří

    2013-01-01

    Roč. 257, 21-22 (2013), s. 3107-3124 ISSN 0010-8545 R&D Projects: GA AV ČR IAA400400805; GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : Olefin metathesis * mesoporous molecular sieves * Heterogeneous catalysts Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 12.098, year: 2013

  4. Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts.

    Science.gov (United States)

    Merle, Nicolas; Le Quéméner, Frédéric; Barman, Samir; Samantaray, Manoja K; Szeto, Kai C; De Mallmann, Aimery; Taoufik, Mostafa; Basset, Jean-Marie

    2017-10-12

    A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-) 2 Mo([double bond, length as m-dash]O)(CH 2 t Bu) 2 , was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH 2 t Bu) 3 Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO 3 /SiO 2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

  5. Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

    KAUST Repository

    Merle, Nicolas

    2017-09-25

    A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

  6. Adsorption heats of olefins on supported MoO3/Al2O3 catalists

    International Nuclear Information System (INIS)

    Grinev, V.E.; Madden, M.; Khalit, V.A.; Aptekar', E.L.; Aldag, A.; Krylov, O.V.

    1983-01-01

    Adsorption heats of C 2 H 4 , C 3 H 6 and C 4 H 8 on supported MoO 3 /Al 2 O 3 catalysts containing 6, 10 and 15 wt. % of MoO 3 at 25, 77 and 195 deg are determimed. Adsorption heat of an olefin increases with a growing length of its carbonic chain. The number of adsorbed olefin molecules grows with an increase in the MoO 3 concentration, while initial adsorption heats decrease. The number of adsorbed olefins is proportional to mean rate of molybdenum reduction in catalysts. Adsorption heats of oxygen on the surface of the catalysts with preliminarily adsorbed olefins are determined. It is shown that adsorption of oxygen and olefins proceeeds both on the same and on different centres of the surface. Mechanisms of surface interactions are discussed

  7. Mesoporous Molecular Sieves as Advanced Supports for Olefin Metathesis Catalysts

    Czech Academy of Sciences Publication Activity Database

    Balcar, Hynek; Čejka, Jiří

    2010-01-01

    Roč. 293, č. 1 (2010), s. 43-47 ISSN 1022-1360 R&D Projects: GA AV ČR IAA400400805; GA AV ČR KAN100400701 Institutional research plan: CEZ:AV0Z40400503 Keywords : heterogeneous catalysts * mesoporous molecular sieves * olefin metathesis Subject RIV: CF - Physical ; Theoretical Chemistry

  8. Request for Symposia Support: Advances in Olefin Polymerization Catalysis

    Science.gov (United States)

    2014-11-24

    included, but were not limited to, heterogeneous catalysis , homogeneous catalysis , advances in catalyst activation, methods for polymer topological...SECURITY CLASSIFICATION OF: This Advances in Olefin Polymerization Catalysis symposium was held at the 247th ACS National Meeting and Exposition...March 19, 2014 in Dallas, Texas and consisted of twelve (12) invited/contributed talks. The hosting ACS division was the Division of Catalysis Science

  9. Half-sandwich group 4 metal siloxy and silsesquioxane complexes : Soluble model systems for silica-grafted olefin polymerization catalysts

    NARCIS (Netherlands)

    Duchateau, R; Cremer, U; Harmsen, RJ; Mohamud, SI; Abbenhuis, HCL; van Santen, RA; Meetsma, A; Thiele, SKH; van Tol, MFH; Kranenburg, M

    1999-01-01

    The cuboctameric hydroxysilsesquioxane (c-C5H9)(7)Si8O12(OH) (2), obtained after hydrolysis of (c-C5H9)(7)Si8O12Cl (1), and triphenylsilanol have been applied as model supports for silica-grafted olefin polymerization catalysts. The ligands were introduced on group 4 metals by either chloride

  10. H-ZSM-5 Zeolite Model Crystals: Structure-Diffusion-Activity Relationship in Methanol-to-Olefins Catalysis.

    Czech Academy of Sciences Publication Activity Database

    Losch, P.; Pinar, A.B.; Willinger, M.G.; Soukup, Karel; Chavan, S.; Vincent, B.; Pale, P.; Louis, B.

    2017-01-01

    Roč. 345, JAN 1 (2017), s. 11-23 ISSN 0021-9517 Grant - others:NRFL(LU) 5898454 Institutional support: RVO:67985858 Keywords : zeolite * methanol -to-olefins (MTO) * model catalyst Subject RIV: CI - Industrial Chemistry, Chemical Engineering OBOR OECD: Chemical process engineering Impact factor: 6.844, year: 2016

  11. H-ZSM-5 Zeolite Model Crystals: Structure-Diffusion-Activity Relationship in Methanol-to-Olefins Catalysis.

    Czech Academy of Sciences Publication Activity Database

    Losch, P.; Pinar, A.B.; Willinger, M.G.; Soukup, Karel; Chavan, S.; Vincent, B.; Pale, P.; Louis, B.

    2017-01-01

    Roč. 345, JAN 1 (2017), s. 11-23 ISSN 0021-9517 Grant - others:NRFL(LU) 5898454 Institutional support: RVO:67985858 Keywords : zeolite * methanol-to-olefins (MTO) * model catalyst Subject RIV: CI - Industrial Chemistry, Chemical Engineering OBOR OECD: Chemical process engineering Impact factor: 6.844, year: 2016

  12. Unravelling the olefin cross metathesis on solid support. Factors affecting the reaction outcome.

    Science.gov (United States)

    Poeylaut-Palena, Andrés A; Mata, Ernesto G

    2010-09-07

    Olefin cross metathesis on solid support under a variety of conditions is described. A comprehensive analysis considering diverse factors governing the reaction outcome gives a series of patterns for the application of this useful methodology in organic synthesis. If the intrasite reaction is not possible, homodimerization of the soluble olefin is crucial. When the homodimer is less reactive than its monomer, reaction outcome depends on the homodimerization rate, which, in turn, depends on the precatalyst used and the reaction conditions. If the site-site interaction is a feasible process, the cross metathesis product is obtained exclusively when the newly-formed double bond is resilient to further metathetic events. Taking into account these considerations, we have demonstrated that excellent results in terms of cross metathesis coupling can be obtained under the optimized conditions, and that microwave irradiation is also an interesting alternative for the development of a practical and energy-efficient cross metathesis on solid support.

  13. The generation of efficient supported (Heterogeneous) olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Grubbs, Robert H

    2013-04-05

    Over the past decade, a new family of homogeneous metathesis catalysts has been developed that will tolerate most organic functionalities as well as water and air. These homogeneous catalysts are finding numerous applications in the pharmaceutical industry as well as in the production of functional polymers. In addition the catalysts are being used to convert seed oils into products that can substitute for those that are now made from petroleum products. Seed oils are unsaturated, contain double bonds, and are a ready source of linear hydrocarbon fragments that are specifically functionalized. To increase the number of applications in the area of biomaterial conversion to petrol chemicals, the activity and efficiency of the catalysts need to be as high as possible. The higher the efficiency of the catalysts, the lower the cost of the conversion and a larger number of practical applications become available. Active supported catalysts were prepared and tested in the conversion of seed oils and other important starting materials. The outcome of the work was successful and the technology has been transferred to a commercial operation to develop viable applications of the discovered systems. A biorefinery that converts seed oils is under construction in Indonesia. The catalysts developed in this study will be considered for the next generation of operations.

  14. Effect of catalyst pretreatment on the olefin metathesis catalyzed by alumina-supported (9%) rhenium oxide

    Energy Technology Data Exchange (ETDEWEB)

    Hsu, J.C.

    1979-01-01

    A kinetic model was developed to express the time-on-stream profile of the activity during catalyst break-in and deactivation. The catalyst surface is in geometric and energetic heterogeneity. Partial catalyst reduction is a prerequisite step for olefin metathesis. The metathesis activity may be affected by the coordination number and the type of ligands associated with the sites on the catalyst. The deactivation is proposed due to deposition of residues on the active sites, and to sintering, etc. A dispersion pretreatment increased activity. Oxygen is an activator. The hydrogen reduction at 500/sup 0/C causes partial but permanent loss of activity.

  15. SOMC-Designed Silica Supported Tungsten Oxo Imidazolin-2-iminato Methyl Precatalyst for Olefin Metathesis Reactions.

    Science.gov (United States)

    Qureshi, Ziyauddin S; Hamieh, Ali; Barman, Samir; Maity, Niladri; Samantaray, Manoja K; Ould-Chikh, Samy; Abou-Hamad, Edy; Falivene, Laura; D'Elia, Valerio; Rothenberger, Alexander; Llorens, Isabelle; Hazemann, Jean-Louis; Basset, Jean-Marie

    2017-01-17

    Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH 3 ) 2 -Im Dipp N] (4) (Im Dipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [Im Dipp NW(═O)Cl 3 ] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO 2-700 ) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl 2 -Im Dipp N] (3). 3 underwent alkylation by ZnMe 2 to produce [(≡Si-O-)W(═O)(CH 3 ) 2 -Im Dipp N] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.

  16. SOMC-Designed Silica Supported Tungsten Oxo Imidazolin-2-iminato Methyl Precatalyst for Olefin Metathesis Reactions

    KAUST Repository

    Qureshi, Ziyauddin

    2017-01-05

    Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4) (ImDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [ImDippNW(═O)Cl3] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO2-700) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl2-ImDippN] (3). 3 underwent alkylation by ZnMe2 to produce [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.

  17. Preparation of Mesoporous SBA-16 Silica-Supported Biscinchona Alkaloid Ligand for the Asymmetric Dihydroxylation of Olefins

    Directory of Open Access Journals (Sweden)

    Shaheen M. Sarkar

    2014-01-01

    Full Text Available Optically active cinchona alkaloid was anchored onto mesoporous SBA-16 silica and the as-prepared complex was used as a heterogeneous chiral ligand of osmium tetraoxide for the asymmetric dihydroxylation of olefins. The prepared catalytic system provided 90–93% yield of vicinal diol with 92–99% enantioselectivity. The ordered mesoporous SBA-16 silica was found to be a valuable support for the cinchona alkaloid liganded osmium catalyst system which is frequently used in chemical industries and research laboratories for olefin functionalization.

  18. Direct production of lower olefins from synthesis gas using supported iron catalysts

    NARCIS (Netherlands)

    Torres Galvis, H.M.

    2013-01-01

    Lower olefins (ethylene, propylene and butylenes) are important commodity chemicals used for the manufacture of, amongst others, plastics, solvents and lubricants to cosmetics and drugs. C2 to C4 olefins are conventionally produced by steam cracking of naphtha. In view of economic, strategic, and

  19. Olefin metathesis and catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S. G.; Banks, R. L.

    1985-05-14

    Olefins are converted into other olefins having different numbers of carbon atoms by contact with a catalyst comprising an inorganic refractory oxide support containing at least one of tungsten oxide and molybdenum oxide and a promoting amount of at least one methylating agent under conditions suitable for the methylating agent compounds to promote the activity of tungsten and molybdenum oxides for the disproportionation reaction.

  20. Chemistry of Furan Conversion into Aromatics and Olefins over HZSM-5: A Model Biomass Conversion Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Yu-Ting; Huber, George W.

    2011-06-03

    The conversion of furan (a model of cellulosic biomass) over HZSM-5 was investigated in a thermogravimetric analysis–mass spectrometry system, in situ Fourier transform infrared analysis, and in a continuous-flow fixed-bed reactor. Furan adsorbed as oligomers at room temperature with a 1.73 of adsorbed furan/Al ratio. These oligomers were polycyclic aromatic compounds that were converted to CO, CO₂, aromatics, and olefins at temperatures from 400 to 600 °C. Aromatics (e.g., benzene, toluene, and naphthalene), oligomer isomers (e.g., benzofuran, 2,2-methylenebisfuran, and benzodioxane), and heavy oxygenates (C₁₂{sub +} oligomers) were identified as intermediates formed inside HZSM-5 at different reaction temperatures. During furan conversion, graphite-type coke formed on the catalyst surface, which caused the aromatics and olefins formation to deactivate within the first 30 min of time on-stream. We have measured the effects of space velocity and temperature for furan conversion to help us understand the chemistry of biomass conversion inside zeolite catalysts. The major products for furan conversion included CO, CO₂, allene, C₂–C₆ olefins, benzene, toluene, styrene, benzofuran, indene, and naphthalene. The aromatics (benzene and toluene) and olefins (ethylene and propylene) selectivity decreased with increasing space velocity. Unsaturated hydrocarbons such as allene, cyclopentadiene, and aromatics selectivity increased with increasing space velocity. The product distribution was selective to olefins and CO at high temperatures (650 °C) but was selective to aromatics (benzene and toluene) at intermediate temperatures (450–600 °C). At low temperatures (450 °C), benzofuran and coke contributed 60% of the carbon selectivity. Several different reactions were occurring for furan conversion over zeolites. Some important reactions that we have identified in this study include Diels–Alder condensation (e.g., two furans form benzofuran and water

  1. Silica-supported isolated molybdenum di-oxo species: formation and activation with organosilicon agent for olefin metathesis.

    Science.gov (United States)

    Yamamoto, Keishi; Chan, Ka Wing; Mougel, Victor; Nagae, Haruki; Tsurugi, Hayato; Safonova, Olga V; Mashima, Kazushi; Copéret, Christophe

    2018-04-17

    A well-defined silica-supported molybdenum dioxo species, ([triple bond, length as m-dash]SiO)2Mo(O)2, is prepared by grafting Mo(O)2[OSi(OtBu)3]2 on partially dehydroxylated silica SiO2-700, followed by thermal treatment under high-vaccum and calcination. Activated by an organosilicon agent the resulting material is active for olefin metathesis at 30 °C.

  2. A review on kinetic modeling of deactivation of SAPO-34 catalyst during Methanol to Olefins (MTO) process

    OpenAIRE

    Mohammad Ali Ahmadi, Seyed; Askari, Sima; Halladj, Rouein

    2013-01-01

    The major cause of deactivation in the MTO reaction over SAPO-34 is coke deposition that influences both activity and selectivity. This review describes different kinetic modeling of deactivation  of SAPO-34 during MTO process. It also presents different deactivation functions for the methanol conversion and the yields of olefins, which are hyperbolic and exponential respectively. A modified Voorhies model that estimates the average coke selectivity and catalyst capacity for olefin formation ...

  3. The intriguing modeling of cis–trans selectivity in ruthenium-catalyzed olefin metathesis

    Directory of Open Access Journals (Sweden)

    Luigi Cavallo

    2011-01-01

    Full Text Available In this study we have investigated computationally the origin of the cis–trans selectivity in the Ru-catalyzed cross metathesis (CM of a prototype monosubstituted olefin, i.e., propene. Our calculations suggest that the origin of the preferential formation of trans-olefins is in the product release step, which prevents the initially formed cis-olefin from escaping the metal, and returns it to the reaction pool until the trans-olefin is formed.

  4. Use of water in aiding olefin/paraffin (liquid + liquid) extraction via complexation with a silver bis(trifluoromethylsulfonyl)imide salt

    International Nuclear Information System (INIS)

    Wang, Yu; Thompson, Jillian; Zhou, Jingjing; Goodrich, Peter; Atilhan, Mert; Pensado, Alfonso S.; Kirchner, Barbara; Rooney, David; Jacquemin, Johan; Khraisheh, Majeda

    2014-01-01

    Highlights: • Silver-based ILs used as olefin extracting agents for olefin/paraffin mixtures. • Each extraction process is based on the olefin complexation and solvation. • The presence of water influences positively each extraction process. • Each extraction process was evaluated by DFT calculations, NMR, IR and Raman. • LLE data were then correlated by using the UNIQUAC model. - Abstract: This paper describes the extraction of C 5 –C 8 linear α-olefins from olefin/paraffin mixtures of the same carbon number via a reversible complexation with a silver salt (silver bis(trifluoromethylsulfonyl)imide, Ag[Tf 2 N]) to form room temperature ionic liquids [Ag(olefin) x ][Tf 2 N]. From the experimental (liquid + liquid) equilibrium data for the olefin/paraffin mixtures and Ag[Tf 2 N], 1-pentene showed the best separation performance while C 7 and C 8 olefins could only be separated from the corresponding mixtures on addition of water which also improves the selectivity at lower carbon numbers like the C 5 and C 6 , for example. Using infrared and Raman spectroscopy of the complex and Ag[Tf 2 N] saturated by olefin, the mechanism of the extraction was found to be based on both chemical complexation and the physical solubility of the olefin in the ionic liquid ([Ag(olefin) x ][Tf 2 N]). These experiments further support the use of such extraction techniques for the separation of olefins from paraffins

  5. Synthesis and characterization of a homogeneous and silica supported homoleptic cationic tungsten(vi) methyl complex: application in olefin metathesis

    KAUST Repository

    Dey, Raju

    2016-08-19

    A method for the synthesis of a homogeneous cationic tungsten(VI)penta-methyl complex [(WMe5)(+)(C6F5)(3)BMe-] from neutral tungstenhexamethyl (WMe6) and a silica supported cationic tungstentetramethyl complex [( Si-O-)WMe4+ (C6F5)(3)BMe-] from a neutral silica supported tungstenpentamethyl complex [( Si-O-)WMe5] is described. In both cases a direct demethylation using the B(C6F5)(3) reagent was used. The aforesaid complexes were characterized by liquid or solid state NMR spectroscopy. Interestingly, the homogeneous cationic complex [(WMe5)(+)(C6F5)(3)BMe-] shows moderate activity whereas the supported cationic complex [( Si-O-)WMe4+(C6F5)(3)BMe-] exhibits good activity in olefin metathesis reactions.

  6. Synthesis and characterization of a homogeneous and silica supported homoleptic cationic tungsten(vi) methyl complex: application in olefin metathesis.

    Science.gov (United States)

    Dey, Raju; Samantaray, Manoja K; Poater, Albert; Hamieh, Ali; Kavitake, Santosh; Abou-Hamad, Edy; Callens, Emmanuel; Emwas, Abdul-Hamid; Cavallo, Luigi; Basset, Jean-Marie

    2016-09-13

    A method for the synthesis of a homogeneous cationic tungsten(vi)pentamethyl complex [(WMe 5 ) + (C 6 F 5 ) 3 BMe - ] from neutral tungstenhexamethyl (WMe 6 ) and a silica supported cationic tungstentetramethyl complex [([triple bond, length as m-dash]Si-O-)WMe 4 + (C 6 F 5 ) 3 BMe - ] from a neutral silica supported tungstenpentamethyl complex [([triple bond, length as m-dash]Si-O-)WMe 5 ] is described. In both cases a direct demethylation using the B(C 6 F 5 ) 3 reagent was used. The aforesaid complexes were characterized by liquid or solid state NMR spectroscopy. Interestingly, the homogeneous cationic complex [(WMe 5 ) + (C 6 F 5 ) 3 BMe - ] shows moderate activity whereas the supported cationic complex [([triple bond, length as m-dash]Si-O-)WMe 4 + (C 6 F 5 ) 3 BMe - ] exhibits good activity in olefin metathesis reactions.

  7. Update: An efficient synthesis of poly(ethylene glycol)-supported iron(II) porphyrin using a click reaction and its application for the catalytic olefination of aldehydes

    KAUST Repository

    Chinnusamy, Tamilselvi R.

    2012-05-09

    The facile synthesis of polyethylene glycol (PEG)-immobilized iron(II) porphyrin using a copper-catalyzed azide-alkyne [3+2] cycloaddition "click" reaction is reported. The prepared complex 5 (PEG-C 51H 39FeN 7O) was found to be an efficient catalyst for the selective olefination of aldehydes with ethyl diazoacetate in the presence of triphenylphosphine, and afforded excellent olefin yields with high (E) selectivities. The PEG-supported catalyst 5 was readily recovered by precipitation and filtration, and was recycled through ten runs without significant activity loss. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst

    KAUST Repository

    Merle, Nicolas

    2016-12-05

    The well-defined silica-supported molybdenum oxo alkyl species (SiO−)MoO(CH Bu) was selectively prepared by grafting of MoO(CH Bu)Cl onto partially dehydroxylated silica (silica) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO/SiO olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

  9. Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst.

    Science.gov (United States)

    Merle, Nicolas; Le Quéméner, Frédéric; Bouhoute, Yassine; Szeto, Kai C; De Mallmann, Aimery; Barman, Samir; Samantaray, Manoja K; Delevoye, Laurent; Gauvin, Régis M; Taoufik, Mostafa; Basset, Jean-Marie

    2017-02-15

    The well-defined silica-supported molybdenum oxo alkyl species (≡SiO-)MoO(CH 2 t Bu) 3 was selectively prepared by grafting of MoO(CH 2 t Bu) 3 Cl onto partially dehydroxylated silica (silica 700 ) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO 3 /SiO 2 olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

  10. The Rearrangement of 1-Methylcyclohex-1-ene during the Hydrodesulfurization of FCC Gasoline over Supported Co(Ni)Mo/Al2O3 Sulfide Catalysts: the Isolation and Identification of Branched Cyclic C7 Olefins

    Czech Academy of Sciences Publication Activity Database

    Žáček, Petr; Kaluža, Luděk; Karban, Jindřich; Storch, Jan; Sýkora, Jan

    2014-01-01

    Roč. 112, č. 2 (2014), s. 335-346 ISSN 1878-5190 R&D Projects: GA ČR GAP106/11/0902 Institutional support: RVO:67985858 ; RVO:61388963 Keywords : hydrodesulfurization * olefin hydrogenation * branched cyclic olefins Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.170, year: 2014

  11. "Hydro-metathesis" of olefins: A catalytic reaction using a bifunctional single-site tantalum hydride catalyst supported on fibrous silica (KCC-1) nanospheres

    KAUST Repository

    Polshettiwar, Vivek

    2011-02-18

    Tantalizing hydrocarbons: Tantalum hydride supported on fibrous silica nanospheres (KCC-1) catalyzes, in the presence of hydrogen, the direct conversion of olefins into alkanes that have higher and lower numbers of carbon atoms (see scheme). This catalyst shows remarkable catalytic activity and stability, with excellent potential of regeneration. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Development of the first well-defined tungsten oxo alkyl derivatives supported on silica by SOMC: towards a model of WO3/SiO2 olefin metathesis catalyst

    KAUST Repository

    Mazoyer, Etienne

    2010-01-01

    A well-defined, silica-supported tungsten oxo alkyl species prepared by the surface organometallic chemistry approach displays high and sustained activity in propene metathesis. Remarkably, its catalytic performances outpace those of the parent imido derivative, underlining the importance of the oxo ligand in the design of robust catalysts. © 2010 The Royal Society of Chemistry.

  13. Delocalization model of regioselectivity and reactivity of free radicals in reactions of addition to olefins

    International Nuclear Information System (INIS)

    Volovik, S.V.; Dyadyusha, G.G.; Staninets, V.I.

    1987-01-01

    On the basis of the concept of polarity (philicity) of free radicals as proposed by the authors, within the framework of methods of qualitative surfaces of potential energy (linear combinations of configurations of fragments) and stabilization energy, an effective model has been developed for the regioselectivity and reactivity of radicals in processes of addition. A critical examination is made of certain key aspects of the change in regiochemistry and reactivity with changes in the electronic structure of the free radical and substrate. The dominant trends in regioselectivity and reactivity in processes of free-radical addition to olefins are controlled by electronic effects and can be predicted by analyzing interactions of diabatic potential energy surfaces or orbital interactions for a system consisting of a free radical and an unsaturated substrate

  14. Mechanistic studies of olefin and alkyne trimerization with chromium catalysts: deuterium labeling and studies of regiochemistry using a model chromacyclopentane complex.

    Science.gov (United States)

    Agapie, Theodor; Labinger, Jay A; Bercaw, John E

    2007-11-21

    A system for catalytic trimerization of ethylene utilizing chromium(III) precursors supported by diphosphine ligand PNP(O4) = (o-MeO-C6H4)2PN(Me)P(o-MeO-C6H4)2 has been investigated. The mechanism of the olefin trimerization reaction was examined using deuterium labeling and studies of reactions with alpha-olefins and internal olefins. A well-defined chromium precursor utilized in this studies is Cr(PNP(O4))(o,o'-biphenyldiyl)Br. A cationic species, obtained by halide abstraction with NaB[C6H3(CF3)2]4, is required for catalytic turnover to generate 1-hexene from ethylene. The initiation byproduct is vinylbiphenyl; this is formed even without activation by halide abstraction. Trimerization of 2-butyne is accomplished by the same cationic system but not by the neutral species. Catalytic trimerization, with various (PNP(O4))Cr precursors, of a 1:1 mixture of C2D4 and C2H4 gives isotopologs of 1-hexene without H/D scrambling (C6D12, C6D8H4, C6D4H8, and C6H12 in a 1:3:3:1 ratio). The lack of crossover supports a mechanism involving metallacyclic intermediates. Using a SHOP catalyst to perform the oligomerization of a 1:1 mixture of C2D4 and C2H4 leads to the generation of a broader distribution of 1-hexene isotopologs, consistent with a Cossee-type mechanism for 1-hexene formation. The ethylene trimerization reaction was further studied by the reaction of trans-, cis-, and gem-ethylene-d2 upon activation of Cr(PNP(O4))(o,o'-biphenyldiyl)Br with NaB[C6H3(CF3)2]4. The trimerization of cis- and trans-ethylene-d2 generates 1-hexene isotopomers having terminal CDH groups, with an isotope effect of 3.1(1) and 4.1(1), respectively. These results are consistent with reductive elimination of 1-hexene from a putative Cr(H)[(CH2)4CH=CH2] occurring much faster than a hydride 2,1-insertion or with concerted 1-hexene formation from a chromacycloheptane via a 3,7-H shift. The trimerization of gem-ethylene-d2 has an isotope effect of 1.3(1), consistent with irreversible formation of a

  15. Cationic Silica-Supported N-Heterocyclic Carbene Tungsten Oxo Alkylidene Sites: Highly Active and Stable Catalysts for Olefin Metathesis.

    Science.gov (United States)

    Pucino, Margherita; Mougel, Victor; Schowner, Roman; Fedorov, Alexey; Buchmeiser, Michael R; Copéret, Christophe

    2016-03-18

    Designing supported alkene metathesis catalysts with high activity and stability is still a challenge, despite significant advances in the last years. Described herein is the combination of strong σ-donating N-heterocyclic carbene ligands with weak σ-donating surface silanolates and cationic tungsten sites leading to highly active and stable alkene metathesis catalysts. These well-defined silica-supported catalysts, [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(OTf)] and [(≡SiO)W(=O)(=CHCMe2 Ph)(IMes)(+) ][B(Ar(F) )4 (-) ] [IMes=1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene, B(Ar(F) )4 =B(3,5-(CF3 )2 C6 H3 )4 ] catalyze alkene metathesis, and the cationic species display unprecedented activity for a broad range of substrates, especially for terminal olefins with turnover numbers above 1.2 million for propene. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. A Silica-Supported Monoalkylated Tungsten Dioxo Complex Catalyst for Olefin Metathesis

    KAUST Repository

    Maity, Niladri

    2018-02-15

    A well-defined silica-supported monoalkylated tungsten dioxo complex [(Si-O-)W(=O)(CH-Bu)] was prepared by treatment of highly dehydroxylated silica (SiO: silica treated at 700 °C under high vacuum) with an ionic precursor complex [NEt][W(=O)(CH-Bu)]. The identity of the resulting neutral monoalkylated tungsten dioxo surface complex was established by means of elemental microanalysis and spectroscopic studies (IR, solid-state NMR, Raman, and X-ray absorption spectroscopies). The supported tungsten complex was found to act as a precatalyst for the self-metathesis of 1-octene in a batch reactor. The mechanistic implications of this reaction are discussed with the support of DFT calculations highlighting the potential occurrence of thus-far unexplored mechanistic pathways.

  17. The mechanism for catalytic hydrosilylation by bis(imino)pyridine iron olefin complexes supported by broken symmetry density functional theory.

    Science.gov (United States)

    Lam, Yan Choi; Nielsen, Robert J; Goddard, William A; Dash, Aswini K

    2017-09-26

    Density functional theory (DFT, B3LYP-D3 with implicit solvation in toluene) was used to investigate the mechanisms of olefin hydrosilylation catalyzed by PDI(Fe) (bis(imino)pyridine iron) complexes, where PDI = 2,6-(ArN[double bond, length as m-dash]CMe) 2 (C 5 H 3 N) with Ar = 2,6-R 2 -C 6 H 3 . We find that the rate-determining step for hydrosilylation is hydride migration from Et 3 SiH onto the Fe-bound olefin to form (PDI)Fe(alkyl)(SiEt 3 ). This differs from the mechanism for the Pt Karstedt catalyst in that there is no prior Si-H oxidative addition onto the Fe center. (PDI)Fe(alkyl)(SiEt 3 ) then undergoes C-Si reductive elimination to form (PDI)Fe, which coordinates an olefin ligand to regenerate the resting state (PDI)Fe(olefin). In agreement with experimental observations, we found that anti-Markovnikov hydride migration has a 5.1 kcal mol -1 lower activation enthalpy than Markovnikov migration. This system has an unusual anti-ferromagnetic coupling between high spin electrons on the Fe center and the unpaired spin in the pi system of the non-innocent redox-active PDI ligand. To describe this with DFT, we used the "broken-symmetry" approach to establish the ground electronic and spin state of intermediates and transition states over the proposed catalytic cycles.

  18. Oxidative Heck Reaction as a Tool for Para-selective Olefination of Aniline: A DFT Supported Mechanism.

    Science.gov (United States)

    Moghaddam, Firouz Matloubi; Pourkaveh, Raheleh; Karimi, Ashkan

    2017-10-06

    This study describes the first para-selective palladium-catalyzed alkenylation of tertiary amines. This regioselective C-H activation was conducted without any chelation moieties. A series of olefins were reacted under mild reaction conditions at 60 °C, and the corresponding products were obtained in good yields with high selectivity.

  19. Silicoaluminates as “Support Activator” Systems in Olefin Polymerization Processes

    Science.gov (United States)

    Tabernero, Vanessa; Camejo, Claudimar; Terreros, Pilar; Alba, María Dolores; Cuenca, Tomás

    2010-01-01

    In this work we report the polymerization behaviour of natural clays (montmorillonites, MMT) as activating supports. These materials have been modified by treatment with different aluminium compounds in order to obtain enriched aluminium clays and to modify the global Brönsted/Lewis acidity. As a consequence, the intrinsic structural properties of the starting materials have been changed. These changes were studied and these new materials used for ethylene polymerization using a zirconocene complex as catalyst. All the systems were shown to be active in ethylene polymerization. The catalyst activity and the dependence on acid strength and textural properties have been also studied. The behaviour of an artificial silica (SBA 15) modified with an aluminium compound to obtain a silicoaluminate has been studied, but no ethylene polymerization activity has been found yet.

  20. A Generic Model for Prediction of Separation Performance of Olefin/Paraffin Mixture by Glassy Polymer Membranes

    Directory of Open Access Journals (Sweden)

    A.A. Ghoreyshi

    2008-02-01

    Full Text Available The separation of olefin/paraffin mixtures is an important process in petrochemical industries, which is traditionally performed by low temperature distillation with a high-energy consumption, or complex extractive distillationand adsorption techniques. Membrane separation process is emerging as an alternative for traditional separation processes with respect to low energy and simple operation. Investigations made by various researchers on polymeric membranes it is found that special glassy polymers render them as suitable materials for olefin/paraffin mixture separation. In this regard, having some knowledge on the possible transport mechanism of these processes would play a significant role in their design and applications. In this study, separation behavior of olefin/paraffin mixtures through glassy polymers was modeled by three different approaches: the so-called dual transport model, the basic adsorption-diffusion theory and the general Maxwell-Stefan formulation. The systems chosen to validate the developed transport models are separation of ethane-ethylene mixture by 6FDA-6FpDA polyimide membrane and propane-propylene mixture by 6FDA-TrMPD polyimide membrane for which the individual sorption and permeation data are available in the literature. Acritical examination of dual transport model shows that this model fails clearly to predict even the proper trend for selectivities. The adjustment of pemeabilities by accounting for the contribution of non-selective bulk flow in the transport model introduced no improvement in the predictability of the model. The modeling results based on the basic adsorption-diffusion theory revealed that in this approach only using mixed permeability data, an acceptable result is attainable which fades out the advantages of predictibility of multicomponent separation performance from pure component data. Finally, the results obtained from the model developed based on Maxwell-Stefan formulation approach show a

  1. Olefin metathesis catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S.G.; Banks, R.L.

    1986-05-20

    A process is described for preparing a disproportionation catalyst comprising admixing a catalytically effective amount of a calcined and activated catalyst consisting essentially of at least one metal oxide selected from molybdenum oxide and tungsten oxide and a support containing a major proportion of silica or alumina with a promoting amount of a methylating agent selected from the group consisting of dimethyl sulfate, dimethylsulfoxide, trimethyloxonium tetrafluorborate, methyl iodide, and methyl bromide, and subjecting same to inert atmospheric conditions for the methylating agent to promote the activity of the calcined molybdenum and tungsten oxides for the disproportionation of olefins.

  2. Olefin metathesis over silica-supported molybdena catalysts activated by UV-irradiation in the presence of alkanes

    International Nuclear Information System (INIS)

    Subbotina, I.R.; Shelimov, B.N.; Kazanskij, V.B.

    1997-01-01

    It is established that molybdenum-silica catalysts (MoO 3 /SiO 2 ) applied after their irradiation by UV-light in the alkanes atmosphere acquire high activity in the reaction of propylen and hexene metathesis at the temperature of 293 K. The efficiency of photoactivated catalysts during these reactions is determined. It is shown that by UV-irradiation of MoO 3 /SiO 2 in presence of alkanes there take place the Mo 6+ ions conversion to Mo 5+ and Mo 4+ , formation the of Mo 4+ solid π-complexes with olefins and, probably, the surface carbene complexes Mo=CH-R

  3. Hydro-Metathesis of Long-Chain Olefin (1-decene) using Well-Defined Silica-Supported Tungsten (VI), Molybdenum (VI) and Tantalum (V) Catalysts

    KAUST Repository

    Saidi, Aya

    2016-11-01

    Nowadays, catalysis lies at the heart of economy growth mainly in the petroleum industry. Catalysis can offer real and potential solutions to the current challenges for a long-term sustainable energy, green chemistry, and environmental protection. In this context, one of the most important and future prosperity promising catalytic applications in the petrochemical field is hydrocarbons metathesis; it consists on the conversion of both renewable and non-petroleum fossil carbon sources to transportation fuels. Olefin metathesis has become one of the standard methodologies for constructing C-C bonds in many organic transformation reactions. This owed to the numerous types of metathesis reactions that have been developed, for example, enyne, ring-opening and closing, self and cross metathesis, etc. But the one step conversion of olefin to alkanes has not been studied much. Recently, only one such a work has been published for the hydro-metathesis of propylene by tantalum hydride supported on KCC-1 in dynamic reactor. With this knowledge, we thought to study the hydro-metathesis using liquid olefin (1-decene). Another aspect of using 1-decene comes from our previous experience on metathesis of n-decane where the first step is the conversion of decane to 1-decene and subsequently to different chain length alkanes with W-alkyl/alkylidene catalyst. In this way, it would be easy for us to use different catalysts and compare them with parent catalyst concerning TON. We found 100% conversion with TON of 1010 using supported WMe6 onto SiO2-700 [(≡Si-O-)WMe5] against the previous results for n-decane showing 20% conversion and TON of 153. In this work, we disclose the hydro-metathesis reaction of 1-decene using well-defined silica supported W(VI), Mo(VI) and Ta(V) alkyl catalysts in batch reactor condition. This work is divided into three major sections; first chapter contains an introduction to the field of catalysis and surface organometallic chemistry. In second chapter

  4. Ruthenium Catalysts Supported by Amino-Substituted N-Heterocyclic Carbene Ligands for Olefin Metathesis of Challenging Substrates.

    Science.gov (United States)

    César, Vincent; Zhang, Yin; Kośnik, Wioletta; Zieliński, Adam; Rajkiewicz, Adam A; Ruamps, Mirko; Bastin, Stéphanie; Lugan, Noël; Lavigne, Guy; Grela, Karol

    2017-02-03

    N-Heterocyclic carbene (NHC) ligands IMesNMe2 and IMes(NMe2)2 derived from the well-known IMes ligand by substituting the carbenic heterocycle with one and two dimethylamino groups, respectively, were employed for the synthesis of second-generation Grubbs- and Grubbs-Hoveyda-type ruthenium metathesis precatalysts. Whereas the stability of the complexes was found to depend on the degree of dimethylamino-substitution and on the type of complex, the backbone-substitution was shown to have a positive impact on their catalytic activity in ring-closing metathesis, with a more pronounced effect in the second-generation Grubbs-type series. The new complexes were successfully implemented in a number of challenging olefin metathesis reactions leading to the formation of tetra-substituted C=C double bonds and/or functionalized compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Predicting Alkylate Yield and its Hydrocarbon Composition for Sulfuric Acid Catalyzed Isobutane Alkylation with Olefins Using the Method of Mathematical Modeling

    OpenAIRE

    Nurmakanova, А. Е.; Ivashkina, Elena Nikolaevna; Ivanchina, Emilia Dmitrievna; Dolganov, I. A.; Boychenko, S. S.

    2015-01-01

    The article provides the results of applied mathematical model of isobutane alkylation with olefins catalyzed by sulfuric acid to predict yield and hydrocarbon composition of alkylate caused by the changes in the feedstock composition and process parameters. It is shown that the alkylate produced from feedstock with less mass fraction of isobutane has lower octane value. Wherein the difference in composition of the feedstock contributes to antiknock index by the amount of 1.0-2.0 points.

  6. (Z)-Selective Takai olefination of salicylaldehydes.

    Science.gov (United States)

    Geddis, Stephen M; Hagerman, Caroline E; Galloway, Warren R J D; Sore, Hannah F; Goodman, Jonathan M; Spring, David R

    2017-01-01

    The Takai olefination (or Takai reaction) is a method for the conversion of aldehydes to vinyl iodides, and has seen widespread implementation in organic synthesis. The reaction is usually noted for its high ( E )-selectivity; however, herein we report the highly ( Z )-selective Takai olefination of salicylaldehyde derivatives. Systematic screening of related substrates led to the identification of key factors responsible for this surprising inversion of selectivity, and enabled the development of a modified mechanistic model to rationalise these observations.

  7. Experimental and modeling study of kinetics and selectivity in the oxidation of a poly([alpha]-olefin) lubricant

    Energy Technology Data Exchange (ETDEWEB)

    Koh, C.S.; Butt, J.B. (Northwestern Univ., Evanston, IL (United States))

    1995-02-01

    A major means of lubricant oil degradation is by oxidation in the presence of metal surfaces that can have catalytic activity. In this work an experimental and modeling study has been carried out on the oxidation kinetics and selectivity of a typical poly([alpha]-olefin) (PAO) lubricant in the presence of both inert (glass) and active (brass, steel) surfaces in the temperature range 170--240 C. Inhibition of the reaction by zinc dialkyl dithiophosphate (ZDP) has been investigated. A batch recycling trickle-bed reactor system has been developed which provides reliable data on intrinsic chemical kinetics. Reaction rates are a strong function of temperature, with products appearing in the order of water, carbon dioxide, aldehydes, ketones, acids, and alcohols in both gas and liquid phases. Significant changes in viscosity and molecular weight were observed for T > 200 C. A four-lump (PAO, carbonyl-containing compounds in the liquid phase, gaseous products, and deposits) kinetic model has been developed that gives good agreement with experimental results, including oxidation rate promotion by metals and inhibition by ZDP.

  8. Latent olefin metathesis catalysts

    OpenAIRE

    Monsaert, Stijn; Lozano Vila, Ana; Drozdzak, Renata; Van Der Voort, Pascal; Verpoort, Francis

    2009-01-01

    Olefin metathesis is a versatile synthetic tool for the redistribution of alkylidene fragments at carbon-carbon double bonds. This field, and more specifically the development of task-specific, latent catalysts, attracts emerging industrial and academic interest. This tutorial review aims to provide the reader with a concise overview of early breakthroughs and recent key developments in the endeavor to develop latent olefin metathesis catalysts, and to illustrate their use by prominent exampl...

  9. Olefin metathesis and catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kukes, S. G.; Banks, R. L.

    1985-03-12

    Olefins are converted into other olefins having different numbers of carbon atoms by contact with a catalyst comprising an inorganic refractory material containing at least one of tungsten oxide and molybdenum oxide and a promoting amount of at least one treating agent selected from chlorinated silicon compounds, thionyl chloride, and sulfuryl chloride under conditions suitable for the treating agent to promote the activity of tungsten and molybdenum oxides for the disporoportionation reaction.

  10. Covalent organic frameworks as supports for a molecular Ni based ethylene oligomerization catalyst for the synthesis of long chain olefins

    NARCIS (Netherlands)

    Rozhko, E.; Bavykina, A.V.; Osadchii, D.; Makkee, M.; Gascon Sabate, J.

    2017-01-01

    The use of two different classes of covalent organic frameworks (covalent triazine and imine linked frameworks) as supports for molecular Ni2+ catalysts is presented. For COFs, a large concentration of N heteroatoms, either in the form of quasi bipyridine or as diiminopyridine

  11. Cyclic olefin copolymer-silica nanocomposites foams

    Czech Academy of Sciences Publication Activity Database

    Pegoretti, A.; Dorigato, A.; Biani, A.; Šlouf, Miroslav

    2016-01-01

    Roč. 51, č. 8 (2016), s. 3907-3916 ISSN 0022-2461 R&D Projects: GA MŠk(CZ) LO1507 Institutional support: RVO:61389013 Keywords : cyclic olefin copolymer * nanocomposites * silica Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.599, year: 2016

  12. Influence of the acid and basic properties of rhenium oxide supported on alumina catalyst on the catalytic performance in olefin metathesis; Influence des proprietes acido-basiques de l`oxyde de rhenium supporte sur les performances catalytiques en metathese des olefines

    Energy Technology Data Exchange (ETDEWEB)

    Nahama, F.

    1996-11-30

    The aim of this work is to study the influence of the acid-basic properties of rhenium oxide supported on alumina catalyst on the catalytic performance in olefin metathesis. The literature data indicate that the environment of the active site does possess acid properties. However, the nature of the acid sites is still matter of debate. Concerning the Re O{sub x} - Al{sub 2}O{sub 3} interactions, we have shown that perrhenate ions are electrostatically absorbed on alumina. The uptake of rhenium is favoured at acidic pH (below 4), and the absorbed rhenium is in equilibrium with rhenium in solution. The results of rhenium extraction by water strongly suggest that the surface compounds of the calcined Re{sub 2}O{sub 7}/Al{sub 2}O{sub 3} materials is aluminium perrhenate. Characterization of surface acidity of the catalyst by infrared spectroscopy reveals that the initiation of the metathesis reaction is governed essentially by Lewis acidity. This strongly supports the role of Lewis acidity, which is exalted by the increase of the rhenium content and the calcination temperature. Finally, we point out by ammonia adsorption-thermodesorption a band at 1320 cm{sup -1} characteristic of the Lewis acidity of aluminium perrhenate. This result is a second indication of the presence of aluminium perrhenate on the Re{sub 2}O{sub 7}/Al{sub 2}O{sub 3} catalyst surface. (author)

  13. (Z-Selective Takai olefination of salicylaldehydes

    Directory of Open Access Journals (Sweden)

    Stephen M. Geddis

    2017-02-01

    Full Text Available The Takai olefination (or Takai reaction is a method for the conversion of aldehydes to vinyl iodides, and has seen widespread implementation in organic synthesis. The reaction is usually noted for its high (E-selectivity; however, herein we report the highly (Z-selective Takai olefination of salicylaldehyde derivatives. Systematic screening of related substrates led to the identification of key factors responsible for this surprising inversion of selectivity, and enabled the development of a modified mechanistic model to rationalise these observations.

  14. Recovery of olefin monomers

    Science.gov (United States)

    Golden, Timothy Christoph; Weist, Jr., Edward Landis; Johnson, Charles Henry

    2004-03-16

    In a process for the production of a polyolefin, an olefin monomer is polymerised said polyolefin and residual monomer is recovered. A gas stream comprising the monomer and nitrogen is subjected to a PSA process in which said monomer is adsorbed on a periodically regenerated silica gel or alumina adsorbent to recover a purified gas stream containing said olefin and a nitrogen rich stream containing no less than 99% nitrogen and containing no less than 50% of the nitrogen content of the gas feed to the PSA process.

  15. Living olefin polymerization processes

    Science.gov (United States)

    Schrock, Richard R.; Baumann, Robert

    2003-08-26

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  16. Living olefin polymerization processes

    Science.gov (United States)

    Schrock, Richard R.; Bauman, Robert

    2006-11-14

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  17. Ruthenium carbenes supported on mesoporous silicas as highly active and selective hybrid catalysts for olefin metathesis reactions under continuous flow.

    Science.gov (United States)

    Bru, Miriam; Dehn, Richard; Teles, J Henrique; Deuerlein, Stephan; Danz, Manuel; Müller, Imke B; Limbach, Michael

    2013-08-26

    In the search for a highly active and selective heterogenized metathesis catalyst, we systematically varied the pore geometry and size of various silica-based mesoporous (i.e., MCM-41, MCM-48, and SBA-15) and microporous (ZSM-5 and MWW) versus macroporous materials (D11-10 and Aerosil 200), besides other process parameters (temperature, dilution, and mean residence time). The activity and, especially, selectivity of such "linker-free" supports for ruthenium metathesis catalysts were evaluated in the cyclodimerization of cis-cyclooctene to form 1,9-cyclohexadecadiene, a valuable intermediate in the flavor and fragrance industry. The optimized material showed not only exceptionally high selectivity to the valuable product, but also turned out to be a truly heterogeneous catalyst with superior activity relative to the unsupported homogeneous complex. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Functionalized SBA-15 supported nickel (II)–oxime–imine catalysts for liquid phase oxidation of olefins under solvent-free conditions

    International Nuclear Information System (INIS)

    Paul, Luna; Banerjee, Biplab; Bhaumik, Asim; Ali, Mahammad

    2016-01-01

    A new oxime–imine functionalized highly ordered mesoporous SBA-15 (SBA-15-NH 2 -DAMO) has been synthesized via post-synthesis functionalization of SBA-15 with 3-aminopropyl-triethoxysilane followed by the Schiff base condensation with diacetylmonooxime, which was further reacted with Ni(ClO 4 ) 2 to yield the functionalized nickel catalyst SBA-15-NH 2 -DAMO-Ni. All the synthesized materials were thoroughly characterized using different characterization techniques. It was found that SBA-15-NH 2 -DAMO-Ni catalyzes the one-pot oxidation of olefins like styrene, cyclohexene, cyclooctene, 1-hexene and 1-octene to the corresponding benzaldehyde, cyclohexene-1-ol and cyclooctene-oxide, respectively under solvent-free conditions by using tert-butylhydroperoxide as oxidant. - Graphical abstract: A new well characterized oxime–imine functionalized highly ordered mesoporous SBA-15-NH 2 -DAMO-Ni complex catalyzes the one-pot oxidation of olefins under solvent free mild conditions.

  19. Production and use of light olefins. Preprints of the conference

    Energy Technology Data Exchange (ETDEWEB)

    Ernst, S.; Buzzoni, R.; Leitner, W.; Lercher, J.A.; Lichtscheidl, J.; Nees, F.; Santacesaria, E. (eds.)

    2009-07-01

    Within the conference of the German Society for Petroleum and Coal Science and Technology e.V. (Hamburg, Federal Republic of Germany) in Berlin (Federal Republic of Germany) at 28th to 30th September, 2009, the following lectures were held: (1) Steamcracking - State of the Art (H. Zimmermann); (2) Diversify Feedstock Options to Olefin Production (Q. Ling et al.); (3) Syngas to lower olefins (E. Schwab et al.); (4) STAR process registered for the on-purpose production of propylene (K. Bueker); (5) The catalytic activity of zinc oxide supported on aerosil for C-H activation of light alkanes (S. Arndt et al.); (6) Novel catalytic approaches for the oxidative dehydrogenation of ethane (D. Hartmann); (7) A comparison of the active sites structures of homogeneous and heterogeneous olefin polymerisation catalysts (A. Zecchina); (8) Catalytic strategies in metathesis (C. Coperet); (9) Multi-technology integrated production and consumption of olefins (J. Popp et al.); (10) Olefin oligomerization for the production of fuels and petrochemicals (H. Olivier-Bourbigou et al.); (11) Dieselization of the world - How to increase diesel yield in a refinery (A. Dueker); (12) Isomerization of butenes: LyondellBasell's Isomplus technology development (T. Zak et al.); (13) Valuable products from butadiene, carbon dioxide and further base chemicals (A. Behr); (14) The partial oxidation of propene to propylene oxide using N{sub 2}O as an oxidant (T. Thoemmes); (15) Alternative feedstocks for olefin production: What role will ethanol play? (B.R. Maughon); (16) Production of light olefins from renewable resources - The effect of deoxygenation degree on yields of light olefins (D. Kubicka et al.); (17) Recovery of low olefins from refinery offgases (M. Bender).

  20. Direct observation of OH production from the ozonolysis of olefins

    Science.gov (United States)

    Donahue, Neil M.; Kroll, Jesse H.; Anderson, James G.; Demerjian, Kenneth L.

    Ozone olefin reactions may be a significant source of OH in the urban atmosphere, but current evidence for OH production is indirect and contested. We report the first direct observation of OH radicals from the reaction of ozone with a series of olefins (ethene, isoprene, trans-2-butene and 2,3 dimethyl-2-butene) in 4-6 torr of nitrogen. Using LIF to directly observe the steady-state of OH produced by the initial ozone-olefin reaction and subsequently destroyed by the OH-olefin reaction, we are able to establish OH yields broadly consistent with indirect values. The identification of the OH is unequivocal, and there is no indication that it is produced by a secondary process. To support these observations, we present a complete ab-initio potential energy surface for the O3-ethene reaction, extending from the reactants to available products.

  1. Olefin metathesis in air.

    Science.gov (United States)

    Piola, Lorenzo; Nahra, Fady; Nolan, Steven P

    2015-01-01

    Since the discovery and now widespread use of olefin metathesis, the evolution of metathesis catalysts towards air stability has become an area of significant interest. In this fascinating area of study, beginning with early systems making use of high oxidation state early transition metal centers that required strict exclusion of water and air, advances have been made to render catalysts more stable and yet more functional group tolerant. This review summarizes the major developments concerning catalytic systems directed towards water and air tolerance.

  2. Photolithographic Olefin Metathesis Polymerization

    OpenAIRE

    Weitekamp, Raymond A.; Atwater, Harry A.; Grubbs, Robert H.

    2013-01-01

    Patterning functional materials is a central challenge across many fields of science. The ability to lithographically fabricate micro- and nanostructures has been one of the most impactful technological breakthroughs of the last century. In part due to the complexity of the chemical processes in photoresists, there is a limited variety of materials that can currently be patterned by photolithography. We report a negative tone photoresist using a photoactivated olefin metathesis catalyst, whic...

  3. Olefin metathesis in air

    OpenAIRE

    Lorenzo Piola; Fady Nahra; Steven P. Nolan

    2015-01-01

    Summary Since the discovery and now widespread use of olefin metathesis, the evolution of metathesis catalysts towards air stability has become an area of significant interest. In this fascinating area of study, beginning with early systems making use of high oxidation state early transition metal centers that required strict exclusion of water and air, advances have been made to render catalysts more stable and yet more functional group tolerant. This review summarizes the major developments...

  4. Presenting a new kinetic model for methanol to light olefins reactions over a hierarchical SAPO-34 catalyst using the Langmuir-Hinshelwood-Hougen-Watson mechanism

    Science.gov (United States)

    Javad Azarhoosh, Mohammad; Halladj, Rouein; Askari, Sima

    2017-10-01

    In this study, a new kinetic model for methanol to light olefins (MTO) reactions over a hierarchical SAPO-34 catalyst using the Langmuir-Hinshelwood-Hougen-Watson (LHHW) mechanism was presented and the kinetic parameters was obtained using a genetic algorithm (GA) and genetic programming (GP). Several kinetic models for the MTO reactions have been presented. However, due to the complexity of the reactions, most reactions are considered lumped and elementary, which cannot be deemed a completely accurate kinetic model of the process. Therefore, in this study, the LHHW mechanism is presented as kinetic models of MTO reactions. Because of the non-linearity of the kinetic models and existence of many local optimal points, evolutionary algorithms (GA and GP) are used in this study to estimate the kinetic parameters in the rate equations. Via the simultaneous connection of the code related to modelling the reactor and the GA and GP codes in the MATLAB R2013a software, optimization of the kinetic models parameters was performed such that the least difference between the results from the kinetic models and experiential results was obtained and the best kinetic parameters of MTO process reactions were achieved. A comparison of the results from the model with experiential results showed that the present model possesses good accuracy.

  5. Functionalized SBA-15 supported nickel (II)–oxime–imine catalysts for liquid phase oxidation of olefins under solvent-free conditions

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Luna [Department of Chemistry, Jadavpur University, Kolkata 700 032 (India); Banerjee, Biplab [Department of Materials Science, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032 (India); Bhaumik, Asim, E-mail: msab@iacs.res.in [Department of Materials Science, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032 (India); Ali, Mahammad, E-mail: m_ali2062@yahoo.com [Department of Chemistry, Jadavpur University, Kolkata 700 032 (India)

    2016-05-15

    A new oxime–imine functionalized highly ordered mesoporous SBA-15 (SBA-15-NH{sub 2}-DAMO) has been synthesized via post-synthesis functionalization of SBA-15 with 3-aminopropyl-triethoxysilane followed by the Schiff base condensation with diacetylmonooxime, which was further reacted with Ni(ClO{sub 4}){sub 2} to yield the functionalized nickel catalyst SBA-15-NH{sub 2}-DAMO-Ni. All the synthesized materials were thoroughly characterized using different characterization techniques. It was found that SBA-15-NH{sub 2}-DAMO-Ni catalyzes the one-pot oxidation of olefins like styrene, cyclohexene, cyclooctene, 1-hexene and 1-octene to the corresponding benzaldehyde, cyclohexene-1-ol and cyclooctene-oxide, respectively under solvent-free conditions by using tert-butylhydroperoxide as oxidant. - Graphical abstract: A new well characterized oxime–imine functionalized highly ordered mesoporous SBA-15-NH{sub 2}-DAMO-Ni complex catalyzes the one-pot oxidation of olefins under solvent free mild conditions.

  6. Industrial processes of olefin metathesis. Pt. 1

    Energy Technology Data Exchange (ETDEWEB)

    Warwel, S.

    1987-05-01

    Olefin metathesis opens new synthetic routes to typical petrochemicals (ethylene, propylene, n-butenes), special olefins (neohexene, higher molecular linear olefins, , -dienes) and unsaturated polymers (polynorbornene, -cyclooctene, -dicyclopentadiene) in an industrial scale. The 8 metathesis processes used in industry and further possible applications of olefin metathesis are reviewed.

  7. Olefin metathesis in air

    Directory of Open Access Journals (Sweden)

    Lorenzo Piola

    2015-10-01

    Full Text Available Since the discovery and now widespread use of olefin metathesis, the evolution of metathesis catalysts towards air stability has become an area of significant interest. In this fascinating area of study, beginning with early systems making use of high oxidation state early transition metal centers that required strict exclusion of water and air, advances have been made to render catalysts more stable and yet more functional group tolerant. This review summarizes the major developments concerning catalytic systems directed towards water and air tolerance.

  8. Isobutane/olefin-alkylation

    Energy Technology Data Exchange (ETDEWEB)

    Waitkamp, J.; Maixner, S.

    1983-11-01

    Isobutane/olefin-alkylation - technology and reaction mechanism of a refinery process for production of high octane gasoline components: The alkylation of i-butane with olefins, especially with butenes, is a process for the conversion of light byproducts of a catalytic cracker to high quality gasoline components. Alkylate is a complex mixture of i-paraffins containing 5 to ca. 12 carbon atoms. Due to their octane numbers the four trimethylpentane isomers are the most desirable product components. Indeed, under optimum process conditions these isomers are the main products. Presently, alkylation capacity in the western world amounts to more than 40x10/sup 6/ t/a. Most units are located in the USA. Two liquid-phase processes using sulfuric acid and hydrofluoric acid, respectively, are of commercial importance. At present, there is a definite trend towards HF-alkylation. The reaction mechanism which proceeds via carbocations, is extremely complex. It is composed of a great variety of individual steps. Modern mechanistic concepts are discussed.

  9. Mechanistic studies of olefin metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Grubbs, R.H.

    1979-03-01

    A review covers studies of the olefin metathesis mechanism which indicated that the reaction proceeds by a non-pairwise mechanism; detailed mechanistic studies on the homogeneously and heterogeneously catalyzed metathesis; and stereochemical investigations.

  10. Hyperbranched Macromolecules via Olefin Metathesis

    OpenAIRE

    Gorodetskaya, Irina A.; Choi, Tae-Lim; Grubbs, Robert H.

    2007-01-01

    A facile route to hyperbranched polymers via acyclic diene metathesis is reported. Any molecule functionalized with two or more acrylate groups and one terminal olefin can serve as an AB_n monomer when exposed to an imidazolinylidene-based ruthenium olefin metathesis catalyst, due to the cross metathesis selectivity of this catalyst. For the polymers obtained by this method, both ^1H NMR spectroscopy and triple detector size exclusion chromatography conclusively indicate a branched architecture.

  11. Methyltrioxorhenium as catalyst for olefin metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Herrmann, W.A. (Technische Univ. Muenchen, Garching (Germany). Anorganisch-Chemisches Inst.); Wagner, W. (Consortium fuer Elektrochemische Industrie GmbH, Muenchen (Germany)); Flessner, U.N.; Volkhardt, U.; Komber, H. (Institut fuer Technologie der Polymere, Dresden (Germany))

    1991-12-01

    No cocatalysts are needed as additives when methyltrioxorhenium (MTO) supported on acidic carriers is employed to catalyze the metathesis of functionalized olefins. A typical system is MTO/Al{sub 2}O{sub 3}-SiO{sub 2}, which is active, for instance, in the metathesis of allyl halides, allylsilanes, unsaturated carboxylates, and nitriles. MTO in combination with R{sub n}AlCl{sub 3-n} is a homogeneous catalyst in ring-opening polymerizations (R = CH{sub 3}, C{sub 2}H{sub 5}; n = 1,2). (orig.).

  12. Highly Active Water-Soluble Olefin Metathesis Catalyst

    OpenAIRE

    Hong, Soon Hyeok; Grubbs, Robert H.

    2006-01-01

    A novel water-soluble ruthenium olefin metathesis catalyst supported by a poly(ethylene glycol) conjugated saturated 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene ligand is reported. The catalyst displays improved activity in ring-opening metathesis polymerization, ring-closing metathesis, and cross-metathesis reactions in aqueous media.

  13. Direct Wittig Olefination of Alcohols.

    Science.gov (United States)

    Li, Qiang-Qiang; Shah, Zaher; Qu, Jian-Ping; Kang, Yan-Biao

    2018-01-05

    A base-promoted transition metal-free approach to substituted alkenes using alcohols under aerobic conditions using air as the inexpensive and clean oxidant is described. Aldehydes are relatively difficult to handle compared to corresponding alcohols due to their volatility and penchant to polymerize and autoxidize. Wittig ylides are easily oxidized to aldehydes and consequently form homo-olefination products. By the strategy of simultaneously in situ generation of ylides and aldehydes, for the first time, alcohols are directly transferred to olefins with no need of prepreparation of either aldehydes or ylides. Thus, the di/monocontrollable olefination of diols is accomplished. This synthetically practical method has been applied in the gram-scale synthesis of pharmaceuticals, such as DMU-212 and resveratrol from alcohols.

  14. Application of olefin metathesis in petrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Warwel, S.

    1979-01-01

    A survey covers the catalysts used in olefin metathesis; olefin types which undergo metathesis, e.g., ring-opening metathetic polymerization of cycloolefins; equilibria and side reactions; the Phillips Triolefin process for 2-butene production; the Shell Higher Olefin Process (SHOP) for the production of C/sub 11/-C/sub 14/ ..cap alpha..-olefins; the Phillips Petroleum 225 ton/yr process for the conversion of trimethylpentane to neohexene, which is used in gasoline and pharmaceutical manufacture; the production of isoprene precursors; and various other metathesis reactions used in synthesizing specific olefins.

  15. Light-induced olefin metathesis

    Science.gov (United States)

    Vidavsky, Yuval

    2010-01-01

    Summary Light activation is a most desirable property for catalysis control. Among the many catalytic processes that may be activated by light, olefin metathesis stands out as both academically motivating and practically useful. Starting from early tungsten heterogeneous photoinitiated metathesis, up to modern ruthenium methods based on complex photoisomerisation or indirect photoactivation, this survey of the relevant literature summarises past and present developments in the use of light to expedite olefin ring-closing, ring-opening polymerisation and cross-metathesis reactions. PMID:21160912

  16. Light-induced olefin metathesis

    Directory of Open Access Journals (Sweden)

    Yuval Vidavsky

    2010-11-01

    Full Text Available Light activation is a most desirable property for catalysis control. Among the many catalytic processes that may be activated by light, olefin metathesis stands out as both academically motivating and practically useful. Starting from early tungsten heterogeneous photoinitiated metathesis, up to modern ruthenium methods based on complex photoisomerisation or indirect photoactivation, this survey of the relevant literature summarises past and present developments in the use of light to expedite olefin ring-closing, ring-opening polymerisation and cross-metathesis reactions.

  17. The asymmetric Schrock olefin metathesis catalysts. A computational study

    NARCIS (Netherlands)

    Goumans, T.P.M.; Ehlers, A.W.; Lammertsma, K.

    2005-01-01

    The mechanism of the transition metal catalyzed olefin metathesis reaction with the Schrock catalyst is investigated with pure (BP86) and hybrid (B3LYP) density functional theory. On the free-energy surface there is no adduct between ethylene and model catalyst (MeO)

  18. Rhodium(I) catalysis in olefin photoreactions

    International Nuclear Information System (INIS)

    Salomon, R.G.; El Sanadi, N.

    1975-01-01

    The photorearrangement (254 nm) of 1,5-cyclooctadiene (1) in the presence of rhodium(I) chloride to give 1,4-cyclooctadiene (4) was found by deuterium labeling to involve an intramolecular [1,3] shift of hydrogen. A rate-determining cleavage of an allylic C--H bond is indicated by a deuterium isotope effect, k/sub H//k/sub D/ = 1.55 +- 0.03 for the 1 → 4 rearrangement. The acyclic 1,5-diene, 3,3-dimethyl-1,5-hexadiene (8), rearranges in the presence of rhodium(I) chloride upon uv irradiation (254 nm) to give cis-3,3-dimethyl-1,4-hexadiene (10) and the trans isomer 11 in a 1:4 ratio, respectively. This observation supports a mechanism for the photorearrangement of olefins catalyzed by rhodium(I) involving an initial photodissociation of one of two rhodium(I) coordinated carbon-carbon double bonds. This results in an increase in the coordinative unsaturation of rhodium(I) and enhances the proclivity of this d/sub s/ metal atom toward oxidative addition of an allylic C--H bond. A eta 3 -allylrhodium hydride intermediate then gives rearranged olefin by reductive elimination. Lastly, a novel photochemical, rhodium(I) catalyzed hydrogen transfer is reported which gives cyclooctene (7) from cyclooctadienes under unprecedentedly mild conditions. (auth)

  19. Recent Advancements in Stereoselective Olefin Metathesis Using Ruthenium Catalysts

    OpenAIRE

    Montgomery, T. Patrick; Johns, Adam M.; Grubbs, Robert H.

    2017-01-01

    Olefin metathesis is a prevailing method for the construction of organic molecules. Recent advancements in olefin metathesis have focused on stereoselective transformations. Ruthenium olefin metathesis catalysts have had a particularly pronounced impact in the area of stereoselective olefin metathesis. The development of three categories of Z-selective olefin metathesis catalysts has made Z-olefins easily accessible to both laboratory and industrial chemists. Further design enhancements to as...

  20. Olefins from Biomass Intermediates: A Review

    Directory of Open Access Journals (Sweden)

    Vasiliki Zacharopoulou

    2017-12-01

    Full Text Available Over the last decade, increasing demand for olefins and their valuable products has prompted research on novel processes and technologies for their selective production. As olefins are predominately dependent on fossil resources, their production is limited by the finite reserves and the associated economic and environmental concerns. The need for alternative routes for olefin production is imperative in order to meet the exceedingly high demand, worldwide. Biomass is considered a promising alternative feedstock that can be converted into the valuable olefins, among other chemicals and fuels. Through processes such as fermentation, gasification, cracking and deoxygenation, biomass derivatives can be effectively converted into C2–C4 olefins. This short review focuses on the conversion of biomass-derived oxygenates into the most valuable olefins, e.g., ethylene, propylene, and butadiene.

  1. Rh(III)-catalyzed olefination of N-sulfonyl imines: synthesis of ortho-olefinated benzaldehydes.

    Science.gov (United States)

    Zhang, Tao; Wu, Lamei; Li, Xingwei

    2013-12-20

    Rh(III)-catalyzed olefination of N-sulfonyl imines using acrylates and styrenes has been achieved for the synthesis of ortho-olefinated benaldehydes. This reaction proceeds via a chelation assisted C-H olefination/in situ hydrolysis process.

  2. Theoretical investigations of olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Cundari, T.R.; Gordon, M.S. [North Dakota State Univ., Fargo, ND (United States)

    1992-01-01

    An ab initio analysis of the electronic structure of high-valent, transition-metal alkylidenes as models for olefin metathesis catalysts is presented. The catalyst models studied fall into three categories: {open_quotes}new{close_quotes} metathesis catalyst models-tetrahedral M(OH){sup 2}(XH)(CH{sub 2}) complexes; {open_quotes}old{close_quotes} metathesis catalyst models-tetrahedral MCl{sub 2}(Y)(CH{sub 2}) complexes and alkylidene-substituted Mo metathesis catalysts, Mo(OH){sub 2}(NH)(=C(H)Z). The effect on the bonding caused by modification of either the metal, ligands, or alkylidene substitutents is considered. 21 refs., 2 figs., 5 tabs.

  3. At the frontier between heterogeneous and homogeneous catalysis: hydrogenation of olefins and alkynes with soluble iron nanoparticles.

    Science.gov (United States)

    Rangheard, Claudine; de Julián Fernández, César; Phua, Pim-Huat; Hoorn, Johan; Lefort, Laurent; de Vries, Johannes G

    2010-09-28

    The use of non-supported Fe nanoparticles in the hydrogenation of unsaturated C-C bonds is a green catalytic concept at the frontier between homogeneous and heterogeneous catalysis. Iron nanoparticles can be obtained by reducing Fe salts with strong reductants in various solvents. FeCl(3) reduced by 3 equivalents of EtMgCl forms an active catalyst for the hydrogenation of a range of olefins and alkynes. Olefin hydrogenation is relatively fast at 5 bar using 5 mol% of catalyst. The catalyst is also active for terminal olefins and 1,1' and 1,2-cis disubstituted olefins while trans-olefins react much slower. 1-Octyne is hydrogenated to mixtures of 1-octene and octane. Kinetic studies led us to propose a mechanism for this latter transformation where octane is obtained by two different pathways. Characterization of the nanoparticles via TEM, magnetic measurements and poisoning experiments were undertaken to understand the true nature of our catalyst.

  4. Microwave-Assisted Olefin Metathesis

    Science.gov (United States)

    Nicks, François; Borguet, Yannick; Sauvage, Xavier; Bicchielli, Dario; Delfosse, Sébastien; Delaude, Lionel; Demonceau, Albert

    Since the first reports on the use of microwave irradiation to accelerate organic chemical transformations, a plethora of papers have been published in this field. In most examples, microwave heating has been shown to dramatically reduce reaction times, increase product yields, and enhance product purity by reducing unwanted side reactions compared to conventional heating methods. The present contribution aims at illustrating the advantages of this technology in olefin metathesis and, when data are available, at comparing microwave-heated and conventionally heated experiments

  5. Olefin Metathesis for Chemical Biology

    OpenAIRE

    Binder, Joseph B; Raines, Ronald T

    2008-01-01

    Chemical biology relies on effective synthetic chemistry for building molecules to probe and modulate biological function. Olefin metathesis in organic solvents is a valuable addition to this armamentarium, and developments during the previous decade are enabling metathesis in aqueous solvents for the manipulation of biomolecules. Functional group-tolerant ruthenium metathesis catalysts modified with charged moieties or hydrophilic polymers are soluble and active in water, enabling ring-openi...

  6. Light-induced olefin metathesis

    OpenAIRE

    Yuval Vidavsky; N. Gabriel Lemcoff

    2010-01-01

    Summary Light activation is a most desirable property for catalysis control. Among the many catalytic processes that may be activated by light, olefin metathesis stands out as both academically motivating and practically useful. Starting from early tungsten heterogeneous photoinitiated metathesis, up to modern ruthenium methods based on complex photoisomerisation or indirect photoactivation, this survey of the relevant literature summarises past and present developments in the use of light to...

  7. Detailed Mechanistic Studies on Palladium-Catalyzed Selective C-H Olefination with Aliphatic Alkenes: A Significant Influence of Proton Shuttling.

    Science.gov (United States)

    Deb, Arghya; Hazra, Avijit; Peng, Qian; Paton, Robert S; Maiti, Debabrata

    2017-01-18

    Directing group-assisted regioselective C-H olefination with electronically biased olefins is well studied. However, the incorporation of unactivated olefins has remained largely unsuccessful. A proper mechanistic understanding of olefination involving unactivated alkenes is therefore essential for enhancing their usage in future. In this Article, detailed experimental and computational mechanistic studies on palladium catalyzed C-H olefination with unactivated, aliphatic alkenes are described. The isolation of Pd(II) intermediates is shown to be effective for elucidating the elementary steps involved in catalytic olefination. Reaction rate and order determination, control experiments, isotopic labeling studies, and Hammett analysis have been used to understand the reaction mechanism. The results from these experimental studies implicate β-hydride elimination as the rate-determining step and that a mechanistic switch occurs between cationic and neutral pathway. Computational studies support this interpretation of the experimental evidence and are used to uncover the origins of selectivity.

  8. Olefins and chemical regulation in Europe: REACH.

    Science.gov (United States)

    Penman, Mike; Banton, Marcy; Erler, Steffen; Moore, Nigel; Semmler, Klaus

    2015-11-05

    REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) is the European Union's chemical regulation for the management of risk to human health and the environment (European Chemicals Agency, 2006). This regulation entered into force in June 2007 and required manufacturers and importers to register substances produced in annual quantities of 1000 tonnes or more by December 2010, with further deadlines for lower tonnages in 2013 and 2018. Depending on the type of registration, required information included the substance's identification, the hazards of the substance, the potential exposure arising from the manufacture or import, the identified uses of the substance, and the operational conditions and risk management measures applied or recommended to downstream users. Among the content developed to support this information were Derived No-Effect Levels or Derived Minimal Effect Levels (DNELs/DMELs) for human health hazard assessment, Predicted No Effect Concentrations (PNECs) for environmental hazard assessment, and exposure scenarios for exposure and risk assessment. Once registered, substances may undergo evaluation by the European Chemicals Agency (ECHA) or Member State authorities and be subject to requests for additional information or testing as well as additional risk reduction measures. To manage the REACH registration and related activities for the European olefins and aromatics industry, the Lower Olefins and Aromatics REACH Consortium was formed in 2008 with administrative and technical support provided by Penman Consulting. A total of 135 substances are managed by this group including 26 individual chemical registrations (e.g. benzene, 1,3-butadiene) and 13 categories consisting of 5-26 substances. This presentation will describe the content of selected registrations prepared for 2010 in addition to the significant post-2010 activities. Beyond REACH, content of the registrations may also be relevant to other European activities, for

  9. Institutional model for supporting standardization

    International Nuclear Information System (INIS)

    Sanford, M.O.; Jackson, K.J.

    1993-01-01

    Restoring the nuclear option for utilities requires standardized designs. This premise is widely accepted by all parties involved in ALWR development activities. Achieving and maintaining standardization, however, demands new perspectives on the roles and responsibilities for the various commercial organizations involved in nuclear power. Some efforts are needed to define a workable model for a long-term support structure that will allow the benefits of standardization to be realized. The Nuclear Power Oversight Committee (NPOC) has developed a strategic plan that lays out the steps necessary to enable the nuclear industry to be in a position to order a new nuclear power plant by the mid 1990's. One of the key elements of the plan is the, ''industry commitment to standardization: through design certification, combined license, first-of-a-kind engineering, construction, operation, and maintenance of nuclear power plants.'' This commitment is a result of the recognition by utilities of the substantial advantages to standardization. Among these are economic benefits, licensing benefits from being treated as one of a family, sharing risks across a broader ownership group, sharing operating experiences, enhancing public safety, and a more coherent market force. Utilities controlled the construction of the past generation of nuclear units in a largely autonomous fashion procuring equipment and designs from a vendor, engineering services from an architect/engineer, and construction from a construction management firm. This, in addition to forcing the utility to assume virtually all of the risks associated with the project, typically resulted in highly customized designs based on preferences of the individual utility. However, the benefits of standardization can be realized only through cooperative choices and decision making by the utilities and through working as partners with reactor vendors, architect/engineers, and construction firms

  10. Producing alpha-olefins using polyketide synthases

    Energy Technology Data Exchange (ETDEWEB)

    Fortman, Jeffrey L.; Katz, Leonard; Steen, Eric J.; Keasling, Jay D.

    2018-01-02

    The present invention provides for a polyketide synthase (PKS) capable of synthesizing an .alpha.-olefin, such as 1-hexene or butadiene. The present invention also provides for a host cell comprising the PKS and when cultured produces the .alpha.-olefin.

  11. Mathematical models for planning support

    NARCIS (Netherlands)

    L.G. Kroon (Leo); R.A. Zuidwijk (Rob)

    2003-01-01

    textabstractIn this paper we describe how computer systems can provide planners with active planning support, when these planners are carrying out their daily planning activities. This means that computer systems actively participate in the planning process by automatically generating plans or

  12. Olefins metathesis, synthesis and properties of homogeneous models of the Re{sub 2}O{sub 7}/Al{sub 2}O{sub 3} catalyst; Methathese des olefines, synthese et proprietes des modeles homogenes du catalyseur Re{sub 2}O{sub 7}/Al{sub 2}O{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Doledec, G.

    1999-10-05

    The aim of this work was to synthesize and to study homogeneous models of the rhenium oxide on alumina catalyst in order to better understand the influence of the alumina environment over the activity in olefin metathesis. A series of aluminium complexes (ArO){sub 2}Al-Y have been synthesised, where ArO is a 4-substituted-2,6-di-tert-butyl-phenoxy, or (ArO){sub 2} is a CH{sub 2{sup -}} or S-ortho bridged-4,4'-di-tert-butyl-di-phenoxy, and Y is an alkyl or chlorine ligand. The reaction of (ArO){sub 2}Al-Cl with AgReO{sub 4} led to new complexes (ArO){sub 2}Al-OReO{sub 3} (A). These complexes exhibit a low to moderate activity in metathesis of 2-pentene (TOF = 0,5 min{sup -1} at 25 deg. C in a toluene solution). Complexes (ArO){sub 2}Al-R (R = iBu, Et) react with Re{sub 2}O{sub 7} in THF or dioxane giving type B complexes including oligomeric linkages like O{sub 3}Re-[Al(OAr)-O){sub 2}-ReO{sub 3}. They show a fairly high activity in the metathesis of 2-pentene, with TOF values as high as 100 min{sup -1}. As far as we know, these are the most active rhenium-based homogeneous metathesis catalysts. Complexes type A may be converted into type B complexes upon reaction with (ArO){sub 2}Al-R in an ether solvent. The high activity of B complexes is tentatively related to the Al-O-Al linkages that are molecular in the homogeneous models or present at the surface of the alumina in the heterogeneous catalyst. These results bear out again the role of the Lewis acidity in these catalysts. We used (ArO){sub 2}Al-R complexes to modify the heterogenous catalyst. It appears that it is an excellent way to reduce the rhenium loading without any loss of activity. (author)

  13. Olefin polymerization over supported chromium oxide catalysts

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Schoonheydt, R.A.

    1999-01-01

    Cr/SiO2 or Phillips-type catalysts are nowadays responsible for a large fraction of all polyethylene (HDPE and LLDPE) worldwide produced. In this review, several key-properties of Cr/SiO2 catalysts will be discussed in relation to their polymerization characteristics. It will be shown how the

  14. Understanding the desensitizing mechanism of olefin in explosives: shear slide of mixed HMX-olefin systems.

    Science.gov (United States)

    Zhang, Chaoyang; Cao, Xia; Xiang, Bin

    2012-04-01

    We simulated the shear slide behavior of typical mixed HMX-olefin systems and the effect of thickness of olefin layers (4-22 Å) on the behavior at a molecular level by considering two cases: bulk shear and interfacial shear. The results show that: (1) the addition of olefin into HMX can reduce greatly the shear sliding barriers relative to the pure HMX in the two cases, suggesting that the desensitizing mechanism of olefin is controlled dominantly by its good lubricating property; (2) the change of interaction energy in both systoles of shear slide is strongly dominated by van der Waals interaction; and (3) the thickness of olefin layers in the mixed explosives can influence its desensitizing efficiency. That is, the excessive thinness of olefin layers in the mixed explosive systems, for example, several angstroms, can lead to very high sliding barriers.

  15. Alkylation of isobutane with light olefins: Yields of alkylates for different olefins

    Energy Technology Data Exchange (ETDEWEB)

    Albright, L.F. [Purdue Univ., West Lafayette, IN (United States); Kranz, K.E.; Masters, K.R. [STRATCO, Inc., Leawood, KS (United States)

    1993-12-01

    For alkylation of isobutane with C{sub 3}-C{sub 5} olefins using sulfuric acid as the catalyst, the yields of alkylates with different olefins are compared as the operating conditions are changed. The results of recent pilot plant experiments with propylene, C{sub 4} olefins, and C{sub 5} olefins permit such comparisons. The yields expressed as weight of alkylate produced per 100 wt of olefin consumed varied from about 201:100 to 220:100. Weight ratios of the isobutane consumed per olefin consumed vary from about 101:100 to 120:100. differences of yield values are explained by the changes in the overall chemistry. The procedure employed to calculate yields with good accuracy is based on the analysis of the alkylate and the amount of conjunct polymers produced. Based on literature data, yields are also reported for alkylations using HF as the catalyst.

  16. New Trends in Olefin Production

    Directory of Open Access Journals (Sweden)

    Ismaël Amghizar

    2017-04-01

    Full Text Available Most olefins (e.g., ethylene and propylene will continue to be produced through steam cracking (SC of hydrocarbons in the coming decade. In an uncertain commodity market, the chemical industry is investing very little in alternative technologies and feedstocks because of their current lack of economic viability, despite decreasing crude oil reserves and the recognition of global warming. In this perspective, some of the most promising alternatives are compared with the conventional SC process, and the major bottlenecks of each of the competing processes are highlighted. These technologies emerge especially from the abundance of cheap propane, ethane, and methane from shale gas and stranded gas. From an economic point of view, methane is an interesting starting material, if chemicals can be produced from it. The huge availability of crude oil and the expected substantial decline in the demand for fuels imply that the future for proven technologies such as Fischer-Tropsch synthesis (FTS or methanol to gasoline is not bright. The abundance of cheap ethane and the large availability of crude oil, on the other hand, have caused the SC industry to shift to these two extremes, making room for the on-purpose production of light olefins, such as by the catalytic dehydrogenation of propane.

  17. Tandem Olefin Metathesis/Oxidative Cyclization: Synthesis of Tetrahydrofuran Diols from Simple Olefins

    OpenAIRE

    Dornan, Peter K.; Lee, Daniel; Grubbs, Robert H.

    2016-01-01

    A tandem olefin metathesis/oxidative cyclization has been developed to synthesize 2,5-disubstituted tetrahydrofuran (THF) diols in a stereocontrolled fashion from simple olefin precursors. The ruthenium metathesis catalyst is converted into an oxidation catalyst in the second step and is thus responsible for both catalytic steps. The stereochemistry of the 1,5-diene intermediate can be controlled through the choice of catalyst and the type of metathesis conducted. This olefin stereochemistry ...

  18. Physics modeling support contract: Final report

    Energy Technology Data Exchange (ETDEWEB)

    1987-09-30

    This document is the final report for the Physics Modeling Support contract between TRW, Inc. and the Lawrence Livermore National Laboratory for fiscal year 1987. It consists of following projects: TIBER physics modeling and systems code development; advanced blanket modeling task; time dependent modeling; and free electron maser for TIBER II.

  19. Physics modeling support contract: Final report

    International Nuclear Information System (INIS)

    1987-01-01

    This document is the final report for the Physics Modeling Support contract between TRW, Inc. and the Lawrence Livermore National Laboratory for fiscal year 1987. It consists of following projects: TIBER physics modeling and systems code development; advanced blanket modeling task; time dependent modeling; and free electron maser for TIBER II

  20. Nurse managers and the sandwich support model.

    Science.gov (United States)

    Chisengantambu, Christine; Robinson, Guy M; Evans, Nina

    2018-03-01

    To explore the interplay between the work of nurse managers and the support they receive and provide. Support is the cornerstone of management practices and is pivotal in employees feeling committed to an organisation. Support for nurse managers is integral to effective health sector management; its characteristics merit more attention. The experiences of 15 nurse managers in rural health institutions in South Australia were explored using structured interviews, observation and document review. Effective decision making requires adequate support, which influences the perceptions and performance of nurse managers, creating an environment in which they feel appreciated and valued. An ideal support system is proposed, the "sandwich support model," to promote effective functioning and desirable patient outcomes via support "from above" and "from below." The need to support nurse managers effectively is crucial to how they function. The sandwich support model can improve management practices, more effectively assisting nurse managers. Organisations should revisit and strengthen support processes for nurse managers to maximize efficiencies. This paper contributes to understanding the importance of supporting nurse managers, identifying the processes used and the type of support offered. It highlights challenges and issues affecting support practices within the health sector. © 2017 John Wiley & Sons Ltd.

  1. Uncertainty modeling and decision support

    International Nuclear Information System (INIS)

    Yager, Ronald R.

    2004-01-01

    We first formulate the problem of decision making under uncertainty. The importance of the representation of our knowledge about the uncertainty in formulating a decision process is pointed out. We begin with a brief discussion of the case of probabilistic uncertainty. Next, in considerable detail, we discuss the case of decision making under ignorance. For this case the fundamental role of the attitude of the decision maker is noted and its subjective nature is emphasized. Next the case in which a Dempster-Shafer belief structure is used to model our knowledge of the uncertainty is considered. Here we also emphasize the subjective choices the decision maker must make in formulating a decision function. The case in which the uncertainty is represented by a fuzzy measure (monotonic set function) is then investigated. We then return to the Dempster-Shafer belief structure and show its relationship to the fuzzy measure. This relationship allows us to get a deeper understanding of the formulation the decision function used Dempster- Shafer framework. We discuss how this deeper understanding allows a decision analyst to better make the subjective choices needed in the formulation of the decision function

  2. The allylic chalcogen effect in olefin metathesis

    Directory of Open Access Journals (Sweden)

    Yuya A. Lin

    2010-12-01

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

  3. The allylic chalcogen effect in olefin metathesis.

    Science.gov (United States)

    Lin, Yuya A; Davis, Benjamin G

    2010-12-23

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

  4. Myoglobin-Catalyzed Olefination of Aldehydes.

    Science.gov (United States)

    Tyagi, Vikas; Fasan, Rudi

    2016-02-12

    The olefination of aldehydes constitutes a most valuable and widely adopted strategy for constructing carbon-carbon double bonds in organic chemistry. While various synthetic methods have been made available for this purpose, no biocatalysts are known to mediate this transformation. Reported herein is that engineered myoglobin variants can catalyze the olefination of aldehydes in the presence of α-diazoesters with high catalytic efficiency (up to 4,900 turnovers) and excellent E diastereoselectivity (92-99.9 % de). This transformation could be applied to the olefination of a variety of substituted benzaldehydes and heteroaromatic aldehydes, also in combination with different alkyl α-diazoacetate reagents. This work provides a first example of biocatalytic aldehyde olefination and extends the spectrum of synthetically valuable chemical transformations accessible using metalloprotein-based catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Olefin metathesis in nano-sized systems

    OpenAIRE

    Astruc, Didier; Diallo, Abdou K; Gatard, Sylvain; Liang, Liyuan; Ornelas, Cátia; Martinez, Victor; Méry, Denise; Ruiz, Jaime

    2011-01-01

    The interplay between olefin metathesis and dendrimers and other nano systems is addressed in this mini review mostly based on the authors’ own contributions over the last decade. Two subjects are presented and discussed: (i) The catalysis of olefin metathesis by dendritic nano-catalysts via either covalent attachment (ROMP) or, more usefully, dendrimer encapsulation – ring closing metathesis (RCM), cross metathesis (CM), enyne metathesis reactions (EYM) – for reactions in w...

  6. Template-Directed Olefin Cross Metathesis

    OpenAIRE

    Cantrill, Stuart J.; Grubbs, Robert H.; Lanari, Daniela; Leung, Ken C.-F.; Nelson, Alshakim; Poulin-Kerstien, Katherine G.; Smidt, Sebastian P.; Stoddart, J. Fraser; Tirrell, David A.

    2005-01-01

    A template containing two secondary dialkylammonium ion recognition sites for encirclement by olefin-bearing dibenzo[24]crown-8 derivatives has been used to promote olefin cross metatheses with ruthenium-alkylidene catalysts. For monoolefin monomers, the rates of metatheses and yields of the dimers are both amplified in the presence of the template. Likewise, for a diolefin monomer, the yield of the dimer is enhanced in the presence of the template under conditions where higher oligomers are ...

  7. Direct catalytic olefination of alcohols with sulfones.

    Science.gov (United States)

    Srimani, Dipankar; Leitus, Gregory; Ben-David, Yehoshoa; Milstein, David

    2014-10-06

    The synthesis of terminal, as well as internal, olefins was achieved by the one-step olefination of alcohols with sulfones catalyzed by a ruthenium pincer complex. Furthermore, performing the reaction with dimethyl sulfone under mild hydrogen pressure provides a direct route for the replacement of alcohol hydroxy groups by methyl groups in one step. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Olefin metathesis for chemical biology.

    Science.gov (United States)

    Binder, Joseph B; Raines, Ronald T

    2008-12-01

    Chemical biology relies on effective synthetic chemistry for building molecules to probe and modulate biological function. Olefin metathesis in organic solvents is a valuable addition to this armamentarium, and developments during the previous decade are enabling metathesis in aqueous solvents for the manipulation of biomolecules. Functional group-tolerant ruthenium metathesis catalysts modified with charged moieties or hydrophilic polymers are soluble and active in water, enabling ring-opening metathesis polymerization, cross metathesis, and ring-closing metathesis. Alternatively, conventional hydrophobic ruthenium complexes catalyze a similar array of metathesis reactions in mixtures of water and organic solvents. This strategy has enabled cross metathesis on the surface of a protein. Continuing developments in catalyst design and methodology will popularize the bioorthogonal reactivity of metathesis.

  9. Olefin Metathesis for Chemical Biology

    Science.gov (United States)

    Binder, Joseph B; Raines, Ronald T

    2009-01-01

    Summary Chemical biology relies on effective synthetic chemistry for building molecules to probe and modulate biological function. Olefin metathesis in organic solvents is a valuable addition to this armamentarium, and developments during the previous decade are enabling metathesis in aqueous solvents for the manipulation of biomolecules. Functional group-tolerant ruthenium metathesis catalysts modified with charged moieties or hydrophilic polymers are soluble and active in water, enabling ring-opening metathesis polymerization, cross metathesis, and ring-closing metathesis. Alternatively, conventional hydrophobic ruthenium complexes catalyze a similar array of metathesis reactions in mixtures of water and organic solvents. This strategy has enabled cross metathesis on the surface of a protein. Continuing developments in catalyst design and methodology will popularize the bioorthogonal reactivity of metathesis. PMID:18935975

  10. Mathematical Modeling Of Life-Support Systems

    Science.gov (United States)

    Seshan, Panchalam K.; Ganapathi, Balasubramanian; Jan, Darrell L.; Ferrall, Joseph F.; Rohatgi, Naresh K.

    1994-01-01

    Generic hierarchical model of life-support system developed to facilitate comparisons of options in design of system. Model represents combinations of interdependent subsystems supporting microbes, plants, fish, and land animals (including humans). Generic model enables rapid configuration of variety of specific life support component models for tradeoff studies culminating in single system design. Enables rapid evaluation of effects of substituting alternate technologies and even entire groups of technologies and subsystems. Used to synthesize and analyze life-support systems ranging from relatively simple, nonregenerative units like aquariums to complex closed-loop systems aboard submarines or spacecraft. Model, called Generic Modular Flow Schematic (GMFS), coded in such chemical-process-simulation languages as Aspen Plus and expressed as three-dimensional spreadsheet.

  11. Isomerizing olefin metathesis as a strategy to access defined distributions of unsaturated compounds from fatty acids.

    Science.gov (United States)

    Ohlmann, Dominik M; Tschauder, Nicole; Stockis, Jean-Pierre; Goossen, Käthe; Dierker, Markus; Goossen, Lukas J

    2012-08-22

    The dimeric palladium(I) complex [Pd(μ-Br)(t)Bu(3)P](2) was found to possess unique activity for the catalytic double-bond migration within unsaturated compounds. This isomerization catalyst is fully compatible with state-of-the-art olefin metathesis catalysts. In the presence of bifunctional catalyst systems consisting of [Pd(μ-Br)(t)Bu(3)P](2) and NHC-indylidene ruthenium complexes, unsaturated compounds are continuously converted into equilibrium mixtures of double-bond isomers, which concurrently undergo catalytic olefin metathesis. Using such highly active catalyst systems, the isomerizing olefin metathesis becomes an efficient way to access defined distributions of unsaturated compounds from olefinic substrates. Computational models were designed to predict the outcome of such reactions. The synthetic utility of isomerizing metatheses is demonstrated by various new applications. Thus, the isomerizing self-metathesis of oleic and other fatty acids and esters provides olefins along with unsaturated mono- and dicarboxylates in distributions with adjustable widths. The cross-metathesis of two olefins with different chain lengths leads to regular distributions with a mean chain length that depends on the chain length of both starting materials and their ratio. The cross-metathesis of oleic acid with ethylene serves to access olefin blends with mean chain lengths below 18 carbons, while its analogous reaction with hex-3-enedioic acid gives unsaturated dicarboxylic acids with adjustable mean chain lengths as major products. Overall, the concept of isomerizing metatheses promises to open up new synthetic opportunities for the incorporation of oleochemicals as renewable feedstocks into the chemical value chain.

  12. Manganese oxide as a promoter for C2-C4 olefin production in the hydrogenation of carbon dioxide

    International Nuclear Information System (INIS)

    Kim, C.; Chen, K.; Hanson, F.V.; Oblad, A.G.; Tsai, Y.

    1986-01-01

    A number of active research and development programs have been initiated to explore the potential of CO hydrogenation process as a source of low molecular weight (C 2 -C 4 ) olefins. Metal catalysts such as Co-Mn, Ni-zeolite, Rd and Mo have been evaluated for low molecular weight olefin selectivity. The coprecipitated Fe-Mn system (Mn/Fe=9/1) was reported to be highly olefin selective. Recently, many investigators reported supporting evidence for the promotional effect of Mn for precipitated Fe catalysts. In this study, Raney Fe promoted with Mn has been evaluated for C 2 -C 4 olefin selectivity in the hydrogenation of CO relative to coprecipitated Fe-Mn catalysts. Catalyst characterization, including BET surface area, X-ray diffraction, selective chemisorption and ESCA, has been carried to provide insight into the role of manganese in both the Coprecipitated and Raney catalyst systems

  13. Direct Olefination of Alcohols with Sulfones by Using Heterogeneous Platinum Catalysts.

    Science.gov (United States)

    Siddiki, S M A Hakim; Touchy, Abeda Sultana; Kon, Kenichi; Shimizu, Ken-Ichi

    2016-04-18

    Carbon-supported Pt nanoparticles (Pt/C) were found to be effective heterogeneous catalysts for the direct Julia olefination of alcohols in the presence of sulfones and KOtBu under oxidant-free conditions. Primary alcohols, including aryl, aliphatic, allyl, and heterocyclic alcohols, underwent olefination with dimethyl sulfone and aryl alkyl sulfones to give terminal and internal olefins, respectively. Secondary alcohols underwent methylenation with dimethyl sulfone. Under 2.5 bar H2, the same reaction system was effective for the transformation of alcohol OH groups to alkyl groups. Structural and mechanistic studies of the terminal olefination system suggested that Pt(0) sites on the Pt metal particles are responsible for the rate-limiting dehydrogenation of alcohols and that KOtBu may deprotonate the sulfone reagent. The Pt/C catalyst was reusable after the olefination, and this method showed a higher turnover number (TON) and a wider substrate scope than previously reported methods, which demonstrates the high catalytic efficiency of the present method. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. The DIAMOND Model of Peace Support Operations

    National Research Council Canada - National Science Library

    Bailey, Peter

    2005-01-01

    DIAMOND (Diplomatic And Military Operations in a Non-warfighting Domain) is a high-level stochastic simulation developed at Dstl as a key centerpiece within the Peace Support Operations (PSO) 'modelling jigsaw...

  15. Optimization of catalytic glycerol steam reforming to light olefins using Cu/ZSM-5 catalyst

    International Nuclear Information System (INIS)

    Zakaria, Z.Y.; Amin, N.A.S.; Linnekoski, J.

    2014-01-01

    Highlights: • Glycerol steam reforming to light olefin using Cu/ZSM-5 process was optimized. • Response surface methodology and multi-objective genetic algorithm were employed. • Second order polynomial model produced adequately fitted experimental data. • Thermodynamic study inferred high temperature requirement for ethylene formation. • Turn-over-frequency at optimized responses is higher than the non-optimized process. - Abstract: Response surface methodology (RSM) and multi-objective genetic algorithm was employed to optimize the process parameters for catalytic conversion of glycerol, a byproduct from biodiesel production, to light olefins using Cu/ZSM-5 catalyst. The effects of operating temperature, weight hourly space velocity (WHSV) and glycerol concentration on light olefins selectivity and yield were observed. Experimental results revealed the data adequately fitted into a second-order polynomial model. The linear temperature and quadratic WHSV terms gave significant effect on both responses. Optimization of both the responses indicated that temperature favouring high light olefin formation lied beyond the experimental design range. The trend in the temperature profile concurred commensurately with the thermodynamic analysis. Multi-objective genetic algorithm was performed to attain a single set of processing parameters that could produce both the highest light olefin selectivity and yield. The turn-over-frequency (TOF) of the optimized responses demonstrated a slightly higher value than the one which was not optimized. Combination of RSM, multi-objective response and thermodynamic is useful to determine the process optimal operating conditions for industrial applications

  16. Synthesis of interlocked molecules by olefin metathesis

    Science.gov (United States)

    Clark, Paul Gregory

    polyammonium scaffold. Diolefin polyether fragments were coordinated and "clipped" around the ammonium sites within the polymer backbone using ring-closing olefin metathesis, giving the molecular "charm bracelet". Confirmation of the interlocked nature of the product was achieved via 1H NMR spectroscopy and two-dimensional diffusion ordered NMR spectroscopy. A simple strategy for a one-pot, multi-component synthesis of polyrotaxanes using acyclic diene metathesis polymerization was developed. The polyrotaxanes were characterized by traditional 1H NMR spectroscopy as well as size exclusion chromatography, and the interlocked topology was confirmed using two-dimension diffusion-ordered NMR spectroscopy. The dynamic, self-correcting nature of the ADMET polymerization was also explored through the equilibration of a capped polyammonium polymer in the presence of dibenzo-24-crown-8 ether and olefin metathesis catalysts. The efficiency and ease with which these mechanically interlocked macromolecules can be assembled should facilitate rapid modulation to achieve versatile polyrotaxane architectures. Flexible, switchable [c2]daisy-chain dimers (DCDs) were synthesized, where the macromer ammonium binding site was adjacent to the crown-type recognition structure and separated from the cap by an alkyl chain. A DCD of this topology is expected to have an extended structure in the bound conformation (when the ammonium was coordinated to the crown). Several different macromer candidates were designed to allow access to DCDs with flexible alkyl chains between the ammonium binding site and the cap, and a number of synthetic routes were explored in an effort to access these challenging materials. While the first generation DCD structure proved to be unstable due to a labile ester linkage, work is continuing toward the development of several cap structures in an effort to replace the ester linkage with an ether linkage, which, in the second generation model systems, has proven much more stable

  17. Recent Advancements in Stereoselective Olefin Metathesis Using Ruthenium Catalysts

    Directory of Open Access Journals (Sweden)

    T. Patrick Montgomery

    2017-03-01

    Full Text Available Olefin metathesis is a prevailing method for the construction of organic molecules. Recent advancements in olefin metathesis have focused on stereoselective transformations. Ruthenium olefin metathesis catalysts have had a particularly pronounced impact in the area of stereoselective olefin metathesis. The development of three categories of Z-selective olefin metathesis catalysts has made Z-olefins easily accessible to both laboratory and industrial chemists. Further design enhancements to asymmetric olefin metathesis catalysts have streamlined the construction of complex molecules. The understanding gained in these areas has extended to the employment of ruthenium catalysts to stereoretentive olefin metathesis, the first example of a kinetically E-selective process. These advancements, as well as synthetic applications of the newly developed catalysts, are discussed.

  18. A mechanistic investigation of the ruthenium porphyrin catalysed aziridination of olefins by aryl azides.

    Science.gov (United States)

    Zardi, P; Pozzoli, A; Ferretti, F; Manca, G; Mealli, C; Gallo, E

    2015-06-14

    A mechanism for the aziridination of olefins by aryl azides (ArN3), promoted by ruthenium(ii) porphyrin complexes, is proposed on the basis of kinetic and theoretical studies. All the recorded data support the involvement of a mono-imido ruthenium complex as the active intermediate in the transfer of the nitrene moiety "ArN" to the olefin. The selectivity of the aziridination vs. the uncatalysed triazoline formation can be enhanced by fine-tuning the electronic features of the porphyrin ligand and the olefin/azide catalytic ratio. The DFT study highlights the importance of an accessible triplet ground state of the intermediate ruthenium mono-imido complex to allow the evolution of the aziridination process.

  19. Olefin-borane "van der Waals complexes": intermediates in frustrated Lewis pair addition reactions.

    Science.gov (United States)

    Zhao, Xiaoxi; Stephan, Douglas W

    2011-08-17

    The nature of the borane-olefin interactions that take place prior to frustrated Lewis pair addition reactions has been probed employing a Lewis acidic borane tethered to a vinyl group through an alkyl chain. (1)H{(19)F} HOESY spectral data obtained at -50 °C demonstrated the spatial proximity of the boryl and vinyl groups and computational data support the initial formation of a van der Waals borane-olefin complex. Such species serve as intermediates undergoing facile addition reactions with phosphine bases to afford cyclic zwitterionic products.

  20. Synthesis of Fluoroolefins via Julia-Kocienski Olefination

    OpenAIRE

    Zajc, Barbara; Kumar, Rakesh

    2010-01-01

    The Julia-Kocienski olefination provides a versatile platform for the synthesis of fluorovinyl compounds. This review describes our efforts as well as those of others in the synthesis of various fluorinated aryl and heteroaryl sulfones and their utility as olefination reagents for the modular assembly of fluoroalkenes. Where data is available, the influence of the fluorine atom on the reactivity of the olefination reagents and the stereochemical outcome of the olefination are described.

  1. Synthesis of Fluoroolefins via Julia-Kocienski Olefination.

    Science.gov (United States)

    Zajc, Barbara; Kumar, Rakesh

    2010-01-01

    The Julia-Kocienski olefination provides a versatile platform for the synthesis of fluorovinyl compounds. This review describes our efforts as well as those of others in the synthesis of various fluorinated aryl and heteroaryl sulfones and their utility as olefination reagents for the modular assembly of fluoroalkenes. Where data is available, the influence of the fluorine atom on the reactivity of the olefination reagents and the stereochemical outcome of the olefination are described.

  2. Catalytic olefin polymerization with early transition metal compounds

    NARCIS (Netherlands)

    Eshuis, Johan Jan Willem

    1991-01-01

    The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and

  3. Ru-Based Complexes with Quaternary Ammonium Tags Immobilized on Mesoporous Silica as Olefin Metathesis Catalysts

    Czech Academy of Sciences Publication Activity Database

    Pastva, Jakub; Skowerski, K.; Czarnocki, S. J.; Žilková, Naděžda; Čejka, Jiří; Bastl, Zdeněk; Balcar, Hynek

    2014-01-01

    Roč. 4, č. 9 (2014), s. 3227-3236 ISSN 2155-5435 R&D Projects: GA ČR(CZ) GAP106/12/0189 Institutional support: RVO:61388955 Keywords : olefin metathesis * heterogeneous catalysts * mesoporous molecular sieves Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 9.312, year: 2014

  4. Olefin metathesis : tapping into breakthrough chemical technology

    Energy Technology Data Exchange (ETDEWEB)

    Granson, E.

    2010-06-15

    Olefin metathesis is a catalyst technology where 2 double bond-containing molecules or olefins are split in order to exchange atoms and result in the formation of 2 new molecules or substances. Earlier researchers used a variety of materials to convert propylene into a mixture of butenes and ethylenes. A method developed by Shell researchers produces linear olefins used as detergent feedstocks. In 1971, scientists used a metal-carbene catalyst to react with the olefins to produce both a new olefin and a new metal carbene in order to perpetuate the process. In 2002, a new metathesis technology was developed using renewable natural oils as a feedstock. The catalyst is introduced as a solid into the oil, and then agitated by stirring. The modified oil is then reacted with hydrogen to remove the double bonds and filter off the catalyst. The method is offered on a contract basis by Elevance Renewable Sciences in a variety of application. The process was designed to take place at lower temperatures with the release of fewer greenhouse gases (GHGs). New metathesis technologies are also being developed to reduce the molecular weight of polymers in order to reduce viscosity and increase flow. 3 figs.

  5. Tandem Olefin Metathesis/Oxidative Cyclization: Synthesis of Tetrahydrofuran Diols from Simple Olefins.

    Science.gov (United States)

    Dornan, Peter K; Lee, Daniel; Grubbs, Robert H

    2016-05-25

    A tandem olefin metathesis/oxidative cyclization has been developed to synthesize 2,5-disubstituted tetrahydrofuran (THF) diols in a stereocontrolled fashion from simple olefin precursors. The ruthenium metathesis catalyst is converted into an oxidation catalyst in the second step and is thus responsible for both catalytic steps. The stereochemistry of the 1,5-diene intermediate can be controlled through the choice of catalyst and the type of metathesis conducted. This olefin stereochemistry then controls the THF diol stereochemistry through a highly stereospecific oxidative cyclization.

  6. Gamma radiolysis of 3-methylpentane. Effect of added olefins on the formation of C12-olefins

    International Nuclear Information System (INIS)

    Laet, M. de; Tilquin, B.

    1991-01-01

    Contributions of congruent (parent derived) olefins to the formation of unsaturated heavy products (C 12 H 24 ) are investigated. Effects of dose or of olefinic additives on the G yield values are studied by capillary gas chromatography. The dose dependence is explained by transfer of positive charge to congruent olefins (C 6 H 12 ) even though their concentrations build up linearly with dose. γ Irradiation of 3-methylpentane containing pentenes or butenes (0.2-2 mol %) provides good examples of transfer of energy, however the results are unexpected. C-H scission in the radiolysis of solid 3-methylpentane is also reviewed. (author)

  7. The Olefin Metathesis Reactions in Dendrimers

    Science.gov (United States)

    Astruc, Didier

    Dendrimers containing terminal olefins or ruthenium-benzylidene terminal groups undergo olefin metathesis reactions (RCM and ROMP types), and essentially results from our group are reviewed here. Dendrimers have been loaded at their periphery with ruthenium-chelating bis-phosphines, which leads to the formation of dendrimer-cored stars by ring-opening-metathesis polymerization (ROMP). CpFe+-induced perallylation of polymethylaromatics (Cp = η5-C5H5) followed by ring-closing metathesis (RCM) and/or cross metathesis (CM) leads to poly-ring, cage, oligomeric and polymeric architectures. In the presence of acrylic acid or metha-crylate, stereospecific CM inhibits oligomerization, and dendritic olefins yield polyacid dendrimers. Finally, cros-metahesis reactions with dendronic acrylate allow dendritic construction and growth.

  8. Towards better modelling and decision support

    DEFF Research Database (Denmark)

    Meli, Mattia; Grimm, V; Augusiak, J.

    2014-01-01

    The potential of ecological models for supporting environmental decision making is increasingly acknowledged. However, it often remains unclear whether a model is realistic and reliable enough. Good practice for developing and testing ecological models has not yet been established. Therefore, TRACE......, thereby also linking modellers and model users, for example stakeholders, decision makers, and developers of policies. We report on first experiences in producing TRACE documents. We found that the original idea underlying TRACE was valid, but to make its use more coherent and efficient, an update of its......, a general framework for documenting a model's rationale, design, and testing was recently suggested. Originally TRACE was aimed at documenting good modelling practice. However, the word 'documentation' does not convey TRACE's urgency. Therefore, we re-define TRACE as a tool for planning, performing...

  9. Autism Treatment and Family Support Models Review

    Directory of Open Access Journals (Sweden)

    Mehrnoush Esbati

    2009-04-01

    Full Text Available Autism is a lifelong neurological disability of unknown etiology. The criteria for a diagnosis of autism are based on a triad of impairments in social interaction, communication and a lack of flexibility in thinking and behavior There are several factors which are likely to contribute to this variation including the definition of autism and variability in diagnosis amongst professionals, however anecdotally there appears to have been a steadily increasing demand for services. The purpose of this review of research literature relating to the management and treatment of children with autism is to identify the most effective models of best practice. The review includes Comparative evidence supporting a range of treatment and intervention models, across the range of individuals included within autism spectrum disorders, psychodynamic treatment/management which are based on the assumption that autism is the result of emotional damage to the child, usually because of failure to develop a close attachment to parents, especially the mother, biological treatments, educational and behavioral interventions, communication therapies, cost benefits and supporting families.The research is examined for evidence to support best practice models in supporting families at the time of diagnosis and assessment and an overview of the nature of comprehensive supports that help reduce stresses that may be experienced by families of a child with autism and promote inclusion in community activities.

  10. Metatheases: artificial metalloproteins for olefin metathesis.

    Science.gov (United States)

    Sauer, D F; Gotzen, S; Okuda, J

    2016-10-21

    The incorporation of organometallic catalyst precursors in proteins results in so-called artificial metalloenzymes. The protein structure will control activity, selectivity and stability of the organometallic site in aqueous medium and allow non-natural reactions in biological settings. Grubbs-Hoveyda type ruthenium catalysts with an N-heterocyclic carbene (NHC) as ancillary ligand, known to be active in olefin metathesis, have recently been incorporated in various proteins. An overview of these artificial metalloproteins and their potential application in olefin metathesis is given.

  11. Olefin metathesis in nano-sized systems

    Directory of Open Access Journals (Sweden)

    Denise Méry

    2011-01-01

    Full Text Available The interplay between olefin metathesis and dendrimers and other nano systems is addressed in this mini review mostly based on the authors’ own contributions over the last decade. Two subjects are presented and discussed: (i The catalysis of olefin metathesis by dendritic nano-catalysts via either covalent attachment (ROMP or, more usefully, dendrimer encapsulation – ring closing metathesis (RCM, cross metathesis (CM, enyne metathesis reactions (EYM – for reactions in water without a co-solvent and (ii construction and functionalization of dendrimers by CM reactions.

  12. Stereoretentive Olefin Metathesis: An Avenue to Kinetic Selectivity.

    Science.gov (United States)

    Montgomery, T Patrick; Ahmed, Tonia S; Grubbs, Robert H

    2017-09-04

    Olefin metathesis is an incredibly valuable transformation that has gained widespread use in both academic and industrial settings. Lately, stereoretentive olefin metathesis has garnered much attention as a method for the selective generation of both E- and Z-olefins. Early studies employing ill-defined catalysts showed evidence for retention of the stereochemistry of the starting olefins at low conversion. However, thermodynamic ratios E/Z were reached as the reaction proceeded to equilibrium. Recent studies in olefin metathesis have focused on the synthesis of catalysts that can overcome the inherent thermodynamic preference of an olefin, providing synthetically useful quantities of a kinetically favored olefin isomer. These reports have led to the development of stereoretentive catalysts that not only generate Z-olefins selectively, but also kinetically produce E-olefins, a previously unmet challenge in olefin metathesis. Advancements in stereoretentive olefin metathesis using tungsten, ruthenium, and molybdenum catalysts are presented. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Metathesis process for preparing an alpha, omega-functionalized olefin

    Science.gov (United States)

    Burdett, Kenneth A.; Mokhtarzadeh, Morteza; Timmers, Francis J.

    2010-10-12

    A cross-metathesis process for preparing an .alpha.,.omega.-functionalized olefin, such as methyl 9-decenoate, and an .alpha.-olefin having three or more carbon atoms, such as 1-decene. The process involves contacting in a first reaction zone an .alpha.-functionalized internal olefin, such as methyl oleate, and an .alpha.-olefinic monomer having three or more carbon atoms, such as 1-decene, with a first metathesis catalyst to prepare an effluent stream containing the .alpha.,.omega.-functionalized olefin, such as methyl 9-decenoate, an unfunctionalized internal olefin, such as 9-octadecene, unconverted reactant olefins, and optionally, an .alpha.,.omega.-difunctionalized internal olefinic dimer, such as dimethyl 9-octadecen-1,18-dioate; separating said effluent streams; then contacting in a second reaction zone the unfunctionalized internal olefin with ethylene in the presence of a second metathesis catalyst to obtain a second product effluent containing the .alpha.-olefinic monomer having three or more carbon atoms; and cycling a portion of the .alpha.-olefinic monomer stream(s) to the first zone.

  14. Olefin polymerization from single site catalysts confined within porous media

    Science.gov (United States)

    Kasi, Rajeswari M.

    Single Site Catalysts (SSCs) have been utilized for olefin polymerization. Altering the metal-ligand architecture in the SSCs, polyolefin properties can be enhanced in a rational manner. This influence of the ligands in the SSC on the property of polyolefins prepared can be referred to as the primary ligand influence. Extending this understanding and subsequent control of the metal-ligand framework to the interaction of SSCs within organic and inorganic supports is vital for the synthesis of polyolefins with tailored properties. The motivation behind this thesis was to explore the support influence on the reactivity of the SSC tethered to a support matrix during ethylene homo and copolymerization. In order to address this question of the support influence on the final polyolefin properties, synthetic routes to covalently bind SSCs on different matrices have been explored. Two distinct supported SSCs have been used to prepare branched polyethylenes. Branched polyethylenes can be prepared by either copolymerization (ethylene and alpha-olefin) or oligomerization/copolymerization processes (ethylene and in situ generated alpha-olefin). Synthetic routes to prepare precursor catalysts to Constrained Geometry Catalysts (CGCs) by silyl elimination chemistry have been developed (Chapter 2). Efficient synthetic protocols to assemble CGCs on aminomethylpolysytrene matrices (Chapter 3) and amine-functionalized mesoporous silica (Chapter 4) are also reported. These supported catalysts, with appropriate cocatalysts have been used to prepare ethylene homo and copolymers, the polymer thermal properties and microstructures were analyzed by various analytical techniques. Branched polyethylenes (LLDPE) can be prepared by copolymerization chemistry. It has been observed is that the influence of the support is seen in the production of lower crystalline forms of high density polyethylene (HDPE, 20--50% crystalline), while homogeneous polymerization of analogous soluble CGCs afford HDPE

  15. Modelagem do Processo de Fragmentação de Catalisadores Suportados Durante a Pré-polimerização de Olefinas Modeling of Catalyst Fragmentation During Olefin Pre-polymerizations

    Directory of Open Access Journals (Sweden)

    Douglas M. Merquior

    2002-01-01

    Full Text Available Uma metodologia é proposta para descrever a morfologia das partículas de polímero que são obtidas durante os momentos iniciais da polimerização de olefinas via catálise heterogênea. O método é baseado na análise matemática da capacidade da partícula em liberar a energia mecânica acumulada no seu interior devido à rápida produção de polímero. O balanço entre as quantidades de energia acumulada e liberada é calculado com o auxílio de um modelo dinâmico da reação de pré-polimerização. A combinação da metodologia proposta com o modelo dinâmico permitiu a análise dos mecanismos de fragmentação, indicando a morfologia da partícula de polímero produzida em função do tamanho da partícula e da temperatura do reator.A model-based methodology is proposed for describing the morphology of the polymer particles that are obtained during the very early stages of the olefin polymerization. The method is based on the analysis of the particle capacity to release the amount of energy that is accumulated in its interior during the polymerization, due to the fast polymer production. The balance between the accumulated and released amounts of energy is calculated with the help of a dynamic pre-polymerization reaction model. The combination of the fragmentation criteria and of the polymerization model allows the analysis of the prepolymerization step, indicating the morphology of the final polymer particles as a function of the catalyst particle diameter and reactor temperature.

  16. Techno-economic analysis of the coal-to-olefins process in comparison with the oil-to-olefins process

    International Nuclear Information System (INIS)

    Xiang, Dong; Qian, Yu; Man, Yi; Yang, Siyu

    2014-01-01

    Highlights: • Present the opportunities and challenges of coal-to-olefins (CTO) development. • Conduct a techno-economic analysis on CTO compared with oil-to-olefins (OTO). • Suggest approaches for improving energy efficiency and economic performance of CTO. • Analyze effects of plant scale, feedstock price, CO 2 tax on CTO and OTO. - Abstract: Olefins are one of the most important oil derivatives widely used in industry. To reduce the dependence of olefins industry on oil, China is increasing the production of olefins from alternative energy resources, especially from coal. This study is concerned with the opportunities and obstacles of coal-to-olefins development, and focuses on making an overall techno-economic analysis of a coal-to-olefins plant with the capacity of 0.7 Mt/a olefins. Comparison is made with a 1.5 Mt/a oil-to-olefins plant based on three criteria including energy efficiency, capital investment, and product cost. It was found that the coal-based olefins process show prominent advantage in product cost because of the low price of its feedstock. However, it suffers from the limitations of higher capital investment, lower energy efficiency, and higher emissions. The effects of production scale, raw material price, and carbon tax were varied for the two production routes, and thus the operational regions were found for the coal-to-olefins process to be competitive

  17. Numerical simulation of scale-up effects of methanol-to-olefins fluidized bed reactors

    DEFF Research Database (Denmark)

    Lu, Bona; Zhang, Jingyuan; Luo, Hao

    2017-01-01

    factors and is expected to speed up the experiment-based scale-up process with lower cost. In this study, we aim to investigate the scale-up effects through simulations of a series of methanol-to-olefins (MTO) reactors of different sizes. The two-fluid model and energy-minimization multi-scale (EMMS...

  18. 21 CFR 177.1520 - Olefin polymers.

    Science.gov (United States)

    2010-04-01

    ... catalyst deactivator and antioxidant in the production of olefin polymers complying with § 177.1520(c... measure of the solvent extractable fraction. Alternatively, the sample is reweighed after the extraction... section. (a) Extraction apparatus. Two-liter, straight-walled, Pyrex (or equivalent) resin kettles, fitted...

  19. Bromination of olefins with HBr and DMSO.

    Science.gov (United States)

    Karki, Megha; Magolan, Jakob

    2015-04-03

    A simple and inexpensive methodology is reported for the conversion of alkenes to 1,2-dibromo alkanes via oxidative bromination using HBr paired with dimethyl sulfoxide, which serves as the oxidant as well as cosolvent. The substrate scope includes 21 olefins brominated in good to excellent yields. Three of six styrene derivatives yielded bromohydrins under the reaction conditions.

  20. Tandem Catalysis Utilizing Olefin Metathesis Reactions.

    Science.gov (United States)

    Zieliński, Grzegorz K; Grela, Karol

    2016-07-04

    Since olefin metathesis transformation has become a favored synthetic tool in organic synthesis, more and more distinct non-metathetical reactions of alkylidene ruthenium complexes have been developed. Depending on the conditions applied, the same olefin metathesis catalysts can efficiently promote isomerization reactions, hydrogenation of C=C double bonds, oxidation reactions, and many others. Importantly, these transformations can be carried out in tandem with olefin metathesis reactions. Through addition of one portion of a catalyst, a tandem process provides structurally advanced products from relatively simple substrates without the need for isolation of the intermediates. These aspects not only make tandem catalysis very attractive from a practical point of view, but also open new avenues in (retro)synthetic planning. However, in the literature, the term "tandem process" is sometimes used improperly to describe other types of multi-reaction sequences. In this Concept, a number of examples of tandem catalysis involving olefin metathesis are discussed with an emphasis on their synthetic value. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Post-metallocene catalysts for olefin polymerisation

    International Nuclear Information System (INIS)

    Bryliakov, Konstantin P

    2007-01-01

    The main types of post-metallocene catalysts for olefin polymerisation based on bis(imino), bis(imino)pyridyl, bis(phenoxyimino), bis(pyrrolylimino) and other complexes of transition metals developed in the last 10-15 years and having prospects for practical use are considered. Modern views on the mechanism of action of these catalysts are discussed.

  2. Post-metallocene catalysts for olefin polymerisation

    Energy Technology Data Exchange (ETDEWEB)

    Bryliakov, Konstantin P [G K Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences (Russian Federation)

    2007-03-31

    The main types of post-metallocene catalysts for olefin polymerisation based on bis(imino), bis(imino)pyridyl, bis(phenoxyimino), bis(pyrrolylimino) and other complexes of transition metals developed in the last 10-15 years and having prospects for practical use are considered. Modern views on the mechanism of action of these catalysts are discussed.

  3. Post-metallocene catalysts for olefin polymerisation

    Science.gov (United States)

    Bryliakov, Konstantin P.

    2007-03-01

    The main types of post-metallocene catalysts for olefin polymerisation based on bis(imino), bis(imino)pyridyl, bis(phenoxyimino), bis(pyrrolylimino) and other complexes of transition metals developed in the last 10-15 years and having prospects for practical use are considered. Modern views on the mechanism of action of these catalysts are discussed.

  4. Synthesis of pterostilbene by Julie Olefination

    Science.gov (United States)

    A simple, stereoselective route for the synthesis of the biologically active compounds trans-pterostilbene and tetramethoxy stilbene from the readily available starting materials 3,5-dimethoxy benzyl alcohol and 4-hydroxy benzaldehyde was developed using Julia olefination as a key reaction....

  5. High Trans Kinetic Selectivity in Ruthenium-Based Olefin Cross-Metathesis through Stereoretention.

    Science.gov (United States)

    Johns, Adam M; Ahmed, Tonia S; Jackson, Bradford W; Grubbs, Robert H; Pederson, Richard L

    2016-02-19

    The first kinetically controlled, highly trans-selective (>98%) olefin cross-metathesis reaction is demonstrated using Ru-based catalysts. Reactions with either trans or cis olefins afford products with highly trans or cis stereochemistry, respectively. This E-selective olefin cross-metathesis is shown to occur between two trans olefins and between a trans olefin and a terminal olefin. Additionally, new stereoretentive catalysts have been synthesized for improved reactivity.

  6. Decision support models for natural gas dispatch

    Energy Technology Data Exchange (ETDEWEB)

    Chin, L. (Bentley College, Waltham, MA (United States)); Vollmann, T.E. (International Inst. for Management Development, Lausanne (Switzerland))

    A decision support model is presented which will give utilities the support tools to manage the purchasing of natural gas supplies in the most cost effective manner without reducing winter safety stocks to below minimum levels. In Business As Usual (BAU) purchasing quantities vary with the daily forecasts. With Material Requirements Planning (MRP) and Linear Programming (LP), two types of factors are used: seasonal weather and decision rule. Under current practices, BAU simulation uses the least expensive gas source first, then adding successively more expensive sources. Material Requirements Planning is a production planning technique which uses a parent item master production schedule to determine time phased requirements for component points. Where the MPS is the aggregate gas demand forecasts for the contract year. This satisfies daily demand with least expensive gas and uses more expensive when necessary with automatic computation of available-to-promise (ATP) gas a dispacher knows daily when extra gas supplies may be ATP. Linear Programming is a mathematical algorithm used to determine optimal allocations of scarce resources to achieve a desired result. The LP model determines optimal daily gas purchase decisions with respect to supply cost minimization. Using these models, it appears possible to raise gross income margins 6 to 10% with minimal additions of customers and no new gas supply.

  7. Decision support models for natural gas dispatch

    International Nuclear Information System (INIS)

    Chin, L.; Vollmann, T.E.

    1992-01-01

    A decision support model is presented which will give utilities the support tools to manage the purchasing of natural gas supplies in the most cost effective manner without reducing winter safety stocks to below minimum levels. In Business As Usual (BAU) purchasing quantities vary with the daily forecasts. With Material Requirements Planning (MRP) and Linear Programming (LP), two types of factors are used: seasonal weather and decision rule. Under current practices, BAU simulation uses the least expensive gas source first, then adding successively more expensive sources. Material Requirements Planning is a production planning technique which uses a parent item master production schedule to determine time phased requirements for component points. Where the MPS is the aggregate gas demand forecasts for the contract year. This satisfies daily demand with least expensive gas and uses more expensive when necessary with automatic computation of available-to-promise (ATP) gas a dispacher knows daily when extra gas supplies may be ATP. Linear Programming is a mathematical algorithm used to determine optimal allocations of scarce resources to achieve a desired result. The LP model determines optimal daily gas purchase decisions with respect to supply cost minimization. Using these models, it appears possible to raise gross income margins 6 to 10% with minimal additions of customers and no new gas supply

  8. Olefin hydroformylation catalysis with RuCl2(DMSO4.

    Directory of Open Access Journals (Sweden)

    Marisela Reyes*

    2008-05-01

    Full Text Available The RuCl2(DMSO4 complex was used as catalytic precursor in olefin hydroformylation reactions, giving good percent yield and better selectivity for linear aldehydes. The reactions were tested in homogeneous medium and biphasic organic solvent/ water systems. The substrates tried were 1-hexene, cyclohexene, 2-methyl-2-pentene, 2,3-dimethyl-2-butene; binary mixtures and synthetic naphtha and real naphtha. The activity is better for linear olefins compared with substituted olefins.

  9. Radiation-induced copolymerizations of perfluorovinyl acetic acid and its methyl ester with α-olefin

    International Nuclear Information System (INIS)

    Kawaguchi, M.; Watanabe, T.; Matsuda, O.; Tabata, Y.; Machi, S.

    1981-01-01

    Homopolymerizations and copolymerizations of perfluorovinyl acetic acid (FVA) and its methyl ester (MFVA) were carried out by γ radiation at a temperature of 25 0 C, a dose rate of 1 x 10 6 rad/hr, and FVA/α-olefin and MFVA/α-olefin ratios of 10/90-90/10 in the monomer mixture. FVA and MFVA gave small quantities of brown and greasy low-molecular-weight homopolymers. The polymerization rates of both FVA and MFVA were extremely small, as shown by the maximum G value of monomer consumption of 12. FVA and MFVA reacted with α-olefin to form waxlike copolymers. The copolymerization rates of both FVA and MFVA with α-olefin were remarkably larger than those of the homopolymerizations, particularly with ethylene. The polymer compositions of FVA/ethylene or MFVA/ethylene were nearly 1/2 over a wide range of the monomer compositions. The Mayo-Lewis method gave negative r 1 (FVA) and r 1 (MFVA). The polymer composition curves could be well interpreted by introducing the penultimate model

  10. Olefin recovery from FCC off-gas can pay off

    International Nuclear Information System (INIS)

    Brahn, M.G.

    1992-01-01

    This paper reports on olefins recovery from refinery FCC offgas streams which offers an attractive cash flow from olefins from a tail-gas stream that has typically been consumed as refinery fuel. Such recovery schemes can be employed in refineries or olefins plants, and can be tailored to fit individual requirements. Mobil Chemical Co. has operated such a dephlegmator-based off-gas recovery unit at its Beaumont, Tex., olefin plant since 1987. It reported that the project was paid out within 11 months of initial start-up

  11. Rhodium-catalyzed regioselective olefination directed by a carboxylic group.

    Science.gov (United States)

    Mochida, Satoshi; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro

    2011-05-06

    The ortho-olefination of benzoic acids can be achieved effectively through rhodium-catalyzed oxidative coupling with alkenes. The carboxylic group is readily removable to allow ortho-olefination/decarboxylation in one pot. α,β-Unsaturated carboxylic acids such as methacrylic acid also undergo the olefination at the β-position. Under the rhodium catalysis, the cine-olefination of heteroarene carboxylic acids such as thiophene-2-carboxylic acid proceeds smoothly accompanied by decarboxylation to selectively produce the corresponding vinylheteroarene derivatives. © 2011 American Chemical Society

  12. The olefin metathesis reaction: reorganization and cyclization of organic compounds

    International Nuclear Information System (INIS)

    Frederico, Daniel; Brocksom, Ursula; Brocksom, Timothy John

    2005-01-01

    The olefin metathesis reaction allows the exchange of complex alkyl units between two olefins, with the formation of a new olefinic link and a sub-product olefin usually ethylene. This reaction has found extensive application in the last ten years with the development of the Grubbs and Schrock catalysts, in total synthesis of complex organic molecules, as opposed to the very important use in the petrochemical industry with relatively simple molecules. This review intends to trace a historical and mechanistic pathway from industry to academy, before illustrating the more recent advances. (author)

  13. Organic synthesis with olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Grubbs, R.H. [California Institute of Technology, Pasadena, CA (United States)

    1995-12-31

    Over the past nine years, early transition metal catalysts for the ring opening metathesis polymerization of cyclic olefins have been developed. These catalysts are simple organometallic complexes containing metal carbon multiple bonds that in most cases polymerize olefins by a living process. These catalysts have been used to prepare a family of near monodispersed and structurally homogeneous polymers. A series of group VII ROMP catalysts that allow a wide range of functionality to be incorporated into the polymer side chains have been prepared. The most important member of this family of complexes are the bisphosphinedihalo-ruthenium carbene complexes. These polymerization catalysts can also be used in the synthesis of fine chemicals by ring closing (RCM) and vinyl coupling reactions. The availability of the group VII catalysts allow metathesis to be carried out on highly functionalized substrates such as polypeptides and in unusual environments such as in aqueous emulsions.

  14. Conversion of olefins to liquid motor fuels

    Science.gov (United States)

    Rabo, Jule A.; Coughlin, Peter K.

    1988-01-01

    Linear and/or branched claim C.sub.2 to C.sub.12 olefins are converted to hydrocarbon mixtures suitable for use as liquid motor fuels by contact with a catalyst capable of ensuring the production of desirable products with only a relatively minor amount of heavy products boiling beyond the diesel oil range. The catalyst having desirable stability during continuous production operations, comprises a steam stabilized zeolite Y catalyst of hydrophobic character, desirably in aluminum-extracted form. The olefins such as propylene, may be diluted with inerts, such as paraffins or with water, the latter serving to moderate the acidity of the catalyst, or to further moderate the activity of the aluminum-extracted catalyst, so as to increase the effective life of the catalyst.

  15. Thermally Stable, Latent Olefin Metathesis Catalysts

    OpenAIRE

    Thomas, Renee M.; Fedorov, Alexey; Keitz, Benjamin K.; Grubbs, Robert H.

    2011-01-01

    Highly thermally stable N-aryl,N-alkyl N-heterocyclic carbene (NHC) ruthenium catalysts were designed and synthesized for latent olefin metathesis. These catalysts showed excellent latent behavior toward metathesis reactions, whereby the complexes were inactive at ambient temperature and initiated at elevated temperatures, a challenging property to achieve with second generation catalysts. A sterically hindered N-tert-butyl substituent on the NHC ligand of the ruthenium complex was found to i...

  16. Stereospecific olefin polymerization with chiral metallocene catalysts

    OpenAIRE

    Brintzinger, Hans-Herbert; Fischer, David; Mülhaupt, Rolf; Rieger, Bernhard; Waymouth, Robert M.

    1995-01-01

    Current studies on novel, metallocenebased catalysts for the polymerization of α-olefins have far-reaching implications for the development of new materials as well as for the understanding of basic reaction mechanisms responsible for the growth of a polymer chain at a catalyst center and the control of its stereoregularity. In contrast to heterogeneous Ziegler–Natta catalysts, polymerization by a homogeneous, metallocene-based catalyst occurs principally at a single type of metal center with...

  17. Thermal 18F atom addition to olefins

    International Nuclear Information System (INIS)

    Rogers, P.J.M.

    1986-01-01

    The addition of thermal 18 F atoms to olefins was investigated using various substrate molecules. The 18 F atoms were produced by the 19 F(n,2n) 18 F nuclear reaction with >10 5 eV of energy which is removed by multiple collisions with SF 6 molecules before reaction occurs with an olefin. By varying the SF 6 /substrate mole ratio it was demonstrated that the fraction of non-thermal reactions is dependent upon the frequency of non-reactive energy reducing collisions with SF 6 . The rate constants for addition and abstraction reactions with propene, cis-1-chloropropene and trans-1-chloropropene were determined. The substitution of a C1 atom for the olefinic H atom in the C 1 position does not affect the rate of 18 F bond formation but it changes the orientation of attack. The 18 F atom prefers the terminal carbon-in propene and propene-d 6 by a factor of 1.35 while the preference is less than 0.5 for the terminal carbon in cis-1-chloropropene and trans-1-chloropropene. The addition of 18 F atoms to olefins creates vibrationally excited fluoroalkyl radicals which can either decompose or stabilize by collision with another molecule. The rate constants for decomposition of excited CH 3 CHCHC1F radicals formed by 18 F addition to cis-1-chloropropene and trans-1-chloropropene are competitive with C 1 -C 2 bond rotation. The 18 F atoms add to the parent molecule with retention of geometry and a memory of the geometry persists as demonstrated by the cis-1-fluoropropene/trans-1-fluoropropene decomposition product ratio

  18. Catalytic conversion of methanol to light olefins

    Energy Technology Data Exchange (ETDEWEB)

    Lee, C.S.; Stead, G.E.

    1987-05-12

    A process is described for converting a methanol-containing feed to an olefin-containing hydrocarbon product having a propylene-methylene weight ratio of at least 35.1:6.4. The process comprises contacting the methanol-containing feed in a reaction zone under methanol conversion conditions with a ZSM-12 zeolite catalyst modified by incorporation of a minor amount of a modifier selected from magnesium oxide, manganese oxide and a combination of both magnesium oxide and manganese oxide.

  19. Overload prevention in model supports for wind tunnel model testing

    Directory of Open Access Journals (Sweden)

    Anton IVANOVICI

    2015-09-01

    Full Text Available Preventing overloads in wind tunnel model supports is crucial to the integrity of the tested system. Results can only be interpreted as valid if the model support, conventionally called a sting remains sufficiently rigid during testing. Modeling and preliminary calculation can only give an estimate of the sting’s behavior under known forces and moments but sometimes unpredictable, aerodynamically caused model behavior can cause large transient overloads that cannot be taken into account at the sting design phase. To ensure model integrity and data validity an analog fast protection circuit was designed and tested. A post-factum analysis was carried out to optimize the overload detection and a short discussion on aeroelastic phenomena is included to show why such a detector has to be very fast. The last refinement of the concept consists in a fast detector coupled with a slightly slower one to differentiate between transient overloads that decay in time and those that are the result of aeroelastic unwanted phenomena. The decision to stop or continue the test is therefore conservatively taken preserving data and model integrity while allowing normal startup loads and transients to manifest.

  20. Chelated ruthenium catalysts for Z-selective olefin metathesis.

    Science.gov (United States)

    Endo, Koji; Grubbs, Robert H

    2011-06-08

    We report the development of ruthenium-based metathesis catalysts with chelating N-heterocyclic carbene (NHC) ligands that catalyze highly Z-selective olefin metathesis. A very simple and convenient procedure for the synthesis of such catalysts has been developed. Intramolecular C-H bond activation of the NHC ligand, promoted by anion ligand substitution, forms the appropriate chelate for stereocontrolled olefin metathesis.

  1. NHC Backbone Configuration in Ruthenium-Catalyzed Olefin Metathesis.

    Science.gov (United States)

    Paradiso, Veronica; Costabile, Chiara; Grisi, Fabia

    2016-01-20

    The catalytic properties of olefin metathesis ruthenium complexes bearing N-heterocyclic carbene ligands with stereogenic centers on the backbone are described. Differences in catalytic behavior depending on the backbone configurations of symmetrical and unsymmetrical NHCs are discussed. In addition, an overview on asymmetric olefin metathesis promoted by chiral catalysts bearing C₂-symmetric and C₁-symmetric NHCs is provided.

  2. NHC Backbone Configuration in Ruthenium-Catalyzed Olefin Metathesis

    Directory of Open Access Journals (Sweden)

    Veronica Paradiso

    2016-01-01

    Full Text Available The catalytic properties of olefin metathesis ruthenium complexes bearing N-heterocyclic carbene ligands with stereogenic centers on the backbone are described. Differences in catalytic behavior depending on the backbone configurations of symmetrical and unsymmetrical NHCs are discussed. In addition, an overview on asymmetric olefin metathesis promoted by chiral catalysts bearing C2-symmetric and C1-symmetric NHCs is provided.

  3. Covalently stabilized self-assembled chlorophyll nanorods by olefin metathesis.

    Science.gov (United States)

    Sengupta, Sanchita; Würthner, Frank

    2012-06-11

    A new chlorophyll derivative with peripheral olefinic chains has been synthesised and its self-assembly properties have been studied, revealing formation of well-defined nanorods. These nanorods were stabilized and rigidified by olefin metathesis reaction as confirmed by spectroscopic and microscopic methods.

  4. Rhodium(iii)-catalyzed ortho-olefination of aryl phosphonates.

    Science.gov (United States)

    Chary, Bathoju Chandra; Kim, Sunggak

    2013-09-25

    Rhodium(iii)-catalyzed C-H olefination of aryl phosphonic esters is reported for the first time. In this mild and efficient process, the phosphonic ester group is utilized successfully as a new directing group. In addition, mono-olefination for aryl phosphonates is observed using a phosphonic diamide directing group.

  5. Alkylation of isobutane with light olefins catalyzed by zeolite beta

    NARCIS (Netherlands)

    Nivarthy, G.S.; Feller, A.P.; Seshan, Kulathuiyer; Lercher, J.A.

    2000-01-01

    Alkylation of isobutane with ethene and propene was studied over an H-BEA catalyst in a well-stirred reactor. Under similar conditions of space velocity and paraffin-to-olefin feed ratio, lower initial olefin conversions were observed with ethene or propene than those reported earlier for butene.

  6. Carbonyl-Olefin Exchange Reaction: Present State and Outlook

    Science.gov (United States)

    Kalinova, Radostina; Jossifov, Christo

    The carbonyl-olefin exchange reaction (COER) is a new reaction between carbonyl group and olefin double bond, which has a formal similarity with the olefin metathesis (OM) - one carbon atom in the latter is replaced with an oxygen atom. Till now the new reaction is performed successfully only when the two functional groups (carbonyl group and olefin double bond) are in one molecule and are conjugated. The α, β-unsaturated carbonyl compounds (substituted propenones) are the compounds with such a structure. They polymerize giving substituted polyacetylenes. The chain propagation step of this polymerization is in fact the COER. The question arises: is it possible the COER to take place when the two functional groups are not in one molecule and are not conjugated, and could this reaction became an alternative of the existing carbonyl olefination reactions?

  7. Facilitated olefin transport by reversible olefin coordination to silver ions in a dry cellulose acetate membrane.

    Science.gov (United States)

    Ryu, J H; Lee, H; Kim, Y J; Kang, Y S; Kim, H S

    2001-04-01

    The highly selective dry complex membrane AgBF4-cellulose acetate (CA) was prepared and tested for the separation of ethylene/ethane and propylene/propane mixtures. The maximum selectivity for olefin over paraffin was found to be 280 for the ethylene/ethane mixture and 200 for the propylene/propane mixture. Solid-state interactions of AgBF4 with cellulose acetate (CA) and/or olefins have been investigated by using FT-IR, UV, and X-ray photoelectron spectroscopy (XPS). FT-IR and XPS studies clearly show that the silver ions are coordinated by carbonyl oxygen atoms among three different types of oxygen atoms present in CA-two in the acetate group and one in the ether linkage. Upon incorporation of AgBF4 into CA, the carbonyl stretching frequency of the free cellulose acetate at 1750 cm(-1) shifts to a lower frequency by about 41 cm(-1). The binding energy corresponding to a carbonyl oxygen atom in the O 1s XPS spectrum shifts to a more positive binding energy by the incorporation of AgBF4. Reversible olefin coordination to silver ions has been observed by FT-IR and UV studies. Treatment of the AgBF4-CA membrane placed in a gas cell with propylene produces a propylene-coordinated membrane in which coordinated propylene is easily replaced by other olefins such as 1,3-butadiene.

  8. The activation mechanism of Ru-indenylidene complexes in olefin metathesis.

    Science.gov (United States)

    Urbina-Blanco, César A; Poater, Albert; Lebl, Tomas; Manzini, Simone; Slawin, Alexandra M Z; Cavallo, Luigi; Nolan, Steven P

    2013-05-08

    Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations.

  9. The activation mechanism of Ru-indenylidene complexes in olefin metathesis

    KAUST Repository

    Urbina-Blanco, César A.

    2013-05-08

    Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations. © 2013 American Chemical Society.

  10. Catalyst compositions useful for olefin isomerization and disproportionation

    International Nuclear Information System (INIS)

    Drake, C.A.

    1987-01-01

    A process is described for the double bond isomerization of an aliphatic olefinic hydrocarbon feed which comprises contacting the feed under isomerization conditions with a catalyst prepared by: (a) impregnating an alumina support having a surface area of at least 200 m/sup 2//g and a pore volume of at least 0.45 cm/sup 3//g with: 1 up to 20 wt. % of at least one magnesium compound convertible to the oxide, based on the weight of support and calculated as the metal; 0 up to 5 wt. % of at least one alkali metal compound convertible to the oxide, based on the weight of support and calculated as the metal; and 0 up to 5 wt. % of at least one zirconium compound convertible to the oxide, based on the weight of support and calculated as the metal; and (b) heating the alumina support impregnated in accordance with step (a) in an oxygen-containing atmosphere under conditions suitable to convert at least a portion of the magnesium, alkali metal, and zirconium compounds to the oxide form

  11. Olefin metathesis over UV-irradiated silica

    Science.gov (United States)

    Tanaka, Tsunehiro; Matsuo, Shigehiro; Maeda, Takashi; Yoshida, Hisao; Funabiki, Takuzo; Yoshida, Satohiro

    1997-11-01

    Photoirradiated silica evacuated at temperatures higher than 800 K was found to be active for olefin metathesis reactions. The analysis of products shows that the metalacyclobutane intermediate is likely. The instantaneous response of the reaction to the irradiation and the activity change with various UV filter showed that the reaction is induced by UV-excitation of silica. The correlation between the evacuation temperature and the activity showed that the surface free from water molecules plays a role in the reaction and the removal of isolated OH groups strongly relates to the generation of active sites.

  12. Ruthenium-Aryloxide Catalysts for Olefin Metathesis

    Science.gov (United States)

    Monfette, Sebastien; Blacquiere, Johanna M.; Conrad, Jay C.; Beach, Nicholas J.; Fogg, Deryn E.

    : Advances in design of ruthenium aryloxide catalysts for olefin metathesis are described. The target complexes are accessible on reaction of RuCl2(NHC)(py)2 (CHPh) (NHC - N-heterocyclic carbene) with electron-deficient, monodentate aryl- oxides, or aryloxides that yield small, rigid chelate rings. The best of these catalysts offer activity comparable to or greater than that of the parent chloride (Grubbs) systems in ring-closing metathesis (RCM). Preliminary studies of the electronic nature of the Ru-X bond suggest that the metal center is more electropositive in the aryloxide complexes than in the Grubbs systems.

  13. Mutual Support: A Model of Participatory Support by and for People with Learning Difficulties

    Science.gov (United States)

    Keyes, Sarah E.; Brandon, Toby

    2012-01-01

    Mutual Support, a model of peer support by and for people with learning difficulties, was constructed through a participatory research process. The research focussed on individual narratives from people with learning difficulties. These narratives were then brought together to form a collective model of support. This paper outlines the detailed…

  14. Conformations of N-Heterocyclic Carbene Ligands in Ruthenium Complexes Relevant to Olefin Metathesis

    Science.gov (United States)

    Stewart, Ian C.; Benitez, Diego; O'Leary, Daniel J.; Tkatchouk, Ekaterina; Day, Michael W.; Goddard, William A.; Grubbs, Robert H.

    2009-01-01

    The structure of ruthenium-based olefin metathesis catalyst 3 and model π-complex 5 in solution and in the solid state are reported. The N-tolyl ligands, due to their lower symmetry than the traditional N-mesityl substituents, complicate this analysis, but ultimately provide explanation for the enhanced reactivity of 3 relative to standard catalyst 2. The tilt of the N-tolyl ring provides additional space near the ruthenium center, which is consistent with the enhanced reactivity of 3 towards sterically demanding substrates. Due to this tilt, the more sterically accessible face bears the two methyl substituents of the N-aryl rings. These experimental studies are supported by computational studies of these complexes by DFT. The experimental data provides a means to validate the accuracy of the B3LYP and M06 functionals. B3LYP provides geometries that match X-ray crystal structural data more closely, though it leads to slightly less (∼0.5 kcal mol−1) accuracy than M06 most likely because it underestimates attractive non-covalent interactions. PMID:19146414

  15. Support Center for Regulatory Atmospheric Modeling (SCRAM)

    Science.gov (United States)

    This technical site provides access to air quality models (including computer code, input data, and model processors) and other mathematical simulation techniques used in assessing air emissions control strategies and source impacts.

  16. SAXS observation of structural evolution of heated olefin

    International Nuclear Information System (INIS)

    Sun Minhua; Mou Hongchen; Wang Yuxi; Li Demin; Wang Aiping; Ma Congxiao; Cheng Weidong; Wang Dan; Liu Jia

    2007-01-01

    Structural evolution of olefin during its heating process was observed with SAXS method at Beijing Synchrotron Radiation Facility. The mean square fluctuation of electron density increased from 468.5 nm -2 at 22 degree C to 2416 nm -2 at 100 degree C, while the electronic gyration radius decreased from 11.61 nm at 22 degree C to 11.16 nm at 100 degree C. Therefore, the olefin softens as a result of the increased thermal motion of the molecules, rather than the shrinking size of fundamental structural units of olefin. (authors)

  17. Reactions of dihydridotetrakis(triphenylphosphine)ruthenium(II) with olefins and isolation of new ruthenium-olefin complexes

    International Nuclear Information System (INIS)

    Komiya, Sanshiro; Yamamoto, Akio

    1976-01-01

    Dihydridotetrakis(triphenylphosphine)ruthenium (II), RuH 2 (PPh 3 ) 4 , reacts with olefins (ethylene, propylene, stylene and butadiene) to give olefin-coordinated complexes of the type, Ru(olefin)(PPh 3 ) 3 and equimolar amounts of their hydrogenation products per mol of the dihydride complex. The olefin coordinated with ruthenium can be exchanged with other olefins. Olefin-coordinated complexes easily react with molecular hydrogen to afford tetrahydridotris(triphenylphosphine)ruthenium, RuH 4 (PPh 3 ) 3 , releasing alkane at room temperature, Under hydrogen atmosphere catalytic hydrogenation of the olefins smoothly takes place with RuH 2 (PPh 3 ) 4 . (Ethylene)tris(triphenylphosphine)ruthenium(0) reacts with methyl iodide to give propylene and a trace of butadiene along with methane, ethylene, and small amounts of ethane and butenes. The formation of propylene suggests that oxidative addition involving cleavage of the C-H bond of ethylene to ruthenium giving a hydridovinyl complex may be taking place. Reactions of Ru(C 2 H 4 )(PPh 3 ) 3 with methyl-d 3 iodide and ethyl iodide, and of Ru(C 3 H 6 )(PPh 3 ) 3 with methyl iodide were examined to test the generality of this type of reaction. The reaction of Ru(C 2 H 4 )(PPh 3 ) 3 with CD 3 I released CD 4 and CD 2 H 2 together with CD 3 H suggesting the involvement of α-hydrogen abstraction. (auth.)

  18. Examining the Support Peer Supporters Provide Using Structural Equation Modeling: Nondirective and Directive Support in Diabetes Management.

    Science.gov (United States)

    Kowitt, Sarah D; Ayala, Guadalupe X; Cherrington, Andrea L; Horton, Lucy A; Safford, Monika M; Soto, Sandra; Tang, Tricia S; Fisher, Edwin B

    2017-12-01

    Little research has examined the characteristics of peer support. Pertinent to such examination may be characteristics such as the distinction between nondirective support (accepting recipients' feelings and cooperative with their plans) and directive (prescribing "correct" choices and feelings). In a peer support program for individuals with diabetes, this study examined (a) whether the distinction between nondirective and directive support was reflected in participants' ratings of support provided by peer supporters and (b) how nondirective and directive support were related to depressive symptoms, diabetes distress, and Hemoglobin A1c (HbA1c). Three hundred fourteen participants with type 2 diabetes provided data on depressive symptoms, diabetes distress, and HbA1c before and after a diabetes management intervention delivered by peer supporters. At post-intervention, participants reported how the support provided by peer supporters was nondirective or directive. Confirmatory factor analysis (CFA), correlation analyses, and structural equation modeling examined the relationships among reports of nondirective and directive support, depressive symptoms, diabetes distress, and measured HbA1c. CFA confirmed the factor structure distinguishing between nondirective and directive support in participants' reports of support delivered by peer supporters. Controlling for demographic factors, baseline clinical values, and site, structural equation models indicated that at post-intervention, participants' reports of nondirective support were significantly associated with lower, while reports of directive support were significantly associated with greater depressive symptoms, altogether (with control variables) accounting for 51% of the variance in depressive symptoms. Peer supporters' nondirective support was associated with lower, but directive support was associated with greater depressive symptoms.

  19. Mass transport models for a single particle in gas phase propylene polymerization

    NARCIS (Netherlands)

    Parasu Veera, U.

    2003-01-01

    Olefin polymerisation on heterogeneous catalysts is gaining importance due to widening of the polymer properties window. The supported active catalyst on the heterogeneous particle reacts with the monomer and produces polymer. Polymeric flow (PF) model is relatively simple and assume that particle

  20. Improving olefin tolerance and production in E. coli using native and evolved AcrB.

    Science.gov (United States)

    Mingardon, Florence; Clement, Camille; Hirano, Kathleen; Nhan, Melissa; Luning, Eric G; Chanal, Angelique; Mukhopadhyay, Aindrila

    2015-05-01

    Microorganisms can be engineered for the production of chemicals utilized in the polymer industry. However many such target compounds inhibit microbial growth and might correspondingly limit production levels. Here, we focus on compounds that are precursors to bioplastics, specifically styrene and representative alpha-olefins; 1-hexene, 1-octene, and 1-nonene. We evaluated the role of the Escherichia coli efflux pump, AcrAB-TolC, in enhancing tolerance towards these olefin compounds. AcrAB-TolC is involved in the tolerance towards all four compounds in E. coli. Both styrene and 1-hexene are highly toxic to E. coli. Styrene is a model plastics precursor with an established route for production in E. coli (McKenna and Nielsen, 2011). Though our data indicates that AcrAB-TolC is important for its optimal production, we observed a strong negative selection against the production of styrene in E. coli. Thus we used 1-hexene as a model compound to implement a directed evolution strategy to further improve the tolerance phenotype towards this alpha-olefin. We focused on optimization of AcrB, the inner membrane domain known to be responsible for substrate binding, and found several mutations (A279T, Q584R, F617L, L822P, F927S, and F1033Y) that resulted in improved tolerance. Several of these mutations could also be combined in a synergistic manner. Our study shows efflux pumps to be an important mechanism in host engineering for olefins, and one that can be further improved using strategies such as directed evolution, to increase tolerance and potentially production. © 2015 Wiley Periodicals, Inc.

  1. Modeling uncertainty in requirements engineering decision support

    Science.gov (United States)

    Feather, Martin S.; Maynard-Zhang, Pedrito; Kiper, James D.

    2005-01-01

    One inherent characteristic of requrements engineering is a lack of certainty during this early phase of a project. Nevertheless, decisions about requirements must be made in spite of this uncertainty. Here we describe the context in which we are exploring this, and some initial work to support elicitation of uncertain requirements, and to deal with the combination of such information from multiple stakeholders.

  2. Modeling a support system for the evaluator

    International Nuclear Information System (INIS)

    Lozano Lima, B.; Ilizastegui Perez, F; Barnet Izquierdo, B.

    1998-01-01

    This work gives evaluators a tool they can employ to give more soundness to their review of operational limits and conditions. The system will establish the most adequate method to carry out the evaluation, as well as to evaluate the basis for technical operational specifications. It also includes the attainment of alternative questions to be supplied to the operating entity to support it in decision-making activities

  3. Cobalt catalyzed hydroesterification of a wide range of olefins

    Energy Technology Data Exchange (ETDEWEB)

    Van Rensburg, H.; Hanton, M.; Tooze, R.P.; Foster, D.F. [Sasol Technology UK, St Andrews (United Kingdom)

    2011-07-01

    Petrochemical raw materials are an essential raw material for the production of detergents with a substantial portion of synthetic fatty alcohols being produced via hydroformylation of oil or coal derived olefins. Carbonylation processes other than hydroformylation have to date not been commercially employed for the production of fatty esters or alcohols. In this document we highlight the opportunities of converting olefins to esters using cobalt catalyzed alkoxycarbonylation. This process is highly versatile and applicable to a wide range of olefins, linear or branched, alpha or internal in combination with virtually any chain length primary or secondary alcohol allowing the synthesis of a diverse array of compounds such as ester ethoxylated surfactants, methyl branched detergents, lubricants and alkyl propanoates. Furthermore, alkoxycarbonylation of a broad olefin/paraffin hydrocarbon range could be used to produce the corresponding broad cut detergent alcohols. (orig.)

  4. Olefin Metathesis in Peptidomimetics, Dynamic Combinatorial Chemistry, and Molecular Imprinting

    National Research Council Canada - National Science Library

    Low, Tammy K

    2006-01-01

    .... Our research goals consisted of employing olefin metathesis in the synthesis of peptidomimetics, and studying the feasibility of this method in dynamic combinatorial chemistry and molecular imprinting of nerve agents...

  5. Hafnium metallocene catalyst for the polymerization of olefins

    Energy Technology Data Exchange (ETDEWEB)

    Ewen, J.A.

    1988-12-27

    A catalyst is described for the polymerization and copolymerization of olefins comprising a an alumoxane and chiral, stereorigid hafnium metallocene catalyst. It includes a cyclopentadienyl ring and germanium, silicon, phosphorus, nitrogen, boron, and aluminum radicals.

  6. Mechanistic insights in the olefin epoxidation with cyclohexyl hydroperoxide

    NARCIS (Netherlands)

    Hereijgers, B.P.C.|info:eu-repo/dai/nl/314131116; Parton, R.F.; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

    2012-01-01

    Olefin epoxidation with cyclohexyl hydroperoxide offers great perspective in increasing the yield from industrial cyclohexane oxidation and the production of epoxides in an apolar medium. Two competing hydroperoxide conversion routes, namely direct epoxidation and thermal decomposition, were

  7. Predictive analytics can support the ACO model.

    Science.gov (United States)

    Bradley, Paul

    2012-04-01

    Predictive analytics can be used to rapidly spot hard-to-identify opportunities to better manage care--a key tool in accountable care. When considering analytics models, healthcare providers should: Make value-based care a priority and act on information from analytics models. Create a road map that includes achievable steps, rather than major endeavors. Set long-term expectations and recognize that the effectiveness of an analytics program takes time, unlike revenue cycle initiatives that may show a quick return.

  8. Rh(III)-catalyzed oxidative olefination of N-(1-naphthyl)sulfonamides using activated and unactivated alkenes.

    Science.gov (United States)

    Li, Xuting; Gong, Xue; Zhao, Miao; Song, Guoyong; Deng, Jian; Li, Xingwei

    2011-11-04

    Rhodium(III)-catalyzed oxidative olefination of N-(1-naphthyl)sulfonamides has been achieved at the peri position. Three categories of olefins have been successfully applied. Activated olefins reacted to afford five-membered azacycles as a result of oxidative olefination-hydroamination. Unactivated olefins reacted to give the olefination product. 2-fold oxidative C-C and C-N coupling was achieved for allylbenzenes. © 2011 American Chemical Society

  9. Methods for suppressing isomerization of olefin metathesis products

    Energy Technology Data Exchange (ETDEWEB)

    Firth, Bruce E.; Kirk, Sharon E.

    2015-10-27

    A method for suppressing isomerization of an olefin metathesis product produced in a metathesis reaction includes adding an isomerization suppression agent that includes nitric acid to a mixture that includes the olefin metathesis product and residual metathesis catalyst from the metathesis reaction under conditions that are sufficient to passivate at least a portion of the residual metathesis catalyst. Methods of refining a natural oil are described.

  10. Methods for suppressing isomerization of olefin metathesis products

    Energy Technology Data Exchange (ETDEWEB)

    Firth, Bruce E.; Kirk, Sharon E.; Gavaskar, Vasudeo S.

    2015-09-22

    A method for suppressing isomerization of an olefin metathesis product produced in a metathesis reaction includes adding an isomerization suppression agent to a mixture that includes the olefin metathesis product and residual metathesis catalyst from the metathesis reaction under conditions that are sufficient to passivate at least a portion of the residual metathesis catalyst. The isomerization suppression agent is phosphorous acid, a phosphorous acid ester, phosphinic acid, a phosphinic acid ester or combinations thereof. Methods of refining natural oils are described.

  11. Chelated Ruthenium Catalysts for Z-Selective Olefin Metathesis

    OpenAIRE

    Endo, Koji; Grubbs, Robert H.

    2011-01-01

    We report the development of ruthenium-based metathesis catalysts with chelating N-heterocyclic carbene (NHC) ligands which catalyze highly Z-selective olefin metathesis. A very simple and convenient synthetic procedure of such a catalyst has been developed. An intramolecular C-H bond activation of the NHC ligand, which is promoted by anion ligand substitution, forms the appropriate chelate for stereo- controlled olefin metathesis.

  12. Total Synthesis of Mycalolides A and B through Olefin Metathesis.

    Science.gov (United States)

    Kita, Masaki; Oka, Hirotaka; Usui, Akihiro; Ishitsuka, Tomoya; Mogi, Yuzo; Watanabe, Hidekazu; Tsunoda, Masaki; Kigoshi, Hideo

    2015-11-16

    An asymmetric total synthesis of the trisoxazole marine macrolides mycalolides A and B is described. This synthesis involves the convergent assembly of highly functionalized C1-C19 trisoxazole and C20-C35 side-chain segments through the use of olefin metathesis and esterification as well as Julia-Kocienski olefination and enamide formation as key steps. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Carbonyl-Olefin Exchange Reaction and Related Chemistry

    Science.gov (United States)

    Jossifov, Christo; Kalinova, Radostina

    A new carbon—carbon double bond forming reaction (carbonyl olefin exchange reaction) mediated by transition metal catalytic systems has been discovered. The catalytic systems used (transition metal halides or oxohalides alone or in combination with Lewis acids) are active only in the case when the two reacting groups are in one molecules and are conjugated. In addition these systems accelerate other reactions which run simultaneously with the carbonyl olefin metathesis rendering a detailed investigation of the process very complicated.

  14. Consideration of applications of olefin metathesis in synthetic fuel production

    Energy Technology Data Exchange (ETDEWEB)

    Heveling, J.

    1984-07-01

    One of the characteristics of Fischer-Tropsch synthesis and many oligomerization processes, is insufficient selectivity. Efforts have to be made to bring the products obtained in line with the market requirements. The olefin metathesis reaction has the potential to convert less desirable olefins to more useful ones and provides new ways of producing petrochemicals. Based on existing and suggested process technologies, applications of this reaction for the production of synthetic liquid fuels are discussed.

  15. 1-O-vinyl glycosides via Tebbe olefination, their use as chiral auxiliaries and monomers.

    Science.gov (United States)

    Yuan, Jialong; Lindner, Kristof; Frauenrath, Holger

    2006-07-21

    A series of anomerically pure 1-O-formyl glycosides 1 was prepared and converted into the corresponding 1-O-vinyl glycosides 2 by Tebbe olefination. The unsubstituted vinyl glycosides were obtained as anomerically pure compounds in good yields, and the method of preparation was compatible with the presence of a variety of functional groups. Remarkably, the anomeric formate group was regioselectively converted into the corresponding olefin in the presence of acetate and benzoate protecting groups. With the perspective to use the 1-O-vinyl glycosides as monomers for the preparation of glycosylated poly(vinyl alcohol) derivatives with controlled tacticity, their scope as chiral auxiliaries for a stereodifferentiation in addition reactions to the olefin function was investigated by using the [2+2] cycloaddition to dichloroketene as a model reaction. In particular, vinyl 2,3,4,6-tetra-O-benzoyl-alpha-d-mannopyranoside (2i) exhibited excellent diastereoselectivity. Finally, the 1-O-vinyl glycosides were successfully subjected to radical homopolymerization in bulk or used as electron-rich comonomers in radical copolymerizations with maleic anhydride, yielding alternating, glycosylated poly(vinyl alcohol-alt-maleic anhydride).

  16. Enantioselective olefin metathesis with cyclometalated ruthenium complexes.

    Science.gov (United States)

    Hartung, John; Dornan, Peter K; Grubbs, Robert H

    2014-09-17

    The success of enantioselective olefin metathesis relies on the design of enantioenriched alkylidene complexes capable of transferring stereochemical information from the catalyst structure to the reactants. Cyclometalation of the NHC ligand has proven to be a successful strategy to incorporate stereogenic atoms into the catalyst structure. Enantioenriched complexes incorporating this design element catalyze highly Z- and enantioselective asymmetric ring opening/cross metathesis (AROCM) of norbornenes and cyclobutenes, and the difference in ring strain between these two substrates leads to different propagating species in the catalytic cycle. Asymmetric ring closing metathesis (ARCM) of a challenging class of prochiral trienes has also been achieved. The extent of reversibility and effect of reaction setup was also explored. Finally, promising levels of enantioselectivity in an unprecedented Z-selective asymmetric cross metathesis (ACM) of a prochiral 1,4-diene was demonstrated.

  17. Controlled Ecological Life Support System (CELSS) modeling

    Science.gov (United States)

    Drysdale, Alan; Thomas, Mark; Fresa, Mark; Wheeler, Ray

    1992-01-01

    Attention is given to CELSS, a critical technology for the Space Exploration Initiative. OCAM (object-oriented CELSS analysis and modeling) models carbon, hydrogen, and oxygen recycling. Multiple crops and plant types can be simulated. Resource recovery options from inedible biomass include leaching, enzyme treatment, aerobic digestion, and mushroom and fish growth. The benefit of using many small crops overlapping in time, instead of a single large crop, is demonstrated. Unanticipated results include startup transients which reduce the benefit of multiple small crops. The relative contributions of mass, energy, and manpower to system cost are analyzed in order to determine appropriate research directions.

  18. On Support Functions for the Development of MFM Models

    DEFF Research Database (Denmark)

    Heussen, Kai; Lind, Morten

    2012-01-01

    A modeling environment and methodology are necessary to ensure quality and reusability of models in any domain. For MFM in particular, as a tool for modeling complex systems, awareness has been increasing for this need. Introducing the context of modeling support functions, this paper provides...... a review of MFM applications, and contextualizes the model development with respect to process design and operation knowledge. Developing a perspective for an environment for MFM-oriented model- and application-development a tool-chain is outlined and relevant software functions are discussed....... With a perspective on MFM-modeling for existing processes and automation design, modeling stages and corresponding formal model properties are identified. Finally, practically feasible support functions and model-checks to support the model-development are suggested....

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

    Science.gov (United States)

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

    2016-05-01

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

  20. Strategies to Support Students' Mathematical Modeling

    Science.gov (United States)

    Jung, Hyunyi

    2015-01-01

    An important question for mathematics teachers is this: "How can we help students learn mathematics to solve everyday problems, rather than teaching them only to memorize rules and practice mathematical procedures?" Teaching students using modeling activities can help them learn mathematics in real-world problem-solving situations that…

  1. Using Covariation Reasoning to Support Mathematical Modeling

    Science.gov (United States)

    Jacobson, Erik

    2014-01-01

    For many students, making connections between mathematical ideas and the real world is one of the most intriguing and rewarding aspects of the study of mathematics. In the Common Core State Standards for Mathematics (CCSSI 2010), mathematical modeling is highlighted as a mathematical practice standard for all grades. To engage in mathematical…

  2. Dengue human infection models supporting drug development.

    Science.gov (United States)

    Whitehorn, James; Van, Vinh Chau Nguyen; Simmons, Cameron P

    2014-06-15

    Dengue is a arboviral infection that represents a major global health burden. There is an unmet need for effective dengue therapeutics to reduce symptoms, duration of illness and incidence of severe complications. Here, we consider the merits of a dengue human infection model (DHIM) for drug development. A DHIM could allow experimentally controlled studies of candidate therapeutics in preselected susceptible volunteers, potentially using smaller sample sizes than trials that recruited patients with dengue in an endemic country. In addition, the DHIM would assist the conduct of intensive pharmacokinetic and basic research investigations and aid in determining optimal drug dosage. Furthermore, a DHIM could help establish proof of concept that chemoprophylaxis against dengue is feasible. The key challenge in developing the DHIM for drug development is to ensure the model reliably replicates the typical clinical and laboratory features of naturally acquired, symptomatic dengue. © The Author 2014. Published by Oxford University Press on behalf of the Infectious Diseases Society of America.

  3. Electron transfer-induced four-membered cyclic intermediate formation: Olefin cross-coupling vs. olefin cross-metathesis

    International Nuclear Information System (INIS)

    Okada, Yohei; Chiba, Kazuhiro

    2011-01-01

    An electron transfer-induced four-membered cyclic intermediate, formed between a radical cation of an enol ether and an unactivated olefin, played a key role in the pathway toward either cross-coupling or cross-metathesis. The presence of an alkoxy group on the phenyl ring of the olefin entirely determined the synthetic outcome of the reaction, which mirrored the efficiency of the intramolecular electron transfer.

  4. Statistical modeling to support power system planning

    Science.gov (United States)

    Staid, Andrea

    This dissertation focuses on data-analytic approaches that improve our understanding of power system applications to promote better decision-making. It tackles issues of risk analysis, uncertainty management, resource estimation, and the impacts of climate change. Tools of data mining and statistical modeling are used to bring new insight to a variety of complex problems facing today's power system. The overarching goal of this research is to improve the understanding of the power system risk environment for improved operation, investment, and planning decisions. The first chapter introduces some challenges faced in planning for a sustainable power system. Chapter 2 analyzes the driving factors behind the disparity in wind energy investments among states with a goal of determining the impact that state-level policies have on incentivizing wind energy. Findings show that policy differences do not explain the disparities; physical and geographical factors are more important. Chapter 3 extends conventional wind forecasting to a risk-based focus of predicting maximum wind speeds, which are dangerous for offshore operations. Statistical models are presented that issue probabilistic predictions for the highest wind speed expected in a three-hour interval. These models achieve a high degree of accuracy and their use can improve safety and reliability in practice. Chapter 4 examines the challenges of wind power estimation for onshore wind farms. Several methods for wind power resource assessment are compared, and the weaknesses of the Jensen model are demonstrated. For two onshore farms, statistical models outperform other methods, even when very little information is known about the wind farm. Lastly, chapter 5 focuses on the power system more broadly in the context of the risks expected from tropical cyclones in a changing climate. Risks to U.S. power system infrastructure are simulated under different scenarios of tropical cyclone behavior that may result from climate

  5. Key Elements of the Tutorial Support Management Model

    Science.gov (United States)

    Lynch, Grace; Paasuke, Philip

    2011-01-01

    In response to an exponential growth in enrolments the "Tutorial Support Management" (TSM) model has been adopted by Open Universities Australia (OUA) after a two-year project on the provision of online tutor support in first year, online undergraduate units. The essential focus of the TSM model was the development of a systemic approach…

  6. Rhode Island Model Evaluation & Support System: Building Administrator. Edition III

    Science.gov (United States)

    Rhode Island Department of Education, 2015

    2015-01-01

    Rhode Island educators believe that implementing a fair, accurate, and meaningful educator evaluation and support system will help improve teaching, learning, and school leadership. The primary purpose of the Rhode Island Model Building Administrator Evaluation and Support System (Rhode Island Model) is to help all building administrators improve.…

  7. Invention software support by integrating function and mathematical modeling

    NARCIS (Netherlands)

    Chechurin, L.S.; Wits, Wessel Willems; Bakker, H.M.

    2015-01-01

    New idea generation is imperative for successful product innovation and technology development. This paper presents the development of a novel type of invention support software. The support tool integrates both function modeling and mathematical modeling, thereby enabling quantitative analyses on a

  8. A Traceability-based Method to Support Conceptual Model Evolution

    OpenAIRE

    Ruiz Carmona, Luz Marcela

    2014-01-01

    Renewing software systems is one of the most cost-effective ways to protect software investment, which saves time, money and ensures uninter- rupted access to technical support and product upgrades. There are several mo- tivations to promote investment and scientific effort for specifying systems by means of conceptual models and supporting its evolution. As an example, the software engineering community is addressing solutions for supporting model traceability, continuous improvement of busi...

  9. A methodology to support multidisciplinary model-based water management

    NARCIS (Netherlands)

    Scholten, H.; Kassahun, A.; Refsgaard, J.C.; Kargas, Th.; Gavardinas, C.; Beulens, A.J.M.

    2007-01-01

    Quality assurance in model based water management is needed because of some frequently perceived shortcomings, e.g. a lack of mutual understanding between modelling team members, malpractice and a tendency of modellers to oversell model capabilities. Initiatives to support quality assurance focus on

  10. Organizational Learning Supported by Reference Architecture Models

    DEFF Research Database (Denmark)

    Nardello, Marco; Møller, Charles; Gøtze, John

    2017-01-01

    The wave of the fourth industrial revolution (Industry 4.0) is bringing a new vision of the manufacturing industry. In manufacturing, one of the buzzwords of the moment is “Smart production”. Smart production involves manufacturing equipment with many sensors that can generate and transmit large...... amounts of data. These data and information from manufacturing operations are however not shared in the organization. Therefore the organization is not using them to learn and improve their operations. To address this problem, the authors implemented in an Industry 4.0 laboratory an instance...... of an emerging technical standard specific for the manufacturing industry. Global manufacturing experts consider the Reference Architecture Model Industry 4.0 (RAMI4.0) as one of the corner stones for the implementation of Industry 4.0. The instantiation contributed to organizational learning in the laboratory...

  11. High-Yield Process for Selectively Converting CO2 to Aromatics and Olefins, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — This proposed Phase I addresses the selective conversion of CO2 to hydrocarbons via integrated CO2-to-methanol, methanol-to-olefins, and olefins-to-aromatics...

  12. Studies of Olefin Dimerization, Oligomerization, and Polymerization Catalyzed by Cationic (alpha-Diimine)Ni(II) Complexes

    National Research Council Canada - National Science Library

    Svejda, Steven

    1999-01-01

    .... The development of cationic (alpha-diimine)nickel(II) and palladium(II) complexes which catalyze the polymerization of both ethylene and alpha-olefins to high polymers represents a major advance in the field of olefin polymerization catalysis...

  13. Are complex DCE-MRI models supported by clinical data?

    DEFF Research Database (Denmark)

    Duan, Chong; Kallehauge, Jesper F; Bretthorst, G Larry

    2016-01-01

    PURPOSE: To ascertain whether complex dynamic contrast enhanced (DCE) MRI tracer kinetic models are supported by data acquired in the clinic and to determine the consequences of limited contrast-to-noise. METHODS: Generically representative in silico and clinical (cervical cancer) DCE-MRI data were...... selection is particularly important when high-order, multiparametric models are under consideration. (Parameters obtained from kinetic modeling of cervical cancer clinical DCE-MRI data showed significant changes at an early stage of radiotherapy.)...... examined. Bayesian model selection evaluated support for four compartmental DCE-MRI models: the Tofts model (TM), Extended Tofts model, Compartmental Tissue Uptake model (CTUM), and Two-Compartment Exchange model. RESULTS: Complex DCE-MRI models were more sensitive to noise than simpler models with respect...

  14. Direct observation of supported W bis-methylidene from supported W-methyl/methylidyne species

    KAUST Repository

    Callens, Emmanuel

    2014-01-01

    Extensive solid-state NMR analyses unambiguously determine the formation of silica supported W bis-methylidene methyl species by reaction of the corresponding methyl carbyne with trimethylphosphine or a cyclic olefin. © 2014 the Partner Organisations.

  15. Divergent Approach to a Family of Tyrosine-Derived Ru-Alkylidene Olefin Metathesis Catalysts.

    Science.gov (United States)

    Gleeson, Ellen C; Wang, Zhen J; Jackson, W Roy; Robinson, Andrea J

    2015-07-17

    A simple and generic approach to access a new family of Ru-alkylidene olefin metathesis catalysts with specialized properties is reported. This strategy utilizes a late stage, utilitarian Hoveyda-type ligand derived from tyrosine, which can be accessed via a multigram-scale synthesis. Further functionalization allows the catalyst properties to be tuned, giving access to modified second-generation Hoveyda-Grubbs-type catalysts. This divergent synthetic approach can be used to access solid-supported catalysts and catalysts that function under solvent-free and aqueous conditions.

  16. C-H to C-N Cross-Coupling of Sulfonamides with Olefins.

    Science.gov (United States)

    Ma, Rulin; White, M Christina

    2018-03-07

    Cross-coupling of nitrogen with hydrocarbons under fragment coupling conditions stands to significantly impact chemical synthesis. Herein, we disclose a C(sp 3 )-N fragment coupling reaction between terminal olefins and N-triflyl protected aliphatic and aromatic amines via Pd(II)/SOX (sulfoxide-oxazoline) catalyzed intermolecular allylic C-H amination. A range of (56) allylic amines are furnished in good yields (avg. 75%) and excellent regio- and stereoselectivity (avg. >20:1 linear:branched, >20:1 E: Z). Mechanistic studies reveal that the SOX ligand framework is effective at promoting functionalization by supporting cationic π-allyl Pd.

  17. Effects of the Linking of Cyclopentadienyl and Ketimide Ligands in Titanium Half-sandwich Olefin Polymerization Catalysts

    Czech Academy of Sciences Publication Activity Database

    Varga, Vojtěch; Večeřa, M.; Gyepes, R.; Pinkas, Jiří; Horáček, Michal; Merna, J.; Lamač, Martin

    2017-01-01

    Roč. 9, č. 16 (2017), s. 3160-3172 ISSN 1867-3880 R&D Projects: GA ČR(CZ) GA14-08531S; GA ČR(CZ) GA17-13778S Institutional support: RVO:61388955 Keywords : ketimide ligands * olefin polymerization catalysts * cyclopentadienyl Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 4.803, year: 2016

  18. Reactivity of olefin and allyl ligands in π-complexes of metals

    International Nuclear Information System (INIS)

    Kukushkin, Yu.N.

    1987-01-01

    The data on reactivity of olefin and allyl ligands in transition metal (Ru, W) π-complexes, published up to 1984 are presented. Metal ion coordination of olefins causes their appreciable reactivity change. Transformations of π-olefin ligands into σ-alkyl ones, interaction of π-complexes with oxygen nucleophilic reagents, amines, halogenides and pseudohalogenides are considered

  19. Palladium(II)-catalyzed ortho-olefination of arenes applying sulfoxides as remote directing groups.

    Science.gov (United States)

    Wang, Binjie; Shen, Chuang; Yao, Jinzhong; Yin, Hong; Zhang, Yuhong

    2014-01-03

    A novel palladium-catalyzed ortho-C(sp(2))-H olefination protocol has been developed by the use of sulfoxide as the directing group. Importantly, relatively remote coordination can be accessed to achieve the ortho olefination of benzyl, 2-arylethyl, and 3-arylpropenyl sulfoxide substrates, and the olefinated sulfoxide can be easily transformed to other functionalities.

  20. Reference models supporting enterprise networks and virtual enterprises

    DEFF Research Database (Denmark)

    Tølle, Martin; Bernus, Peter

    2003-01-01

    This article analyses different types of reference models applicable to support the set up and (re)configuration of Virtual Enterprises (VEs). Reference models are models capturing concepts common to VEs aiming to convert the task of setting up of VE into a configuration task, and hence reducing ...

  1. A well-defined rhenium(VII) olefin metathesis catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Toreki, R.; Schrock, R.R. (Massachusetts Institute of Technology, Cambridge (USA))

    1990-03-14

    Molybdenum tungsten, and rhenium are the three most active metals in classical olefin metathesis systems. Molybdenum (VI){sup 2} and tungsten(VI){sup 3} alkylidene complexes of the type M-(CHR{prime})(NAr)(OR){sub 2} (Ar = 2,6-C{sub 6}H{sub 3}-i-Pr{sub 2}) have been shown to be well-behaved olefin metathesis catalysts with an activity that can be controlled through the choice of OR. Although several rhenium alkylidene complexes have been reported, none has shown any confirmable metathesis activity, even toward strained cyclic olefins such as norbornene. Since Re{triple bond}CR{double prime} and M{double bond}NR{double prime} (M = Mo or W) can be regarded as isoelectronic units, plausible candidates as olefin metathesis catalysts are complexes of the type Re(CHR{prime})(CR{double prime})(OR){sub 2}. The authors report here that such a complex in which OR = OCMe(CF{sub 3}){sub 2} is a well-behaved olefin metathesis catalyst.

  2. Ruthenium olefin metathesis catalysts featuring unsymmetrical N-heterocyclic carbenes.

    Science.gov (United States)

    Paradiso, Veronica; Bertolasi, Valerio; Costabile, Chiara; Grisi, Fabia

    2016-01-14

    New ruthenium Grubbs' and Hoveyda-Grubbs' second generation catalysts bearing N-alkyl/N-isopropylphenyl N-heterocyclic carbene (NHC) ligands with syn or anti backbone configuration were obtained and compared in model olefin metathesis reactions. Different catalytic efficiencies were observed depending on the size of the N-alkyl group (methyl or cyclohexyl) and on the backbone configuration. The presence of an N-cyclohexyl substituent determined the most significant reactivity differences between catalysts with syn or anti phenyl groups on the backbone. In particular, anti catalysts proved highly efficient, especially in the ring-closing metathesis (RCM) of encumbered diolefins, while syn catalysts showed low efficiency in the RCM of less hindered diolefins. This peculiar behavior, rationalized through DFT studies, was found to be related to the high propensity of these catalysts to give nonproductive metathesis events. Enantiopure anti catalysts were also tested in asymmetric metathesis reactions, where moderate enantioselectivities were observed. The steric and electronic properties of unsymmetrical NHCs with the N-cyclohexyl group were then evaluated using the corresponding rhodium complexes. While steric factors proved unimportant for both syn and anti NHCs, a major electron-donating character was found for the unsymmetrical NHC with anti phenyl substituents on the backbone.

  3. A bis-calixarene from olefin metathesis

    Directory of Open Access Journals (Sweden)

    Shimelis T. Hailu

    2012-06-01

    Full Text Available A ring-closing olefin metathesis reaction of tetrakis(allyloxycalix[4]arene gave the bis calixarene, (15E,40E,60E-65,74-bis(prop-2-en-1-yloxy-13,18,38,43,58,63-hexaoxadodecacyclo[28.26.8.720,36.111,45.151,55.05,57.07,12.019,24.026,64.032,37.044,49.168,72]tetraheptaconta-1,3,5(57,7,9,11,15,19(24,20,22,26,28,30(64,32,34,36,40,44(49,45,47,51,53,55(65,60,68,70,72(74-heptacosaene, C74H68O8. It is a cage formed from two calix[4]arene units joined by butenyl groups at three of the O atoms on the narrow rim. The fourth O atom on each calixarene unit is joined with an allyl group. Each of the calix[4]arene units has a flattened cone conformation in which the allyloxy-substituted aryl group and the opposite aryl group are close together and almost parallel [dihedral angle between planes = 1.09 (11°], and the other two aryl groups are splayed outward [dihedral angle between planes = 79.53 (11°]. No guest molecule (e.g. solvent was observed within the cage. The alkene C atoms of one of the links between the calixarene moieties are disordered over two orientations with occupancies of 0.533 (9 and 0.467 (9.

  4. High performance cyclo olefin polymer ZEONEX

    Science.gov (United States)

    Konishi, Yuichiro; Sawaguchi, Taichi; Kubomura, Kyoichi; Minami, Koji

    2005-09-01

    Zeon Corporation developed quite new optical plastic Cyclo Olefin Polymer; COP(ZEONEX) with own technology in 1990 then started sales for ZEONEX for optical application with its very unique properties such as low birefringence, low water absorption, high glass-transition temperature 136 °C and high light transmission etc. Currently, ZEONEX is well known in optical market and used widely as optical plastic for pick up lens and other many kinds of optical parts for laser beam printer and digital camera. Addition to those ZEONEX grades, in last year, Zeon Corporation developed a new ZEONEX grade called ZEONEX340R, which was designed for blue laser devices requiring more severe specification. ZEONEX340R has high transmission at 405nm which is used laser wavelength for Blu-ray Disk / HD-DVD as well as enough durability under exposure of 405nm laser, addition to those new properties, keeps other optical properties such as low birefringence and very low water absorption.

  5. Spreadsheet Decision Support Model for Training Exercise Material Requirements Planning

    National Research Council Canada - National Science Library

    Tringali, Arthur

    1997-01-01

    This thesis focuses on developing a spreadsheet decision support model that can be used by combat engineer platoon and company commanders in determining the material requirements and estimated costs...

  6. A Generic Modeling Process to Support Functional Fault Model Development

    Science.gov (United States)

    Maul, William A.; Hemminger, Joseph A.; Oostdyk, Rebecca; Bis, Rachael A.

    2016-01-01

    Functional fault models (FFMs) are qualitative representations of a system's failure space that are used to provide a diagnostic of the modeled system. An FFM simulates the failure effect propagation paths within a system between failure modes and observation points. These models contain a significant amount of information about the system including the design, operation and off nominal behavior. The development and verification of the models can be costly in both time and resources. In addition, models depicting similar components can be distinct, both in appearance and function, when created individually, because there are numerous ways of representing the failure space within each component. Generic application of FFMs has the advantages of software code reuse: reduction of time and resources in both development and verification, and a standard set of component models from which future system models can be generated with common appearance and diagnostic performance. This paper outlines the motivation to develop a generic modeling process for FFMs at the component level and the effort to implement that process through modeling conventions and a software tool. The implementation of this generic modeling process within a fault isolation demonstration for NASA's Advanced Ground System Maintenance (AGSM) Integrated Health Management (IHM) project is presented and the impact discussed.

  7. Olefin metathesis for site-selective protein modification.

    Science.gov (United States)

    Lin, Yuya A; Chalker, Justin M; Davis, Benjamin G

    2009-04-17

    For a reaction to be generally useful for protein modification, it must be site-selective and efficient under conditions compatible with proteins: aqueous media, low to ambient temperature, and at or near neutral pH. To engineer a reaction that satisfies these conditions is not a simple task. Olefin metathesis is one of most useful reactions for carbon-carbon bond formation, but does it fit these requirements? This minireview is an account of the development of olefin metathesis for protein modification. Highlighted below are examples of olefin metathesis in peptidic systems and in aqueous media that laid the groundwork for successful metathesis on protein substrates. Also discussed are the opportunities in protein engineering for the genetic introduction of amino acids suitable for metathesis and the related challenges in chemistry and biology.

  8. Ionic liquids for separation of olefin-paraffin mixtures

    Science.gov (United States)

    Dai, Sheng; Luo, Huimin; Huang, Jing-Fang

    2013-09-17

    The invention is directed to an ionic liquid comprising (i) a cationic portion containing a complex of a silver (I) ion and one or more neutral ligands selected from organoamides, organoamines, olefins, and organonitriles, and (ii) an anionic portion having the chemical formula ##STR00001## wherein m and n are independently 0 or an integer of 1 or above, and p is 0 or 1, provided that when p is 0, the group --N--SO.sub.2--(CF.sub.2).sub.nCF.sub.3 subtended by p is replaced with an oxide atom connected to the shown sulfur atom. The invention is also directed to a method for separating an olefin from an olefin-paraffin mixture by passing the mixture through a layer of the ionic liquid described above.

  9. Synthetic and mechanistic aspects of titanium-mediated carbonyl olefinations

    Energy Technology Data Exchange (ETDEWEB)

    Petasis, N.A.; Staszewski, J.P.; Hu, Yong-Han; Lu, Shao-Po [Univ. of Southern California, Los Angeles, CA (United States)

    1995-12-31

    A new method for the olefination of carbonyl compounds with dimethyl titanocene, and other related bishydrocarbyl titanocene derivatives has been recently developed in the author`s laboratories. This process is experimentally convenient and works with various types of carbonyl compounds, including aldehydes, ketones, esters, lactones, carbonates, anhydrides, amides, imides, lactams, thioesters, selenoesters, and acylsilanes. More recent studies have focused on the scope and utility of this reaction, including mechanistic studies and synthetic applications. In addition to varying the reaction conditions, the authors have examined several mixed titanocene derivatives and have found ways for carrying out this type of olefination at room temperature, such as the use of tris(trimethylsilyl) titanacyclobutene. The authors have also employed this reaction in the modification of carbohydrates and cyclobutenediones. This olefination was also followed-up with subsequent transformations to produce carbocycles and heterocycles, including tetrahydrofurans and tetrahydropyrans.

  10. Olefination reactions of phosphorus-stabilized carbon nucleophiles.

    Science.gov (United States)

    Gu, Yonghong; Tian, Shi-Kai

    2012-01-01

    A range of phosphorus-stabilized carbon nucleophiles have been employed for alkene synthesis with high chemo-, regio-, and stereoselectivity. The Wittig, Horner-Wadsworth-Emmons, Horner-Wittig, and Evans-Akiba reactions utilize phosphonium-, phosphonate-, phosphine oxide-, and pentacoordinated phosphorane-stabilized carbanions as nucleophiles, respectively, to undergo olefination with aldehydes or ketones, and each of these transformations has its own advantages and limitations. Modifying the structures of these nucleophiles along with optimizing reaction conditions results in the formation of a wide variety of polysubstituted alkenes in a highly stereoselective manner. The olefination of imines with phosphonium ylides has recently emerged as a useful approach to tune the stereoselectivity for alkene synthesis. This review focuses on recent advances in the stereoselective olefination of phosphorus-stabilized carbon nucleophiles.

  11. Cyberinfrastructure to Support Collaborative and Reproducible Computational Hydrologic Modeling

    Science.gov (United States)

    Goodall, J. L.; Castronova, A. M.; Bandaragoda, C.; Morsy, M. M.; Sadler, J. M.; Essawy, B.; Tarboton, D. G.; Malik, T.; Nijssen, B.; Clark, M. P.; Liu, Y.; Wang, S. W.

    2017-12-01

    Creating cyberinfrastructure to support reproducibility of computational hydrologic models is an important research challenge. Addressing this challenge requires open and reusable code and data with machine and human readable metadata, organized in ways that allow others to replicate results and verify published findings. Specific digital objects that must be tracked for reproducible computational hydrologic modeling include (1) raw initial datasets, (2) data processing scripts used to clean and organize the data, (3) processed model inputs, (4) model results, and (5) the model code with an itemization of all software dependencies and computational requirements. HydroShare is a cyberinfrastructure under active development designed to help users store, share, and publish digital research products in order to improve reproducibility in computational hydrology, with an architecture supporting hydrologic-specific resource metadata. Researchers can upload data required for modeling, add hydrology-specific metadata to these resources, and use the data directly within HydroShare.org for collaborative modeling using tools like CyberGIS, Sciunit-CLI, and JupyterHub that have been integrated with HydroShare to run models using notebooks, Docker containers, and cloud resources. Current research aims to implement the Structure For Unifying Multiple Modeling Alternatives (SUMMA) hydrologic model within HydroShare to support hypothesis-driven hydrologic modeling while also taking advantage of the HydroShare cyberinfrastructure. The goal of this integration is to create the cyberinfrastructure that supports hypothesis-driven model experimentation, education, and training efforts by lowering barriers to entry, reducing the time spent on informatics technology and software development, and supporting collaborative research within and across research groups.

  12. Reviewing model application to support animal health decision making.

    Science.gov (United States)

    Singer, Alexander; Salman, Mo; Thulke, Hans-Hermann

    2011-04-01

    Animal health is of societal importance as it affects human welfare, and anthropogenic interests shape decision making to assure animal health. Scientific advice to support decision making is manifold. Modelling, as one piece of the scientific toolbox, is appreciated for its ability to describe and structure data, to give insight in complex processes and to predict future outcome. In this paper we study the application of scientific modelling to support practical animal health decisions. We reviewed the 35 animal health related scientific opinions adopted by the Animal Health and Animal Welfare Panel of the European Food Safety Authority (EFSA). Thirteen of these documents were based on the application of models. The review took two viewpoints, the decision maker's need and the modeller's approach. In the reviewed material three types of modelling questions were addressed by four specific model types. The correspondence between tasks and models underpinned the importance of the modelling question in triggering the modelling approach. End point quantifications were the dominating request from decision makers, implying that prediction of risk is a major need. However, due to knowledge gaps corresponding modelling studies often shed away from providing exact numbers. Instead, comparative scenario analyses were performed, furthering the understanding of the decision problem and effects of alternative management options. In conclusion, the most adequate scientific support for decision making - including available modelling capacity - might be expected if the required advice is clearly stated. Copyright © 2011 Elsevier B.V. All rights reserved.

  13. Reactivation of a Ruthenium-Based Olefin Metathesis Catalyst

    Science.gov (United States)

    Tabari, Daniel S.; Tolentino, Daniel R.; Schrodi, Yann

    2013-01-01

    1st Generation Hoveyda-Grubbs olefin metathesis catalyst was purposely decomposed in the presence of ethylene yielding inorganic species that are inactive in the ring-closing metathesis (RCM) of benchmark substrate diethyldiallyl malonate (DEDAM). The decomposed catalyst was treated with 1-(3,5-diisopropoxyphenyl)-1-phenylprop-2-yn-1-ol (3) to generate an olefin metathesis active ruthenium indenylidene-ether complex in 43 % yield. This complex was also prepared independently by reacting RuCl2(p-cymene)(PCy3) with organic precursor 3. The activity of the isolated reactivated catalyst in the RCM of DEDAM is similar to that of the independently prepared complex. PMID:23355756

  14. Comparing Ru and Fe-catalyzed olefin metathesis

    KAUST Repository

    Poater, Albert

    2014-01-01

    Density functional theory calculations have been used to explore the potential of Fe-based complexes with an N-heterocyclic carbene ligand, as olefin metathesis catalysts. Apart from a less endothermic reaction energy profile, a small reduction in the predicted upper energy barriers (≈ 2 kcal mol -1) is calculated in the Fe catalyzed profile with respect to the Ru catalysed profile. Overall, this study indicates that Fe-based catalysts have the potential to be very effective olefin metathesis catalysts. This journal is © the Partner Organisations 2014.

  15. Surface-Confined Dynamic Covalent System Driven by Olefin Metathesis.

    Science.gov (United States)

    Liu, Chunhua; Park, Eunsol; Jin, Yinghua; Liu, Jie; Yu, Yanxia; Zhang, Wei; Lei, Shengbin; Hu, Wenping

    2018-02-12

    Understanding how the constitutional dynamics of a dynamic combinatorial library (DCL) adapts to surfaces (compared to bulk solution) is of fundamental importance to the design of adaptive materials. Submolecular resolved scanning tunneling microscopy (STM) can provide detailed insights into olefin metathesis at the interface. Analysis of the distribution of products has revealed the important role of environmental pressure, reaction temperature, and substituent effects in surface-confined olefin metathesis. We also report an unprecedented preferred deposition and assembly of linear polymers, and some specific oligomers, on the surface that are hard to obtain otherwise. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. The activation mechanism of Fe-based olefin metathesis catalysts

    Science.gov (United States)

    Poater, Albert; Pump, Eva; Vummaleti, Sai Vikrama Chaitanya; Cavallo, Luigi

    2014-08-01

    Density functional theory calculations have been used to describe the first turnover for olefin metathesis reaction of a homogenous Fe-based catalyst bearing a N-heterocyclic carbene ligand with methoxyethene as a substrate. Equal to conventional Ru-based catalysts, the activation of its Fe congener occurs through a dissociative mechanism, however with a more exothermic reaction energy profile. Predicted upper energy barriers were calculated to be on average ∼2 kcal/mol more beneficial for Fe catalyzed metathesis. Overall, this present computational study emphasises on advantages of Fe-based metathesis and gives a potential recipe for the design of an efficient Fe-based olefin metathesis catalysts.

  17. Enhanced Olefin Cross Metathesis Reactions: The Copper Iodide Effect

    Science.gov (United States)

    Voigtritter, Karl; Ghorai, Subir

    2011-01-01

    Copper iodide has been shown to be an effective co-catalyst for the olefin cross metathesis reaction. In particular, it has both a catalyst stabilizing effect due to iodide ion, as well as copper(I)-based phosphine-scavenging properties that apply to use of the Grubbs-2 catalyst. A variety of Michael acceptors and olefinic partners can be cross-coupled under mild conditions in refluxing diethyl ether that avoid chlorinated solvents. This effect has also been applied to chemistry in water at room temperature using the new surfactant TPGS-750-M. PMID:21528868

  18. Olefin cross-metathesis for the synthesis of heteroaromatic compounds.

    Science.gov (United States)

    Donohoe, Timothy J; Bower, John F; Chan, Louis K M

    2012-02-21

    The olefin metathesis reaction has underpinned spectacular achievements in organic synthesis in recent years. Arguably, metathesis has now become the foremost choice for a carbon-carbon double bond disconnection. Despite this general utility, de novo routes to heteroaromatic compounds using the cross-metathesis (CM) reaction have only recently emerged as an efficient strategy. This approach allows a convergent union of simple, functionalised, three- to four-carbon olefinic core building blocks, to generate furans, pyrroles and pyridines with a high degree of control of substitution pattern in the product.

  19. Cardanol-Based Materials as Natural Precursors for Olefin Metathesis

    Directory of Open Access Journals (Sweden)

    Giuseppe Vasapollo

    2011-08-01

    Full Text Available Cardanol is a renewable, low cost natural material, widely available as a by-product of the cashew industry. It is a mixture of 3-n-pentadecylphenol, 3-(pentadeca-8-enylphenol, 3-(pentadeca-8,11-dienylphenol and 3-(pentadeca-8,11,14-trienylphenol. Olefin metathesis (OM reaction on cardanol is an important class of reactions that allows for the synthesis of new olefins that are sometime impossible to prepare via other methods. The application of this natural and renewable material to both academic and industrial research will be discussed.

  20. Application of olefin metathesis in the synthesis of steroids.

    Science.gov (United States)

    Morzycki, Jacek W

    2011-01-01

    Over the past decade, ruthenium-mediated metathesis transformations, including cross-metathesis, ring-closing metathesis, enyne metathesis, ring-opening metathesis polymerization, and also tandem processes, belong to the most intensively studied reactions. Many applications of olefin metathesis in the synthesis of natural products have been recently described. Also in the field of steroid chemistry new methods of total synthesis and hemisynthesis based on metathesis reactions have been elaborated. Various biologically active compounds, e.g. vitamin D and hormone analogues, steroid dimers and macrocycles, etc. have been prepared using a variety of olefin-metathesis protocols. Copyright © 2011 Elsevier Inc. All rights reserved.

  1. Methylenation of perfluoroalkyl ketones using a Peterson olefination approach.

    Science.gov (United States)

    Hamlin, Trevor A; Kelly, Christopher B; Cywar, Robin M; Leadbeater, Nicholas E

    2014-02-07

    An operationally simple, inexpensive, and rapid route for the olefination of a wide array of trifluoromethyl ketones to yield 3,3,3-trifluoromethylpropenes is reported. Using a Peterson olefination approach, the reaction gives good to excellent yields of the alkene products and can be performed without purification of the β-hydroxysilyl intermediate. The reaction can be extended to other perfluoroalkyl substituents and is easily scaled up. The alkenes prepared can be readily transformed into a variety of other perfluoroalkyl-containing compounds.

  2. Silver-Catalyzed Aldehyde Olefination Using Siloxy Alkynes.

    Science.gov (United States)

    Sun, Jianwei; Keller, Valerie A; Meyer, S Todd; Kozmin, Sergey A

    2010-03-20

    We describe the development of a silver-catalyzed carbonyl olefination employing electron rich siloxy alkynes. This process constitutes an efficient synthesis of trisubstituted unsaturated esters, and represents an alternative to the widely utilized Horner-Wadsworth-Emmons reaction. Excellent diastereoselectivities are observed for a range of aldehydes using either 1-siloxy-1-propyne or 1-siloxy-1-hexyne. This mild catalytic process also enables chemoselective olefination of aldehydes in the presence of either ester or ketone functionality. Furthermore, since no by-products are generated, this catalytic process is perfectly suited for development of sequential reactions that can be carried out in a single flask.

  3. Model based decision support for planning of road maintenance

    NARCIS (Netherlands)

    van Harten, Aart; Worm, J.M.; Worm, J.M.

    1996-01-01

    In this article we describe a Decision Support Model, based on Operational Research methods, for the multi-period planning of maintenance of bituminous pavements. This model is a tool for the road manager to assist in generating an optimal maintenance plan for a road. Optimal means: minimising the

  4. Integrating Collaborative and Decentralized Models to Support Ubiquitous Learning

    Science.gov (United States)

    Barbosa, Jorge Luis Victória; Barbosa, Débora Nice Ferrari; Rigo, Sandro José; de Oliveira, Jezer Machado; Rabello, Solon Andrade, Jr.

    2014-01-01

    The application of ubiquitous technologies in the improvement of education strategies is called Ubiquitous Learning. This article proposes the integration between two models dedicated to support ubiquitous learning environments, called Global and CoolEdu. CoolEdu is a generic collaboration model for decentralized environments. Global is an…

  5. [Model transfer method based on support vector machine].

    Science.gov (United States)

    Xiong, Yu-hong; Wen, Zhi-yu; Liang, Yu-qian; Chen, Qin; Zhang, Bo; Liu, Yu; Xiang, Xian-yi

    2007-01-01

    The model transfer is a basic method to build up universal and comparable performance of spectrometer data by seeking a mathematical transformation relation among different spectrometers. Because of nonlinear effect and small calibration sample set in fact, it is important to solve the problem of model transfer under the condition of nonlinear effect in evidence and small sample set. This paper summarizes support vector machines theory, puts forward the method of model transfer based on support vector machine and piecewise direct standardization, and makes use of computer simulation method, giving a example to explain the method and compare it with artificial neural network in the end.

  6. Multiple Olefin Metathesis Polymerization That Combines All Three Olefin Metathesis Transformations: Ring-Opening, Ring-Closing, and Cross Metathesis.

    Science.gov (United States)

    Lee, Ho-Keun; Bang, Ki-Taek; Hess, Andreas; Grubbs, Robert H; Choi, Tae-Lim

    2015-07-29

    We demonstrated tandem ring-opening/ring-closing metathesis (RO/RCM) polymerization of monomers containing two cyclopentene moieties and postmodification via insertion polymerization. In this system, well-defined polymers were efficiently formed by tandem cascade RO/RCM reaction pathway. Furthermore, these polymers could be transformed to new A,B-alternating copolymers via a sequential cross metathesis reaction with a diacrylate. Additionally, we demonstrated the concept of multiple olefin metathesis polymerization in which the dicyclopentene and diacrylate monomers underwent all three olefin metathesis transformations (ring-opening, ring-closing, and cross metathesis) in one shot to produce A,B-alternating copolymer.

  7. P(O)R2-Directed Enantioselective C-H Olefination toward Chiral Atropoisomeric Phosphine-Olefin Compounds.

    Science.gov (United States)

    Li, Shi-Xia; Ma, Yan-Na; Yang, Shang-Dong

    2017-04-07

    An effective synthesis of chiral atropoisomeric biaryl phosphine-olefin compounds via palladium-catalyzed enantioselective C-H olefination has been developed for the first time. The reactions are operationally simple, tolerate wide functional groups, and have a good ee value. Notably, P(O)R 2 not only acts as the directing group to direct C-H activation in order to make a useful ligand but also serves to facilitate composition of the product in a useful manner in this transformation.

  8. Alkane metathesis by tandem alkane-dehydrogenation-olefin-metathesis catalysis and related chemistry.

    Science.gov (United States)

    Haibach, Michael C; Kundu, Sabuj; Brookhart, Maurice; Goldman, Alan S

    2012-06-19

    stable solid metal oxides as the olefin-metathesis catalysts. Both the pincer complexes and the alkylidene complexes have been supported on alumina via adsorption through basic para-substituents. This process does not significantly affect catalyst activity, and in some cases it increases both the catalyst lifetime and the compatibility of the co-catalysts. These molecular catalysts are the first systems that effect alkane metathesis with molecular-weight selectivity, particularly for the conversion of C(n)n-alkanes to C(2n-2)n-alkanes plus ethane. This molecular-weight selectivity offers a critical advantage over the few previously reported alkane metathesis systems. We have studied the factors that determine molecular-weight selectivity in depth, including the isomerization of the olefinic intermediates and the regioselectivity of the pincer-iridium catalyst for dehydrogenation at the terminal position of the n-alkane. Our continuing work centers on the development of co-catalysts with improved interoperability, particularly olefin-metathesis catalysts that are more robust at high temperature and dehydrogenation catalysts that are more active at low temperature. We are also designing dehydrogenation catalysts based on metals other than iridium. Our ongoing mechanistic studies are focused on the apparently complex combination of factors that determine molecular-weight selectivity.

  9. Prioritization of engineering support requests and advanced technology projects using decision support and industrial engineering models

    Science.gov (United States)

    Tavana, Madjid

    1995-01-01

    The evaluation and prioritization of Engineering Support Requests (ESR's) is a particularly difficult task at the Kennedy Space Center (KSC) -- Shuttle Project Engineering Office. This difficulty is due to the complexities inherent in the evaluation process and the lack of structured information. The evaluation process must consider a multitude of relevant pieces of information concerning Safety, Supportability, O&M Cost Savings, Process Enhancement, Reliability, and Implementation. Various analytical and normative models developed over the past have helped decision makers at KSC utilize large volumes of information in the evaluation of ESR's. The purpose of this project is to build on the existing methodologies and develop a multiple criteria decision support system that captures the decision maker's beliefs through a series of sequential, rational, and analytical processes. The model utilizes the Analytic Hierarchy Process (AHP), subjective probabilities, the entropy concept, and Maximize Agreement Heuristic (MAH) to enhance the decision maker's intuition in evaluating a set of ESR's.

  10. Model Checking for Licensing Support in the Finnish Nuclear Industry

    Energy Technology Data Exchange (ETDEWEB)

    Antti, Pakonen; Janne, Valkonen [VTT Technical Research, VTT (Finland); Sami, Matinaho; Markus, Hartikainen [Protum Power and Heat, Fortum (Finland)

    2014-08-15

    This paper examines how model checking can be used to support the qualification of digital I and C software in nuclear power plants, in a way that is consistent with regulatory demands specifically, the common position of seven European nuclear regulators and authorised technical support organisations. As a practical example, we discuss the third-party review service provided by VTT for the power company Fortum in the I and C renewal project of the Loviisa plant in southern Finland.

  11. "SERPS Up": Support, Engagement and Retention of Postgraduate Students--A Model of Postgraduate Support

    Science.gov (United States)

    Alston, Margaret; Allan, Julaine; Bell, Karen; Brown, Andy; Dowling, Jane; Hamilton, Pat; McKinnon, Jenny; McKinnon, Noela; Mitchell, Rol; Whittenbury, Kerri; Valentine, Bruce; Wicks, Alison; Williams, Rachael

    2005-01-01

    The federal government's 1999 White Paper Knowledge and Innovation: a policy statement on research and research training, notes concerns about retention and completion rates in doctoral studies programs in Australia. This paper outlines a model of higher education support developed at the Centre for Rural Social Research at Charles Sturt…

  12. Design Approaches to Support Preservice Teachers in Scientific Modeling

    Science.gov (United States)

    Kenyon, Lisa; Davis, Elizabeth A.; Hug, Barbara

    2011-02-01

    Engaging children in scientific practices is hard for beginning teachers. One such scientific practice with which beginning teachers may have limited experience is scientific modeling. We have iteratively designed preservice teacher learning experiences and materials intended to help teachers achieve learning goals associated with scientific modeling. Our work has taken place across multiple years at three university sites, with preservice teachers focused on early childhood, elementary, and middle school teaching. Based on results from our empirical studies supporting these design decisions, we discuss design features of our modeling instruction in each iteration. Our results suggest some successes in supporting preservice teachers in engaging students in modeling practice. We propose design principles that can guide science teacher educators in incorporating modeling in teacher education.

  13. Effective Team Support: From Modeling to Software Agents

    Science.gov (United States)

    Remington, Roger W. (Technical Monitor); John, Bonnie; Sycara, Katia

    2003-01-01

    The purpose of this research contract was to perform multidisciplinary research between CMU psychologists, computer scientists and engineers and NASA researchers to design a next generation collaborative system to support a team of human experts and intelligent agents. To achieve robust performance enhancement of such a system, we had proposed to perform task and cognitive modeling to thoroughly understand the impact technology makes on the organization and on key individual personnel. Guided by cognitively-inspired requirements, we would then develop software agents that support the human team in decision making, information filtering, information distribution and integration to enhance team situational awareness. During the period covered by this final report, we made substantial progress in modeling infrastructure and task infrastructure. Work is continuing under a different contract to complete empirical data collection, cognitive modeling, and the building of software agents to support the teams task.

  14. Mesoporous Molecular Sieves Based Catalysts for Olefin Metathesis and Metathesis Polymerization

    Science.gov (United States)

    Balcar, Hynek; Čejka, Jiří

    Heterogeneous catalysts for olefin metathesis using different types of (i) siliceous mesoporous molecular sieves, and (ii) organized mesoporous alumina as supports are reported. The catalysts were prepared either by spreading of transition metal oxidic phase on the support surface or by immobilizing transition metal compounds (mostly organometallic) on the support. The activity of these catalysts in various types of metathesis reactions (i.e. alkene and diene metathesis, metathesis of unsaturated esters and ethers, RCM, ROMP and metathesis polymerization of alkynes) was described. The main advantages of these catalysts consist generally in their high activity and selectivity, easy separation of catalysts from reaction products and the preparation of products free of catalyst residue. The examples of pore size influence on the selectivity in metathesis reactions are also given.

  15. Ru complexes of Hoveyda-Grubbs type immobilized on lamellar zeolites: activity in olefin metathesis reactions.

    Science.gov (United States)

    Balcar, Hynek; Žilková, Naděžda; Kubů, Martin; Mazur, Michal; Bastl, Zdeněk; Čejka, Jiří

    2015-01-01

    Hoveyda-Grubbs type catalysts with cationic tags on NHC ligands were linker-free immobilized on the surface of lamellar zeolitic supports (MCM-22, MCM-56, MCM-36) and on mesoporous molecular sieves SBA-15. The activity of prepared hybrid catalysts was tested in olefin metathesis reactions: the activity in ring-closing metathesis of citronellene and N,N-diallyltrifluoroacetamide decreased in the order of support MCM-22 ≈ MCM-56 > SBA-15 > MCM-36; the hybrid catalyst based on SBA-15 was found the most active in self-metathesis of methyl oleate. All catalysts were reusable and exhibited low Ru leaching (<1% of Ru content). XPS analysis revealed that during immobilization ion exchange between Hoveyda-Grubbs type catalyst and zeolitic support occurred in the case of Cl(-) counter anion; in contrast, PF6 (-) counter anion underwent partial decomposition.

  16. Factors influencing ring closure through olefin metathesis-A ...

    Indian Academy of Sciences (India)

    Success of ring closure reactions of substrates having two terminal alkenes through olefin metathesis depends on a number of factors such as catalysts, nature and size of the rings to be formed and the substituents/functional groups present on the alkenes as well as at the allylic position. This article presents an overview of ...

  17. Olefin metathesis in Brazil: Brazil is romping it!

    International Nuclear Information System (INIS)

    Matos, Jose Milton E.; Batista, Nouga C.; Carvalho, Rogerio M.; Santana, Sirlane A. A.; Puzzi, Paula N.; Sanches, Mario; Lima-Neto, Benedito S.

    2007-01-01

    Some aspects of the olefin metathesis reactions are summarized here (types of reactions, mechanism and catalysts). In particular, the research groups that have been working on this chemistry in Brazil are presented. The main goal of this paper is to make this type of reaction more widely known in the Brazilian chemical community. (author)

  18. Ruthenium-based four-coordinate olefin metathesis catalysts

    International Nuclear Information System (INIS)

    Sanford, M.S.; Henling, L.M.; Day, M.W.; Grubbs, R.H.

    2000-01-01

    A series of four-coordinate Ru II alkylidenes has been prepared as analogues of the proposed olefin metathesis intermediate [(PCy 3 )Cl 2 Ru=CHPh]. These complexes exhibit unusual trigonal-pyramidal solid-state geometries, and are rendered highly active for ring-closing metathesis by the addition of HCl. (orig.)

  19. Halide exchanged Hoveyda-type complexes in olefin metathesis

    Directory of Open Access Journals (Sweden)

    Julia Wappel

    2010-11-01

    Full Text Available The aims of this contribution are to present a straightforward synthesis of 2nd generation Hoveyda-type olefin metathesis catalysts bearing bromo and iodo ligands, and to disclose the subtle influence of the different anionic co-ligands on the catalytic performance of the complexes in ring opening metathesis polymerisation, ring closing metathesis, enyne cycloisomerisation and cross metathesis reactions.

  20. Halide exchanged Hoveyda-type complexes in olefin metathesis

    Science.gov (United States)

    Wappel, Julia; Urbina-Blanco, César A; Abbas, Mudassar; Albering, Jörg H; Saf, Robert; Nolan, Steven P

    2010-01-01

    Summary The aims of this contribution are to present a straightforward synthesis of 2nd generation Hoveyda-type olefin metathesis catalysts bearing bromo and iodo ligands, and to disclose the subtle influence of the different anionic co-ligands on the catalytic performance of the complexes in ring opening metathesis polymerisation, ring closing metathesis, enyne cycloisomerisation and cross metathesis reactions. PMID:21160566

  1. Ruthenium-based four-coordinate olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Sanford, M.S.; Henling, L.M.; Day, M.W.; Grubbs, R.H. [California Inst. of Tech., Pasadena (United States). Div. of Chemistry and Chemical Engineering

    2000-10-02

    A series of four-coordinate Ru{sup II} alkylidenes has been prepared as analogues of the proposed olefin metathesis intermediate [(PCy{sub 3})Cl{sub 2}Ru=CHPh]. These complexes exhibit unusual trigonal-pyramidal solid-state geometries, and are rendered highly active for ring-closing metathesis by the addition of HCl. (orig.)

  2. Bio-olefins from unsaturated fatty acids via tandem catalysis

    Science.gov (United States)

    A new catalytic route to bio-olefins from unsaturated fatty acids will be described. At the heart of the process, the catalyst apparently functions in a tandem mode by both dynamically isomerizing the positions of double bonds in an aliphatic chain and, subsequently, decarboxylating specific isomers...

  3. Capturing of the monoterpene olefin limonene produced in Saccharomyces cerevisiae

    NARCIS (Netherlands)

    Jongedijk, E.J.; Cankar, K.; Ranzijn, J.; Krol, van der A.R.; Bouwmeester, H.J.; Beekwilder, M.J.

    2015-01-01

    Monoterpene olefins such as limonene are plant compounds with applications as flavouring and fragrance agents, as solvents and potentially also in polymer and fuel chemistry. We engineered baker's yeast Saccharomyces cerevisiae to express a (-)-limonene synthase from Perilla frutescens and a

  4. Sterically shielded diboron-containing metallocene olefin polymerization catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Marks, T.J.; Ja, L.; Yang, X.

    1995-09-05

    A non-coordinating anion, preferably containing a sterically shielded diboron hydride, if combined with a cyclopenta-dienyl-substituted metallocene cation component, such as a zirconocene metallocene, is a useful olefin polymerization catalyst component. The anion preferably has the formula as shown in the accompanying diagram where R is branched lower alkyl, such as t-butyl.

  5. Sterically shielded diboron-containing metallocene olefin polymerization catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Marks, Tobin J. (Evanston, IL); Ja, Li (Chicago, IL); Yang, Xinmin (Evanston, IL)

    1995-09-05

    A non-coordinating anion, preferably containing a sterically shielded diboron hydride, if combined with a cyclopenta-dienyl-substituted metallocene cation component, such as a zirconocene metallocene, is a useful olefin polymerization catalyst component. The anion preferably has the formula ##STR1## where R is branched lower alkyl, such as t-butyl.

  6. Radiation-induced copolymerization of hexafluoroacetone with α-olefins

    International Nuclear Information System (INIS)

    Matsuda, O.; Watanabe, S.; Okamoto, J.; Machi, S.; Tabata, Y.

    1977-01-01

    The copolymerization of hexafluoroacetone with higher α-olefins above butene, such as 1-pentene (I), 1-hexene (II), 1-octene (III), 2-methyl-1-butene (IV), 2-methyl-1-pentene (V), 3-methyl-1-butene (VI), and 4-methyl-1-pentene (VII) was studied at relatively low temperatures by γ-ray irradiation. Copolymerization of II, IV, V, and VII with hexafluoroacetone was found to scarcely take place at -78 0 C in bulk, but the addition of trichlorotrifluoroethane in amounts to yield equimolar mixtures resulted in conversion of 15.7 percent for IV and of 2.1 to 4.0 percent for the other α-olefins. Higher conversion of V at -78 0 C than at 0 0 C suggest that copolymerization may take place via an ionic mechanism. The effects of various additives on the copolymerization are reported. Infrared spectral studies indicated that the double bond of the α-olefins is opened to form a polymer. The C--O double bond of the hexafluoroacetone and the α-olefin double bond are opened to form the copolymer

  7. Optical fibre Bragg grating recorded in TOPAS cyclic olefin copolymer

    DEFF Research Database (Denmark)

    Johnson, I.P.; Yuan, Scott Wu; Stefani, Alessio

    2011-01-01

    A report is presented on the inscription of a fibre Bragg grating into a microstructured polymer optical fibre fabricated from TOPAS cyclic olefin copolymer. This material offers two important advantages over poly (methyl methacrylate), which up to now has formed the basis for polymer fibre Bragg...

  8. Olefination of carbonyl compounds: modern and classical methods

    Energy Technology Data Exchange (ETDEWEB)

    Korotchenko, V N; Nenajdenko, Valentine G; Balenkova, Elizabeth S [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation); Shastin, Aleksey V [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2004-10-31

    The published data on the methods for alkene synthesis by olefination of carbonyl compounds are generalised and systematised. The main attention is given to the use of transition metals and organoelement compounds. The review covers the data on both classical and newly developed methods that are little known to chemists at large.

  9. Manganese Catalyzed α-Olefination of Nitriles by Primary Alcohols.

    Science.gov (United States)

    Chakraborty, Subrata; Das, Uttam Kumar; Ben-David, Yehoshoa; Milstein, David

    2017-08-30

    Catalytic α-olefination of nitriles using primary alcohols, via dehydrogenative coupling of alcohols with nitriles, is presented. The reaction is catalyzed by a pincer complex of an earth-abundant metal (manganese), in the absence of any additives, base, or hydrogen acceptor, liberating dihydrogen and water as the only byproducts.

  10. Olefination of carbonyl compounds: modern and classical methods

    Science.gov (United States)

    Korotchenko, V. N.; Nenajdenko, Valentine G.; Balenkova, Elizabeth S.; Shastin, Aleksey V.

    2004-10-01

    The published data on the methods for alkene synthesis by olefination of carbonyl compounds are generalised and systematised. The main attention is given to the use of transition metals and organoelement compounds. The review covers the data on both classical and newly developed methods that are little known to chemists at large.

  11. Access to Functionalized Steroid Side Chains via Modified Julia Olefination

    Science.gov (United States)

    Izgu, Enver Cagri; Burns, Aaron C.; Hoye, Thomas R.

    2011-01-01

    Various functionalized steroidal side chains were conveniently accessed by a modified Julia olefination strategy using a common sulfone donor and an appropriate α-branched aldehyde acceptor. For the coupling of these hindered classes of reaction partners (and in contrast to typically observed trends), the benzothiazolyl(BT)-sulfone anion gave superior outcomes compared to the phenyltetrazolyl(PT)-sulfone anion. PMID:21244047

  12. Internal Models Support Specific Gaits in Orthotic Devices

    DEFF Research Database (Denmark)

    Matthias Braun, Jan; Wörgötter, Florentin; Manoonpong, Poramate

    2014-01-01

    such limitations is to supply the patient—via the orthosis—with situation-dependent gait models. To achieve this, we present a method for gait recognition using model invalidation. We show that these models are capable to predict the individual patient's movements and supply the correct gait. We investigate...... the system's accuracy and robustness on a Knee-Ankle-Foot-Orthosis, introducing behaviour changes depending on the patient's current walking situation. We conclude that the here presented model-based support of different gaits has the power to enhance the patient's mobility....

  13. Visualisation and interpretation of Support Vector Regression models.

    Science.gov (United States)

    Ustün, B; Melssen, W J; Buydens, L M C

    2007-07-09

    This paper introduces a technique to visualise the information content of the kernel matrix and a way to interpret the ingredients of the Support Vector Regression (SVR) model. Recently, the use of Support Vector Machines (SVM) for solving classification (SVC) and regression (SVR) problems has increased substantially in the field of chemistry and chemometrics. This is mainly due to its high generalisation performance and its ability to model non-linear relationships in a unique and global manner. Modeling of non-linear relationships will be enabled by applying a kernel function. The kernel function transforms the input data, usually non-linearly related to the associated output property, into a high dimensional feature space where the non-linear relationship can be represented in a linear form. Usually, SVMs are applied as a black box technique. Hence, the model cannot be interpreted like, e.g., Partial Least Squares (PLS). For example, the PLS scores and loadings make it possible to visualise and understand the driving force behind the optimal PLS machinery. In this study, we have investigated the possibilities to visualise and interpret the SVM model. Here, we exclusively have focused on Support Vector Regression to demonstrate these visualisation and interpretation techniques. Our observations show that we are now able to turn a SVR black box model into a transparent and interpretable regression modeling technique.

  14. Applications of system dynamics modelling to support health policy.

    Science.gov (United States)

    Atkinson, Jo-An M; Wells, Robert; Page, Andrew; Dominello, Amanda; Haines, Mary; Wilson, Andrew

    2015-07-09

    The value of systems science modelling methods in the health sector is increasingly being recognised. Of particular promise is the potential of these methods to improve operational aspects of healthcare capacity and delivery, analyse policy options for health system reform and guide investments to address complex public health problems. Because it lends itself to a participatory approach, system dynamics modelling has been a particularly appealing method that aims to align stakeholder understanding of the underlying causes of a problem and achieve consensus for action. The aim of this review is to determine the effectiveness of system dynamics modelling for health policy, and explore the range and nature of its application. A systematic search was conducted to identify articles published up to April 2015 from the PubMed, Web of Knowledge, Embase, ScienceDirect and Google Scholar databases. The grey literature was also searched. Papers eligible for inclusion were those that described applications of system dynamics modelling to support health policy at any level of government. Six papers were identified, comprising eight case studies of the application of system dynamics modelling to support health policy. No analytic studies were found that examined the effectiveness of this type of modelling. Only three examples engaged multidisciplinary stakeholders in collective model building. Stakeholder participation in model building reportedly facilitated development of a common 'mental map' of the health problem, resulting in consensus about optimal policy strategy and garnering support for collaborative action. The paucity of relevant papers indicates that, although the volume of descriptive literature advocating the value of system dynamics modelling is considerable, its practical application to inform health policy making is yet to be routinely applied and rigorously evaluated. Advances in software are allowing the participatory model building approach to be extended to

  15. Fracture network modeling and GoldSim simulation support

    International Nuclear Information System (INIS)

    Sugita, Kenichiro; Dershowitz, William

    2004-01-01

    During Heisei-15, Golder Associates provided support for JNC Tokai through discrete fracture network data analysis and simulation of the MIU Underground Rock Laboratory, participation in Task 6 of the Aespoe Task Force on Modelling of Groundwater Flow and Transport, and development of methodologies for analysis of repository site characterization strategies and safety assessment. MIU Underground Rock Laboratory support during H-15 involved development of new discrete fracture network (DFN) models for the MIU Shoba-sama Site, in the region of shaft development. Golder developed three DFN models for the site using discrete fracture network, equivalent porous medium (EPM), and nested DFN/EPM approaches. Each of these models were compared based upon criteria established for the multiple modeling project (MMP). Golder supported JNC participation in Task 6AB, 6D and 6E of the Aespoe Task Force on Modelling of Groundwater Flow and Transport during H-15. For Task 6AB, Golder implemented an updated microstructural model in GoldSim, and used this updated model to simulate the propagation of uncertainty from experimental to safety assessment time scales, for 5 m scale transport path lengths. Task 6D and 6E compared safety assessment (PA) and experimental time scale simulations in a 200 m scale discrete fracture network. For Task 6D, Golder implemented a DFN model using FracMan/PA Works, and determined the sensitivity of solute transport to a range of material property and geometric assumptions. For Task 6E, Golder carried out demonstration FracMan/PA Works transport calculations at a 1 million year time scale, to ensure that task specifications are realistic. The majority of work for Task 6E will be carried out during H-16. During H-15, Golder supported JNC's Total System Performance Assessment (TSPO) strategy by developing technologies for the analysis of precipitant concentration. These approaches were based on the GoldSim precipitant data management features, and were

  16. Fracture network modeling and GoldSim simulation support

    International Nuclear Information System (INIS)

    Sugita, Kenichiro; Dershowitz, William

    2003-01-01

    During Heisei-14, Golder Associates provided support for JNC Tokai through data analysis and simulation of the MIU Underground Rock Laboratory, participation in Task 6 of the Aespoe Task Force on Modelling of Groundwater Flow and Transport, and analysis of repository safety assessment technologies including cell networks for evaluation of the disturbed rock zone (DRZ) and total systems performance assessment (TSPA). MIU Underground Rock Laboratory support during H-14 involved discrete fracture network (DFN) modelling in support of the Multiple Modelling Project (MMP) and the Long Term Pumping Test (LPT). Golder developed updated DFN models for the MIU site, reflecting updated analyses of fracture data. Golder also developed scripts to support JNC simulations of flow and transport pathways within the MMP. Golder supported JNC participation in Task 6 of the Aespoe Task Force on Modelling of Groundwater Flow and Transport during H-14. Task 6A and 6B compared safety assessment (PA) and experimental time scale simulations along a pipe transport pathway. Task 6B2 extended Task 6B simulations from 1-D to 2-D. For Task 6B2, Golder carried out single fracture transport simulations on a wide variety of generic heterogeneous 2D fractures using both experimental and safety assessment boundary conditions. The heterogeneous 2D fractures were implemented according to a variety of in plane heterogeneity patterns. Multiple immobile zones were considered including stagnant zones, infillings, altered wall rock, and intact rock. During H-14, JNC carried out extensive studies of the distributed rock zone (DRZ) surrounding repository tunnels and drifts. Golder supported this activity be evaluating the calculation time necessary for simulating a reference heterogeneous DRZ cell network for a range of computational strategies. To support the development of JNC's total system performance assessment (TSPA) strategy, Golder carried out a review of the US DOE Yucca Mountain Project TSPA. This

  17. Fracture network modeling and GoldSim simulation support

    International Nuclear Information System (INIS)

    Sugita, Kenichirou; Dershowitz, W.

    2005-01-01

    During Heisei-16, Golder Associates provided support for JNC Tokai through discrete fracture network data analysis and simulation of the Mizunami Underground Research Laboratory (MIU), participation in Task 6 of the AEspoe Task Force on Modeling of Groundwater Flow and Transport, and development of methodologies for analysis of repository site characterization strategies and safety assessment. MIU support during H-16 involved updating the H-15 FracMan discrete fracture network (DFN) models for the MIU shaft region, and developing improved simulation procedures. Updates to the conceptual model included incorporation of 'Step2' (2004) versions of the deterministic structures, and revision of background fractures to be consistent with conductive structure data from the DH-2 borehole. Golder developed improved simulation procedures for these models through the use of hybrid discrete fracture network (DFN), equivalent porous medium (EPM), and nested DFN/EPM approaches. For each of these models, procedures were documented for the entire modeling process including model implementation, MMP simulation, and shaft grouting simulation. Golder supported JNC participation in Task 6AB, 6D and 6E of the AEspoe Task Force on Modeling of Groundwater Flow and Transport during H-16. For Task 6AB, Golder developed a new technique to evaluate the role of grout in performance assessment time-scale transport. For Task 6D, Golder submitted a report of H-15 simulations to SKB. For Task 6E, Golder carried out safety assessment time-scale simulations at the block scale, using the Laplace Transform Galerkin method. During H-16, Golder supported JNC's Total System Performance Assessment (TSPA) strategy by developing technologies for the analysis of the use site characterization data in safety assessment. This approach will aid in the understanding of the use of site characterization to progressively reduce site characterization uncertainty. (author)

  18. Olefin cross-metathesis as a source of polysaccharide derivatives: cellulose ω-carboxyalkanoates.

    Science.gov (United States)

    Meng, Xiangtao; Matson, John B; Edgar, Kevin J

    2014-01-13

    Cross-metathesis has been shown for the first time to be a useful method for the synthesis of polysaccharide derivatives, focusing herein on preparation of cellulose ω-carboxyalkanoates. Commercially available cellulose esters were first acylated with 10-undecenoyl chloride, providing esters with olefin-terminated side chains. Subsequent cross-metathesis of these terminal olefin moieties with acrylic acid was performed in solvents including acrylic acid, THF, and CH2Cl2. Complete conversion to discrete, soluble cross-metathesis products was achieved by using the Hoveyda-Grubbs second generation ruthenium catalyst and an excess of acrylic acid. Oligomerization during storage, caused by a free radical mechanism, was observed and successfully suppressed by the addition of a free radical scavenger (BHT). Furthermore, the cross-metathesis products exhibited glass transition temperatures (Tg) that were at least 50 °C higher than ambient temperature, supporting the potential for application of these polymers as amorphous solid dispersion matrices for enhancing drug aqueous solubility.

  19. Resonant infrared pulsed laser deposition of cyclic olefin copolymer films

    Science.gov (United States)

    Singaravelu, S.; Klopf, J. M.; Schriver, K. E.; Park, H. K.; Kelley, M. J.; Haglund, R. F.

    2014-03-01

    Barrier materials on thin-film organic optoelectronic devices inhibit the uptake of water, oxygen, or environmental contaminants, and fabricating them is a major challenge. By definition, these barrier layers must be insoluble, so the usual routes to polymer- or organic-film deposition by spin coating are not problematic. In this paper, we report comparative studies of pulsed laser deposition of cyclic olefin copolymer (COC), an excellent moisture barrier and a model system for a larger class of protective materials that are potentially useful in organic electronic devices, such as organic light-emitting diodes (OLEDs). Thin films of COC were deposited by resonant and nonresonant infrared pulsed laser ablation of solid COC targets, using a free-electron laser tuned to the 3.43 μm C-H stretch of the COC, and a high-intensity nanosecond Q-switched laser operated at 1064 nm. The ablation craters and deposited films were characterized by scanning-electron microscopy, Fourier-transform infrared spectrometry, atomic-force microscopy, high-resolution optical microscopy, and surface profilometry. Thermal-diffusion calculations were performed to determine the temperature rise induced in the film at the C-H resonant wavelength. The results show that resonant infrared pulsed laser deposition (RIR-PLD) is an effective, low-temperature thin-film deposition technique that leads to evaporation and deposition of intact molecules in homogeneous, smooth films. Nonresonant PLD, on the other hand, leads to photothermal damage, degradation of the COC polymers, and to the deposition only of particulates.

  20. A telepsychiatry model to support psychiatric outreach in the public ...

    African Journals Online (AJOL)

    A telepsychiatry model to support psychiatric outreach in the public sector in South Africa. J Chipps, S Ramlall, M Mars. Abstract. The access of rural Mental Health Care Users in South Africa to specialist psychiatrists and quality mental health care is currently sub-optimal. Health professionals and planners working in ...

  1. Fracture Network Modeling and GoldSim Simulation Support

    OpenAIRE

    杉田 健一郎; Dershowiz, W.

    2003-01-01

    During Heisei-14, Golder Associates provided support for JNC Tokai through data analysis and simulation of the MIU Underground Rock Laboratory, participation in Task 6 of the Aspo Task Force on Modelling of Groundwater Flow and Transport, and analysis of repository safety assessment technologies including cell networks for evaluation of the disturbed rock zone (DRZ) and total systems performance assessment (TSPA).

  2. Making Risk Models Operational for Situational Awareness and Decision Support

    International Nuclear Information System (INIS)

    Paulson, P.R.; Coles, G.; Shoemaker, S.

    2012-01-01

    We present CARIM, a decision support tool to aid in the evaluation of plans for converting control systems to digital instruments. The model provides the capability to optimize planning and resource allocation to reduce risk from multiple safety and economic perspectives. (author)

  3. Supporting Sophomore Success through a New Learning Community Model

    Science.gov (United States)

    Virtue, Emily E.; Wells, Gayle; Virtue, Andrew D.

    2013-01-01

    The creation of a Sophomore Learning Community (SLC) model can help address concerns about the "sophomore slump" and sophomore attrition. While managing the logistics of a sophomore LC can be difficult, with proper faculty, staff, and administrative support, positive results can be produced. This article outlines the need for Sophomore…

  4. Supporting universal prevention programs: a two-phased coaching model.

    Science.gov (United States)

    Becker, Kimberly D; Darney, Dana; Domitrovich, Celene; Keperling, Jennifer Pitchford; Ialongo, Nicholas S

    2013-06-01

    Schools are adopting evidence-based programs designed to enhance students' emotional and behavioral competencies at increasing rates (Hemmeter et al. in Early Child Res Q 26:96-109, 2011). At the same time, teachers express the need for increased support surrounding implementation of these evidence-based programs (Carter and Van Norman in Early Child Educ 38:279-288, 2010). Ongoing professional development in the form of coaching may enhance teacher skills and implementation (Noell et al. in School Psychol Rev 34:87-106, 2005; Stormont et al. 2012). There exists a need for a coaching model that can be applied to a variety of teacher skill levels and one that guides coach decision-making about how best to support teachers. This article provides a detailed account of a two-phased coaching model with empirical support developed and tested with coaches and teachers in urban schools (Becker et al. 2013). In the initial universal coaching phase, all teachers receive the same coaching elements regardless of their skill level. Then, in the tailored coaching phase, coaching varies according to the strengths and needs of each teacher. Specifically, more intensive coaching strategies are used only with teachers who need additional coaching supports, whereas other teachers receive just enough support to consolidate and maintain their strong implementation. Examples of how coaches used the two-phased coaching model when working with teachers who were implementing two universal prevention programs (i.e., the PATHS curriculum and PAX Good Behavior Game [PAX GBG]) provide illustrations of the application of this model. The potential reach of this coaching model extends to other school-based programs as well as other settings in which coaches partner with interventionists to implement evidence-based programs.

  5. Evaluation of atmospheric dispersion/consequence models supporting safety analysis

    International Nuclear Information System (INIS)

    O'Kula, K.R.; Lazaro, M.A.; Woodard, K.

    1996-01-01

    Two DOE Working Groups have completed evaluation of accident phenomenology and consequence methodologies used to support DOE facility safety documentation. The independent evaluations each concluded that no one computer model adequately addresses all accident and atmospheric release conditions. MACCS2, MATHEW/ADPIC, TRAC RA/HA, and COSYMA are adequate for most radiological dispersion and consequence needs. ALOHA, DEGADIS, HGSYSTEM, TSCREEN, and SLAB are recommended for chemical dispersion and consequence applications. Additional work is suggested, principally in evaluation of new models, targeting certain models for continued development, training, and establishing a Web page for guidance to safety analysts

  6. Coal demand prediction based on a support vector machine model

    Energy Technology Data Exchange (ETDEWEB)

    Jia, Cun-liang; Wu, Hai-shan; Gong, Dun-wei [China University of Mining & Technology, Xuzhou (China). School of Information and Electronic Engineering

    2007-01-15

    A forecasting model for coal demand of China using a support vector regression was constructed. With the selected embedding dimension, the output vectors and input vectors were constructed based on the coal demand of China from 1980 to 2002. After compared with lineal kernel and Sigmoid kernel, a radial basis function(RBF) was adopted as the kernel function. By analyzing the relationship between the error margin of prediction and the model parameters, the proper parameters were chosen. The support vector machines (SVM) model with multi-input and single output was proposed. Compared the predictor based on RBF neural networks with test datasets, the results show that the SVM predictor has higher precision and greater generalization ability. In the end, the coal demand from 2003 to 2006 is accurately forecasted. l0 refs., 2 figs., 4 tabs.

  7. A multicriteria prioritization model to support public safety planning

    Directory of Open Access Journals (Sweden)

    André Morais Gurgel

    2013-08-01

    Full Text Available Setting out to solve operational problems is a frequent part of decision making on public safety. However, the pillars of tactics and strategy are normally disregarded. Thus, this paper focuses on a strategic issue, namely that of a city prioritizing areasin which there is a degree of occurrences for criminality to increase. A multiple criteria approach is taken. The reason for this is that such a situation is normally analyzed from the perspective of the degree of police occurrences. The proposed model is based on a SMARTS multicriteria method and was applied in a Brazilian City. It combines a multicriteria method and a Monte Carlo Simulation to support an analysis of robustness. As a result, we highlight some differences between the model developed and police occurrences model. It might support differentiated policies for zones, by indicating where there should be strong actions, infrastructure investments, monitoring procedures and others public safety policies.

  8. Ru complexes of Hoveyda–Grubbs type immobilized on lamellar zeolites: activity in olefin metathesis reactions

    Directory of Open Access Journals (Sweden)

    Hynek Balcar

    2015-11-01

    Full Text Available Hoveyda–Grubbs type catalysts with cationic tags on NHC ligands were linker-free immobilized on the surface of lamellar zeolitic supports (MCM-22, MCM-56, MCM-36 and on mesoporous molecular sieves SBA-15. The activity of prepared hybrid catalysts was tested in olefin metathesis reactions: the activity in ring-closing metathesis of citronellene and N,N-diallyltrifluoroacetamide decreased in the order of support MCM-22 ≈ MCM-56 > SBA-15 > MCM-36; the hybrid catalyst based on SBA-15 was found the most active in self-metathesis of methyl oleate. All catalysts were reusable and exhibited low Ru leaching (− counter anion; in contrast, PF6− counter anion underwent partial decomposition.

  9. A kinetic mechanistic study of acid-catalyzed alkylation of isobutane with C4-olefins at low temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Doshi, B.M.

    1978-01-01

    A kinetic and mechanistic study of sulfuric acid-catalyzed alkylation of isobutane with C/sub 4/-Olefins at Low Temperatures(-20/sup 0/ to 0/sup 0/C) was based on a new two-step reaction sequence in which the desired first-step reactions are between acid and olefin to form sulfates and the desired second-step reactions are between sulfates and isobutane to form mostly trimethylpentanes. Linear butenes formed stable sulfates that formed alkylates of exceptionally high quality, up to 100 Research octane, whereas isobutylene and trimethylpentene mainly polymerized during the first step, and the alkylate produced had only 90 Research octane. Trimethylpentanes and dimethylhexanes, when contacted with concentrated sulfuric acid at -10/sup 0/ to +25/sup 0/C, degraded and isomerized to form C/sub 4/-C/sub 9/ and higher isoparaffins and acid-soluble hydrocarbons (conjunct polymers). For the two-step process and the degradation and isomerization reactions, kinetic models based on reaction at the interface were developed; but for isoolefins, a polymerization-cracking sequence (via C/sub 12/- and even C/sub 16/-olefins) is the preferred route. Commercial applications of the results are proposed.

  10. The effect of alkylating agents on model supported metal clusters

    Energy Technology Data Exchange (ETDEWEB)

    Erdem-Senatalar, A.; Blackmond, D.G.; Wender, I. (Pittsburgh Univ., PA (USA). Dept. of Chemical and Petroleum Engineering); Oukaci, R. (CERHYD, Algiers (Algeria))

    1988-01-01

    Interactions between model supported metal clusters and alkylating agents were studied in an effort to understand a novel chemical trapping technique developed for identifying species adsorbed on catalyst surfaces. It was found that these interactions are more complex than had previously been suggested. Studies were completed using deuterium-labeled dimethyl sulfate (DMS), (CH{sub 3}){sub 2}SO{sub 4}, as a trapping agent to interact with the supported metal cluster ethylidyne tricobalt enneacarbonyl. Results showed that oxygenated products formed during the trapping reaction contained {minus}OCD{sub 3} groups from the DMS, indicating that the interaction was not a simple alkylation. 18 refs., 1 fig., 3 tabs.

  11. Relationship model and supporting activities of JIT, TQM and TPM

    Directory of Open Access Journals (Sweden)

    Nuttapon SaeTong

    2011-02-01

    Full Text Available This paper gives a relationship model and supporting activities of Just-in-time (JIT, Total Quality Management (TQM,and Total Productive Maintenance (TPM. By reviewing the concepts, 5S, Kaizen, preventive maintenance, Kanban, visualcontrol, Poka-Yoke, and Quality Control tools are the main supporting activities. Based on the analysis, 5S, preventive maintenance,and Kaizen are the foundation of the three concepts. QC tools are required activities for implementing TQM, whereasPoka-Yoke and visual control are necessary activities for implementing TPM. After successfully implementing TQM andTPM, Kanban is needed for JIT.

  12. Support for an expanded tripartite influence model with gay men.

    Science.gov (United States)

    Tylka, Tracy L; Andorka, Michael J

    2012-01-01

    This study investigated whether an expanded tripartite influence model would represent gay men's experiences. This model was extended by adding partners and gay community involvement as sources of social influence and considering dual body image pathways (muscularity and body fat dissatisfaction) to muscularity enhancement and disordered eating behaviors. Latent variable structural equation modeling analyses upheld this model for 346 gay men. Dual body image pathways to body change behaviors were supported, although three unanticipated interrelationships emerged, suggesting that muscularity and body fat concerns and behaviors may be more integrated for gay men. Internalization of the mesomorphic ideal, appearance comparison, muscularity dissatisfaction, and body fat dissatisfaction were key mediators in the model. Of the sources of social influence, friend and media pressure to be lean, gay community involvement, and partner, friend, media, and family pressures to be muscular made incremental contributions. Unexpectedly, certain sources were directly connected to body change behaviors. Copyright © 2011 Elsevier Ltd. All rights reserved.

  13. Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Schrodi, Yann [Agoura Hills, CA

    2011-11-29

    This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

  14. Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Schrodi, Yann

    2016-02-09

    This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

  15. Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Schrodi, Yann

    2015-09-22

    This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

  16. Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Schrodi, Yann

    2013-07-09

    This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

  17. Ternary catalyst-olefin-hydroperoxide complexes and their contribution to epoxidation

    International Nuclear Information System (INIS)

    Svitych, R.B.; Rzhevskaya, N.N.; Buchachenko, A.L.; Yablonskij, O.P.; Petukhov, A.A.; Belyaev, V.A.

    1976-01-01

    Electron and NMR spectroscopy have been used for studying the complex formation of catalysts (Mo 5+ , Mn 2+ , Co 2+ ) in double and triple systems: metal-olefin and metal-olefin-hydroperoxide. It has been established that ions of metals form complexes with olefins in the first sphere. The formation has been proved of ternary complexes metal-olefin-hydroperoxide. The structure of the complexes has been proposed with olefins in the first and hydroperoxide in the second sphere of the metal ion. The structure explains known kinetic regularities of epoxydation and the mechanism of the formation of final products, oxide and alcohol. It has been shown that the best catalysts for epoxydation of olefins with hydroperoxides must be the compounds of the metals with an electron state of ion d 0 [ru

  18. Porflow modeling supporting the FY14 salstone special analysis

    Energy Technology Data Exchange (ETDEWEB)

    Flach, G. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Taylor, G. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2014-04-01

    PORFLOW related analyses supporting the Saltstone FY14 Special Analysis (SA) described herein are based on prior modeling supporting the Saltstone FY13 SA. Notable changes to the previous round of simulations include: a) consideration of Saltstone Disposal Unit (SDU) design type 6 under “Nominal” and “Margin” conditions, b) omission of the clean cap fill from the nominal SDU 2 and 6 modeling cases as a reasonable approximation of greater waste grout fill heights, c) minor updates to the cementitious materials degradation analysis, d) use of updated I-129 sorption coefficient (Kd) values in soils, e) assignment of the pH/Eh environment of saltstone to the underlying floor concrete, considering down flow through an SDU, and f) implementation of an improved sub-model for Tc release in an oxidizing environment. These new model developments are discussed and followed by a cursory presentation of simulation results. The new Tc release sub-model produced significantly improved (smoother) flux results compared to the FY13 SA. Further discussion of PORFLOW model setup and simulation results will be presented in the FY14 SA, including dose results.

  19. Nonthermal plasma reactors for the production of light hydrocarbon olefins from heavy oil

    Directory of Open Access Journals (Sweden)

    G. Prieto

    2003-03-01

    Full Text Available During the last decade, nonthermal plasma technology was applied in many different fields, focusing attention on the destruction of harmful compounds in the air. This paper deals with nonthermal plasma reactors for the conversion of heavy oil into light hydrocarbon olefins, to be employed as gasoline components or to be added in small amounts for the catalytic reduction of nitrogen oxide compounds in the treatment of exhaust gas at power plants. For the process, the plate-plate nonthermal plasma reactor driven by AC high voltage was selected. The reactor was modeled as a function of parameter characteristics, using the methodology provided by the statistical experimental design. The parameters studied were gap distance between electrodes, carrier gas flow and applied power. Results indicate that the reactions occurring in the process of heavy oil conversion have an important selective behavior. The products obtained were C1-C4 hydrocarbons with ethylene as the main compound. Operating the parameters of the reactor within the established operative window of the system and close to the optimum conditions, efficiencies as high as 70 (mul/joule were obtained. These values validate the process as an in-situ method to produce light olefins for the treatment of nitrogen oxides in the exhaust gas from diesel engines.

  20. Reactions of rhodium(I) carbonyl chloride with olefins

    International Nuclear Information System (INIS)

    Varshavskii, Yu.S.; Kiseleva, N.V.; Cherkasova, T.G.; Buzina, N.A.; Bresler, L.S.

    1987-01-01

    The reactions of [Rh(CO) 2 Cl] 2 (Y 0 ) with cyclooctene and several other olefins (1-heptene, 1-hexene, ethylene, and cyclohexene) have been studied by IR and 13 C NMR spectroscopy. The main reaction products are the binuclear complexes Rh 2 L(CO) 3 Cl 2 (Y 1 ) and [RhL(CO)Cl] 2 (Y 2 ), where L denotes the olefin. The extent of replacement of the carbonyl groups depends on the nature of the olefin and the conditions under which the reaction is carried out (the L:Rh ratio and the removal of CO from the reaction sphere). The liquid olefins form the following series according to their ability to replace the carbonyl groups: C 8 H 14 > C 7 H 14 , C 6 H 12 > C 6 H 10 . In the presence of an excess of C 8 H 14 , Y 2 disproportionates with the formation of a dicarbonyl product, which presumably corresponds to the formula Rh(C 8 H 14 ) 2 (CO) 2 Cl (a pentacoordinate complex with a trigonal-bipyramidal structure). The 13 C signal in the NMR spectrum of a solution of Y 2 in C 8 H 14 is a singlet with σ( 13 C) 180.3 ppm, which is an indication of the rapid exchange of the carbonyl groups. Rapid exchange of the CO ligands is also observed in solutions of Y 0 in the olefins (with the exception of C 6 H 10 ). For example, the 13 C signal in the spectrum of a solution of Y 0 in C 8 H 14 is a singlet with σ( 13 C) 179.8 ppm. The spectrum of Y 0 in C 6 H 10 is a doublet with σ( 13 C) = 178.5 ppm and 1 J(CRh) = 76.3 Hz. A scheme for the interaction of Y 0 with olefins based on the conception of the trans antagonism of π-acceptor ligands has been proposed

  1. Twin support vector machines models, extensions and applications

    CERN Document Server

    Jayadeva; Chandra, Suresh

    2017-01-01

    This book provides a systematic and focused study of the various aspects of twin support vector machines (TWSVM) and related developments for classification and regression. In addition to presenting most of the basic models of TWSVM and twin support vector regression (TWSVR) available in the literature, it also discusses the important and challenging applications of this new machine learning methodology. A chapter on “Additional Topics” has been included to discuss kernel optimization and support tensor machine topics, which are comparatively new but have great potential in applications. It is primarily written for graduate students and researchers in the area of machine learning and related topics in computer science, mathematics, electrical engineering, management science and finance.

  2. Modeling the capacity of riverscapes to support beaver dams

    Science.gov (United States)

    Macfarlane, William W.; Wheaton, Joseph M.; Bouwes, Nicolaas; Jensen, Martha L.; Gilbert, Jordan T.; Hough-Snee, Nate; Shivik, John A.

    2017-01-01

    The construction of beaver dams facilitates a suite of hydrologic, hydraulic, geomorphic, and ecological feedbacks that increase stream complexity and channel-floodplain connectivity that benefit aquatic and terrestrial biota. Depending on where beaver build dams within a drainage network, they impact lateral and longitudinal connectivity by introducing roughness elements that fundamentally change the timing, delivery, and storage of water, sediment, nutrients, and organic matter. While the local effects of beaver dams on streams are well understood, broader coverage network models that predict where beaver dams can be built and highlight their impacts on connectivity across diverse drainage networks are lacking. Here we present a capacity model to assess the limits of riverscapes to support dam-building activities by beaver across physiographically diverse landscapes. We estimated dam capacity with freely and nationally-available inputs to evaluate seven lines of evidence: (1) reliable water source, (2) riparian vegetation conducive to foraging and dam building, (3) vegetation within 100 m of edge of stream to support expansion of dam complexes and maintain large colonies, (4) likelihood that channel-spanning dams could be built during low flows, (5) the likelihood that a beaver dam is likely to withstand typical floods, (6) a suitable stream gradient that is neither too low to limit dam density nor too high to preclude the building or persistence of dams, and (7) a suitable river that is not too large to restrict dam building or persistence. Fuzzy inference systems were used to combine these controlling factors in a framework that explicitly also accounts for model uncertainty. The model was run for 40,561 km of streams in Utah, USA, and portions of surrounding states, predicting an overall network capacity of 356,294 dams at an average capacity of 8.8 dams/km. We validated model performance using 2852 observed dams across 1947 km of streams. The model showed

  3. A latent ruthenium based olefin metathesis catalyst with a sterically demanding NHC ligand

    KAUST Repository

    Leitgeb, Anita

    2012-01-01

    An olefin metathesis catalyst featuring a SIPr NHC and an ester chelating carbene ligand is introduced. In contrast to its previously published SIMes analogue, only the trans dichloro configurated isomer was obtained. The two counterparts are tested in various olefin metathesis reactions, revealing a striking superiority of the new complex in the cross metathesis of olefins with methyl vinyl ketone allowing for full conversion with only 500 ppm catalyst loading. © 2012 The Royal Society of Chemistry.

  4. Pd(II)-Catalyzed Olefination of sp3 C–H Bonds

    Science.gov (United States)

    Wasa, Masayuki; Engle, Keary M.; Yu, Jin-Quan

    2010-01-01

    The first Pd(II)-catalyzed sp3 C–H olefination reaction has been developed using N-arylamide directing groups. Following olefination, the resulting intermediates were found to undergo rapid 1,4-addition to give the corresponding γ lactams. Notably, this method was effective with substrates containing α-hydrogen atoms and could be applied to effect methylene C–H olefination of cyclopropane substrates. PMID:20187642

  5. Direct olefination of fluorinated benzothiadiazoles: a new entry to optoelectronic materials.

    Science.gov (United States)

    Xiao, Yu-Lan; Zhang, Bo; He, Chun-Yang; Zhang, Xingang

    2014-04-14

    Fluorinated olefin-containing benzothiadiazoles have important applications in optoelectronic materials. Herein, we reported the direct olefination of fluorinated benzothiadiazoles, as catalyzed by palladium. The reaction proceeds under mild reaction conditions and shows high functional-group compatibility. A preliminary study of the properties of the resulting symmetrical and unsymmetrical olefin-containing fluorinated benzothiadiazoles in red-light-emitting dyes has also been conducted. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. WWER reactor fuel performance, modelling and experimental support. Proceedings

    International Nuclear Information System (INIS)

    Stefanova, S.; Chantoin, P.; Kolev, I.

    1994-01-01

    This publication is a compilation of 36 papers presented at the International Seminar on WWER Reactor Fuel Performance, Modelling and Experimental Support, organised by the Institute for Nuclear Research and Nuclear Energy (BG), in cooperation with the International Atomic Energy Agency. The Seminar was attended by 76 participants from 16 countries, including representatives of all major Russian plants and institutions responsible for WWER reactor fuel manufacturing, design and research. The reports are grouped in four chapters: 1) WWER Fuel Performance and Economics: Status and Improvement Prospects: 2) WWER Fuel Behaviour Modelling and Experimental Support; 3) Licensing of WWER Fuel and Fuel Analysis Codes; 4) Spent Fuel of WWER Plants. The reports from the corresponding four panel discussion sessions are also included. All individual papers are recorded in INIS as separate items

  7. A Model for an Intelligent Support Decision System in Aquaculture

    OpenAIRE

    Novac Ududec, Cornelia / C

    2009-01-01

    The paper purpose an intelligent software system agents–based to support decision in aquculture and the approach of fish diagnosis with informatics methods, techniques and solutions. A major purpose is to develop new methods and techniques for quick fish diagnosis, treatment and prophyilaxis at infectious and parasite-based known disorders, that may occur at fishes raised in high density in intensive raising systems. But, the goal of this paper is to presents a model of an intelligent agents-...

  8. Information Model Translation to Support a Wider Science Community

    Science.gov (United States)

    Hughes, John S.; Crichton, Daniel; Ritschel, Bernd; Hardman, Sean; Joyner, Ronald

    2014-05-01

    The Planetary Data System (PDS), NASA's long-term archive for solar system exploration data, has just released PDS4, a modernization of the PDS architecture, data standards, and technical infrastructure. This next generation system positions the PDS to meet the demands of the coming decade, including big data, international cooperation, distributed nodes, and multiple ways of analysing and interpreting data. It also addresses three fundamental project goals: providing more efficient data delivery by data providers to the PDS, enabling a stable, long-term usable planetary science data archive, and enabling services for the data consumer to find, access, and use the data they require in contemporary data formats. The PDS4 information architecture is used to describe all PDS data using a common model. Captured in an ontology modeling tool it supports a hierarchy of data dictionaries built to the ISO/IEC 11179 standard and is designed to increase flexibility, enable complex searches at the product level, and to promote interoperability that facilitates data sharing both nationally and internationally. A PDS4 information architecture design requirement stipulates that the content of the information model must be translatable to external data definition languages such as XML Schema, XMI/XML, and RDF/XML. To support the semantic Web standards we are now in the process of mapping the contents into RDF/XML to support SPARQL capable databases. We are also building a terminological ontology to support virtually unified data retrieval and access. This paper will provide an overview of the PDS4 information architecture focusing on its domain information model and how the translation and mapping are being accomplished.

  9. Modeling bacteria fate and transport in watersheds to support TMDLs

    OpenAIRE

    Benham, B. L.; Baffaut, C.; Zeckoski, R. W.; Mankin, K. R.; Pachepsky, Y. A.; Sadeghi, A. A.; Brannan, Kevin M.; Soupir, M. L.; Habersack, M. J.

    2006-01-01

    Fecal contamination of surface waters is a critical water-quality issue, leading to human illnesses and deaths. Total Maximum Daily Loads (TMDLs), which set pollutant limits, are being developed to address fecal bacteria impairments. Watershed models are widely used to support TMDLs, although their use for simulating in-stream fecal bacteria concentrations is somewhat rudimentary. This article provides an overview of fecal microorganism fate and transport within watersheds, describes current ...

  10. Support vector machine based battery model for electric vehicles

    International Nuclear Information System (INIS)

    Wang Junping; Chen Quanshi; Cao Binggang

    2006-01-01

    The support vector machine (SVM) is a novel type of learning machine based on statistical learning theory that can map a nonlinear function successfully. As a battery is a nonlinear system, it is difficult to establish the relationship between the load voltage and the current under different temperatures and state of charge (SOC). The SVM is used to model the battery nonlinear dynamics in this paper. Tests are performed on an 80Ah Ni/MH battery pack with the Federal Urban Driving Schedule (FUDS) cycle to set up the SVM model. Compared with the Nernst and Shepherd combined model, the SVM model can simulate the battery dynamics better with small amounts of experimental data. The maximum relative error is 3.61%

  11. PORFLOW Modeling Supporting The H-Tank Farm Performance Assessment

    International Nuclear Information System (INIS)

    Jordan, J. M.; Flach, G. P.; Westbrook, M. L.

    2012-01-01

    Numerical simulations of groundwater flow and contaminant transport in the vadose and saturated zones have been conducted using the PORFLOW code in support of an overall Performance Assessment (PA) of the H-Tank Farm. This report provides technical detail on selected aspects of PORFLOW model development and describes the structure of the associated electronic files. The PORFLOW models for the H-Tank Farm PA, Rev. 1 were updated with grout, solubility, and inventory changes. The aquifer model was refined. In addition, a set of flow sensitivity runs were performed to allow flow to be varied in the related probabilistic GoldSim models. The final PORFLOW concentration values are used as input into a GoldSim dose calculator

  12. PORFLOW Modeling Supporting The H-Tank Farm Performance Assessment

    Energy Technology Data Exchange (ETDEWEB)

    Jordan, J. M.; Flach, G. P.; Westbrook, M. L.

    2012-08-31

    Numerical simulations of groundwater flow and contaminant transport in the vadose and saturated zones have been conducted using the PORFLOW code in support of an overall Performance Assessment (PA) of the H-Tank Farm. This report provides technical detail on selected aspects of PORFLOW model development and describes the structure of the associated electronic files. The PORFLOW models for the H-Tank Farm PA, Rev. 1 were updated with grout, solubility, and inventory changes. The aquifer model was refined. In addition, a set of flow sensitivity runs were performed to allow flow to be varied in the related probabilistic GoldSim models. The final PORFLOW concentration values are used as input into a GoldSim dose calculator.

  13. Life cycle assessment of energy consumption and GHG emissions of olefins production from alternative resources in China

    International Nuclear Information System (INIS)

    Xiang, Dong; Yang, Siyu; Li, Xiuxi; Qian, Yu

    2015-01-01

    Highlights: • Conduct a life cycle energy use and GHG emissions of olefins production processes. • Analyse effects of carbon capture and efficiency on alternative olefins production. • Analyse life cycle performance of Chinese olefins industry in three key periods. • Present the advantages and challenges of alternative olefins routes. - Abstract: Olefins are important platform chemicals widely used in industry. In terms of the short supply of oil resources, natural gas and coal are two significant alternative feedstocks. In this paper, energy consumption and GHG emissions of olefins production are analysed with life cycle assessment methods. Results showed the energy consumption and GHG emissions of natural gas-to-olefins are roughly equivalent to those of oil-to-olefins, while coal-to-olefins suffers from higher energy consumption and serious GHG emissions, including 5793 kg eq. CO 2 /t olefins of direct emissions and 5714 kg eq. CO 2 /t olefins of indirect emissions. To address the problem, the effect of carbon capture on coal-to-olefins is investigated. In comprehensive consideration of energy utilization, environmental impact, and economic benefit, the coal-to-olefins with 80% CO 2 capture of the direct emissions is found to be an appropriate choice. With this carbon capture configuration, the direct emissions of the coal-to-olefins are reduced to 1161 kg eq. CO 2 /t olefins. However, the indirect emissions are still not captured, which should be strictly monitored and significantly reduced. Finally, a scenario analysis is conducted to estimate resource utilization and GHG emissions of olefins production of China in 2020. Several suggestions are also proposed for policy making on the sustainable development of olefins industry

  14. Vector-model-supported approach in prostate plan optimization

    International Nuclear Information System (INIS)

    Liu, Eva Sau Fan; Wu, Vincent Wing Cheung; Harris, Benjamin; Lehman, Margot; Pryor, David; Chan, Lawrence Wing Chi

    2017-01-01

    Lengthy time consumed in traditional manual plan optimization can limit the use of step-and-shoot intensity-modulated radiotherapy/volumetric-modulated radiotherapy (S&S IMRT/VMAT). A vector model base, retrieving similar radiotherapy cases, was developed with respect to the structural and physiologic features extracted from the Digital Imaging and Communications in Medicine (DICOM) files. Planning parameters were retrieved from the selected similar reference case and applied to the test case to bypass the gradual adjustment of planning parameters. Therefore, the planning time spent on the traditional trial-and-error manual optimization approach in the beginning of optimization could be reduced. Each S&S IMRT/VMAT prostate reference database comprised 100 previously treated cases. Prostate cases were replanned with both traditional optimization and vector-model-supported optimization based on the oncologists' clinical dose prescriptions. A total of 360 plans, which consisted of 30 cases of S&S IMRT, 30 cases of 1-arc VMAT, and 30 cases of 2-arc VMAT plans including first optimization and final optimization with/without vector-model-supported optimization, were compared using the 2-sided t-test and paired Wilcoxon signed rank test, with a significance level of 0.05 and a false discovery rate of less than 0.05. For S&S IMRT, 1-arc VMAT, and 2-arc VMAT prostate plans, there was a significant reduction in the planning time and iteration with vector-model-supported optimization by almost 50%. When the first optimization plans were compared, 2-arc VMAT prostate plans had better plan quality than 1-arc VMAT plans. The volume receiving 35 Gy in the femoral head for 2-arc VMAT plans was reduced with the vector-model-supported optimization compared with the traditional manual optimization approach. Otherwise, the quality of plans from both approaches was comparable. Vector-model-supported optimization was shown to offer much shortened planning time and iteration

  15. Mechanistic Investigations of the Iron(III)-Catalyzed Carbonyl-Olefin Metathesis Reaction.

    Science.gov (United States)

    Ludwig, Jacob R; Phan, Susan; McAtee, Christopher C; Zimmerman, Paul M; Devery, James J; Schindler, Corinna S

    2017-08-09

    Iron(III)-catalyzed carbonyl-olefin ring-closing metathesis represents a new approach toward the assembly of molecules traditionally generated by olefin-olefin metathesis or olefination. Herein, we report detailed synthetic, spectroscopic, kinetic, and computational studies to determine the mechanistic features imparted by iron(III), substrate, and temperature to the catalytic cycle. These data are consistent with an iron(III)-mediated asynchronous, concerted [2+2]-cycloaddition to form an intermediate oxetane as the turnover-limiting step. Fragmentation of the oxetane via Lewis acid-activation results in the formation of five- and six-membered unsaturated carbocycles.

  16. A Cost Model for Integrated Logistic Support Activities

    Directory of Open Access Journals (Sweden)

    M. Elena Nenni

    2013-01-01

    Full Text Available An Integrated Logistic Support (ILS service has the objective of improving a system’s efficiency and availability for the life cycle. The system constructor offers the service to the customer, and she becomes the Contractor Logistic Support (CLS. The aim of this paper is to propose an approach to support the CLS in the budget formulation. Specific goals of the model are the provision of the annual cost of ILS activities through a specific cost model and a comprehensive examination of expected benefits, costs and savings under alternative ILS strategies. A simple example derived from an industrial application is also provided to illustrate the idea. Scientific literature is lacking in the topic and documents from the military are just dealing with the issue of performance measurement. Moreover, they are obviously focused on the customer’s perspective. Other scientific papers are general and focused only on maintenance or life cycle management. The model developed in this paper approaches the problem from the perspective of the CLS, and it is specifically tailored on the main issues of an ILS service.

  17. Transformation of UML Behavioral Diagrams to Support Software Model Checking

    Directory of Open Access Journals (Sweden)

    Luciana Brasil Rebelo dos Santos

    2014-04-01

    Full Text Available Unified Modeling Language (UML is currently accepted as the standard for modeling (object-oriented software, and its use is increasing in the aerospace industry. Verification and Validation of complex software developed according to UML is not trivial due to complexity of the software itself, and the several different UML models/diagrams that can be used to model behavior and structure of the software. This paper presents an approach to transform up to three different UML behavioral diagrams (sequence, behavioral state machines, and activity into a single Transition System to support Model Checking of software developed in accordance with UML. In our approach, properties are formalized based on use case descriptions. The transformation is done for the NuSMV model checker, but we see the possibility in using other model checkers, such as SPIN. The main contribution of our work is the transformation of a non-formal language (UML to a formal language (language of the NuSMV model checker towards a greater adoption in practice of formal methods in software development.

  18. Methanol conversion to lower olefins over RHO type zeolite

    KAUST Repository

    Masih, Dilshad

    2013-07-01

    Eight-membered ring small-pore zeolite of RHO-type topology has been synthesized, characterized and tested for methanol-to-olefin (MTO) reaction. The zeolite was hydrothermally crystallized from the gel with Si/Al ratio of 5.0. It showed a high BET specific surface area (812 m2 g-1), micropore volume (0.429 cm3 g-1), and acid amount (2.53 mmol g-1). Scanning electron microscopy observations showed small crystallites of about 1 μm. The zeolite was active for MTO reaction with 100% methanol conversions at 623-723 K, whereas selectivity to lower olefins changed with time. © 2013 Elsevier B.V.

  19. The activation mechanism of Fe-based olefin metathesis catalysts

    KAUST Repository

    Poater, Albert

    2014-08-01

    Density functional theory calculations have been used to describe the first turnover for olefin metathesis reaction of a homogenous Fe-based catalyst bearing a N-heterocyclic carbene ligand with methoxyethene as a substrate. Equal to conventional Ru-based catalysts, the activation of its Fe congener occurs through a dissociative mechanism, however with a more exothermic reaction energy profile. Predicted upper energy barriers were calculated to be on average ∼2 kcal/mol more beneficial for Fe catalyzed metathesis. Overall, this present computational study emphasises on advantages of Fe-based metathesis and gives a potential recipe for the design of an efficient Fe-based olefin metathesis catalysts. © 2014 Elsevier B.V.

  20. Olefin metathesis reaction on a MoS2 catalyst

    International Nuclear Information System (INIS)

    Anon.

    1976-01-01

    Olefin metathesis reaction was found to take place on rather pure MoS 2 evacuated at 450 0 C for several hours. Systematic studies of the isotopic scrambling in ethylene, propylene, 1-butene, and 2-butene on MoS 2 using microwave spectroscopy are reported. These studies were made using 12 C- and 13 C-labelled compounds and D-labelled compounds. Results indicated that the MoS 2 catalyst evacuated at 450 0 C has two kinds of active sites, one is effective for the isomerization and the hydrogen isotopic mixing of olefins, and the other is effective for the hydrogenation reaction. This may be explained by assuming different degrees of coordinative unsaturation for the active sites

  1. Methyltrioxorhenium as catalyst of a novel aldehyde olefination

    Energy Technology Data Exchange (ETDEWEB)

    Herrmann, W.A. (Technische Univ. Muenchen, Garching (Germany). Anorganisch-Chemisches Inst.); Wang Mei (Academia Sinica, Dalian Inst. of Chemical Physics (China))

    1991-12-01

    From aldehydes or cyclic ketones, diazoalkanes, and teritiary phosphanes, olefins may be prepared with MTO as catalyst. In particular, diazoacetates and -malonates (R{sup 2}, R{sup 3} = H, CO{sub 2}Et, or 2 x CO{sub 2}Me) can be transformed into olefins with aliphatic and aromatic aldehydes (R{sup 1} = iPr, trans-PhCH=CH, Ph, 4-NO{sub 2}C{sub 6}H{sub 4}, etc.). Readily accessible starting materials, easy handling, mild reaction conditions, and good yields characterize the new synthesis method. (R' = Ph, 3-C{sub 6}H{sub 4}SO{sub 3}Na, nBu.) (orig.).

  2. A three-membered ring approach to carbonyl olefination.

    Science.gov (United States)

    Niyomchon, Supaporn; Oppedisano, Alberto; Aillard, Paul; Maulide, Nuno

    2017-10-23

    The carbon-carbon double bond, with its diverse and multifaceted reactivity, occupies a prominent position in organic synthesis. Although a variety of simple alkenes are readily available, the mild and chemoselective introduction of a unit of unsaturation into a functionalized organic molecule remains an ongoing area of research, and the olefination of carbonyl compounds is a cornerstone of such approaches. Here we show the direct olefination of hydrazones via the intermediacy of three-membered ring species generated by addition of sulfoxonium ylides, departing from the general dogma of alkenes synthesis from carbonyls. Moreover, the mild reaction conditions and operational simplicity of the transformation render the methodology appealing from a practical point of view.

  3. Alkylation of mixed olefins with isobutane in a stratco chemical reactor

    Energy Technology Data Exchange (ETDEWEB)

    Vichailak, M. [ABB Lummus Global Inc., Houston, TX (United States); Hopper, J.R.; Yaws, C.L. [Lamar Univ., Beaumont, TX (United States); Pike, R.W. [Louisiana State Univ., Baton Rouge, LA (United States)

    1996-12-31

    The 17 reaction model for the sulfuric acid alkylation of isobutane with propylene as proposed by Langley and Pike has been used to simulate the effluent refrigeration reactor. The simulation conditions selected to minimize the formation of light and heavy by-product were determined to be: Temperature: 9 - 10 {degrees}C,- Isobutane/Olefin Ratio: 8 - 10; % Volume of Acid: 50 %. The reactor effluent composition from the simulation program has been used to compare with several sets of published data with reasonable agreement. This model has been extrapolated to simulate the alkylation of isobutane with butylenes and amylenes. The model will be optimized with commercial data. 9 refs., 6 figs., 1 tab.

  4. Allenyl esters as quenching agents for ruthenium olefin metathesis catalysts.

    Science.gov (United States)

    Roy, Animesh; Silvestri, Maximilian A; Hall, Robert A; Lepore, Salvatore D

    2017-01-04

    In the attempt to synthesize substituted allenyl esters through a metathesis coupling of unsubstituted allenyl esters and alkenes using a variety of ruthenium catalysts, it was discovered that allenyl esters themselves cleanly arrested the activity of the catalysts. Further studies suggests possible utility of allene esters as general quenching agents for metathesis reactions. To explore this idea, several representative olefin metathesis reactions, including ring closing, were successfully terminated by the addition of simple allenyl esters for more convenient purification.

  5. Knowledge representation to support reasoning based on multiple models

    Science.gov (United States)

    Gillam, April; Seidel, Jorge P.; Parker, Alice C.

    1990-01-01

    Model Based Reasoning is a powerful tool used to design and analyze systems, which are often composed of numerous interactive, interrelated subsystems. Models of the subsystems are written independently and may be used together while they are still under development. Thus the models are not static. They evolve as information becomes obsolete, as improved artifact descriptions are developed, and as system capabilities change. Researchers are using three methods to support knowledge/data base growth, to track the model evolution, and to handle knowledge from diverse domains. First, the representation methodology is based on having pools, or types, of knowledge from which each model is constructed. In addition information is explicit. This includes the interactions between components, the description of the artifact structure, and the constraints and limitations of the models. The third principle we have followed is the separation of the data and knowledge from the inferencing and equation solving mechanisms. This methodology is used in two distinct knowledge-based systems: one for the design of space systems and another for the synthesis of VLSI circuits. It has facilitated the growth and evolution of our models, made accountability of results explicit, and provided credibility for the user community. These capabilities have been implemented and are being used in actual design projects.

  6. Energy modelling platforms for policy and strategy support

    International Nuclear Information System (INIS)

    Dyner, I.

    2000-01-01

    The energy field has been dominated by 'hard' modelling approaches by researchers from engineering and economics discipline. The recent trend towards a more liberalised environment moves away from central planning to market-based resource allocation, leading to the creation and use of strategic tools, with much 'softer' specifications, in the 'system-thinking' tradition. This paper presents the use of system dynamics in a generalised way, to provide a platform for integrated energy analysis. Issues of modularity and policy evolution are important in the design of the modelling platform to facilitate its use, and reuse. Hence the concepts of a platform, rather than a model, has to be implemented in a coherent way if it is to provide sustained value for ongoing support to both government policy and corporate strategy. (author)

  7. Job Demands-Control-Support model and employee safety performance.

    Science.gov (United States)

    Turner, Nick; Stride, Chris B; Carter, Angela J; McCaughey, Deirdre; Carroll, Anthony E

    2012-03-01

    The aim of this study was to explore whether work characteristics (job demands, job control, social support) comprising Karasek and Theorell's (1990) Job Demands-Control-Support framework predict employee safety performance (safety compliance and safety participation; Neal and Griffin, 2006). We used cross-sectional data of self-reported work characteristics and employee safety performance from 280 healthcare staff (doctors, nurses, and administrative staff) from Emergency Departments of seven hospitals in the United Kingdom. We analyzed these data using a structural equation model that simultaneously regressed safety compliance and safety participation on the main effects of each of the aforementioned work characteristics, their two-way interactions, and the three-way interaction among them, while controlling for demographic, occupational, and organizational characteristics. Social support was positively related to safety compliance, and both job control and the two-way interaction between job control and social support were positively related to safety participation. How work design is related to employee safety performance remains an important area for research and provides insight into how organizations can improve workplace safety. The current findings emphasize the importance of the co-worker in promoting both safety compliance and safety participation. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

  8. Using Built-In Domain-Specific Modeling Support to Guide Model-Based Test Generation

    Directory of Open Access Journals (Sweden)

    Teemu Kanstrén

    2012-02-01

    Full Text Available We present a model-based testing approach to support automated test generation with domain-specific concepts. This includes a language expert who is an expert at building test models and domain experts who are experts in the domain of the system under test. First, we provide a framework to support the language expert in building test models using a full (Java programming language with the help of simple but powerful modeling elements of the framework. Second, based on the model built with this framework, the toolset automatically forms a domain-specific modeling language that can be used to further constrain and guide test generation from these models by a domain expert. This makes it possible to generate a large set of test cases covering the full model, chosen (constrained parts of the model, or manually define specific test cases on top of the model while using concepts familiar to the domain experts.

  9. Distributed Hydrologic Modeling Apps for Decision Support in the Cloud

    Science.gov (United States)

    Swain, N. R.; Latu, K.; Christiensen, S.; Jones, N.; Nelson, J.

    2013-12-01

    Advances in computation resources and greater availability of water resources data represent an untapped resource for addressing hydrologic uncertainties in water resources decision-making. The current practice of water authorities relies on empirical, lumped hydrologic models to estimate watershed response. These models are not capable of taking advantage of many of the spatial datasets that are now available. Physically-based, distributed hydrologic models are capable of using these data resources and providing better predictions through stochastic analysis. However, there exists a digital divide that discourages many science-minded decision makers from using distributed models. This divide can be spanned using a combination of existing web technologies. The purpose of this presentation is to present a cloud-based environment that will offer hydrologic modeling tools or 'apps' for decision support and the web technologies that have been selected to aid in its implementation. Compared to the more commonly used lumped-parameter models, distributed models, while being more intuitive, are still data intensive, computationally expensive, and difficult to modify for scenario exploration. However, web technologies such as web GIS, web services, and cloud computing have made the data more accessible, provided an inexpensive means of high-performance computing, and created an environment for developing user-friendly apps for distributed modeling. Since many water authorities are primarily interested in the scenario exploration exercises with hydrologic models, we are creating a toolkit that facilitates the development of a series of apps for manipulating existing distributed models. There are a number of hurdles that cloud-based hydrologic modeling developers face. One of these is how to work with the geospatial data inherent with this class of models in a web environment. Supporting geospatial data in a website is beyond the capabilities of standard web frameworks and it

  10. Vanadium-catalyzed epoxidations of olefinic alcohols in liquid carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Pesiri, D.R.; Morita, D.K.; Walker, T.; Tumas, W.

    1999-11-22

    The selective epoxidation of olefinic alcohols with t-BuOOH in the presence of vanadium catalysts proceeds in liquid carbon dioxide with high conversions and selectivities. Rates measured in liquid CO{sub 2} for the oxovanadium(V) triisopropoxide catalyzed epoxidation of allylic and homoallylic alcohols using tert-butyl hydroperoxide are comparable to those measured in methylene chloride, toluene, and n-hexane. The reactivity of the vanadium(IV) bis(acetylacetonato) oxide catalyst in liquid CO{sub 2} was found to be substantially lower than in organic solvents, presumably due to its low solubility in CO{sub 2}. Highly fluorinated acac-type ligands increased the catalytic reactivity of VO(acac){sub 2}-catalyzed epoxidations by enhancing catalyst precursor solubility. Heterogeneous epoxidation reactions were also carried out in liquid CO{sub 2} using vanadium complexes supported on cation-exchange polymers.

  11. Numerical Model Metrics Tools in Support of Navy Operations

    Science.gov (United States)

    Dykes, J. D.; Fanguy, P.

    2017-12-01

    Increasing demands of accurate ocean forecasts that are relevant to the Navy mission decision makers demand tools that quickly provide relevant numerical model metrics to the forecasters. Increasing modelling capabilities with ever-higher resolution domains including coupled and ensemble systems as well as the increasing volume of observations and other data sources to which to compare the model output requires more tools for the forecaster to enable doing more with less. These data can be appropriately handled in a geographic information system (GIS) fused together to provide useful information and analyses, and ultimately a better understanding how the pertinent model performs based on ground truth.. Oceanographic measurements like surface elevation, profiles of temperature and salinity, and wave height can all be incorporated into a set of layers correlated to geographic information such as bathymetry and topography. In addition, an automated system that runs concurrently with the models on high performance machines matches routinely available observations to modelled values to form a database of matchups with which statistics can be calculated and displayed, to facilitate validation of forecast state and derived variables. ArcMAP, developed by Environmental Systems Research Institute, is a GIS application used by the Naval Research Laboratory (NRL) and naval operational meteorological and oceanographic centers to analyse the environment in support of a range of Navy missions. For example, acoustic propagation in the ocean is described with a three-dimensional analysis of sound speed that depends on profiles of temperature, pressure and salinity predicted by the Navy Coastal Ocean Model. The data and model output must include geo-referencing information suitable for accurately placing the data within the ArcMAP framework. NRL has developed tools that facilitate merging these geophysical data and their analyses, including intercomparisons between model

  12. Observation of Different Catalytic Activity of Various 1-Olefins during Ethylene/1-Olefin Copolymerization with Homogeneous Metallocene Catalysts

    Directory of Open Access Journals (Sweden)

    Mingkwan Wannaborworn

    2011-01-01

    Full Text Available This research aimed to investigate the copolymerization of ethylene and various 1-olefins. The comonomer lengths were varied from 1-hexene (1-C6 up to 1-octadecene (1-C18 in order to study the effect of comonomer chain length on the activity and properties of the polymer in the metallocene/MAO catalyst system. The results indicated that two distinct cases can be described for the effect of 1-olefin chain length on the activity. Considering the short chain length comonomers, such as 1-hexene, 1-octene and 1-decene, it is obvious that the polymerization activity decreased when the length of comonomer was higher, which is probably due to increased steric hindrance at the catalytic center hindering the insertion of ethylene monomer to the active sites, hence, the polymerization rate decreased. On the contrary, for the longer chain 1-olefins, namely 1-dodecene, 1-tetradecene and 1-octadecene, an increase in the comonomer chain length resulted in better activity due to the opening of the gap aperture between Cp(centroid-M-Cp-(centroid, which forced the coordination site to open more. This effect facilitated the polymerization of the ethylene monomer at the catalytic sites, and thus, the activity increased. The copolymers obtained were further characterized using thermal analysis, X-ray diffraction spectroscopy and 13C-NMR techniques. It could be seen that the melting temperature and comonomer distribution were not affected by the 1-olefin chain length. The polymer crystallinity decreased slightly with increasing comonomer chain length. Moreover, all the synthesized polymers were typical LLDPE having random comonomer distribution.

  13. Observation of different catalytic activity of various 1-olefins during ethylene/1-olefin copolymerization with homogeneous metallocene catalysts.

    Science.gov (United States)

    Wannaborworn, Mingkwan; Praserthdam, Piyasan; Jongsomjit, Bunjerd

    2011-01-07

    This research aimed to investigate the copolymerization of ethylene and various 1-olefins. The comonomer lengths were varied from 1-hexene (1-C₆) up to 1-octadecene (1-C₁₈) in order to study the effect of comonomer chain length on the activity and properties of the polymer in the metallocene/MAO catalyst system. The results indicated that two distinct cases can be described for the effect of 1-olefin chain length on the activity. Considering the short chain length comonomers, such as 1-hexene, 1-octene and 1-decene, it is obvious that the polymerization activity decreased when the length of comonomer was higher, which is probably due to increased steric hindrance at the catalytic center hindering the insertion of ethylene monomer to the active sites, hence, the polymerization rate decreased. On the contrary, for the longer chain 1-olefins, namely 1-dodecene, 1-tetradecene and 1-octadecene, an increase in the comonomer chain length resulted in better activity due to the opening of the gap aperture between C(p)(centroid)-M-C(p)-(centroid), which forced the coordination site to open more. This effect facilitated the polymerization of the ethylene monomer at the catalytic sites, and thus, the activity increased. The copolymers obtained were further characterized using thermal analysis, X-ray diffraction spectroscopy and ¹³C-NMR techniques. It could be seen that the melting temperature and comonomer distribution were not affected by the 1-olefin chain length. The polymer crystallinity decreased slightly with increasing comonomer chain length. Moreover, all the synthesized polymers were typical LLDPE having random comonomer distribution.

  14. Palladium-Catalyzed ortho-Olefination of Phenyl Acetic and Phenyl Propylacetic Esters via C-H Bond Activation.

    Science.gov (United States)

    Hu, Jundie; Guan, Mingyu; Han, Jian; Huang, Zhi-Bin; Shi, Da-Qing; Zhao, Yingsheng

    2015-08-21

    A highly regioselective palladium-catalyzed ester-directed ortho-olefination of phenyl acetic and propionic esters with olefins via C-H bond activation has been developed. A wide variety of phenyl acetic and propionic esters were tolerated in this transformation, affording the corresponding olefinated aromatic compounds. The ortho-olefination of heterocyclic acetic and propionic esters also took place smoothly giving the products in good yields, thus proving the potential utility of this protocol in synthetic chemistry.

  15. Models to support students’ understanding of measuring area of circles

    Science.gov (United States)

    Rejeki, S.; Putri, R. I. I.

    2018-01-01

    Many studies showed that enormous students got confused about the concepts of measuring area of circles. The main reason is because mathematics classroom practices emphasized on memorizing formulas rather than understanding concepts. Therefore, in this study, a set of learning activities were designed as an innovation in learning area measurement of circles. The activities involved two models namely grid paper and reshaping which are respectively as a means and a strategy to support students’ learning of area measurement of circles. Design research was used as the research approach to achieve the aim. Thirty-eight of 8th graders in Indonesia were involved in this study. In this study, together with the contextual problems, the grid paper and reshaping sectors, which used as the models in this learning, helped the students to gradually develop their understanding of the area measurement of circles. The grid papers plays important role in comparing and estimating areas. Whereas, the reshaping sectors might support students’ understanding of the circumference and the area measurement of circles. Those two models could be the tool for promoting the informal theory of area measurement. Besides, the whole activities gave important role on distinguishing the area and perimeter of circles.

  16. Cationic Tungsten(VI) Penta-Methyl Complex: Synthesis, Characterization and its Application in Olefin Metathesis Reaction

    KAUST Repository

    Dey, Raju

    2016-04-13

    Tungsten-hexa-methyl readily reacts with B(C6F5)3 in dichloromethane and generates the corresponding well-defined cationic tungsten-penta-methyl complex which was identified precisely by 1H NMR, 13C NMR, 1H-13C NMR correlation spectroscopy. Unlike WMe6, this cationic complex has low energy barrier to form tungsten carbene intermediate, which was further supported by the fact that WMe6 alone has no activity in olefin metathesis reaction whereas the cationic complex shows catalytic activity for self-metathesis of 1-octene.

  17. Cationic Tungsten(VI Penta-Methyl Complex: Synthesis, Characterization and its Application in Olefin Metathesis Reaction

    Directory of Open Access Journals (Sweden)

    Dey Raju

    2016-03-01

    Full Text Available Tungsten-hexa-methyl readily reacts with B(C6F53 in dichloromethane and generates the corresponding well-defined cationic tungsten-penta-methyl complex which was identified precisely by 1H NMR, 13C NMR, 1H-13C NMR correlation spectroscopy. Unlike WMe6, this cationic complex has low energy barrier to form tungsten carbene intermediate, which was further supported by the fact that WMe6 alone has no activity in olefin metathesis reaction whereas the cationic complex shows catalytic activity for self-metathesis of 1-octene.

  18. A Composite Modelling Approach to Decision Support by the Use of the CBA-DK Model

    DEFF Research Database (Denmark)

    Barfod, Michael Bruhn; Salling, Kim Bang; Leleur, Steen

    2007-01-01

    This paper presents a decision support system for assessment of transport infrastructure projects. The composite modelling approach, COSIMA, combines a cost-benefit analysis by use of the CBA-DK model with multi-criteria analysis applying the AHP and SMARTER techniques. The modelling uncertaintie...

  19. Web-video-mining-supported workflow modeling for laparoscopic surgeries.

    Science.gov (United States)

    Liu, Rui; Zhang, Xiaoli; Zhang, Hao

    2016-11-01

    As quality assurance is of strong concern in advanced surgeries, intelligent surgical systems are expected to have knowledge such as the knowledge of the surgical workflow model (SWM) to support their intuitive cooperation with surgeons. For generating a robust and reliable SWM, a large amount of training data is required. However, training data collected by physically recording surgery operations is often limited and data collection is time-consuming and labor-intensive, severely influencing knowledge scalability of the surgical systems. The objective of this research is to solve the knowledge scalability problem in surgical workflow modeling with a low cost and labor efficient way. A novel web-video-mining-supported surgical workflow modeling (webSWM) method is developed. A novel video quality analysis method based on topic analysis and sentiment analysis techniques is developed to select high-quality videos from abundant and noisy web videos. A statistical learning method is then used to build the workflow model based on the selected videos. To test the effectiveness of the webSWM method, 250 web videos were mined to generate a surgical workflow for the robotic cholecystectomy surgery. The generated workflow was evaluated by 4 web-retrieved videos and 4 operation-room-recorded videos, respectively. The evaluation results (video selection consistency n-index ≥0.60; surgical workflow matching degree ≥0.84) proved the effectiveness of the webSWM method in generating robust and reliable SWM knowledge by mining web videos. With the webSWM method, abundant web videos were selected and a reliable SWM was modeled in a short time with low labor cost. Satisfied performances in mining web videos and learning surgery-related knowledge show that the webSWM method is promising in scaling knowledge for intelligent surgical systems. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Design of Graph Analysis Model to support Decision Making

    International Nuclear Information System (INIS)

    An, Sang Ha; Lee, Sung Jin; Chang, Soon Heung; Kim, Sung Ho; Kim, Tae Woon

    2005-01-01

    Korea is meeting the growing electric power needs by using nuclear, fissile, hydro energy and so on. But we can not use fissile energy forever, and the people's consideration about nature has been changed. So we have to prepare appropriate energy by the conditions before people need more energy. And we should prepare dynamic response because people's need would be changed as the time goes on. So we designed graphic analysis model (GAM) for the dynamic analysis of decision on the energy sources. It can support Analytic Hierarchy Process (AHP) analysis based on Graphic User Interface

  1. Computational Science Research in Support of Petascale Electromagnetic Modeling

    International Nuclear Information System (INIS)

    Lee, L.-Q.

    2008-01-01

    Computational science research components were vital parts of the SciDAC-1 accelerator project and are continuing to play a critical role in newly-funded SciDAC-2 accelerator project, the Community Petascale Project for Accelerator Science and Simulation (ComPASS). Recent advances and achievements in the area of computational science research in support of petascale electromagnetic modeling for accelerator design analysis are presented, which include shape determination of superconducting RF cavities, mesh-based multilevel preconditioner in solving highly-indefinite linear systems, moving window using h- or p- refinement for time-domain short-range wakefield calculations, and improved scalable application I/O

  2. Advancing LGBT Elder Policy and Support Services: The Massachusetts Model.

    Science.gov (United States)

    Krinsky, Lisa; Cahill, Sean R

    2017-12-01

    The Massachusetts-based LGBT Aging Project has trained elder service providers in affirming and culturally competent care for LGBT older adults, supported development of LGBT-friendly meal programs, and advanced LGBT equality under aging policy. Working across sectors, this innovative model launched the country's first statewide Legislative Commission on Lesbian, Gay, Bisexual, and Transgender Aging. Advocates are working with policymakers to implement key recommendations, including cultural competency training and data collection in statewide networks of elder services. The LGBT Aging Project's success provides a template for improving services and policy for LGBT older adults throughout the country.

  3. Hydraulic modeling support for conflict analysis: The Manayunk canal revisited

    International Nuclear Information System (INIS)

    Chadderton, R.A.; Traver, R.G.; Rao, J.N.

    1992-01-01

    This paper presents a study which used a standard, hydraulic computer model to generate detailed design information to support conflict analysis of a water resource use issue. As an extension of previous studies, the conflict analysis in this case included several scenarios for stability analysis - all of which reached the conclusion that compromising, shared access to the water resources available would result in the most benefits to society. This expected equilibrium outcome was found to maximize benefit-cost estimates. 17 refs., 1 fig., 2 tabs

  4. CH3-ReO3 on gamma-Al2O3: understanding its structure, initiation,and reactivity in olefin metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Salameh, Alain; Joubert, Jerome; Baudouin, Anne; Lukens, Wayne; Delbecq, Francoise; Sautet, Philippe; Basset, Jean Marie; Coperet,Christophe

    2007-01-20

    Me-ReO3 on gamma-alumina: understanding the structure, theinitiation and thereactivity of a highly active olefin metathesiscatalyst Heterolytic splitting of the C-H bond of the methyl group ofCH3ReO3 on AlsO reactive sites of alumina as a way to generate the activesite of CH3ReO3 supported on gamma-Al203.

  5. 40 CFR Appendix 8 to Subpart A of... - Reference C16-C18 Internal Olefin Drilling Fluid Formulation

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Reference C16-C18 Internal Olefin... Offshore Subcategory Pt. 435, Subpt. A, App. 8 Appendix 8 to Subpart A of Part 435—Reference C16-C18 Internal Olefin Drilling Fluid Formulation The reference C16-C18 internal olefin drilling fluid used to...

  6. A community college model to support nursing workforce diversity.

    Science.gov (United States)

    Colville, Janet; Cottom, Sherry; Robinette, Teresa; Wald, Holly; Waters, Tomi

    2015-02-01

    Community College of Allegheny County (CCAC), Allegheny Campus, is situated on the North Side of Pittsburgh. The neighborhood is 60% African American. At the time of the Health Resources and Services Administration (HRSA) application, approximately one third of the students admitted to the program were African American, less than one third of whom successfully completed it. With the aid of HRSA funding, CCAC developed a model that significantly improved the success rate of disadvantaged students. Through the formation of a viable cohort, the nursing faculty nurtured success among the most at-risk students. The cohort was supported by a social worker, case managers who were nursing faculty, and tutors. Students formed study groups, actively participated in community activities, and developed leadership skills through participation in the Student Nurse Association of Pennsylvania. This article provides the rationale for the Registered Nurse (RN) Achievement Model, describes the components of RN Achievement, and discusses the outcomes of the initiative.

  7. Mass balances for a biological life support system simulation model

    Science.gov (United States)

    Volk, Tyler; Rummel, John D.

    1987-01-01

    Design decisions to aid the development of future space based biological life support systems (BLSS) can be made with simulation models. The biochemistry stoichiometry was developed for: (1) protein, carbohydrate, fat, fiber, and lignin production in the edible and inedible parts of plants; (2) food consumption and production of organic solids in urine, feces, and wash water by the humans; and (3) operation of the waste processor. Flux values for all components are derived for a steady state system with wheat as the sole food source. The large scale dynamics of a materially closed (BLSS) computer model is described in a companion paper. An extension of this methodology can explore multifood systems and more complex biochemical dynamics while maintaining whole system closure as a focus.

  8. Catalyst system comprising a first catalyst system tethered to a supported catalyst

    Science.gov (United States)

    Angelici, Robert J.; Gao, Hanrong

    1998-08-04

    The present invention provides new catalyst formats which comprise a supported catalyst tethered to a second and different catalyst by a suitable tethering ligand. A preferred system comprises a heterogeneous supported metal catalyst tethered to a homogeneous catalyst. This combination of homogeneous and heterogeneous catalysts has a sufficient lifetime and unusually high catalytic activity in arene hydrogenations, and potentially many other reactions as well, including, but not limited to hydroformylation, hydrosilation, olefin oxidation, isomerization, hydrocyanation, olefin metathesis, olefin polymerization, carbonylation, enantioselective catalysis and photoduplication. These catalysts are easily separated from the products, and can be reused repeatedly, making these systems very economical.

  9. Making Risk Models Operational for Situational Awareness and Decision Support

    Energy Technology Data Exchange (ETDEWEB)

    Paulson, Patrick R.; Coles, Garill A.; Shoemaker, Steven V.

    2012-06-12

    Modernization of nuclear power operations control systems, in particular the move to digital control systems, creates an opportunity to modernize existing legacy infrastructure and extend plant life. We describe here decision support tools that allow the assessment of different facets of risk and support the optimization of available resources to reduce risk as plants are upgraded and maintained. This methodology could become an integrated part of the design review process and a part of the operations management systems. The methodology can be applied to the design of new reactors such as small nuclear reactors (SMR), and be helpful in assessing the risks of different configurations of the reactors. Our tool provides a low cost evaluation of alternative configurations and provides an expanded safety analysis by considering scenarios while early in the implementation cycle where cost impacts can be minimized. The effects of failures can be modeled and thoroughly vetted to understand their potential impact on risk. The process and tools presented here allow for an integrated assessment of risk by supporting traditional defense in depth approaches while taking into consideration the insertion of new digital instrument and control systems.

  10. A KINETIC STUDY OF THE PHOTOCHEMICAL ADDITION OF PHENANTHRENEQUINONE TO OLEFINS.

    Science.gov (United States)

    A detailed kinetic study of the photochemical addition of phenanthrenequinone to olefins has been made using an apparatus which permits the...Additional kinetic results include the absence of quenching by oxygen at high olefin- phenanthrenequinone ratios, a small secondary deuterium isotope

  11. Olefin cross-metathesis for the synthesis of alkenyl acyclonucleoside phosphonates.

    Science.gov (United States)

    Bessières, Maxime; De Schutter, Coralie; Roy, Vincent; Agofoglio, Luigi A

    2014-12-12

    The detailed synthetic protocol for the straightforward, efficient synthesis of various alkenyl acyclonucleosides, including challenging trisubstituted alkenyl acyclonucleoside phosphonates, is described. The key step of those syntheses is an olefin cross-metathesis reaction between two olefins selected based on their reactivity using well-defined ruthenium alkylidene catalysts. Copyright © 2014 John Wiley & Sons, Inc.

  12. Iron(III)-Catalyzed Ring-Closing Carbonyl-Olefin Metathesis.

    Science.gov (United States)

    Saá, Carlos

    2016-09-05

    Recent developments in catalytic carbonyl-olefin metathesis are summarized in this Highlight. Schindler and co-workers have reported that the environmentally benign FeCl3 catalyst promotes ring-closing carbonyl-olefin metathesis (RCCOM) in high yield under very mild conditions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Control of olefin geometry in macrocyclic ring-closing metathesis using a removable silyl group.

    Science.gov (United States)

    Wang, Yikai; Jimenez, Miguel; Hansen, Anders S; Raiber, Eun-Ang; Schreiber, Stuart L; Young, Damian W

    2011-06-22

    Introducing a silyl group at one of the internal olefin positions in diolefinic substrates results in E-selective olefin formation in macrocyclic ring-forming metathesis. The application of this method to a range of macrocyclic (E)-alkenylsiloxanes is described. Protodesilylation of alkenylsiloxane products yields novel Z-configured macrocycles.

  14. Design and Application of Latent Olefin Metathesis Catalysts Featuring S-Chelating Alkylidene Ligands

    Science.gov (United States)

    Szadkowska, Anna; Grela, Karol

    This review article is devoted to recent advances in the design and application of so-called “dormant” or “latent” ruthenium olefin metathesis catalysts bearing S-chelating alkylidene ligands. Selected ruthenium complexes containing S-donor ligands, which possess controllable initiation behaviour are presented. Applications of these complexes in olefin metathesis are described.

  15. Z-Selective Homodimerization of Terminal Olefins with a Ruthenium Metathesis Catalyst

    Science.gov (United States)

    Keitz, Benjamin K.; Endo, Koji; Herbert, Myles B.

    2011-01-01

    The cross-metathesis of terminal olefins using a novel ruthenium catalyst results in excellent selectivity for the Z-olefin homodimer. The reaction was found to tolerate a large number of functional groups, solvents, and temperatures while maintaining excellent Z-selectivity, even at high reaction conversions. PMID:21649443

  16. Pd(II)-Catalyzed Enantioselective C-H Olefination of Diphenylacetic Acids

    Science.gov (United States)

    Shi, Bing-Feng; Zhang, Yang-Hui; Lam, Jonathan K.; Wang, Dong-Hui; Yu, Jin-Quan

    2009-01-01

    Pd(II)-catalyzed enantioselective C-H olefination of diphenylacetic acid substrates has been achieved through the use of mono-protected chiral amino acid ligands. The absolute configuration of the resulting olefinated products is consistent with that of a proposed C-H insertion intermediate. PMID:20017549

  17. Rhodium-Catalyzed Regioselective C7-Olefination of Indazoles Using an N-Amide Directing Group.

    Science.gov (United States)

    Guo, Lei; Chen, Yanyu; Zhang, Rong; Peng, Qiujun; Xu, Lanting; Pan, Xianhua

    2017-02-01

    A rhodium-catalyzed regioselective C-H olefination of indazole is described. This protocol relies on the use of an efficient and removable N,N-diisopropylcarbamoyl directing group, which offers facile access to C7-olefinated indazoles with high regioselectivity, ample substrate scope and broad functional group tolerance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2016-11-18

    The rhodium(III)-catalyzed olefination of various carboxamides with α-CF 3 -substituted allylic carbonate is described. This reaction provides direct access to linear CF 3 -allyl frameworks with complete trans-selectivity. In particular, a rhodium catalyst provided Heck-type γ-CF 3 -allylation products via the β-O-elimination of rhodacycle intermediate and subsequent olefin migration process.

  19. Oxidative conversion of light alkanes to olefins over alkali promoted oxide catalysts.

    NARCIS (Netherlands)

    Leveles, L.; Fuchs, S.; Fuchs, Stefan; Seshan, Kulathuiyer; Lercher, J.A.; Lefferts, Leonardus

    2002-01-01

    Alkali promoted mixed oxides were studied as catalysts for the oxidative dehydrogenation (ODH) and cracking of butane and propane. Olefin yields as high as 50% were obtained with Li/MgO-based catalysts. Magnesia-based catalysts showed higher activity for olefin production than catalysts based on

  20. Subspace identification of Hammer stein models using support vector machines

    International Nuclear Information System (INIS)

    Al-Dhaifallah, Mujahed

    2011-01-01

    System identification is the art of finding mathematical tools and algorithms that build an appropriate mathematical model of a system from measured input and output data. Hammerstein model, consisting of a memoryless nonlinearity followed by a dynamic linear element, is often a good trade-off as it can represent some dynamic nonlinear systems very accurately, but is nonetheless quite simple. Moreover, the extensive knowledge about LTI system representations can be applied to the dynamic linear block. On the other hand, finding an effective representation for the nonlinearity is an active area of research. Recently, support vector machines (SVMs) and least squares support vector machines (LS-SVMs) have demonstrated powerful abilities in approximating linear and nonlinear functions. In contrast with other approximation methods, SVMs do not require a-priori structural information. Furthermore, there are well established methods with guaranteed convergence (ordinary least squares, quadratic programming) for fitting LS-SVMs and SVMs. The general objective of this research is to develop new subspace algorithms for Hammerstein systems based on SVM regression.

  1. Oxide-supported metal clusters: models for heterogeneous catalysts

    International Nuclear Information System (INIS)

    Santra, A K; Goodman, D W

    2003-01-01

    Understanding the size-dependent electronic, structural and chemical properties of metal clusters on oxide supports is an important aspect of heterogeneous catalysis. Recently model oxide-supported metal catalysts have been prepared by vapour deposition of catalytically relevant metals onto ultra-thin oxide films grown on a refractory metal substrate. Reactivity and spectroscopic/microscopic studies have shown that these ultra-thin oxide films are excellent models for the corresponding bulk oxides, yet are sufficiently electrically conductive for use with various modern surface probes including scanning tunnelling microscopy (STM). Measurements on metal clusters have revealed a metal to nonmetal transition as well as changes in the crystal and electronic structures (including lattice parameters, band width, band splitting and core-level binding energy shifts) as a function of cluster size. Size-dependent catalytic reactivity studies have been carried out for several important reactions, and time-dependent catalytic deactivation has been shown to arise from sintering of metal particles under elevated gas pressures and/or reactor temperatures. In situ STM methodologies have been developed to follow the growth and sintering kinetics on a cluster-by-cluster basis. Although several critical issues have been addressed by several groups worldwide, much more remains to be done. This article highlights some of these accomplishments and summarizes the challenges that lie ahead. (topical review)

  2. Model catalytic oxidation studies using supported monometallic and heterobimetallic oxides

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1992-02-03

    This research program is directed toward a more fundamental understanding of the effects of catalyst composition and structure on the catalytic properties of metal oxides. Metal oxide catalysts play an important role in many reactions bearing on the chemical aspects of energy processes. Metal oxides are the catalysts for water-gas shift reactions, methanol and higher alcohol synthesis, isosynthesis, selective catalytic reduction of nitric oxides, and oxidation of hydrocarbons. A key limitation to developing insight into how oxides function in catalytic reactions is in not having precise information of the surface composition under reaction conditions. To address this problem we have prepared oxide systems that can be used to study cation-cation effects and the role of bridging (-O-) and/or terminal (=O) surface oxygen anion ligands in a systematic fashion. Since many oxide catalyst systems involve mixtures of oxides, we selected a model system that would permit us to examine the role of each cation separately and in pairwise combinations. Organometallic molybdenum and tungsten complexes were proposed for use, to prepare model systems consisting of isolated monomeric cations, isolated monometallic dimers and isolated bimetallic dimers supported on silica and alumina. The monometallic and bimetallic dimers were to be used as models of more complex mixed- oxide catalysts. Our current program was to develop the systems and use them in model oxidation reactions.

  3. Modeling Global Urbanization Supported by Nighttime Light Remote Sensing

    Science.gov (United States)

    Zhou, Y.

    2015-12-01

    Urbanization, a major driver of global change, profoundly impacts our physical and social world, for example, altering carbon cycling and climate. Understanding these consequences for better scientific insights and effective decision-making unarguably requires accurate information on urban extent and its spatial distributions. In this study, we developed a cluster-based method to estimate the optimal thresholds and map urban extents from the nighttime light remote sensing data, extended this method to the global domain by developing a computational method (parameterization) to estimate the key parameters in the cluster-based method, and built a consistent 20-year global urban map series to evaluate the time-reactive nature of global urbanization (e.g. 2000 in Fig. 1). Supported by urban maps derived from nightlights remote sensing data and socio-economic drivers, we developed an integrated modeling framework to project future urban expansion by integrating a top-down macro-scale statistical model with a bottom-up urban growth model. With the models calibrated and validated using historical data, we explored urban growth at the grid level (1-km) over the next two decades under a number of socio-economic scenarios. The derived spatiotemporal information of historical and potential future urbanization will be of great value with practical implications for developing adaptation and risk management measures for urban infrastructure, transportation, energy, and water systems when considered together with other factors such as climate variability and change, and high impact weather events.

  4. Towards a Tool-Supported Quality Model for Model-Driven Engineering

    OpenAIRE

    Mohagheghi, Parastoo

    2008-01-01

    This paper reviews definitions of model quality before introducing five properties of models that are important for building high-quality models. These are identified to be correctness, completeness, consistency, comprehensibility and confinement. We have earlier defined a quality model that separates intangible quality goals from tangible quality-carrying properties and practices that should be in place to support these properties.  A part of that work was to define a metamodel for deve...

  5. Urban modeling over Houston in support of SIMMER

    Science.gov (United States)

    Barlage, M. J.; Monaghan, A. J.; Feddema, J. J.; Oleson, K. W.; Brunsell, N. A.; Wilhelmi, O.

    2011-12-01

    Extreme heat is a leading cause of weather-related human mortality in the United States. As global warming patterns continue, researchers anticipate increases in the severity, frequency and duration of extreme heat events, especially in the southern and western U.S. Many cities in these regions may have amplified vulnerability due to their rapidly evolving socioeconomic fabric (for example, growing elderly populations). This raises a series of questions about the increased health risks of urban residents to extreme heat, and about effective means of mitigation and adaptation in present and future climates. We will introduce a NASA-funded project aimed at addressing these questions via the System for Integrated Modeling of Metropolitan Extreme Heat Risk (SIMMER). Through SIMMER, we hope to advance methodology for assessing current and future urban vulnerabilities from the heat waves through the refinement and integration of physical and social science models, and to build local capacity for heat hazard mitigation and climate change adaptation in the public health sector. We will also present results from a series of sensitivity studies over Houston and surrounding area employing a recently-implemented multi-layer urban canopy model (UCM) within the Noah Land Surface Model. The UCM has multiple layers in the atmosphere to explicitly resolve the effects of buildings, and has an indoor-outdoor exchange model that directly interacts with the atmospheric boundary layer. The goal of this work, which supports the physical science component of SIMMER, is to characterize the ill-defined and uncertain parameter space, including building characteristics and spatial organization, in the new multi-layer UCM for Houston, and to assess whether and how this parameter space is sensitive to the choice of urban morphology datasets. Results focus on the seasonal and inter-annual range of both the modeled urban heat island effect and the magnitude of surface energy components and

  6. Integrated models to support multiobjective ecological restoration decisions.

    Science.gov (United States)

    Fraser, Hannah; Rumpff, Libby; Yen, Jian D L; Robinson, Doug; Wintle, Brendan A

    2017-12-01

    Many objectives motivate ecological restoration, including improving vegetation condition, increasing the range and abundance of threatened species, and improving species richness and diversity. Although models have been used to examine the outcomes of ecological restoration, few researchers have attempted to develop models to account for multiple, potentially competing objectives. We developed a combined state-and-transition, species-distribution model to predict the effects of restoration actions on vegetation condition and extent, bird diversity, and the distribution of several bird species in southeastern Australian woodlands. The actions reflected several management objectives. We then validated the models against an independent data set and investigated how the best management decision might change when objectives were valued differently. We also used model results to identify effective restoration options for vegetation and bird species under a constrained budget. In the examples we evaluated, no one action (improving vegetation condition and extent, increasing bird diversity, or increasing the probability of occurrence for threatened species) provided the best outcome across all objectives. In agricultural lands, the optimal management actions for promoting the occurrence of the Brown Treecreeper (Climacteris picumnus), an iconic threatened species, resulted in little improvement in the extent of the vegetation and a high probability of decreased vegetation condition. This result highlights that the best management action in any situation depends on how much the different objectives are valued. In our example scenario, no management or weed control were most likely to be the best management options to satisfy multiple restoration objectives. Our approach to exploring trade-offs in management outcomes through integrated modeling and structured decision-support approaches has wide application for situations in which trade-offs exist between competing

  7. Selective alkane activation with single-site atoms on amorphous support

    Science.gov (United States)

    Hock, Adam S.; Schweitzer, Neil M.; Miller, Jeffrey T.; Hu, Bo

    2015-11-24

    The present invention relates generally to catalysts and methods for use in olefin production. More particularly, the present invention relates to novel amorphously supported single-center, Lewis acid metal ions and use of the same as catalysts.

  8. Green Transport Balanced Scorecard Model with Analytic Network Process Support

    Directory of Open Access Journals (Sweden)

    David Staš

    2015-11-01

    Full Text Available In recent decades, the performance of economic and non-economic activities has required them to be friendly with the environment. Transport is one of the areas having considerable potential within the scope. The main assumption to achieve ambitious green goals is an effective green transport evaluation system. However, these systems are researched from the industrial company and supply chain perspective only sporadically. The aim of the paper is to design a conceptual framework for creating the Green Transport (GT Balanced Scorecard (BSC models from the viewpoint of industrial companies and supply chains using an appropriate multi-criteria decision making method. The models should allow green transport performance evaluation and support of an effective implementation of green transport strategies. Since performance measures used in Balanced Scorecard models are interdependent, the Analytic Network Process (ANP was used as the appropriate multi-criteria decision making method. The verification of the designed conceptual framework was performed on a real supply chain of the European automotive industry.

  9. Early diagnosis model for meningitis supports public health decision making.

    Science.gov (United States)

    Close, Rebecca M; Ejidokun, Oluwatoyin O; Verlander, Neville Q; Fraser, Graham; Meltzer, Margie; Rehman, Yasmin; Muir, Peter; Ninis, Nelly; Stuart, James M

    2011-07-01

    To develop a predictive model for rapid differential diagnosis of meningitis and meningococcal septicaemia to support public health decisions on chemoprophylaxis for contacts. Prospective study of suspected cases of acute meningitis and meningococcal septicaemia admitted to hospitals in the South West, West Midlands and London Regions of England from July 2008 to June 2009. Epidemiological, clinical and laboratory variables on admission were recorded. Logistic regression was used to derive a predictive model. Of the 719 suspect cases reported, 385 confirmed cases were included in analysis. Peripheral blood polymorphonuclear count of >16 × 10(9)/l, serum C-reactive protein of >100 mg/l and haemorrhagic rash were strongly and independently associated with diagnosis of bacterial meningitis and meningococcal septicaemia. Using a simple scoring system, the presence of any one of these factors gave a probability of >95% in predicting the final diagnosis. We have developed a model using laboratory and clinical factors, but not dependent on availability of CSF, for differentiating acute bacterial from viral meningitis within a few hours of admission to hospital. This scoring system is recommended in public health management of suspected cases of meningitis and meningococcal septicaemia to inform decisions on chemoprophylaxis. Copyright © 2011 The British Infection Association. Published by Elsevier Ltd. All rights reserved.

  10. Scour around Support Structures of Scaled Model Marine Hydrokinetic Devices

    Science.gov (United States)

    Volpe, M. A.; Beninati, M. L.; Krane, M.; Fontaine, A.

    2013-12-01

    Experiments are presented to explore scour due to flows around support structures of marine hydrokinetic (MHK) devices. Three related studies were performed to understand how submergence, scour condition, and the presence of an MHK device impact scour around the support structure (cylinder). The first study focuses on clear-water scour conditions for a cylinder of varying submergence: surface-piercing and fully submerged. The second study centers on three separate scour conditions (clear-water, transitional and live-bed) around the fully submerged cylinder. Lastly, the third study emphasizes the impact of an MHK turbine on scour around the support structure, in live-bed conditions. Small-scale laboratory testing of model devices can be used to help predict the behavior of MHK devices at full-scale. Extensive studies have been performed on single cylinders, modeling bridge piers, though few have focused on fully submerged structures. Many of the devices being used to harness marine hydrokinetic energy are fully submerged in the flow. Additionally, scour hole dimensions and scour rates have not been addressed. Thus, these three studies address the effect of structure blockage/drag, and the ambient scour conditions on scour around the support structure. The experiments were performed in the small-scale testing platform in the hydraulic flume facility (9.8 m long, 1.2 m wide and 0.4 m deep) at Bucknell University. The support structure diameter (D = 2.54 cm) was held constant for all tests. The submerged cylinder (l/D = 5) and sediment size (d50 = 790 microns) were held constant for all three studies. The MHK device (Dturbine = 10.2 cm) is a two-bladed horizontal axis turbine and the rotating shaft is friction-loaded using a metal brush motor. For each study, bed form topology was measured after a three-hour time interval using a traversing two-dimensional bed profiler. During the experiments, scour hole depth measurements at the front face of the support structure

  11. Role of Tricoordinate Al Sites in CH3ReO3/Al2O3 Olefin Metathesis Catalysts.

    Science.gov (United States)

    Valla, Maxence; Wischert, Raphael; Comas-Vives, Aleix; Conley, Matthew P; Verel, René; Copéret, Christophe; Sautet, Philippe

    2016-06-01

    Re2O7 supported on γ-alumina is an alkene metathesis catalyst active at room temperature, compatible with functional groups, but the exact structures of the active sites are unknown. Using CH3ReO3/Al2O3 as a model for Re2O7/Al2O3, we show through a combination of reactivity studies, in situ solid-state NMR, and an extensive series of DFT calculations, that μ-methylene structures (Al-CH2-ReO3-Al) containing a Re═O bound to a tricoordinated Al (AlIII) and CH2 bound to a four-coordinated Al (AlIVb) are the precursors of the most active sites for olefin metathesis. The resting state of CH3ReO3/Al2O3 is a distribution of μ-methylene species formed by the activation of the C-H bond of CH3ReO3 on different surface Al-O sites. In situ reaction with ethylene results in the formation of Re metallacycle intermediates, which were studied in detail through a combination of solid-state NMR experiments, using labeled ethylene, and DFT calculations. In particular, we were able to distinguish between metallacycles in TBP (trigonal-bipyramidal) and SP (square-pyramidal) geometry, the latter being inactive and detrimental to catalytic activity. The SP sites are more likely to be formed on other Al sites (AlIVa/AlIVa). Experimentally, the activity of CH3ReO3/Al2O3 depends on the activation temperature of alumina; catalysts activated at or above 500 °C contain more active sites than those activated at 300 °C. We show that the dependence of catalytic activity on the Al2O3 activation temperature is related to the quantity of available AlIII-defect sites and adsorbed H2O.

  12. Odor supported place cell model and goal navigation in rodents

    DEFF Research Database (Denmark)

    Kulvicius, Tomas; Tamosiunaite, Minija; Ainge, James

    2008-01-01

    -generated scent marks to find a food source. Here we model odor supported place cells by using a simple feed-forward network and analyze the impact of olfactory cues on place cell formation and spatial navigation. The obtained place cells are used to solve a goal navigation task by a novel mechanism based on self......-marking by odor patches combined with a Q-learning algorithm. We also analyze the impact of place cell remapping on goal directed behavior when switching between two environments. We emphasize the importance of olfactory cues in place cell formation and show that the utility of environmental and self......-generated olfactory cues, together with a mixed navigation strategy, improves goal directed navigation....

  13. Neutronic Modelling in Support of the Irradiation Programmes

    International Nuclear Information System (INIS)

    Koonen, E.

    2005-01-01

    Irradiation experiments are generally conducted to determine some specific characteristics of the concerned fuels and structural materials under well defined irradiation conditions. For the determination of the latter the BR2 division has an autonomous reactor physics cell and has implemented the required computational tools. The major tool used is a three-dimensional full-scale Monte Carlo model of the BR2 reactor developed under MCNP-4C for the simulation of irradiation conditions. The objectives of work performed by SCK-CEN are to evaluate and adjust irradiation conditions by adjustments of the environment, differential rod positions, axial and azimuthal positioning of the samples, global power level, ...; to deliver reliable, well defined irradiation condition and fluence data during and after irradiation; to assist the designer of new irradiation devices by simulations and neutronic optimisations of design options; to provide computational support to related projects as a way to valorise the capabilities that the BR2 reactor can offer

  14. Experiments and Modeling in Support of Generic Salt Repository Science

    Energy Technology Data Exchange (ETDEWEB)

    Bourret, Suzanne Michelle [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Stauffer, Philip H. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Weaver, Douglas James [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Caporuscio, Florie Andre [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Otto, Shawn [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Boukhalfa, Hakim [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Jordan, Amy B. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Chu, Shaoping [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Zyvoloski, George Anthony [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Johnson, Peter Jacob [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-01-19

    Salt is an attractive material for the disposition of heat generating nuclear waste (HGNW) because of its self-sealing, viscoplastic, and reconsolidation properties (Hansen and Leigh, 2012). The rate at which salt consolidates and the properties of the consolidated salt depend on the composition of the salt, including its content in accessory minerals and moisture, and the temperature under which consolidation occurs. Physicochemical processes, such as mineral hydration/dehydration salt dissolution and precipitation play a significant role in defining the rate of salt structure changes. Understanding the behavior of these complex processes is paramount when considering safe design for disposal of heat-generating nuclear waste (HGNW) in salt formations, so experimentation and modeling is underway to characterize these processes. This report presents experiments and simulations in support of the DOE-NE Used Fuel Disposition Campaign (UFDC) for development of drift-scale, in-situ field testing of HGNW in salt formations.

  15. Progressor: social navigation support through open social student modeling

    Science.gov (United States)

    Hsiao, I.-Han; Bakalov, Fedor; Brusilovsky, Peter; König-Ries, Birgitta

    2013-06-01

    The increased volumes of online learning content have produced two problems: how to help students to find the most appropriate resources and how to engage them in using these resources. Personalized and social learning have been suggested as potential ways to address these problems. Our work presented in this paper combines the ideas of personalized and social learning in the context of educational hypermedia. We introduce Progressor, an innovative Web-based tool based on the concepts of social navigation and open student modeling that helps students to find the most relevant resources in a large collection of parameterized self-assessment questions on Java programming. We have evaluated Progressor in a semester-long classroom study, the results of which are presented in this paper. The study confirmed the impact of personalized social navigation support provided by the system in the target context. The interface encouraged students to explore more topics attempting more questions and achieving higher success rates in answering them. A deeper analysis of the social navigation support mechanism revealed that the top students successfully led the way to discovering most relevant resources by creating clear pathways for weaker students.

  16. Separation of Olefin/Paraffin Mixtures with Carrier Facilitated Membrane Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Merkel, T.C.; Blanc, R.; Zeid, J.; Suwarlim, A.; Firat, B.; Wijmans, H.; Asaro, M. (SRI); Greene, M.(Lummus)

    2007-03-12

    This document describes the results of a DOE funded joint effort of Membrane Technology and Research Inc. (MTR), SRI International (SRI), and ABB Lummus (ABB) to develop facilitated transport membranes for olefin/paraffin separations. Currently, olefin/paraffin separation is done by distillation—an extremely energy-intensive process because of the low relative volatilities of olefins and paraffins. If facilitated transport membranes could be successfully commercialized, the potential energy savings achievable with this membrane technology are estimated to be 48 trillion Btu per year by the year 2020. We discovered in this work that silver salt-based facilitated transport membranes are not stable even in the presence of ideal olefin/paraffin mixtures. This decline in membrane performance appears to be caused by a previously unrecognized phenomenon that we have named olefin conditioning. As the name implies, this mechanism of performance degradation becomes operative once a membrane starts permeating olefins. This project is the first study to identify olefin conditioning as a significant factor impacting the performance of facilitated olefin transport membranes. To date, we have not identified an effective strategy to mitigate the impact of olefin conditioning. other than running at low temperatures or with low olefin feed pressures. In our opinion, this issue must be addressed before further development of facilitated olefin transport membranes can proceed. In addition to olefin conditioning, traditional carrier poisoning challenges must also be overcome. Light, hydrogen, hydrogen sulfide, and acetylene exposure adversely affect membrane performance through unwanted reaction with silver ions. Harsh poisoning tests with these species showed useful membrane lifetimes of only one week. These tests demonstrate a need to improve the stability of the olefin complexing agent to develop membranes with lifetimes satisfactory for commercial application. A successful effort

  17. Synthesis of thermoplastic poly(ester-olefin elastomers

    Directory of Open Access Journals (Sweden)

    Tanasijević Branka

    2004-01-01

    Full Text Available A series of thermoplastic poly(ester-olefin elastomers, based on poly(ethylene-stat-butylene, HO-PEB-OH, as the soft segment and poly (butylene terephthalate, PBT, as the hard segment, were synthesized by a catalyzed transesterification reaction in solution. The incorporation of soft hydrogenated poly(butadiene segments into the copolyester backbone was accomplished by the polycondensation of α, ω-dihydroxyl telechelic HO-PEB-OH, (PEB Mn = 3092 g/mol with 1,4-butanediol (BD and dimethyl terephthalate (DMT in the presence of a 50 wt-% high boiling solvent i.e., 1,2,4-trichlorobenzene. The molar ratio of the starting comonomers was selected to result in a constant hard to soft weight ratio of 60:40. The synthesis was optimized in terms of both the concentration of catalyst, tetra-n-butyl-titanate (Ti(OBu4, and stabilizer, N,N'-diphenyl-p-phenylenediamine (DPPD, as well as the reaction time. It was found that the optimal catalyst concentration (Ti(OBu4 for the synthesis of these thermoplastic elastomers was 1.0 mmol/mol ester and the optimal DPPD concentration was 1.0 wt-%. The extent of the reaction was followed by measuring the inherent viscosity of the reaction mixture. The effectiveness of the incorporation of the soft segments into the copolymer chains was proved by Soxhlet extraction with chloroform. The molecular structures, composition and the size of the synthesized poly(ester-butylenes were verified by 1H NMR spectroscopy, viscometry of dilute solutions and the complex dynamic melt viscosity. The thermal properties of poly(ester-olefins were investigated by differential scanning calorimetry (DSC. The degree of crystallinity was also determined by DSC. The thermal and thermo-oxidative stability were investigated by thermogravimetric analysis (TGA. The rheological properties of poly(ester-olefins were investigated by dynamic mechanical spectroscopy in the melt and solid state.

  18. Refining of plant oils to chemicals by olefin metathesis.

    Science.gov (United States)

    Chikkali, Samir; Mecking, Stefan

    2012-06-11

    Plant oils are attractive substrates for the chemical industry. Their scope for the production of chemicals can be expanded by sophisticated catalytic conversions. Olefin metathesis is an example, which also illustrates generic issues of "biorefining" to chemicals. Utilization on a large scale requires high catalyst activities, which influences the choice of the metathesis reaction. The mixture of different fatty acids composing a technical-grade plant oil substrate gives rise to a range of products. This decisively determines possible process schemes, and potentially provides novel chemicals and intermediates not employed to date. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. N-Heterocyclic Carbene Complexes in Olefin Metathesis

    Science.gov (United States)

    Luan, Xinjun; Dorta, Reto; Leitgeb, Anita; Slugovc, Christian; Tiede, Sascha; Blechert, Siegfried

    Olefin metathesis is now a synthetic tool found ubiquitously in various fields involving synthesis. Of its many variations, three are prominently used: (1) catalytic ring closing metathesis (RCM) is an extremely powerful method for the construction of carbon-carbon double bonds in organic chemistry; (2) ring opening metathesis polymerisation (ROMP) where polymers are formed by use of the energy released from cyclic strain; and (3) cross metathesis (CM) where non-cyclic partners are coupled through C-C double bond formation. These important transformations and variations on these themes mediated by second generation ruthenium complexes bearing a NHC ligand will be presented in the following sections.

  20. Radiation chemical addition of dimethylformamide to α-olefins

    International Nuclear Information System (INIS)

    Dederichs, B.; Saus, A.; Lennertz, A.M.

    1977-10-01

    With n-hexene-1, n-octene-1 and n-decene-1 the radiation-initiated addition of demethyl formamide to α-olefins is described for the fist time. N,N-dimethyl alkane carbonic acid amides and N-methyl-N-alkyl formamides are formed in a ratio of about 50:50. The addition reaction is investigated in depencence of a solvent, of the ratio of the reaction, temperature, reaction time and dose rate. Mechanistic considerations are performed by radiolysis experiments of dimethyl formamide. (orig.) [de

  1. Transmissive Olefination Route to Putative “Morinol I” Lignans

    Science.gov (United States)

    Yao, Lihua; Pitta, Bhaskar; Ravikumar, P. C.; Purzycki, Matthew; Fleming, Fraser F.

    2012-01-01

    A series of morinol-type lignans were rapidly assembled using a Grignard-based transmissive olefination. In combination with palladium-catalyzed arylations, the strategy provides stereoselective access to (7Z, 7′E), (7E, 7′E), (7E, 7′Z) morinol diastereomers and the (7Z, 8′E) and (7E, 8′E) conjugated analogs. Critical for the E/Z-stereoselectivity is a new, general method for converting alkenenitriles to alkenemethanols that circumvents the enal E/Z isomerization commonly encountered during conventional i-Bu2AlH reduction. PMID:22432777

  2. Thermoplastic Adhesives based on polyolefin and olefinic copolymers

    Science.gov (United States)

    Paul, Rituparna

    2014-03-01

    H.B. Fuller has been a leading global industrial adhesive manufacturer for over 125 years. It is a company with a rich history of consistently delivering adhesive innovations for enhancing product performance in the market place. H.B. Fuller technologies/products find application in several markets including packaging, personal hygiene and nonwovens, durable assembly and electronics. In this presentation, H. B. Fuller's technology innovation journey will be shared with emphasis on groundbreaking technologies/products based on polyolefin and olefin copolymers.

  3. SIMULATION MODEL FOR DESIGN SUPPORT OF INFOCOMM REDUNDANT SYSTEMS

    Directory of Open Access Journals (Sweden)

    V. A. Bogatyrev

    2016-09-01

    Full Text Available Subject of Research. The paper deals with the effectiveness of multipath transfer of request copies through the network and their redundant service without the use of laborious analytical modeling. The model and support tools for the design of highly reliable distributed systems based on simulation modeling have been created. Method. The effectiveness of many variants of service organization and delivery through the network to the query servers is formed and analyzed. Options for providing redundant service and delivery via the network to the servers of request copies are also considered. The choice of variants for the distribution and service of requests is carried out taking into account the criticality of queries to the time of their stay in the system. The request is considered successful if at least one of its copies is accurately delivered to the working server, ready to service the request received through a network, if it is fulfilled in the set time. Efficiency analysis of the redundant transmission and service of requests is based on the model built in AnyLogic 7 simulation environment. Main Results. Simulation experiments based on the proposed models have shown the effectiveness of redundant transmission of copies of queries (packets to the servers in the cluster through multiple paths with redundant service of request copies by a group of servers in the cluster. It is shown that this solution allows increasing the probability of exact execution of at least one copy of the request within the required time. We have carried out efficiency evaluation of destruction of outdated request copies in the queues of network nodes and the cluster. We have analyzed options for network implementation of multipath transfer of request copies to the servers in the cluster over disjoint paths, possibly different according to the number of their constituent nodes. Practical Relevance. The proposed simulation models can be used when selecting the optimal

  4. Caregiver social support quality when interacting with cancer survivors: advancing the dual-process model of supportive communication.

    Science.gov (United States)

    Harvey-Knowles, Jacquelyn; Faw, Meara H

    2018-04-01

    Cancer caregivers often experience significant challenges in their motivation and ability to comfort cancer survivors, particularly in a spousal or romantic context. Spousal cancer caregivers have been known to report even greater levels of burden and distress than cancer sufferers, yet still take on the role of acting as an informal caregiver so they can attend to their partner's needs. The current study tested whether a theoretical model of supportive outcomes-the dual-process model of supportive communication-explained variations in cancer caregivers' motivation and ability to create high-quality support messages. The study also tested whether participant engagement with reflective journaling on supportive acts was associated with increased motivation or ability to generate high-quality support messages. Based upon the dual-process model, we posited that, following supportive journaling tasks, caregivers of spouses currently managing a cancer experience would report greater motivation but also greater difficulty in generating high-quality support messages, while individuals caring for a patient in remission would report lower motivation but greater ability to create high-quality support messages. Findings provided support for these assertions and suggested that reflective journaling tasks might be a useful tool for improving remission caregivers' ability to provide high-quality social support to survivors. Corresponding theoretical and applied implications are discussed.

  5. Modelling of the Human Knee Joint Supported by Active Orthosis

    Science.gov (United States)

    Musalimov, V.; Monahov, Y.; Tamre, M.; Rõbak, D.; Sivitski, A.; Aryassov, G.; Penkov, I.

    2018-02-01

    The article discusses motion of a healthy knee joint in the sagittal plane and motion of an injured knee joint supported by an active orthosis. A kinematic scheme of a mechanism for the simulation of a knee joint motion is developed and motion of healthy and injured knee joints are modelled in Matlab. Angles between links, which simulate the femur and tibia are controlled by Simulink block of Model predictive control (MPC). The results of simulation have been compared with several samples of real motion of the human knee joint obtained from motion capture systems. On the basis of these analyses and also of the analysis of the forces in human lower limbs created at motion, an active smart orthosis is developed. The orthosis design was optimized to achieve an energy saving system with sufficient anatomy, necessary reliability, easy exploitation and low cost. With the orthosis it is possible to unload the knee joint, and also partially or fully compensate muscle forces required for the bending of the lower limb.

  6. Overcoming barriers to development of cooperative medical decision support models.

    Science.gov (United States)

    Hudson, Donna L; Cohen, Maurice E

    2012-01-01

    Attempts to automate the medical decision making process have been underway for the at least fifty years, beginning with data-based approaches that relied chiefly on statistically-based methods. Approaches expanded to include knowledge-based systems, both linear and non-linear neural networks, agent-based systems, and hybrid methods. While some of these models produced excellent results none have been used extensively in medical practice. In order to move these methods forward into practical use, a number of obstacles must be overcome, including validation of existing systems on large data sets, development of methods for including new knowledge as it becomes available, construction of a broad range of decision models, and development of non-intrusive methods that allow the physician to use these decision aids in conjunction with, not instead of, his or her own medical knowledge. None of these four requirements will come easily. A cooperative effort among researchers, including practicing MDs, is vital, particularly as more information on diseases and their contributing factors continues to expand resulting in more parameters than the human decision maker can process effectively. In this article some of the basic structures that are necessary to facilitate the use of an automated decision support system are discussed, along with potential methods for overcoming existing barriers.

  7. Modelling of the Human Knee Joint Supported by Active Orthosis

    Directory of Open Access Journals (Sweden)

    Musalimov V.

    2018-02-01

    Full Text Available The article discusses motion of a healthy knee joint in the sagittal plane and motion of an injured knee joint supported by an active orthosis. A kinematic scheme of a mechanism for the simulation of a knee joint motion is developed and motion of healthy and injured knee joints are modelled in Matlab. Angles between links, which simulate the femur and tibia are controlled by Simulink block of Model predictive control (MPC. The results of simulation have been compared with several samples of real motion of the human knee joint obtained from motion capture systems. On the basis of these analyses and also of the analysis of the forces in human lower limbs created at motion, an active smart orthosis is developed. The orthosis design was optimized to achieve an energy saving system with sufficient anatomy, necessary reliability, easy exploitation and low cost. With the orthosis it is possible to unload the knee joint, and also partially or fully compensate muscle forces required for the bending of the lower limb.

  8. Observations and models of centrifugally supported magnetospheres in massive stars

    Science.gov (United States)

    Oksala, Mary Elizabeth

    Magnetic massive stars, via their strong magnetic fields and radiation-driven winds, strongly influence the dynamical and chemical evolution of their surroundings. The interaction between these two intrinsic stellar properties can produce dynamic circumstellar structures, and, in the case of rapidly rotating stars, centrifugally supported magnetospheres. This thesis uses new observations to confront current magnetosphere models, testing their predictive power using photometry and spectropolarimetry of the prototypical magnetic B2Vp star sigma Ori E. In addition, we present the discovery of a magnetic field in a second rapidly rotating massive star. At the time of its discovery, this star was the most rapidly rotating non-degenerate magnetic star. We begin with an overview of magnetism in massive stars and wind-field interactions (Chapter 2) and the observational techniques involved in their study (Chapter 3), and summarize historical studies of sigma Ori E (Chapter 4). Chapter 5 describes the detection of rotational braking in sigma Ori E. We find a 77 ms yr-1 lengthening of the rotational period, corresponding to a spindown time of 1.34+0.10 -0.09 Myr. This observed period change agrees well with theoretical predictions for angular momentum loss in a magnetically channeled, line-driven wind. Next we present new spectropolarimetric observations of sigma Ori E (Chapter 6). The observed Halpha variability matches the predictions from a rigidly rotating magnetosphere (RRM) model with an offset dipole magnetic field configuration. However, our new, precise longitudinal magnetic field measurements reveal significant discrepancies with respect to the RRM model, challenging the current form as applied to sigma Ori E and suggesting that the field configuration of this star is more complex than a simple dipole. Chapter 7 describes the first detection of a magnetic field in the B2Vn star HR 7355. From analyzing photometric data, we find a 0.5214404(6) d rotational period

  9. Support Vector Machines for Petrophysical Modelling and Lithoclassification

    Science.gov (United States)

    Al-Anazi, Ammal Fannoush Khalifah

    2011-12-01

    Given increasing challenges of oil and gas production from partially depleted conventional or unconventional reservoirs, reservoir characterization is a key element of the reservoir development workflow. Reservoir characterization impacts well placement, injection and production strategies, and field management. Reservoir characterization projects point and line data to a large three-dimensional volume. The relationship between variables, e.g. porosity and permeability, is often established by regression yet the complexities between measured variables often lead to poor correlation coefficients between the regressed variables. Recent advances in machine learning methods have provided attractive alternatives for constructing interpretation models of rock properties in heterogeneous reservoirs. Here, Support Vector Machines (SVMs), a class of a learning machine that is formulated to output regression models and classifiers of competitive generalization capability, has been explored to determine its capabilities for determining the relationship, both in regression and in classification, between reservoir rock properties. This thesis documents research on the capability of SVMs to model petrophysical and elastic properties in heterogeneous sandstone and carbonate reservoirs. Specifically, the capabilities of SVM regression and classification has been examined and compared to neural network-based methods, namely multilayered neural networks, radial basis function neural networks, general regression neural networks, probabilistic neural networks, and linear discriminant analysis. The petrophysical properties that have been evaluated include porosity, permeability, Poisson's ratio and Young's modulus. Statistical error analysis reveals that the SVM method yields comparable or superior predictions of petrophysical and elastic rock properties and classification of the lithology compared to neural networks. The SVM method also shows uniform prediction capability under the

  10. Techno-economic analysis and comparison of coal based olefins processes

    International Nuclear Information System (INIS)

    Xiang, Dong; Yang, Siyu; Qian, Yu

    2016-01-01

    Highlights: • The coal based Fischer–Tropsch-to-olefins (CFTO) process is proposed and analyzed. • The CFTO suffers from lower energy efficiency and serious CO 2 emissions. • Approaches for improving techno-economic performance of the CFTO are obtained. - Abstract: Traditional olefins production is heavily dependent on oil. In the background of the scarcity of oil and richness of coal in China, olefins production from coal has been attracting more attention of the chemical process industry. The first coal based methanol-to-olefins (CMTO) plant has been commercialized in China. For shorter process route and lower capital cost, Fischer–Fropsch has been put forward in the last few years. The coal based Fischer–Tropsch-to-olefins (CFTO) process is designed in this paper and then its techno-economic and environmental performance was detailed studied in this paper, in comparison with the CMTO. Results show that at the present olefins selectivity, the CFTO suffers from relative lower energy efficiency and higher CO 2 emissions. In economic aspect, the capital investment and product cost of the CFTO are roughly equivalent to that of the CMTO. Although the conversion route of the CFTO is shorter, its techno-economic performance is still inferior to that of the CMTO. It is also found that increase of olefins selectivity by cracking oil or decrease of CO 2 selectivity by improving catalyst could significantly improve the performance of the CFTO.

  11. using explanatory models to derive simple tools for Avanced Life Support system studies - Crop Modelling

    Science.gov (United States)

    Cavazzoni, J.

    System-level analyses for Advanced Life Support (ALS) require mathematical models for various processes, such as biomass production and waste management, which would ideally be integrated into overall system models. Explanatory models (also referred to as mechanistic or process models) would provide the basis for a more robust system model, as these would be based on an understanding of processes specific to ALS studies. However, integrating such models may not always be practicable because of their complexity, especially for initial system-level analyses where simple sub-models may be satisfactory. One way to address this is to capture important features of explanatory models in simple models that may be readily integrated for system-level analyses. In this paper, explanatory crop models were used to generate parameters and multi-variable polynomial equations for basic models that are suitable for estimating the direction and magnitude of daily changes in canopy gas-exchange, harvest index, and production scheduling due to off- nominal conditions for ALS system studies. The simplest variant of these models consists of only a few equations, and has been integrated into a top-level SIMULINK model for the Bioregenerative Planetary Life Support Systems Test Complex (BIO-Plex), a large-scale human-rated test facility under development at NASA Johnson Space Center. When included in systems studies, the simple crop models may help identify issues that need to be addressed using more detailed modeling studies and specific experiments. Similar modeling simplifications may also prove useful for other ALS sub-systems, as well as for Earth system applications.

  12. Autonomy support, need satisfaction, and motivation for support among adults with intellectual disability : Testing a self-determination theory model

    NARCIS (Netherlands)

    Frielink, Noud; Schuengel, Carlo; Embregts, Petri J.C.M.

    2018-01-01

    The tenets of self-determination theory as applied to support were tested with structural equation modelling for 186 people with ID with a mild to borderline level of functioning. The results showed that (a) perceived autonomy support was positively associated with autonomous motivation and with

  13. Autonomy Support, Need Satisfaction, and Motivation for Support among Adults with Intellectual Disability: Testing a Self-Determination Theory Model

    Science.gov (United States)

    Frielink, Noud; Schuengel, Carlo; Embregts, Petri J. C. M.

    2018-01-01

    The tenets of self-determination theory as applied to support were tested with structural equation modelling for 186 people with ID with a mild to borderline level of functioning. The results showed that (a) perceived autonomy support was positively associated with autonomous motivation and with satisfaction of need for autonomy, relatedness, and…

  14. Kinetic model and mathematical description of oligomerization of ethylene to higher linear alpha-olefins, catalyzed by the system Zr(OCOiso-C3H7)-(C2H5)3AL2CL3

    International Nuclear Information System (INIS)

    Byrikhina, N.A.; Brikenstein, K.M.; Gerasina, M.P.; Matkovskii, P.E.; Pechatnikov, E L.

    1986-01-01

    The authors have formulated a mathematical model of ethylene oligomerization in the presence of the system Zr (OCOR) 4 - (C 2 H 5 ) 3 AL 2 CL 3 , worked out an approximate analytical description of the kinetic relationships of ethylene consumption in the course of its oligomerization in presence of this system, and estimated the effective rate constants of the principal oligomerization stages

  15. Conversion of Syngas-Derived C2+ Mixed Oxygenates to C3-C5 Olefins over ZnxZryOz Mixed Oxides Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Colin D.; Lebarbier, Vanessa M.; Flake, Matthew D.; Ramasamy, Karthikeyan K.; Kovarik, Libor; Bowden, Mark E.; Onfroy, Thomas; Dagle, Robert A.

    2016-04-01

    In this study we report on a ZnxZryOz mixed oxide type catalyst capable of converting a syngas-derived C2+ mixed oxygenate feedstock to isobutene-rich olefins. Aqueous model feed comprising of ethanol, acetaldehyde, acetic acid, ethyl acetate, methanol, and propanol was used as representative liquid product derived from a Rh-based mixed oxygenate synthesis catalyst. Greater than 50% carbon yield to C3-C5 mixed olefins was demonstrated when operating at 400-450oC and 1 atm. In order to rationalize formation of the products observed feed components were individually evaluated. Major constituents of the feed mixture (ethanol, acetaldehyde, acetic acid, and ethyl acetate) were found to produce isobutene-rich olefins. C-C coupling was also demonstrated for propanol feedstock - a minor constituent of the mixed oxygenate feed - producing branched C6 olefins, revealing scalability to alcohols higher than ethanol following an analogous reaction pathway. Using ethanol and propanol feed mixtures, cross-coupling reactions produced mixtures of C4, C5, and C6 branched olefins. The presence of H2 in the feed was found to facilitate hydrogenation of the ketone intermediates, thus producing straight chain olefins as byproducts. While activity loss from coking is observed complete catalyst regeneration is achieved by employing mild oxidation. For conversion of the mixed oxygenate feed a Zr/Zn ratio of 2.5 and a reaction temperature of 450oC provides the best balance of stability, activity, and selectivity. X-ray diffraction and scanning transmission electron microscopy analysis reveals the presence of primarily cubic phase ZrO2 and a minor amount of the monoclinic phase, with ZnO being highly dispersed in the lattice. The presence of ZnO appears to stabilize the cubic phase resulting in less monoclinic phase as the ZnO concentration increases. Infrared spectroscopy shows the mixed oxide acid sites are characterized as primarily Lewis type acidity. The direct relationship between

  16. Z-Selective Catalytic Olefin Cross-Metathesis

    Science.gov (United States)

    Meek, Simon J.; O’Brien, Robert V.; Llaveria, Josep; Schrock, Richard R.; Hoveyda, Amir H.

    2011-01-01

    Alkenes are found in a great number of biologically active molecules and are employed in numerous transformations in organic chemistry. Many olefins exist as E or higher energy Z isomers. Catalytic procedures for stereoselective formation of alkenes are therefore valuable; nonetheless, methods for synthesis of 1,2-disubstituted Z olefins are scarce. Here we report catalytic Z-selective cross-metathesis reactions of terminal enol ethers, which have not been reported previously, and allylic amides, employed thus far only in E-selective processes; the corresponding disubstituted alkenes are formed in up to >98% Z selectivity and 97% yield. Transformations, promoted by catalysts that contain the highly abundant and inexpensive molybdenum, are amenable to gram scale operations. Use of reduced pressure is introduced as a simple and effective strategy for achieving high stereoselectivity. Utility is demonstrated by syntheses of anti-oxidant C18 (plasm)-16:0 (PC), found in electrically active tissues and implicated in Alzheimer’s disease, and the potent immunostimulant KRN7000. PMID:21430774

  17. Homobimetallic Ruthenium-N-Heterocyclic Carbene Complexes For Olefin Metathesis

    Science.gov (United States)

    Sauvage, Xavier; Demonceau, Albert; Delaude, Lionel

    In this chapter, the synthesis and catalytic activity towards olefin metathesis of homobimetallic ruthenium (Ru)-alkylidene, -cyclodiene or -arene complexes bearing phosphine or N-heterocyclic carbene (NHC) ligands are reviewed. Emphasis is placed on the last category of bimetallic compounds. Three representatives of this new type of molecular scaffold were investigated. Thus, [(p-cymene)Ru(m-Cl)3RuCl (h2-C2H4)(L)] complexes with L = PCy3 (15a), IMes (16a), or IMesCl2 (16b) were prepared. They served as catalyst precursors for cross-metathesis (CM) of various styrene derivatives. These experiments revealed the outstanding aptitude of complex 16a (and to a lesser extent of 16b) to catalyze olefin metathesis reactions. Contrary to monometallic Ru-arene complexes of the [RuCl2(p-cymene)(L)] type, the new homobimetallic species did not require the addition of a diazo compound nor visible light illumination to initiate the ring-opening metathesis of norbornene or cyclooctene. When diethyl 2,2-diallylmalonate and N,N-diallyltosylamide were exposed to 16a,b, a mixture of cycloisomerization and ring-closing metathesis (RCM) products was obtained in a nonselective way. Addition of phenylacetylene enhanced the metathetical activity while completely repressing the cycloisomerization process.

  18. Hydroxycarbonylation of olefins and alcohols in ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Eliseev, O.L.; Bondarenko, T.N.; Stepin, N.N. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Institute of Organic Chemistry

    2006-07-01

    Palladium-catalysed hydroxycarbonylation of olefins and alcohols proceeds in ionic liquid media. Terminal and internal olefins, cyclohexene, styrene, methanol, ethanol, n-butanol, cyclohexanol, benzyl alcohol and 1-phenylethanol were tested as substrates for the reaction. A number of molten salts were applied as a reaction medium and tetrabutylammonium bromide (m.p. 103 C) seemed to be the best. Carbon monoxide pressure of 2 MPa and reaction temperature of 110 C are suitable conditions to furnish the reaction in 2 hours in the presence of palladium acetate as a precursor. Triphenylphosphine added as a ligand reduces reaction rate. The critical role of counter anion in molten salt was also recognised. Yield of acids decreased in the order: Br{sup -} > Cl{sup -} > BF{sub 4} {approx}PF{sub 6}{sup -}. A two-route reaction scheme is proposed to explain the regularities of styrene and 1-phenylethanol hydroxycarbonylation. The catalytic system can be used repeatedly by simple extraction of products with diethyl ether. Nine cycles were carried out without loss of activity. (orig.)

  19. Catalytic oxidation. VI. Oxidation of labeled olefins over silver

    International Nuclear Information System (INIS)

    Cant, N.W.; Hall, W.K.

    1978-01-01

    The oxidation of ethylene and propylene labeled with deuterium in various positions and the cooxidation of unlabeled olefins with the corresponding 14 C-labeled epoxides have been studied over a silver catalyst. The latter measurements showed that, in both systems at 200 to 220 0 C, a portion of the CO 2 was produced by destruction of the product epoxide, but that the oxygen exchange between olefin and epoxide was nil. Oxidation of either cis- or trans-ethylene-d 2 yielded a mixture of the cis- and trans-d 2 epoxides which was about 92% equilibrated. Relative rate measurements showed that substitution of deuterium for hydrogen in ethylene increased the yield of epoxide substantially. Such kinetic isotope effects were even more pronounced with propylene for which the oxidation of CD 3 CHCH 2 and CD 3 CDCD 2 gave a 10 to 14% selectivity to the corresponding epoxides compared with 2 to 5% for CH 3 CHCH 2 , CH 3 CDCH 2 , and CH 3 CHCD 2 . The kinetic isotope effects can be qualitatively explained in terms of a normal primary effect in the further oxidation of an intermediate which is common to both epoxide formation and total oxidation. The significance of these findings to previous suggestions regarding surface intermediates and the mechanism of these oxidations is discussed. 4 figures, 5 tables

  20. Connecting Biochemical Photosynthesis Models with Crop Models to Support Crop Improvement

    Science.gov (United States)

    Wu, Alex; Song, Youhong; van Oosterom, Erik J.; Hammer, Graeme L.

    2016-01-01

    The next advance in field crop productivity will likely need to come from improving crop use efficiency of resources (e.g., light, water, and nitrogen), aspects of which are closely linked with overall crop photosynthetic efficiency. Progress in genetic manipulation of photosynthesis is confounded by uncertainties of consequences at crop level because of difficulties connecting across scales. Crop growth and development simulation models that integrate across biological levels of organization and use a gene-to-phenotype modeling approach may present a way forward. There has been a long history of development of crop models capable of simulating dynamics of crop physiological attributes. Many crop models incorporate canopy photosynthesis (source) as a key driver for crop growth, while others derive crop growth from the balance between source- and sink-limitations. Modeling leaf photosynthesis has progressed from empirical modeling via light response curves to a more mechanistic basis, having clearer links to the underlying biochemical processes of photosynthesis. Cross-scale modeling that connects models at the biochemical and crop levels and utilizes developments in upscaling leaf-level models to canopy models has the potential to bridge the gap between photosynthetic manipulation at the biochemical level and its consequences on crop productivity. Here we review approaches to this emerging cross-scale modeling framework and reinforce the need for connections across levels of modeling. Further, we propose strategies for connecting biochemical models of photosynthesis into the cross-scale modeling framework to support crop improvement through photosynthetic manipulation. PMID:27790232

  1. Metallocene-catalyzed ethylene−α-olefin isomeric copolymerization: A perspective from hydrodynamic boundary layer mass transfer and design of MAO anion

    KAUST Repository

    Adamu, Sagir

    2015-11-28

    This study reports a novel conceptual framework that can be easily experimented to evaluate the effects of hydrodynamic boundary layer mass transfer, methylaluminoxane (MAO) anion design, and comonomer steric hindrance on metallocene-catalyzed ethylene polymerization. This approach was illustrated by conducting homo- and isomeric copolymerization of ethylene with 1-hexene and 4-methyl-1-pentene in the presence of bis(n-butylcyclopentadienyl) zirconium dichloride (nBuCp)2ZrCl2, using (i) MAO anion 1 (unsupported [MAOCl2]−) and pseudo-homogeneous reference polymerization, and (ii) MAO anion 2 (supported Si−O−[MAOCl2]−) and in-situ heterogeneous polymerization. The measured polymer morphology, catalyst productivity, molecular weight distribution, and inter-chain composition distribution were related to the locus of polymerization, comonomer effect, in-situ chain transfer process, and micromixing effect, respectively. The peak melting and crystallization temperatures and %crystallinity were mathematically correlated to the parameters of microstructural composition distributions, melt fractionation temperatures, and average lamellar thickness. These relations showed to be insightful. The comonomer-induced enchainment defects and the eventual partial disruption of the crystal lattice were successfully modeled using Flory and Gibbs–Thompson equations. The present methodology can also be applied to study ethylene−α-olefin copolymerization, performed using MAO-activated non-metallocene precatalysts.

  2. Primary Alcohols from Terminal Olefins: Formal Anti-Markovnikov Hydration via Triple Relay Catalysis

    KAUST Repository

    Dong, G.

    2011-09-15

    Alcohol synthesis is critical to the chemical and pharmaceutical industries. The addition of water across olefins to form primary alcohols (anti-Markovnikov olefin hydration) would be a broadly useful reaction but has largely proven elusive; an indirect hydroboration/oxidation sequence requiring stoichiometric borane and oxidant is currently the most practical methodology. Here, we report a more direct approach with the use of a triple relay catalysis system that couples palladium-catalyzed oxidation, acid-catalyzed hydrolysis, and ruthenium-catalyzed reduction cycles. Aryl-substituted terminal olefins are converted to primary alcohols by net reaction with water in good yield and excellent regioselectivity.

  3. Pd-Boron-Catalyzed One Carbon Isomerization of Olefins: Water Assisted Process at Room Temperature.

    Science.gov (United States)

    Ojha, Devi Prasan; Gadde, Karthik; Prabhu, Kandikere Ramaiah

    2017-05-05

    A palladium-boronate/borane-system -catalyzed isomerization of olefins has been uncovered. An efficient catalytic combination of [Pd(OAc) 2 ] 3 -boronate-PCy 3 -enabled olefin isomerization at 80 °C has been investigated. Addition of water to the reaction showed a remarkable improvement and the isomerization occurred at ambient temperature. These catalytic systems function efficiently for the isomerization of functionalized as well as unfunctionalized olefins. The catalytic conditions demonstrate the involvement of both nonhydride and metal-hydride medium and can be switchable with water as an additive.

  4. In vivo and in vitro olefin cyclopropanation catalyzed by heme enzymes

    Science.gov (United States)

    Coelho, Pedro S; Brustad, Eric M; Arnold, Frances H; Wang, Zhan; Lewis, Jared C

    2015-03-31

    The present invention provides methods for catalyzing the conversion of an olefin to any compound containing one or more cyclopropane functional groups using heme enzymes. In certain aspects, the present invention provides a method for producing a cyclopropanation product comprising providing an olefinic substrate, a diazo reagent, and a heme enzyme; and admixing the components in a reaction for a time sufficient to produce a cyclopropanation product. In other aspects, the present invention provides heme enzymes including variants and fragments thereof that are capable of carrying out in vivo and in vitro olefin cyclopropanation reactions. Expression vectors and host cells expressing the heme enzymes are also provided by the present invention.

  5. FeCl3 -Catalyzed Ring-Closing Carbonyl-Olefin Metathesis.

    Science.gov (United States)

    Ma, Lina; Li, Wenjuan; Xi, Hui; Bai, Xiaohui; Ma, Enlu; Yan, Xiaoyu; Li, Zhiping

    2016-08-22

    Exploiting catalytic carbonyl-olefin metathesis is an ongoing challenge in organic synthesis. Reported herein is an FeCl3 -catalyzed ring-closing carbonyl-olefin metathesis. The protocol allows access to a range of carbo-/heterocyclic alkenes with good efficiency and excellent trans diastereoselectivity. The methodology presents one of the rare examples of catalytic ring-closing carbonyl-olefin metathesis. This process is proposed to take place by FeCl3 -catalyzed oxetane formation followed by retro-ring-opening to deliver metathesis products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Simple and highly Z-selective ruthenium-based olefin metathesis catalyst.

    Science.gov (United States)

    Occhipinti, Giovanni; Hansen, Fredrik R; Törnroos, Karl W; Jensen, Vidar R

    2013-03-06

    A one-step substitution of a single chloride anion of the Grubbs-Hoveyda second-generation catalyst with a 2,4,6-triphenylbenzenethiolate ligand resulted in an active olefin metathesis catalyst with remarkable Z selectivity, reaching 96% in metathesis homocoupling of terminal olefins. High turnover numbers (up to 2000 for homocoupling of 1-octene) were obtained along with sustained appreciable Z selectivity (>85%). Apart from the Z selectivity, many properties of the new catalyst, such as robustness toward oxygen and water as well as a tendency to isomerize substrates and react with internal olefin products, resemble those of the parent catalyst.

  7. In vivo and in vitro olefin cyclopropanation catalyzed by heme enzymes

    Energy Technology Data Exchange (ETDEWEB)

    Coelho, Pedro S.; Brustad, Eric M.; Arnold, Frances H.; Wang, Zhan; Lewis, Jared C.

    2016-11-15

    The present invention provides methods for catalyzing the conversion of an olefin to any compound containing one or more cyclopropane functional groups using heme enzymes. In certain aspects, the present invention provides a method for producing a cyclopropanation product comprising providing an olefinic substrate, a diazo reagent, and a heme enzyme; and admixing the components in a reaction for a time sufficient to produce a cyclopropanation product. In other aspects, the present invention provides heme enzymes including variants and fragments thereof that are capable of carrying out in vivo and in vitro olefin cyclopropanation reactions. Expression vectors and host cells expressing the heme enzymes are also provided by the present invention.

  8. Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols.

    Science.gov (United States)

    Li, Junjun; Liu, Yuxuan; Tang, Weijun; Xue, Dong; Li, Chaoqun; Xiao, Jianliang; Wang, Chao

    2017-10-17

    The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen-borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks. Mechanistic studies suggest that the alkylation product may be formed through conjugate reduction of an alkene intermediate by a rhodium hydride, whereas the formation of olefin product may be due to the oxidation of the rhodium hydride complex with molecular oxygen. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Ligand-Enabled γ-C(sp(3))-H Olefination of Amines: En Route to Pyrrolidines.

    Science.gov (United States)

    Jiang, Heng; He, Jian; Liu, Tao; Yu, Jin-Quan

    2016-02-17

    Pd(II)-catalyzed olefination of γ-C(sp(3))-H bonds of triflyl (Tf) and 4-nitrobenzenesulfonyl (Ns) protected amines is achieved. Subsequent aza-Wacker oxidative cyclization or conjugate addition of the olefinated intermediates provides a variety of C-2 alkylated pyrrolidines. Three pyridine- and quinoline-based ligands are developed to match different classes of amine substrates, demonstrating a rare example of ligand-enabled C(sp(3))-H olefination reactions. The use of Ns protecting group to direct C(sp(3))-H activation of alkyl amines is also a significant step toward practical C-H functionalizations of alkyl amines.

  10. Stereoselective synthesis of hydroxy stilbenoids and styrenes by atom-efficient olefination with thiophthalides.

    Science.gov (United States)

    Mitra, Prithiba; Shome, Brateen; De, Saroj Ranjan; Sarkar, Anindya; Mal, Dipakranjan

    2012-04-14

    The synthesis of stilbenoids and styryl carboxylic acids is accomplished with high E-stereoselectivity by olefination of aldehydes with thiophthalides under basic conditions. The olefination is highly atom-efficient as it only loses elemental sulfur during the reaction. This olefination, in conjunction with retro Kolbe-Schmitt reaction, allows facile synthesis of E-hydroxystilbenoids with minimal employment of protecting groups. This study also discloses two important findings: formation of i) 4-methylsulfanyl isocoumarins and ii) an 2-arylindenone. This journal is © The Royal Society of Chemistry 2012

  11. Characterization of infiltration rates from landfills: supporting groundwater modeling efforts.

    Science.gov (United States)

    Moo-Young, Horace; Johnson, Barnes; Johnson, Ann; Carson, David; Lew, Christine; Liu, Salley; Hancocks, Katherine

    2004-01-01

    The purpose of this paper is to review the literature to characterize infiltration rates from landfill liners to support groundwater modeling efforts. The focus of this investigation was on collecting studies that describe the performance of liners 'as installed' or 'as operated'. This document reviews the state of the science and practice on the infiltration rate through compacted clay liner (CCL) for 149 sites and geosynthetic clay liner (GCL) for 1 site. In addition, it reviews the leakage rate through geomembrane (GM) liners and composite liners for 259 sites. For compacted clay liners (CCL), there was limited information on infiltration rates (i.e., only 9 sites reported infiltration rates.), thus, it was difficult to develop a national distribution. The field hydraulic conductivities for natural clay liners range from 1 x 10(-9) cm s(-1) to 1 x 10(-4) cm s(-1), with an average of 6.5 x 10(-8) cm s(-1). There was limited information on geosynthetic clay liner. For composite lined and geomembrane systems, the leak detection system flow rates were utilized. The average monthly flow rate for composite liners ranged from 0-32 lphd for geomembrane and GCL systems to 0 to 1410 lphd for geomembrane and CCL systems. The increased infiltration for the geomembrane and CCL system may be attributed to consolidation water from the clay.

  12. Is there a need for hydrological modelling in decision support systems for nuclear emergencies

    International Nuclear Information System (INIS)

    Raskob, W.; Heling, R.; Zheleznyak, M.

    2004-01-01

    This paper discusses the role of hydrological modelling in decision support systems for nuclear emergencies. In particular, most recent developments such as, the radionuclide transport models integrated in to the decision support system RODOS will be explored. Recent progress in the implementation of physically-based distributed hydrological models for operational forecasting in national and supranational centres, may support a closer cooperation between national hydrological services and therefore, strengthen the use of hydrological and radiological models implemented in decision support systems. (authors)

  13. Modelling Supported Driving as an Optimal Control Cycle : Framework and Model Characteristics

    NARCIS (Netherlands)

    Wang, M.; Treiber, M.; Daamen, W.; Hoogendoorn, S.P.; Van Arem, B.

    2013-01-01

    Driver assistance systems support drivers in operating vehicles in a safe, comfortable and efficient way, and thus may induce changes in traffic flow characteristics. This paper puts forward a receding horizon control framework to model driver assistance and cooperative systems. The accelerations of

  14. Production of jet fuel range paraffins by low temperature polymerization of gaseous light olefins using ionic liquid

    International Nuclear Information System (INIS)

    Jiang, Peiwen; Wu, Xiaoping; Zhu, Lijuan; Jin, Feng; Liu, Junxu; Xia, Tongyan; Wang, Tiejun; Li, Quanxin

    2016-01-01

    Graphical abstract: A novel catalytic transformation of light olefins into jet fuel range iso-paraffins by the low-temperature olefin polymerizations under atmospheric conditions. - Highlights: • A novel transformation of light olefins to jet fuel range paraffins was demonstrated. • The synthetic fuels can be produced by atmospheric olefin polymerizations. • C 8 –C 15 iso-paraffins from light olefins was achieved with a selectivity of 80.6%. - Abstract: This work demonstrated a novel catalytic transformation of gaseous olefins into jet fuel range iso-paraffins by the low-temperature olefin polymerizations under atmospheric conditions. The production of the desired C 8 –C 15 iso-paraffins with the selectivity of 80.6 C mol% was achieved by the room-temperature polymerizations of gaseous light olefins using the [BMIM] Al 2 Cl 7 ionic liquid. The influences of the reaction conditions on the olefinic polymerizations were investigated in detail. The properties of hydrocarbons in the synthetic fuels were determined by the GC–MS analyses combined with 1 H NMR, and 13 C NMR analyses. The formation of C 8 –C 15 hydrocarbons from gaseous light olefins was illustrated by the identified products and the functional groups. This transformation potentially provides a useful avenue for the production of the most important components of iso-paraffins required in jet fuels.

  15. Epidemiological models to support animal disease surveillance activities

    DEFF Research Database (Denmark)

    Willeberg, Preben; Paisley, Larry; Lind, Peter

    2011-01-01

    Epidemiological models have been used extensively as a tool in improving animal disease surveillance activities. A review of published papers identified three main groups of model applications: models for planning surveillance, models for evaluating the performance of surveillance systems...... and models for interpreting surveillance data as part of ongoing control or eradication programmes. Two Danish examples are outlined. The first illustrates how models were used in documenting country freedom from disease (trichinellosis) and the second demonstrates how models were of assistance in predicting...

  16. Mechanistic Studies of Ethylene and α-Olefin Co-oligomerization Catalyzed by Chromium-PNP Complexes.

    Science.gov (United States)

    Do, Loi H; Labinger, Jay A; Bercaw, John E

    2012-07-23

    To explore the possibility of producing a narrow distribution of mid- to long-chain hydrocarbons from ethylene as a chemical feedstock, co-oligomerization of ethylene and linear α-olefins (LAOs) was investigated, using a previously reported chromium complex, [CrCl(3)(PNP(OMe))] (1, where PNP(OMe) = N,N-bis(bis(o-methoxyphenyl)phosphino)methylamine). Activation of 1 by treatment with modified methylaluminoxane (MMAO) in the presence of ethylene and 1-hexene afforded mostly C(6) and C(10) alkene products. The identities of the C(10) isomers, assigned by detailed gas chromatographic and mass spectrometric analyses, strongly support a mechanism that involves five- and seven-membered metallacyclic intermediates comprising of ethylene and LAO units. Using 1-heptene as a mechanistic probe, it was established that 1-hexene formation from ethylene is competitive with formation of ethylene/LAO co-trimers, and that co-trimers derived from one ethylene and two LAO molecules are also generated. Complex 1/MMAO is also capable of converting 1-hexene to C(12) dimers and C(18) trimers, albeit with poor efficiency. The mechanistic implications of these studies are discussed and compared to previous reports of olefin co-trimerization.

  17. Parametric vs. Nonparametric Regression Modelling within Clinical Decision Support

    Czech Academy of Sciences Publication Activity Database

    Kalina, Jan; Zvárová, Jana

    2017-01-01

    Roč. 5, č. 1 (2017), s. 21-27 ISSN 1805-8698 R&D Projects: GA ČR GA17-01251S Institutional support: RVO:67985807 Keywords : decision support systems * decision rules * statistical analysis * nonparametric regression Subject RIV: IN - Informatics, Computer Science OBOR OECD: Statistics and probability

  18. Cause and Event: Supporting Causal Claims through Logistic Models

    Science.gov (United States)

    O'Connell, Ann A.; Gray, DeLeon L.

    2011-01-01

    Efforts to identify and support credible causal claims have received intense interest in the research community, particularly over the past few decades. In this paper, we focus on the use of statistical procedures designed to support causal claims for a treatment or intervention when the response variable of interest is dichotomous. We identify…

  19. Decision support telemedicine systems: A conceptual model and reusable templates

    NARCIS (Netherlands)

    Nannings, Barry; Abu-Hanna, A.

    2006-01-01

    Decision support telemedicine systems (DSTSs) are systems combining elements from telemedicine and clinical decision support systems. Although emerging more, these types of systems have not been given much attention in the literature. Our objective is to define the term DSTS, to propose a general

  20. Direct access to triazole-olefins through catalytic cycloaddition of azides to unsaturated aldehydes.

    Science.gov (United States)

    Li, Wenjun; Jia, Qianfa; Du, Zhiyun; Wang, Jian

    2013-10-03

    In situ formed dienamines as HOMO-raising dipolarophiles react with azides to afford the corresponding triazole-olefins in good to excellent yields via a catalytic inverse-electron-demand 1,3-dipolar cycloaddition process.

  1. Rhodium-Catalyzed Enantioselective Cyclopropanation of Olefins with N-Sulfonyl 1,2,3-Triazoles

    Science.gov (United States)

    Chuprakov, Stepan; Kwok, Sen Wai; Zhang, Li; Lercher, Lukas; Fokin, Valery V.

    2009-01-01

    N-Sulfonyl 1,2,3-triazoles readily form rhodium(II) azavinyl carbenes, which react with olefins to produce cyclopropanes with excellent diastereo- and enantioselectivity and in high yield. PMID:19928917

  2. Olefin metathesis for effective polymer healing via dynamic exchange of strong carbon-carbon bonds

    Science.gov (United States)

    Guan, Zhibin; Lu, Yixuan

    2015-09-15

    A method of preparing a malleable and/or self-healing polymeric or composite material is provided. The method includes providing a polymeric or composite material comprising at least one alkene-containing polymer, combining the polymer with at least one homogeneous or heterogeneous transition metal olefin metathesis catalyst to form a polymeric or composite material, and performing an olefin metathesis reaction on the polymer so as to form reversible carbon-carbon double bonds in the polymer. Also provided is a method of healing a fractured surface of a polymeric material. The method includes bringing a fractured surface of a first polymeric material into contact with a second polymeric material, and performing an olefin metathesis reaction in the presence of a transition metal olefin metathesis catalyst such that the first polymeric material forms reversible carbon-carbon double bonds with the second polymeric material. Compositions comprising malleable and/or self-healing polymeric or composite material are also provided.

  3. The preparation of trisubstituted alkenyl nucleoside phosphonates under ultrasound-assisted olefin cross-metathesis.

    Science.gov (United States)

    Sari, Ozkan; Hamada, Manabu; Roy, Vincent; Nolan, Steven P; Agrofoglio, Luigi A

    2013-09-06

    Intermolecular ultrasound-assisted olefin cross-metathesis is reported. This approach allows an easy access to challenging trisubstituted alkenyl nucleoside phosphonates. Regioselective chemoenzymatic deacetylation and Mitsunobu coupling are also described.

  4. Mild Functionalization of Tetraoxane Derivatives via Olefin Metathesis: Compatibility of Ruthenium Alkylidene Catalysts with Peroxides.

    Science.gov (United States)

    Jana, Anupam; Grela, Karol

    2017-02-03

    An easy and mild functionalization method of tetraoxane derivatives via olefin metathesis is reported. This reaction offers a new method to afford fully functionalized tetraoxanes in high yields. This method is also utilized in the functionalization of bioactive compounds.

  5. Organo-Lewis acid as cocatalyst for cationic homogenous metallocene Ziegler-Natta olefin polymerizations

    Energy Technology Data Exchange (ETDEWEB)

    Marks, Tobin J. (Evanston, IL); Chen, You-Xian (Chicago, IL)

    2000-01-01

    The synthesis of the organo-Lewis acid perfluorobiphenylborane (PBB) and the activation of metallocenes for the formation of a variety of highly active homogeneous Ziegler-Natta metallocene olefin polymerization, copolymerization and ring-opening polymerization catalysts is described.

  6. Selective Metathesis of α-Olefins from Bio-Sourced Fischer–Tropsch Feeds

    KAUST Repository

    Rouen, Mathieu

    2016-10-14

    The search for a low-cost process for the valorization of linear alpha-olefins combining high productivity and high selectivity is a longstanding goal for chemists. Herein, we report a soluble ruthenium olefin metathesis catalyst that performs the conversion of linear alpha-olefins to longer internal linear olefins with high selectivity (>99%) under neat conditions at low loadings (50 ppm) and without the need of expensive additives. This robust catalytic process allowed us to efficiently and selectively re-equilibrate the naphtha fraction (C-5-C-8) of a Fischer-Tropsch feed derived from non petroleum resources to a higher-value product range (C-9-C-14), useful as detergent and plasticizer precursors.

  7. Esterase-sensitive sulfur dioxide prodrugs inspired by modified Julia olefination.

    Science.gov (United States)

    Wang, Wenyi; Wang, Binghe

    2017-09-12

    Sulfur dioxide (SO 2 ) is an endogenously produced gaseous molecule, and is emerging as a potential gasotransmitter. Herein, we describe the first series of esterase-sensitive prodrugs inspired by modified Julia olefination as SO 2 donors.

  8. Palladium-catalyzed aryl C-H olefination with unactivated, aliphatic alkenes.

    Science.gov (United States)

    Deb, Arghya; Bag, Sukdev; Kancherla, Rajesh; Maiti, Debabrata

    2014-10-01

    Palladium-catalyzed coupling between aryl halides and alkenes (Mizoroki-Heck reaction) is one of the most popular reactions for synthesizing complex organic molecules. The limited availability, problematic synthesis, and higher cost of aryl halide precursors (or their equivalents) have encouraged exploration of direct olefination of aryl carbon-hydrogen (C-H) bonds (Fujiwara-Moritani reaction). Despite significant progress, the restricted substrate scope, in particular noncompliance of unactivated aliphatic olefins, has discouraged the use of this greener alternative. Overcoming this serious limitation, we report here a palladium-catalyzed chelation-assisted ortho C-H bond olefination of phenylacetic acid derivatives with unactivated, aliphatic alkenes in good to excellent yields with high regio- and stereoselectivities. The versatility of this operationally simple method has been demonstrated through drug diversification and sequential C-H olefination for synthesizing divinylbenzene derivatives.

  9. Nickel-catalysed retro-hydroamidocarbonylation of aliphatic amides to olefins

    Science.gov (United States)

    Hu, Jiefeng; Wang, Minyan; Pu, Xinghui; Shi, Zhuangzhi

    2017-05-01

    Amide and olefins are important synthetic intermediates with complementary reactivity which play a key role in the construction of natural products, pharmaceuticals and manmade materials. Converting the normally highly stable aliphatic amides into olefins directly is a challenging task. Here we show that a Ni/NHC-catalytic system has been established for decarbonylative elimination of aliphatic amides to generate various olefins via C-N and C-C bond cleavage. This study not only overcomes the acyl C-N bond activation in aliphatic amides, but also encompasses distinct chemical advances on a new type of elimination reaction called retro-hydroamidocarbonylation. This transformation shows good functional group compatibility and can serve as a powerful synthetic tool for late-stage olefination of amide groups in complex compounds.

  10. Extreme ultraviolet (EUV) degradation of poly(olefin sulfone)s: Towards applications as EUV photoresists

    International Nuclear Information System (INIS)

    Lawrie, Kirsten; Blakey, Idriss; Blinco, James; Gronheid, Roel; Jack, Kevin; Pollentier, Ivan; Leeson, Michael J.; Younkin, Todd R.; Whittaker, Andrew K.

    2011-01-01

    Poly(olefin sulfone)s, formed by the reaction of sulfur dioxide (SO 2 ) and an olefin, are known to be highly susceptible to degradation by radiation and thus have been identified as candidate materials for chain scission-based extreme ultraviolet lithography (EUVL) resist materials. In order to investigate this further, the synthesis and characterisation of two poly(olefin sulfone)s namely poly(1-pentene sulfone) (PPS) and poly(2-methyl-1-pentene sulfone) (PMPS), was achieved and the two materials were evaluated for possible chain scission EUVL resist applications. It was found that both materials possess high sensitivities to EUV photons; however; the rates of outgassing were extremely high. The only observed degradation products were found to be SO 2 and the respective olefin suggesting that depolymerisation takes place under irradiation in a vacuum environment. In addition to depolymerisation, a concurrent conversion of SO 2 moieties to a sulfide phase was observed using XPS.

  11. Structure and dynamics of olefin radical cation aggregates. Time-resolved fluorescence detected magnetic resonance

    International Nuclear Information System (INIS)

    Desrosiers, M.F.; Trifunac, A.D.

    1986-01-01

    The time-resolved EPR spectra and thus the structure and dynamics of transient hydrocarbon radical cations are obtained by the pulse radiolysis-fluorescence detected magnetic resonance (FDMR) technique. Here the authors report the observation of short-lived radical cations from olefins. FDMR-EPR spectra of radical cations from tetramethylethylene and cyclohexadiene are illustrated. The olefin radical cations, FDMR spectra are concentration-dependent, since dimerization with neutral molecules takes place at higher (>10 -2 M) olefin concentration. Rate constants for the dimerization reaction are derived and the effect of solvent viscosity on aggregate formation is demonstrated. By monitoring the further reactions of dimer cations the authors have obtained EPR evidence for previously unobserved higher-order (multimer) radical cation aggregates of olefins. 16 references, 5 figures

  12. A highly selective route to linear alpha olefins from biomass-derived lactones and unsaturated acids.

    Science.gov (United States)

    Wang, Dong; Hakim, Sikander H; Alonso, David Martin; Dumesic, James A

    2013-08-14

    This work demonstrates the use of Lewis-acid catalysts, such as gamma-alumina and tungstated alumina, for selective production of linear alpha olefins by decarboxylation of lactones and unsaturated carboxylic acids.

  13. A comparative study of slope failure prediction using logistic regression, support vector machine and least square support vector machine models

    Science.gov (United States)

    Zhou, Lim Yi; Shan, Fam Pei; Shimizu, Kunio; Imoto, Tomoaki; Lateh, Habibah; Peng, Koay Swee

    2017-08-01

    A comparative study of logistic regression, support vector machine (SVM) and least square support vector machine (LSSVM) models has been done to predict the slope failure (landslide) along East-West Highway (Gerik-Jeli). The effects of two monsoon seasons (southwest and northeast) that occur in Malaysia are considered in this study. Two related factors of occurrence of slope failure are included in this study: rainfall and underground water. For each method, two predictive models are constructed, namely SOUTHWEST and NORTHEAST models. Based on the results obtained from logistic regression models, two factors (rainfall and underground water level) contribute to the occurrence of slope failure. The accuracies of the three statistical models for two monsoon seasons are verified by using Relative Operating Characteristics curves. The validation results showed that all models produced prediction of high accuracy. For the results of SVM and LSSVM, the models using RBF kernel showed better prediction compared to the models using linear kernel. The comparative results showed that, for SOUTHWEST models, three statistical models have relatively similar performance. For NORTHEAST models, logistic regression has the best predictive efficiency whereas the SVM model has the second best predictive efficiency.

  14. Additional Research Needs to Support the GENII Biosphere Models

    Energy Technology Data Exchange (ETDEWEB)

    Napier, Bruce A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Snyder, Sandra F. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Arimescu, Carmen [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2013-11-01

    In the course of evaluating the current parameter needs for the GENII Version 2 code (Snyder et al. 2013), areas of possible improvement for both the data and the underlying models have been identified. As the data review was implemented, PNNL staff identified areas where the models can be improved both to accommodate the locally significant pathways identified and also to incorporate newer models. The areas are general data needs for the existing models and improved formulations for the pathway models.

  15. Origins of the Stereoretentive Mechanism of Olefin Metathesis with Ru-Dithiolate Catalysts.

    Science.gov (United States)

    Grandner, Jessica M; Shao, Huiling; Grubbs, Robert H; Liu, Peng; Houk, K N

    2017-10-06

    A comprehensive computational study of stereoretentive olefin metathesis with Ru-dithiolate catalysts has been performed. We have determined how the dithiolate ligand enforces a side-bound mechanism and how the side-bound mechanism allows for stereochemical control over the forming olefin. We have used density functional theory (DFT) and ligand steric contour maps to elucidate the origins of stereoretentive metathesis with the goal of understanding how to design a new class of E-selective metathesis catalysts.

  16. Ruthenium-Catalyzed Olefin Cross-Metathesis with Tetrafluoroethylene and Analogous Fluoroolefins.

    Science.gov (United States)

    Takahira, Yusuke; Morizawa, Yoshitomi

    2015-06-10

    This Communication describes a successful olefin cross-metathesis with tetrafluoroethylene and its analogues. A key to the efficient catalytic cycle is interconversion between two thermodynamically stable, generally considered sluggish, Fischer carbenes. This newly demonstrated catalytic transformation enables easy and short-step synthesis of a new class of partially fluorinated olefins bearing plural fluorine atoms, which are particularly important and valuable compounds in organic synthesis and medicinal chemistry as well as the materials and polymer industries.

  17. Facile Synthesis of Effcient and Selective Ruthenium Olefin Metathesis Catalysts with Sulfonate and Phosphate Ligands

    OpenAIRE

    Teo, Peili; Grubbs, Robert H.

    2010-01-01

    A series of novel, air-stable ruthenium NHC catalysts with sulfonate and phosphate anions have been prepared easily in one pot at high yields using commercially available precursors. The catalysts were found to be effective for ring-opening metathesis polymerization, ring-closing metathesis, and cross-metathesis. The catalysts showed higher cis-selectivity in olefin cross-metathesis reactions as compared to earlier known ruthenium-based olefin metathesis catalysts, with allylbenzene and cis-1...

  18. Pd(II/HPMoV-Catalyzed Direct Oxidative Coupling Reaction of Benzenes with Olefins

    Directory of Open Access Journals (Sweden)

    Yasutaka Ishii

    2010-03-01

    Full Text Available The direct aerobic coupling reaction of arenes with olefins was successfully achieved by the use of Pd(OAc2/molybdovanadophosphoric acid (HPMoV as a key catalyst under 1 atm of dioxygen. This catalytic system could be extended to the coupling reaction of various substituted benzenes with olefins such as acrylates, aclrolein, and ethylene through the direct aromatic C-H bond activation.

  19. Stereoselective Wittig Olefination as a Macrocyclization Tool. Synthesis of Large Carbazolophanes.

    Science.gov (United States)

    Myśliwiec, Damian; Lis, Tadeusz; Gregoliński, Janusz; Stępień, Marcin

    2015-06-19

    Z-Selective Wittig olefination was applied to the synthesis of large carbazolophanes containing up to eight heteroaromatic subunits. A number of strategies were devised and tested, showing that cyclooligomerization yields can be significantly improved by using one-component schemes involving heterobifunctional reactants. [4]- and [6]Carbazolophanes were characterized in the solid state, revealing compact, highly folded structures. Electronic and steric effects of substitution and chain length on the Wittig olefination rates and Z-selectivities were explored theoretically using DFT calculations.

  20. Ligand-Promoted C(sp(3) )-H Olefination en Route to Multi-functionalized Pyrazoles.

    Science.gov (United States)

    Yang, Weibo; Ye, Shengqing; Schmidt, Yvonne; Stamos, Dean; Yu, Jin-Quan

    2016-05-17

    A Pd-catalyzed/N-heterocycle-directed C(sp(3) )-H olefination has been developed. The monoprotected amino acid ligand (MPAA) is found to significantly promote Pd-catalyzed C(sp(3) )-H olefination for the first time. Cu(OAc)2 instead of Ag(+) salts are used as the terminal oxidant. This reaction provides a useful method for the synthesis of alkylated pyrazoles. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. On the nature of the olefination reaction involving ditungsten hexaalkoxides and aldehydes or ketones

    Energy Technology Data Exchange (ETDEWEB)

    Chisholm, M.H.; Huffman, J.C.; Lucas, E.A.; Sousa, A.; Streib, W.E. [Indiana Univ., Bloomington, IN (United States)

    1992-03-25

    Reductive coupling of aldehydes and ketones to olefins under the action of ditungsten hexaalkoxides was investigated. In these reactions, reductive cleavage of the aldehyde or ketone carbonyl is followed by formation of the olefinic C-C bond and breaking of the carbonyl C-O bond of the second aldehyde or ketone. Observations concerning the initial C-O bond cleavage and subsequent C-C bond formation are presented. 10 refs., 4 figs.

  2. An Improved Protocol for the Aldehyde Olefination Reaction Using (bmim ( as Reaction Medium

    Directory of Open Access Journals (Sweden)

    Vivek Srivastava

    2013-01-01

    Full Text Available [Ru(CODCl2]/CuCl2·2H2O/LiCl catalytic system works efficiently in ionic liquid media for aldehyde olefination reaction. It offers good yield and selectivity with the added advantage of 5 times recyclability for [Ru(CODCl2] /CuCl2·2H2O/LiCl catalytic system. We also successfully reduced the reaction time from 12 hours to 9 hours for the aldehyde olefination reaction.

  3. Palladium catalyzed selective distal C-H olefination of biaryl systems.

    Science.gov (United States)

    Maity, Soham; Hoque, Ehtasimul; Dhawa, Uttam; Maiti, Debabrata

    2016-11-29

    Palladium catalyzed selective distal C-H activation with nitrile based templates has been of significant research interest in recent times. In this report, we disclose the distal C-H olefination of biphenyl systems with high regio- and stereo-selectivity and useful synthetic yields. The utility of this method has been demonstrated through its wide olefin scope, its operation at the gram scale and the easy removal/recovery of the directing group.

  4. Tandem catalysis in domino olefin cross-metathesis/intramolecular oxa-conjugate cyclization: concise synthesis of 2,6-cis-substituted tetrahydropyran derivatives.

    Science.gov (United States)

    Fuwa, Haruhiko; Noguchi, Takuma; Noto, Kenkichi; Sasaki, Makoto

    2012-10-28

    Herein, we describe the concise synthesis of 2,6-cis-substituted tetrahydropyran derivatives based on a domino olefin cross-metathesis/intramolecular oxa-conjugate cyclization (CM/IOCC) reaction. We have found that the domino CM/IOCC of δ-hydroxy olefins with α,β-unsaturated carbonyl compounds (e.g., trans-crotonaldehyde or N-acryloyl-2,5-dimethylpyrrole) could be efficiently achieved in the presence of the second-generation Hoveyda-Grubbs catalyst under elevated temperature conditions, directly affording 2,6-cis-substituted tetrahydropyrans in excellent yields with synthetically useful diastereoselectivity ("auto-tandem catalysis"). In addition, we have found that the domino CM/IOCC of δ-hydroxy olefins with α,β-unsaturated carbonyl compounds could be achieved simply by performing CM in the presence of a Brønsted acid in CH(2)Cl(2) at 25-35 °C, which delivered 2,6-cis-substituted tetrahydropyrans in good yields with excellent diastereoselectivity ("orthogonal-tandem catalysis"). To understand the mechanism of auto-tandem catalysis in the domino CM/IOCC reaction, we have investigated the role of ruthenium hydride complexes in the IOCC of a ζ-hydroxy α,β-unsaturated ketone as a model case.

  5. Data Collecting and Processing System and Hydraulic Control System of Hydraulic Support Model Test

    OpenAIRE

    Hong-Yu LIU; Jun-Qing LIU; Jun-Jie XI

    2014-01-01

    Hydraulic support is an important equipment of mechanization caving coal in modernization coal mine. Hydraulic support must pass national strength test before it quantity production and use. Hydraulic support model test based on similarity theory is a new effective hydraulic support design and test method. The test information such as displacement, stress, strain and so on can be generalized to hydraulic support prototype, which can prompt hydraulic support design. In order to satisfy the nee...

  6. Enhancing Formal Modelling Tool Support with Increased Automation

    DEFF Research Database (Denmark)

    Lausdahl, Kenneth

    Progress report for the qualification exam report for PhD Student Kenneth Lausdahl. Initial work on enhancing tool support for the formal method VDM and the concept of unifying a abstract syntax tree with the ability for isolated extensions is described. The tool support includes a connection...... to UML and a test automation principle based on traces written as a kind of regular expressions....

  7. The FCC process as a producer of light olefins

    International Nuclear Information System (INIS)

    Yung, K.Y.; Yanik, S.; O'Connor, P.; Pouwels, C.

    1992-01-01

    To reduce emissions from the gasoline engine, aromatics content and vapor pressure of the motor gasoline pool will be reduced and a minimum amount of oxygen will be mandated. This reformulation will limit the application of high octane components like benzene, toluene and butanes and will require the use of oxygenates. To compensate for the loss in octane, the use of alkylate and, of course also oxygenates will grow. The Fluid Catalytic Cracking Unit is, as producer of (olefinic) propanes, butanes and pentanes, an important feedstock producer for alkylate and oxygenate producing process. Hence, process adjustments and FCC catalyst formations to increase the yield of above desirable light products are of prime importance and will be dealt with in this paper

  8. Radiation-chemical alkylation of olefines with adamantane

    International Nuclear Information System (INIS)

    Podkhalyuzin, A.T.; Vikulin, V.V.; Morozov, V.A.; Nazarova, M.P.; Vereshchinskii, I.V.

    1977-01-01

    Radiation-chemical alkylation of C 2 to C 4 olefines with adamantane was studied in gas phase at temperatures 270 to 430 0 C. The main reaction product is monoalkyladamantane. The reaction proceeds by a free radical chain mechanism. The effective activation energy is of the order of 8 to 10 kcal/mole. Thermal alkylation was carried out for comparison and the contribution of the thermal component to the radiation-thermal process was estimated. Liquid phase alkylation of hexafluoropropylene with adamantane was studied in the presence of solvents. Under various conditions mono- and di-substituted adamantanes are produced containing fluorine in end groups. These compounds were converted to corresponding fluoroalkenyladamantanes by dehydrofluorination. The kinetic parameters were calculated and physical-chemical data concerning some of the resulting products were determined. (author)

  9. Molybdenum chloride catalysts for Z-selective olefin metathesis reactions

    Science.gov (United States)

    Koh, Ming Joo; Nguyen, Thach T.; Lam, Jonathan K.; Torker, Sebastian; Hyvl, Jakub; Schrock, Richard R.; Hoveyda, Amir H.

    2017-01-01

    The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.

  10. Improved ruthenium catalysts for Z-selective olefin metathesis.

    Science.gov (United States)

    Keitz, Benjamin K; Endo, Koji; Patel, Paresma R; Herbert, Myles B; Grubbs, Robert H

    2012-01-11

    Several new C-H-activated ruthenium catalysts for Z-selective olefin metathesis have been synthesized. Both the carboxylate ligand and the aryl group of the N-heterocyclic carbene have been altered and the resulting catalysts evaluated using a range of metathesis reactions. Substitution of bidentate with monodentate X-type ligands led to a severe attenuation of metathesis activity and selectivity, while minor differences were observed between bidentate ligands within the same family (e.g., carboxylates). The use of nitrato-type ligands in place of carboxylates afforded a significant improvement in metathesis activity and selectivity. With these catalysts, turnover numbers approaching 1000 were possible for a variety of cross-metathesis reactions, including the synthesis of industrially relevant products. © 2011 American Chemical Society

  11. Nanoporous poly(lactide) by olefin metathesis degradation.

    Science.gov (United States)

    Bertrand, Arthur; Hillmyer, Marc A

    2013-07-31

    We describe an approach to ordered nanoporous poly(lactide) that relies on self-assembly of poly(butadiene)-poly(lactide) (PB-PLA) diblock copolymers followed by selective degradation of PB using olefin metathesis. The block copolymers were obtained by a combination of anionic and ring-opening transesterification polymerizations. The molar mass of each block was tailored to target materials with either a lamellar or cylindrical microphase-separated morphology. Orientation of these nanoscale domains was induced in thin films and monolithic samples through solvent annealing and mechanical deformation, respectively. Selective degradation of PB was achieved by immersing the samples in a solution of Grubbs first-generation catalyst in cyclohexane, a nonsolvent for PLA. Successful elimination of PB was confirmed by size-exclusion chromatography and (1)H NMR spectroscopy. Direct imaging of the resulting nanoporous PLA was obtained by scanning electron microscopy.

  12. Kinetically controlled E-selective catalytic olefin metathesis.

    Science.gov (United States)

    Nguyen, Thach T; Koh, Ming Joo; Shen, Xiao; Romiti, Filippo; Schrock, Richard R; Hoveyda, Amir H

    2016-04-29

    A major shortcoming in olefin metathesis, a chemical process that is central to research in several branches of chemistry, is the lack of efficient methods that kinetically favor E isomers in the product distribution. Here we show that kinetically E-selective cross-metathesis reactions may be designed to generate thermodynamically disfavored alkenyl chlorides and fluorides in high yield and with exceptional stereoselectivity. With 1.0 to 5.0 mole % of a molybdenum-based catalyst, which may be delivered in the form of air- and moisture-stable paraffin pellets, reactions typically proceed to completion within 4 hours at ambient temperature. Many isomerically pure E-alkenyl chlorides, applicable to catalytic cross-coupling transformations and found in biologically active entities, thus become easily and directly accessible. Similarly, E-alkenyl fluorides can be synthesized from simpler compounds or more complex molecules. Copyright © 2016, American Association for the Advancement of Science.

  13. New unit for sulfuric acid alkylation of isobutane by olefins

    Energy Technology Data Exchange (ETDEWEB)

    Khadzhiev, S.N.; Baiburskii, V.L.; Deineko, P.S.; Gruzdev, A.S.; Tagavov, I.T.

    1987-01-01

    The authors describe and illustrate a sulfuric acid alkylation unit with a horizontal contact. As a result of the use of this design solution, the isobutane/olefin ratio is 10/1 in comparison with 4/1 to 5/1 in the other types of units, namely vertical reactors and cascade tank reactors. The unit was designed to process the butane-butylene cut (BBC) and part of the propane-propylene cut (PPC) from the G-43-107 cat cracker. The unit design includes provisions for controlled caustic washing of the feed and dehydration in an electric field. The authors present the basic data obtained in the three months of unit operation after startup, in comparison with the operating indexes of a sulfuric acid alkylation unit.

  14. Modeling snail breeding in Bioregenerative Life Support System

    Science.gov (United States)

    Kovalev, Vladimir; Tikhomirov, Alexander A.; Nickolay Manukovsky, D..

    It is known that snail meat is a high quality food that is rich in protein. Hence, heliciculture or land snail farming spreads worldwide because it is a profitable business. The possibility to use the snails of Helix pomatia in Biological Life Support System (BLSS) was studied by Japanese Researches. In that study land snails were considered to be producers of animal protein. Also, snail breeding was an important part of waste processing, because snails were capable to eat the inedible plant biomass. As opposed to the agricultural snail farming, heliciculture in BLSS should be more carefully planned. The purpose of our work was to develop a model for snail breeding in BLSS that can predict mass flow rates in and out of snail facility. There are three linked parts in the model called “Stoichiometry”, “Population” and “Mass balance”, which are used in turn. Snail population is divided into 12 age groups from oviposition to one year. In the submodel “Stoichiometry” the individual snail growth and metabolism in each of 12 age groups are described with stoichiometry equations. Reactants are written on the left side of the equations, while products are written on the right side. Stoichiometry formulas of reactants and products consist of four chemical elements: C, H, O, N. The reactants are feed and oxygen, products are carbon dioxide, metabolic water, snail meat, shell, feces, slime and eggs. If formulas of substances in the stoichiometry equations are substituted with their molar masses, then stoichiometry equations are transformed to the equations of molar mass balance. To get the real mass balance of individual snail growth and metabolism one should multiply the value of each molar mass in the equations on the scale parameter, which is the ratio between mass of monthly consumed feed and molar mass of feed. Mass of monthly consumed feed and stoichiometry coefficients of formulas of meat, shell, feces, slime and eggs should be determined experimentally

  15. Stereoselective synthesis of macrocyclic peptides via a dual olefin metathesis and ethenolysis approach.

    Science.gov (United States)

    Mangold, Shane L; Grubbs, Robert H

    2015-08-01

    Macrocyclic compounds occupy an important chemical space between small molecules and biologics and are prevalent in many natural products and pharmaceuticals. The growing interest in macrocycles has been fueled, in part, by the design of novel synthetic methods to these compounds. One appealing strategy is ring-closing metathesis (RCM) that seeks to construct macrocycles from acyclic diene precursors using defined transition-metal alkylidene catalysts. Despite its broad utility, RCM generally gives rise to a mixture of E - and Z- olefin isomers that can hinder efforts for the large-scale production and isolation of such complex molecules. To address this issue, we aimed to develop methods that can selectively enrich macrocycles in E - or Z -olefin isomers using an RCM/ethenolysis strategy. The utility of this methodology was demonstrated in the stereoselective formation of macrocyclic peptides, a class of compounds that have gained prominence as therapeutics in drug discovery. Herein, we report an assessment of various factors that promote catalyst-directed RCM and ethenolysis on a variety of peptide substrates by varying the olefin type, peptide sequence, and placement of the olefin in macrocycle formation. These methods allow for control over olefin geometry in peptides, facilitating their isolation and characterization. The studies outlined in this report seek to expand the scope of stereoselective olefin metathesis in general RCM.

  16. Capturing of the monoterpene olefin limonene produced in Saccharomyces cerevisiae.

    Science.gov (United States)

    Jongedijk, Esmer; Cankar, Katarina; Ranzijn, Jorn; van der Krol, Sander; Bouwmeester, Harro; Beekwilder, Jules

    2015-01-01

    Monoterpene olefins such as limonene are plant compounds with applications as flavouring and fragrance agents, as solvents and potentially also in polymer and fuel chemistry. We engineered baker's yeast Saccharomyces cerevisiae to express a (-)-limonene synthase from Perilla frutescens and a (+)-limonene synthase from Citrus limon. Both proteins were expressed either with their native plastid targeting signal or in a truncated form in which the plastidial sorting signal was removed. The yeast host strain for expression was AE9 K197G, which expresses a mutant Erg20 enzyme. This enzyme catalyses the formation of geranyl diphosphate, which is the precursor for monoterpenes. Several methods were tested to capture limonene produced by the yeast. Extraction from the culture medium by pentane, or by the addition of CaCl2 followed by solid-phase micro-extraction, did not lead to detectable limonene, indicating that limonene is rapidly lost from the culture medium. Volatile terpenes such as limonene may also be trapped in a dodecane phase added to the medium during fermentation. This method resulted in recovery of 0.028 mg/l (+)-limonene and 0.060 mg/l (-)-limonene in strains using the truncated Citrus and Perilla synthases, respectively. Trapping the headspace during culture of the limonene synthase-expressing strains resulted in higher titres, at 0.12 mg/l (+)-limonene and 0.49 mg/l (-)-limonene. These results show that the volatile properties of the olefins produced require specific methods for efficient recovery of these molecules from biotechnological production systems. Copyright © 2014 John Wiley & Sons, Ltd.

  17. Mathematical Models for the Education Sector, Supporting Material to the Survey. (Les Modeles Mathematiques du Secteur Enseignement. Annexes.) Technical Report.

    Science.gov (United States)

    Organisation for Economic Cooperation and Development, Paris (France).

    This document contains supporting material for the survey on current practice in the construction and use of mathematical models for education. Two kinds of supporting material are included: (1) the responses to the questionnaire, and (2) supporting documents and other materials concerning the mathematical model-building effort in education.…

  18. Artificial intelligence support for scientific model-building

    Science.gov (United States)

    Keller, Richard M.

    1992-01-01

    Scientific model-building can be a time-intensive and painstaking process, often involving the development of large and complex computer programs. Despite the effort involved, scientific models cannot easily be distributed and shared with other scientists. In general, implemented scientific models are complex, idiosyncratic, and difficult for anyone but the original scientific development team to understand. We believe that artificial intelligence techniques can facilitate both the model-building and model-sharing process. In this paper, we overview our effort to build a scientific modeling software tool that aids the scientist in developing and using models. This tool includes an interactive intelligent graphical interface, a high-level domain specific modeling language, a library of physics equations and experimental datasets, and a suite of data display facilities.

  19. Bridge deterioration models to support Indiana's bridge management system.

    Science.gov (United States)

    2016-02-01

    An effective bridge management system that is equipped with reliable deterioration models enables agency engineers to carry out : monitoring and long-term programming of bridge repair actions. At the project level, deterioration models help the agenc...

  20. Olefins-selective asymmetric carbon molecular sieve hollow fiber membranes for hybrid membrane-distillation processes for olefin/paraffin separations

    KAUST Repository

    Xu, Liren

    2012-12-01

    In this paper, the development of asymmetric carbon molecular sieve (CMS) hollow fiber membranes and advanced processes for olefin/paraffin separations based on the CMS membranes are reported. Membrane-based olefin/paraffin separations have been pursued extensively over the past decades. CMS membranes are promising to exceed the performance upper bound of polymer materials and have demonstrated excellent stability for gas separations. Previously, a substructure collapse phenomenon was found in Matrimid ® precursor derived CMS fiber. To overcome the permeance loss due to the increased separation layer thickness, 6FDA-DAM and 6FDA/BPDA-DAM precursors were selected as potential new precursors for carbon membrane formation. Defect-free asymmetric 6FDA-DAM and 6FDA/BPDA-DAM hollow fibers were successfully fabricated from a dry-jet/wet-quench spinning process. Polymer rigidity, glass-rubber transition and asymmetric morphology were correlated. CMS hollow fiber membranes produced from 6FDA-polymer precursors showed significant improvement in permeance for ethylene/ethane and propylene/propane separations. Further studies revealed that the CMS membranes are olefins-selective, which means the membranes are able to effectively separate olefins (ethylene and propylene) from paraffins (ethane and propane). This unique feature of CMS materials enables advanced hybrid membrane-distillation process designs. By using the olefins-selective membranes, these new processes may provide advantages over previously proposed retrofitting concepts. Further applications of the membranes are explored for hydrocarbons processes. Significant energy savings and even reduced footprint may be achieved in olefins production units. © 2012 Elsevier B.V.

  1. A 3D Geometry Model Search Engine to Support Learning

    Science.gov (United States)

    Tam, Gary K. L.; Lau, Rynson W. H.; Zhao, Jianmin

    2009-01-01

    Due to the popularity of 3D graphics in animation and games, usage of 3D geometry deformable models increases dramatically. Despite their growing importance, these models are difficult and time consuming to build. A distance learning system for the construction of these models could greatly facilitate students to learn and practice at different…

  2. Coupling hydrological modeling and support vector regression to model hydropeaking in alpine catchments.

    Science.gov (United States)

    Chiogna, Gabriele; Marcolini, Giorgia; Liu, Wanying; Pérez Ciria, Teresa; Tuo, Ye

    2018-03-21

    Water management in the alpine region has an important impact on streamflow. In particular, hydropower production is known to cause hydropeaking i.e., sudden fluctuations in river stage caused by the release or storage of water in artificial reservoirs. Modeling hydropeaking with hydrological models, such as the Soil Water Assessment Tool (SWAT), requires knowledge of reservoir management rules. These data are often not available since they are sensitive information belonging to hydropower production companies. In this short communication, we propose to couple the results of a calibrated hydrological model with a machine learning method to reproduce hydropeaking without requiring the knowledge of the actual reservoir management operation. We trained a support vector machine (SVM) with SWAT model outputs, the day of the week and the energy price. We tested the model for the Upper Adige river basin in North-East Italy. A wavelet analysis showed that energy price has a significant influence on river discharge, and a wavelet coherence analysis demonstrated the improved performance of the SVM model in comparison to the SWAT model alone. The SVM model was also able to capture the fluctuations in streamflow caused by hydropeaking when both energy price and river discharge displayed a complex temporal dynamic. Copyright © 2018 Elsevier B.V. All rights reserved.

  3. Sequential meta-C-H olefination of synthetically versatile benzyl silanes: effective synthesis of meta-olefinated toluene, benzaldehyde and benzyl alcohols.

    Science.gov (United States)

    Patra, Tuhin; Watile, Rahul; Agasti, Soumitra; Naveen, Togati; Maiti, Debabrata

    2016-02-04

    Tremendous progress has been made towards ortho-selective C-H functionalization in the last three decades. However, the activation of distal C-H bonds and their functionalization has remained fairly underdeveloped. Herein, we report sequential meta-C-H functionalization by performing selective mono-olefination and bis-olefination with late stage modification of the C-Si as well as Si-O bonds. Temporary silyl connection was found to be advantageous due to its easy installation, easy removal and wide synthetic diversification.

  4. Constitutive modelling of an arterial wall supported by microscopic measurements

    Directory of Open Access Journals (Sweden)

    Vychytil J.

    2012-06-01

    Full Text Available An idealized model of an arterial wall is proposed as a two-layer system. Distinct mechanical response of each layer is taken into account considering two types of strain energy functions in the hyperelasticity framework. The outer layer, considered as a fibre-reinforced composite, is modelled using the structural model of Holzapfel. The inner layer, on the other hand, is represented by a two-scale model mimicing smooth muscle tissue. For this model, material parameters such as shape, volume fraction and orientation of smooth muscle cells are determined using the microscopic measurements. The resulting model of an arterial ring is stretched axially and loaded with inner pressure to simulate the mechanical response of a porcine arterial segment during inflation and axial stretching. Good agreement of the model prediction with experimental data is promising for further progress.

  5. Cognitive Support using BDI Agent and Adaptive User Modeling

    DEFF Research Database (Denmark)

    Hossain, Shabbir

    2012-01-01

    challenges of an ageing population. This thesis work is one attempt towards that. The thesis focused on research the approaches to provide cognitive support for users with cognitive disabilities through ICT-based technological solutions. The recent advancement of Articial Intelligence and wireless sensor...... networks have shown potential to improve the quality of life of elder people with disabilities using current technologies. The primary objective of this thesis is to conduct research on the approach to provide support for the elderly users with cognitive disabilities. In our research conduct, we have dened...... a set of goals for attaining the objective of this thesis. The initial goal is to recognize the activities of the users to assess the need of support for the user during the activity. However, one of the challenges of the recognition process is the adaptability for variant user behaviour due to physical...

  6. Determination of thermodynamic affinities of various polar olefins as hydride, hydrogen atom, and electron acceptors in acetonitrile.

    Science.gov (United States)

    Cao, Ying; Zhang, Song-Chen; Zhang, Min; Shen, Guang-Bin; Zhu, Xiao-Qing

    2013-07-19

    A series of 69 polar olefins with various typical structures (X) were synthesized and the thermodynamic affinities (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the polar olefins obtaining hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the polar olefins (X(•-)) obtaining protons and hydrogen atoms, and the thermodynamic affinities of the hydrogen adducts of the polar olefins (XH(•)) obtaining electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The pure C═C π-bond heterolytic and homolytic dissociation energies of the polar olefins (X) in acetonitrile and the pure C═C π-bond homolytic dissociation energies of the radical anions of the polar olefins (X(•-)) in acetonitrile were estimated. The remote substituent effects on the six thermodynamic affinities of the polar olefins and their related reaction intermediates were examined using the Hammett linear free-energy relationships; the results show that the Hammett linear free-energy relationships all hold in the six chemical and electrochemical processes. The information disclosed in this work could not only supply a gap of the chemical thermodynamics of olefins as one class of very important organic unsaturated compounds but also strongly promote the fast development of the chemistry and applications of olefins.

  7. Atomic structure of graphene supported heterogeneous model catalysts

    International Nuclear Information System (INIS)

    Franz, Dirk

    2017-04-01

    Graphene on Ir(111) forms a moire structure with well defined nucleation centres. Therefore it can be utilized to create hexagonal metal cluster lattices with outstanding structural quality. At diffraction experiments these 2D surface lattices cause a coherent superposition of the moire cell structure factor, so that the measured signal intensity scales with the square of coherently scattering unit cells. This artificial signal enhancement enables the opportunity for X-ray diffraction to determine the atomic structure of small nano-objects, which are hardly accessible with any experimental technique. The uniform environment of every metal cluster makes the described metal cluster lattices on graphene/Ir(111) an attractive model system for the investigation of catalytic, magnetic and quantum size properties of ultra-small nano-objects. In this context the use of x-rays provides a maximum of flexibility concerning the possible sample environments (vacuum, selected gases, liquids, sample temperature) and allows in-situ/operando measurements. In the framework of the present thesis the structure of different metal clusters grown by physical vapor deposition in an UHV environment and after gas exposure have been investigated. On the one hand the obtained results will explore many aspects of the atomic structure of these small metal clusters and on the other hand the presented results will proof the capabilities of the described technique (SXRD on cluster lattices). For iridium, platinum, iridium/palladium and platinum/rhodium the growth on graphene/Ir(111) of epitaxial, crystalline clusters with an ordered hexagonal lattice arrangement has been confirmed using SXRD. The clusters nucleate at the hcp sites of the moire cell and bind via rehybridization of the carbon atoms (sp 2 → sp 3 ) to the Ir(111) substrate. This causes small displacements of the substrate atoms, which is revealed by the diffraction experiments. All metal clusters exhibit a fcc structure, whereupon

  8. Appropriate models in decision support systems for river basin management

    NARCIS (Netherlands)

    Xu, YuePing; Booij, Martijn J.; Morell, M.; Todorovik, O.; Dimitrov, D.; Selenica, A.; Spirkovski, Z.

    2004-01-01

    In recent years, new ideas and techniques appear very quickly, like sustainability, adaptive management, Geographic Information System, Remote Sensing and participations of new stakeholders, which contribute a lot to the development of decision support systems in river basin management. However, the

  9. Zeolite supported palladium catalysts for hydroalkylation of phenolic model compounds

    Czech Academy of Sciences Publication Activity Database

    Akhmetzyanova, U.; Opanasenko, Maksym; Horáček, J.; Montanari, E.; Čejka, Jiří; Kikhtyanin, O.

    2017-01-01

    Roč. 252, NOV 2017 (2017), s. 116-124 ISSN 1387-1811 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : Phenol hydroalkylation * Cyclohexylcyclohexane * MWW Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 3.615, year: 2016

  10. Designing, Modeling and Evaluating Influence Strategiesfor Behavior Change Support Systems

    NARCIS (Netherlands)

    Öörni, Anssi; Kelders, Saskia Marion; van Gemert-Pijnen, Julia E.W.C.; Oinas-Kukkonen, Harri

    2014-01-01

    Behavior change support systems (BCSS) research is an evolving area. While the systems have been demonstrated to work to the effect, there is still a lot of work to be done to better understand the influence mechanisms of behavior change, and work out their influence on the systems architecture. The

  11. Real time traffic models, decision support for traffic management

    NARCIS (Netherlands)

    Wismans, Luc Johannes Josephus; de Romph, E.; Friso, K.; Zantema, K.

    2014-01-01

    Reliable and accurate short-term traffic state prediction can improve the performance of real-time traffic management systems significantly. Using this short-time prediction based on current measurements delivered by advanced surveillance systems will support decision-making processes on various

  12. Real Time Traffic Models, Decision Support for Traffic Management

    NARCIS (Netherlands)

    Wismans, L.; De Romph, E.; Friso, K.; Zantema, K.

    2014-01-01

    Reliable and accurate short-term traffic state prediction can improve the performance of real-time traffic management systems significantly. Using this short-time prediction based on current measurements delivered by advanced surveillance systems will support decision-making processes on various

  13. Ordered mesoporous materials as model supports to study catalyst preparation

    NARCIS (Netherlands)

    Sietsma, J.R.A.

    2007-01-01

    Catalysts are indispensable to modern-day society because of their prominent role in petroleum refining, chemical processing, and the reduction of environmental pollution. The catalytically active component often consists of small metal (oxide) particles that are supported on a carrier such as

  14. Decision support for sustainable forestry: enhancing the basic rational model.

    Science.gov (United States)

    H.R. Ekbia; K.M. Reynolds

    2007-01-01

    Decision-support systems (DSS) have been extensively used in the management of natural resources for nearly two decades. However, practical difficulties with the application of DSS in real-world situations have become increasingly apparent. Complexities of decisionmaking, encountered in the context of ecosystem management, are equally present in sustainable forestry....

  15. Model of Early Support of Child Development in Poland

    Science.gov (United States)

    Czyz, Anna Katarzyna

    2018-01-01

    The development of a child, especially a child with a disability, is conditional upon the initiation of rehabilitation measures immediately after the problem has been identified. The quality of the reaction is conditioned by the functioning of the therapeutic team. The main purpose of the research was the diagnosis of early support system for…

  16. The adapted model of institutional support for Hispanic student degree completion: revisions and recommendations.

    Science.gov (United States)

    Bond, Mary Lou; Cason, Carolyn L; Gray, Jennifer R

    2015-01-01

    This article describes the historical development of the adapted model of institutional support (AMIS) for Hispanic student degree completion. The model was developed using 6 major categories of support: financial support, emotional and moral support, mentoring, professional socialization, academic advising, and technical support. Studies used to validate the inclusion of each of the components are presented. Two self-assessment instruments based on the model, the Institutional Self-Assessment for Factors Supporting Hispanic Student Recruitment and Persistence and the Healthcare Professions Education Program Self-Assessment (PSA), used to evaluate institutional supports for Hispanic student degree completion are described. This article describes the results of 2 studies using the PSA. The findings from these studies provide support for the AMIS. Limitations of the model and recommendations for further research are presented.

  17. Autonomy Support, Need Satisfaction, and Motivation for Support Among Adults With Intellectual Disability: Testing a Self-Determination Theory Model.

    Science.gov (United States)

    Frielink, Noud; Schuengel, Carlo; Embregts, Petri J C M

    2018-01-01

    The tenets of self-determination theory as applied to support were tested with structural equation modelling for 186 people with ID with a mild to borderline level of functioning. The results showed that (a) perceived autonomy support was positively associated with autonomous motivation and with satisfaction of need for autonomy, relatedness, and competence; (b) autonomous motivation and need satisfaction were associated with higher psychological well-being; (c) autonomous motivation and need satisfaction statistically mediated the association between autonomy support and well-being; and (d) satisfaction of need for autonomy and relatedness was negatively associated with controlled motivation, whereas satisfaction of need for relatedness was positively associated with autonomous motivation. The self-determination theory provides insights relevant for improving support for people with intellectual disability.

  18. Unsaturated Fatty Acid Esters Metathesis Catalyzed by Silica Supported WMe5

    KAUST Repository

    Riache, Nassima

    2015-11-14

    Metathesis of unsaturated fatty acid esters (FAEs) by silica supported multifunctional W-based catalyst is disclosed. This transformation represents a novel route towards unsaturated di-esters. Especially, the self-metathesis of ethyl undecylenate results almost exclusively on the homo-coupling product whereas with such catalyst, 1-decene gives ISOMET (isomerization and metathesis olefin) products. The olefin metathesis in the presence of esters is very selective without any secondary cross-metathesis products demonstrating that a high selective olefin metathesis could operate at 150 °C. Additionally, a cross-metathesis of unsaturated FAEs and α-olefins allowed the synthesis of the corresponding ester with longer hydrocarbon skeleton without isomerisation.

  19. Prediction Models and Decision Support: Chances and Challenges

    NARCIS (Netherlands)

    Kappen, T.H.

    2015-01-01

    A clinical prediction model can assist doctors in arriving at the most likely diagnosis or estimating the prognosis. By utilizing various patient- and disease-related properties, such models can yield objective estimations of the risk of a disease or the probability of a certain disease course for

  20. Exploiting Modelling and Simulation in Support of Cyber Defence

    NARCIS (Netherlands)

    Klaver, M.H.A.; Boltjes, B.; Croom-Jonson, S.; Jonat, F.; Çankaya, Y.

    2014-01-01

    The rapidly evolving environment of Cyber threats against the NATO Alliance has necessitated a renewed focus on the development of Cyber Defence policy and capabilities. The NATO Modelling and Simulation Group is looking for ways to leverage Modelling and Simulation experience in research, analysis

  1. Clearing the air : Air quality modelling for policy support

    NARCIS (Netherlands)

    Hendriks, C.

    2018-01-01

    The origin of particulate matter (PM) concentrations in the Netherlands is established using the LOTOS-EUROS model with a source attribution module. Emissions from the ten main economic sectors (SNAP1) were tracked, separating Dutch and foreign sources. Of the modelled PM10 in the Netherlands, about

  2. Support of Modelling in Process-Engineering Education

    NARCIS (Netherlands)

    Schaaf, van der H.; Vermuë, M.H.; Tramper, J.; Hartog, R.J.M.

    2006-01-01

    An objective of the Process Technology curriculum at Wageningen University is to teach students a stepwise modeling approach in the context of process engineering. Many process-engineering students have difficulty with learning to design a model. Some common problems are lack of structure in the

  3. Disaster Reintegration Model: A Qualitative Analysis on Developing Korean Disaster Mental Health Support Model

    Directory of Open Access Journals (Sweden)

    Yun-Jung Choi

    2018-02-01

    Full Text Available This study sought to describe the mental health problems experienced by Korean disaster survivors, using a qualitative research method to provide empirical resources for effective disaster mental health support in Korea. Participants were 16 adults or elderly adults who experienced one or more disasters at least 12 months ago recruited via theoretical sampling. Participants underwent in-depth individual interviews on their disaster experiences, which were recorded and transcribed for qualitative analysis, which followed Strauss and Corbin’s (1998 Grounded theory. After open coding, participants’ experiences were categorized into 130 codes, 43 sub-categories and 17 categories. The categories were further analyzed in a paradigm model, conditional model and the Disaster Reintegration Model, which proposed potentially effective mental health recovery strategies for disaster survivors, health providers and administrators. To provide effective assistance for mental health recovery of disaster survivors, both personal and public resilience should be promoted while considering both cultural and spiritual elements.

  4. Model of hospital-supported discharge after stroke

    DEFF Research Database (Denmark)

    Torp, Claus Rydahl; Vinkler, Sonja; Pedersen, Kirsten Damgaard

    2006-01-01

    BACKGROUND AND PURPOSE: Readmission rate within 6 months after a stroke is 40% to 50%. The purpose of the project was to evaluate whether an interdisciplinary stroke team could reduce length of hospital stay, readmission rate, increase patient satisfaction and reduce dependency of help. METHODS......: One hundred and ninety-eight patients with acute stroke were randomized into 103 patients whose discharge was supported by an interdisciplinary stroke team and 95 control patients who received standard aftercare. Baseline characteristics were comparable in the 2 groups. The patients were evaluated...... services. Furthermore, there was no significant difference in functional scores or patient satisfaction. CONCLUSIONS: In this setting we could not show benefit of an interdisciplinary stroke team supporting patients at discharge perhaps because standard aftercare was very efficient already....

  5. Using Technology to Support the Army Learning Model

    Science.gov (United States)

    2016-02-01

    more graphic scenes which provided the most impact on the student . The in-house team was successful in coming up with innovative and creative ...for instructors to monitor the students ’ use of the product during classroom time in order to provide feedback and support. The training the...a sense, benefits to the students relied on the creativity of the instructor. For example, some instructors used the products to preview or review

  6. An Exploratory Analysis of the Navy Personnel Support Delivery Model

    Science.gov (United States)

    2017-09-01

    of Secretary of Defense PAPA DET Pay and Personnel Afloat Detachment PASS Pay/Personnel Administrative Support System PASSMAN PASS Management Manual ...made manually face-to-face. Current efforts are focused in developing the Integrated Personnel and Pay System-Army (IPPS-A), the Army specific solution...Association, 2017). It is a pioneer of direct marketing , self-service transactions, and online banking services with its patent on remote

  7. Open Models of Decision Support Towards a Framework

    OpenAIRE

    Diasio, Stephen Ray

    2012-01-01

    Aquesta tesi presenta un marc per als models oberts de suport a les decisions en les organitzacions. El treball es vehicula a través d’un compendi d’articles on s’analitzen els fluxos d’entrada i de sortida de coneixement en les organitzacions, així como les tecnologies existents de suport a les decisions. Es presenten els factors subjacents que impulsen nous models per a formes obertes de suport a la decisió. La tesis presenta un estudi de les distintes tipologies de models de suport a les d...

  8. Proceedings of the DGMK-Conference 'Creating value from light olefins - production and conversion'. Authors' manuscripts

    Energy Technology Data Exchange (ETDEWEB)

    Emig, G.; Kraemer, H.J.; Weitkamp, J. (eds.)

    2001-07-01

    Main topics of the conference were: production of light olefin by steamcracking and catalytic cracking processes, catalysts, methanol to olefin processes, oxidative dehydrogenation, partial oxidation, selective oxidation of alkanes with various catalysts. (uke)

  9. Mechanism of Propylene Oxide Polymerization Promoted by N-Heterocyclic Olefins

    KAUST Repository

    Al-Ghamdi, Miasser

    2017-01-11

    We report a mechanistic DFT investigation of the organopolymerization of propylene oxide (PO) promoted by N-heterocyclic olefins (NHOs) in combination with benzylic alcohol (BnOH). Calculations support the experimentally based hypothesis of two competing pathways, namely, the anionic and zwitterionic pathways. The former is based on an acid–base cooperativity between BnOH and the NHO, promoting ring opening of PO by BnO–. The latter occurs through the formation of a zwitterionic adduct by nucleophilic attack of the exocyclic carbon atom of the NHO on the PO, with the concerted ring opening of PO. The two initiating species cannot interconvert, and chain elongation can proceed from both initiation adducts. Potential energy surfaces were computed for a set of NHOs to clarify the effects of the steric and electronic properties of the NHO on the system reactivity. The results achieved represent useful insight toward the synthesis of PPO with better properties with respect to the polymer obtained with the experimental tested systems because the computationally proposed NHO system is the only one that favors the mechanism leading to higher molecular weight.

  10. Atomic structure of graphene supported heterogeneous model catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Franz, Dirk

    2017-04-15

    Graphene on Ir(111) forms a moire structure with well defined nucleation centres. Therefore it can be utilized to create hexagonal metal cluster lattices with outstanding structural quality. At diffraction experiments these 2D surface lattices cause a coherent superposition of the moire cell structure factor, so that the measured signal intensity scales with the square of coherently scattering unit cells. This artificial signal enhancement enables the opportunity for X-ray diffraction to determine the atomic structure of small nano-objects, which are hardly accessible with any experimental technique. The uniform environment of every metal cluster makes the described metal cluster lattices on graphene/Ir(111) an attractive model system for the investigation of catalytic, magnetic and quantum size properties of ultra-small nano-objects. In this context the use of x-rays provides a maximum of flexibility concerning the possible sample environments (vacuum, selected gases, liquids, sample temperature) and allows in-situ/operando measurements. In the framework of the present thesis the structure of different metal clusters grown by physical vapor deposition in an UHV environment and after gas exposure have been investigated. On the one hand the obtained results will explore many aspects of the atomic structure of these small metal clusters and on the other hand the presented results will proof the capabilities of the described technique (SXRD on cluster lattices). For iridium, platinum, iridium/palladium and platinum/rhodium the growth on graphene/Ir(111) of epitaxial, crystalline clusters with an ordered hexagonal lattice arrangement has been confirmed using SXRD. The clusters nucleate at the hcp sites of the moire cell and bind via rehybridization of the carbon atoms (sp{sup 2} → sp{sup 3}) to the Ir(111) substrate. This causes small displacements of the substrate atoms, which is revealed by the diffraction experiments. All metal clusters exhibit a fcc structure

  11. Spreadsheet Decision Support Model for Training Exercise Material Requirements Planning

    National Research Council Canada - National Science Library

    Tringali, Arthur

    1997-01-01

    ... associated with military training exercises. The model combines the business practice of Material Requirements Planning and the commercial spreadsheet software capabilities of Lotus 1-2-3 to calculate the requirements for food, consumable...

  12. Computer supported estimation of input data for transportation models

    OpenAIRE

    Cenek, Petr; Tarábek, Peter; Kopf, Marija

    2010-01-01

    Control and management of transportation systems frequently rely on optimization or simulation methods based on a suitable model. Such a model uses optimization or simulation procedures and correct input data. The input data define transportation infrastructure and transportation flows. Data acquisition is a costly process and so an efficient approach is highly desirable. The infrastructure can be recognized from drawn maps using segmentation, thinning and vectorization. The accurate definiti...

  13. hf alkylation in the 1980's: the role of isobutane/olefin ratio

    Energy Technology Data Exchange (ETDEWEB)

    Hutson, T. Jr.

    1978-08-01

    Research devoted to maximizing no-lead octane numbers in motor fuel is reported. Results of the studies are the basis for the following conclusions: 1. Isobutane alkylate made from either propylene, butene-2, or C/sub 3/--C/sub 4/ mixed olefins is a low sensitivity, high motor octane product. Typically, C/sub 3/--C/sub 4/ mixed olefin alkylate has a clear motor octane number of about 92.2 and a clear Research octane number of about 93.5. 2. In separate studies with propylene, butene-2 and C/sub 3/--C/sub 4/ mixed olefins, increasing the isobutane-to-olefin ratio suppressed the formation of high molecular weight residue, indicating a substantial reduction in the role of olefin polymerization to large ions. The overall result of increasing ratio was an improvement in selectivity to high-octane components in the alkylate. 3. When alkylating isobutane with propylene, increasing the ratio resulted in a decrease in the concentration of C/sub 7/-fraction (primary product) and an increase in the C/sub 8/-fraction (from chain initiation and subsequent hydrogen transfer). At the same time, the production of chain-termination-product propane also increased. 4. When alkylating isobutane with C/sub 3/--C/sub 4/ mixed olefins, increasing the ratio showed the same trend obtained in separate alkylation tests with propylene and butene-2. As the ratio increased, the concentration of C/sub 7/-fraction (primary propylene--isobutane product) decreased and the concentration of C/sub 8/-fraction increased markedly. Thus, increasing isobutane-to-olefin ratio exerted a strong effect on alkylate quality in the area of about 5 to 1 to 20 to 1; this effect diminished at ratios 20:1.

  14. Data to support "Boosted Regression Tree Models to Explain Watershed Nutrient Concentrations & Biological Condition"

    Data.gov (United States)

    U.S. Environmental Protection Agency — Spreadsheets are included here to support the manuscript "Boosted Regression Tree Models to Explain Watershed Nutrient Concentrations and Biological Condition". This...

  15. Agricultural climate impacts assessment for economic modeling and decision support

    Science.gov (United States)

    Thomson, A. M.; Izaurralde, R. C.; Beach, R.; Zhang, X.; Zhao, K.; Monier, E.

    2013-12-01

    A range of approaches can be used in the application of climate change projections to agricultural impacts assessment. Climate projections can be used directly to drive crop models, which in turn can be used to provide inputs for agricultural economic or integrated assessment models. These model applications, and the transfer of information between models, must be guided by the state of the science. But the methodology must also account for the specific needs of stakeholders and the intended use of model results beyond pure scientific inquiry, including meeting the requirements of agencies responsible for designing and assessing policies, programs, and regulations. Here we present methodology and results of two climate impacts studies that applied climate model projections from CMIP3 and from the EPA Climate Impacts and Risk Analysis (CIRA) project in a crop model (EPIC - Environmental Policy Indicator Climate) in order to generate estimates of changes in crop productivity for use in an agricultural economic model for the United States (FASOM - Forest and Agricultural Sector Optimization Model). The FASOM model is a forward-looking dynamic model of the US forest and agricultural sector used to assess market responses to changing productivity of alternative land uses. The first study, focused on climate change impacts on the UDSA crop insurance program, was designed to use available daily climate projections from the CMIP3 archive. The decision to focus on daily data for this application limited the climate model and time period selection significantly; however for the intended purpose of assessing impacts on crop insurance payments, consideration of extreme event frequency was critical for assessing periodic crop failures. In a second, coordinated impacts study designed to assess the relative difference in climate impacts under a no-mitigation policy and different future climate mitigation scenarios, the stakeholder specifically requested an assessment of a

  16. Product Quality Modelling Based on Incremental Support Vector Machine

    International Nuclear Information System (INIS)

    Wang, J; Zhang, W; Qin, B; Shi, W

    2012-01-01

    Incremental Support vector machine (ISVM) is a new learning method developed in recent years based on the foundations of statistical learning theory. It is suitable for the problem of sequentially arriving field data and has been widely used for product quality prediction and production process optimization. However, the traditional ISVM learning does not consider the quality of the incremental data which may contain noise and redundant data; it will affect the learning speed and accuracy to a great extent. In order to improve SVM training speed and accuracy, a modified incremental support vector machine (MISVM) is proposed in this paper. Firstly, the margin vectors are extracted according to the Karush-Kuhn-Tucker (KKT) condition; then the distance from the margin vectors to the final decision hyperplane is calculated to evaluate the importance of margin vectors, where the margin vectors are removed while their distance exceed the specified value; finally, the original SVs and remaining margin vectors are used to update the SVM. The proposed MISVM can not only eliminate the unimportant samples such as noise samples, but also can preserve the important samples. The MISVM has been experimented on two public data and one field data of zinc coating weight in strip hot-dip galvanizing, and the results shows that the proposed method can improve the prediction accuracy and the training speed effectively. Furthermore, it can provide the necessary decision supports and analysis tools for auto control of product quality, and also can extend to other process industries, such as chemical process and manufacturing process.

  17. Product Quality Modelling Based on Incremental Support Vector Machine

    Science.gov (United States)

    Wang, J.; Zhang, W.; Qin, B.; Shi, W.

    2012-05-01

    Incremental Support vector machine (ISVM) is a new learning method developed in recent years based on the foundations of statistical learning theory. It is suitable for the problem of sequentially arriving field data and has been widely used for product quality prediction and production process optimization. However, the traditional ISVM learning does not consider the quality of the incremental data which may contain noise and redundant data; it will affect the learning speed and accuracy to a great extent. In order to improve SVM training speed and accuracy, a modified incremental support vector machine (MISVM) is proposed in this paper. Firstly, the margin vectors are extracted according to the Karush-Kuhn-Tucker (KKT) condition; then the distance from the margin vectors to the final decision hyperplane is calculated to evaluate the importance of margin vectors, where the margin vectors are removed while their distance exceed the specified value; finally, the original SVs and remaining margin vectors are used to update the SVM. The proposed MISVM can not only eliminate the unimportant samples such as noise samples, but also can preserve the important samples. The MISVM has been experimented on two public data and one field data of zinc coating weight in strip hot-dip galvanizing, and the results shows that the proposed method can improve the prediction accuracy and the training speed effectively. Furthermore, it can provide the necessary decision supports and analysis tools for auto control of product quality, and also can extend to other process industries, such as chemical process and manufacturing process.

  18. Single-Particle Spectroscopy on Large SAPO-34 Crystals at Work: Methanol-To-Olefin versus Ethanol-To-Olefin Processes

    NARCIS (Netherlands)

    Qian, Q.; Ruiz-Martinez, J.; Mokhtar, M.; Asiri, A.M.; Al-Thabaiti, S.A.; Basahel, S.N.; van der Bij, H.E.; Kornatowski, J.; Weckhuysen, B.M.

    2013-01-01

    The formation of hydrocarbon pool (HCP) species during methanol- to-olefin (MTO) and ethanol-toolefin (ETO) processes have been studied on individual micron-sized SAPO- 34 crystals with a combination of in situ UV/Vis, confocal fluorescence, and synchrotron-based IR microspectroscopic techniques.

  19. Experimentally supported mathematical modeling of continuous baking processes

    DEFF Research Database (Denmark)

    Stenby Andresen, Mette

    and temperature) and control the process (air flow, temperature, and humidity) are therefore emphasized. The oven is furthermore designed to work outside the range of standard tunnel ovens, making it interesting for manufacturers of both baking products and baking equipment. A mathematical model describing......The scope of the PhD project was to increase knowledge on the process-to-product interactions in continuous tunnel ovens. The work has focused on five main objectives. These objectives cover development of new experimental equipment for pilot plant baking experiments, mathematical modeling of heat...... on mass transfer was examined through comparison of different modeling set-ups and experimental data. It was found that while the baking tray is likely to reduce the evaporation from the bottom surface, it is not correct to assume that no evaporation takes place at the covered surface. Parallel...

  20. Decision Support Model for Introduction of Gamification Solution Using AHP

    Directory of Open Access Journals (Sweden)

    Sangkyun Kim

    2014-01-01

    Full Text Available Gamification means the use of various elements of game design in nongame contexts including workplace collaboration, marketing, education, military, and medical services. Gamification is effective for both improving workplace productivity and motivating employees. However, introduction of gamification is not easy because the planning and implementation processes of gamification are very complicated and it needs interdisciplinary knowledge such as information systems, organization behavior, and human psychology. Providing a systematic decision making method for gamification process is the purpose of this paper. This paper suggests the decision criteria for selection of gamification platform to support a systematic decision making process for managements. The criteria are derived from previous works on gamification, introduction of information systems, and analytic hierarchy process. The weights of decision criteria are calculated through a survey by the professionals on game, information systems, and business administration. The analytic hierarchy process is used to derive the weights. The decision criteria and weights provided in this paper could support the managements to make a systematic decision for selection of gamification platform.