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Sample records for ring-closing metathesis rcm

  1. Synthesis of densely functionalized enantiopure indolizidines by ring-closing metathesis (RCM of hydroxylamines from carbohydrate-derived nitrones

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    Goti Andrea

    2007-12-01

    Full Text Available Abstract Background Indolizidine alkaloids widely occur in nature and display interesting biological activity. This is the reason for which their total synthesis as well as the synthesis of non-natural analogues still attracts the attention of many research groups. To establish new straightforward accesses to these molecules is therefore highly desirable. Results The ring closing metathesis (RCM of enantiopure hydroxylamines bearing suitable unsaturated groups cleanly afforded piperidine derivatives in good yields. Further cyclization and deprotection of the hydroxy groups gave novel highly functionalized indolizidines. The synthesis of a pyrroloazepine analogue is also described. Conclusion We have developed a new straightforward methodology for the synthesis of densely functionalized indolizidines and pyrroloazepine analogues in 6 steps and 30–60% overall yields from enantiopure hydroxylamines obtained straightforwardly from carbohydrate-derived nitrones.

  2. Structural and Pharmacological Effects of Ring-Closing Metathesis in Peptides

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    Pål Rongved

    2010-09-01

    Full Text Available Applications of ring-closing alkene metathesis (RCM in acyclic α- and β-peptides and closely related systems are reviewed, with a special emphasis on the structural and pharmacological effects of cyclization by RCM.

  3. Design and synthesis of novel bis-annulated caged polycycles via ring-closing metathesis: pushpakenediol

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    Sambasivarao Kotha

    2014-11-01

    Full Text Available Intricate caged molecular frameworks are assembled by an atom economical process via a Diels–Alder (DA reaction, a Claisen rearrangement, a ring-closing metathesis (RCM and an alkenyl Grignard addition. The introduction of olefinic moieties in the pentacycloundecane (PCUD framework at appropriate positions followed by RCM led to the formation of novel heptacyclic cage systems.

  4. Catalytic Enantioselective Synthesis of Naturally Occurring Butenolides via Hetero-Allylic Alkylation and Ring Closing Metathesis

    NARCIS (Netherlands)

    Mao, Bin; Geurts, Koen; Fañanás-Mastral, Martín; Zijl, Anthoni W. van; Fletcher, Stephen P.; Minnaard, Adriaan J.; Feringa, Bernard

    2011-01-01

    An efficient catalytic asymmetric synthesis of chiral γ-butenolides was developed based on the hetero-allylic asymmetric alkylation (h-AAA) in combination with ring closing metathesis (RCM). The synthetic potential of the h-AAA-RCM protocol was illustrated with the facile synthesis of (-)-whiskey

  5. Construction of Eight-Membered Carbocycles with Trisubstituted Double Bonds Using the Ring Closing Metathesis Reaction

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    Motoo Tori

    2010-06-01

    Full Text Available Medium sized carbocycles are particularly difficult to synthesize. Ring closing metathesis reactions (RCM have recently been applied to construct eight-membered carbocycles, but trisubstituted double bonds in the eight-membered rings are more difficult to produce using RCM reactions. In this review, model examples and our own results are cited and the importance of the preparation of suitably designed precursors is discussed. Examples of RCM reactions used in the total synthesis of natural products are also outlined.

  6. Tandem radical reactions and ring-closing metathesis. Application in the synthesis of cyclooctenes.

    Science.gov (United States)

    Sibi, Mukund P; Aasmul, Mona; Hasegawa, Hikaru; Subramanian, Thangaiah

    2003-08-07

    [reaction: see text] Fumarate- and acrylate-substituted oxazolidinones undergo tandem radical reaction to form dienes in moderate to good yields. The resulting dienes provide cyclooctenes in moderate to good yields after ring-closing metathesis (RCM). The role of the carbon backbone substituents and other variables in the efficiency of the eight-membered ring formation is discussed.

  7. Efficient synthesis of enantiopure conduritols by ring-closing metathesis

    DEFF Research Database (Denmark)

    Jørgensen, Morten; Iversen, Erik Høgh; Paulsen, Andreas Lundtang

    2001-01-01

    Two short synthetic approaches to enantiopure conduritols are described starting from the chiral pool. In both cases, the cyclohexene ring is assembled via ring-closing olefin metathesis. The terminal diene precursers for the metathesis reaction are prepared either from octitols or from tartaric...

  8. Supported Catalysts Useful in Ring-Closing Metathesis, Cross Metathesis, and Ring-Opening Metathesis Polymerization

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    Jakkrit Suriboot

    2016-04-01

    Full Text Available Ruthenium and molybdenum catalysts are widely used in synthesis of both small molecules and macromolecules. While major developments have led to new increasingly active catalysts that have high functional group compatibility and stereoselectivity, catalyst/product separation, catalyst recycling, and/or catalyst residue/product separation remain an issue in some applications of these catalysts. This review highlights some of the history of efforts to address these problems, first discussing the problem in the context of reactions like ring-closing metathesis and cross metathesis catalysis used in the synthesis of low molecular weight compounds. It then discusses in more detail progress in dealing with these issues in ring opening metathesis polymerization chemistry. Such approaches depend on a biphasic solid/liquid or liquid separation and can use either always biphasic or sometimes biphasic systems and approaches to this problem using insoluble inorganic supports, insoluble crosslinked polymeric organic supports, soluble polymeric supports, ionic liquids and fluorous phases are discussed.

  9. Hybrid macrocycle formation and spiro annulation on cis-syn-cis-tricyclo[6.3.0.02,6]undeca-3,11-dione and its congeners via ring-closing metathesis

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    Sambasivarao Kotha

    2015-07-01

    Full Text Available We have developed a simple methodology to transform cis-syn-cis-triquinane derivative 2 into the diindole based macrocycle 6 involving Fischer indolization and ring-closing metathesis (RCM. Various spiro-polyquinane derivatives have been assembled via RCM as a key step.

  10. Synthesis of the carbocyclic core of the cornexistins by ring-closing metathesis.

    Science.gov (United States)

    Clark, J Stephen; Marlin, Frederic; Nay, Bastien; Wilson, Claire

    2003-01-09

    An advanced intermediate in the synthesis of the phytotoxins cornexistin and hydroxycornexistin has been synthesized. Sequential palladium-mediated sp(2)-sp(3) fragment coupling and ring-closing diene metathesis have been used to construct the nine-membered carbocyclic core found in the natural products. [reaction--see text

  11. Synthesis of Gabosine A and N from Ribose by the Use of Ring-Closing Metathesis

    DEFF Research Database (Denmark)

    Monrad, Rune Nygaard; Fanefjord, Mette; Hansen, Flemming Gundorph

    2009-01-01

    -methylallyl bromide. The functionalized octa-1,7-diene, thus obtained, is converted into the six-membered gabosine skeleton by ring-closing olefin metathesis. Subsequent protective group manipulations and oxidation gives rise to gabosine N in a total of 8 steps from ribose while the synthesis of gabosine...

  12. Combining the [2,3] Sigmatropic Rearrangement and Ring-Closing Metathesis Strategies for the Synthesis of Spirocyclic Alkaloids. A Short and Efficient Route to (+/-)-Perhydrohistrionicotoxin

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Hagberg, Lars; Poulsen, Anders

    1999-01-01

    This paper describes the use of selenium-based [2,3] sigmatropic rearrangement in combination with ruthenium-catalyzed ring-closing metathesis (RCM) for the synthesis of azaspiro ring systems, as exemplified by the reactions of model substrates 5 and 6. The methodology has been applied to a short...... is potentially enantioselective, and key steps were the [2,3] sigmatropic rearrangement of 11 to 12 via the corresponding allylic selenide (86% yield) and ruthenium-catalyzed RCM of 13 to 14 (80%). (C) 1999 Elsevier Science Ltd. All rights reserved....

  13. A stereoselective synthesis of (+)-physoperuvine using a tandem aza-Claisen rearrangement and ring closing metathesis reaction.

    Science.gov (United States)

    Zaed, Ahmed M; Swift, Michael D; Sutherland, Andrew

    2009-07-07

    A stereoselective synthesis of (+)-physoperuvine, a tropane alkaloid from Physalis peruviana Linne has been developed using a one-pot tandem aza-Claisen rearrangement and ring closing metathesis reaction to form the key amino-substituted cycloheptene ring.

  14. Spiro annulation of cage polycycles via Grignard reaction and ring-closing metathesis as key steps

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    Sambasivarao Kotha

    2015-08-01

    Full Text Available A simple synthetic strategy to C2-symmetric bis-spiro-pyrano cage compound 7 involving ring-closing metathesis is reported. The hexacyclic dione 10 was prepared from simple and readily available starting materials such as 1,4-naphthoquinone and cyclopentadiene. The synthesis of an unprecedented octacyclic cage compound through intramolecular Diels–Alder (DA reaction as a key step is described. The structures of three new cage compounds 7, 12 and 18 were confirmed by single crystal X-ray diffraction studies.

  15. Cyclic phosphopeptides for interference with Grb2 SH2 domain signal transduction prepared by ring-closing metathesis and phosphorylation

    NARCIS (Netherlands)

    Dekker, Frank J; de Mol, Nico J; Fischer, Marcel J E; Kemmink, Johan; Liskamp, Rob M J; Dekker, Frank

    2003-01-01

    Cyclic phosphopeptides were prepared using ring-closing metathesis followed by phosphorylation. These cyclic phosphopeptides were designed to interact with the SH2 domain of Grb2, which is a signal transduction protein of importance as a target for antiproliferative drug development. Binding of

  16. Phosphate Tether-Mediated Ring-Closing Metathesis for the Generation of P-Stereogenic, Z-Configured Bicyclo[7.3.1]- and Bicyclo[8.3.1]phosphates.

    Science.gov (United States)

    Markley, Jana L; Maitra, Soma; Hanson, Paul R

    2016-02-05

    A phosphate tether-mediated ring-closing metathesis (RCM) study to the synthesis of Z-configured, P-stereogenic bicyclo[7.3.1]- and bicyclo[8.3.1]phosphates is reported. Investigations suggest that C3-substitution, olefin substitution, and proximity of the forming olefin to the bridgehead carbon of the bicyclic affect the efficiency and stereochemical outcome of the RCM event. This study demonstrates the utility of phosphate tether-mediated desymmetrization of C2-symmetric, 1,3-anti-diol-containing dienes in the generation of macrocyclic phosphates with potential synthetic and biological utility.

  17. Synthesis of a natural product-inspired eight-membered ring lactam library via ring-closing metathesis.

    Science.gov (United States)

    Brown, Neil; Xie, Baohan; Markina, Nataliya; Vandervelde, David; Perchellet, Jean-Pierre H; Perchellet, Elisabeth M; Crow, Kyle R; Buszek, Keith R

    2008-09-01

    We have prepared a novel speculative eight-membered lactam demonstration library based on the skeletal structure of the potent antitumor marine natural product octalactin A. The basic scaffold was readily constructed in a convergent fashion via ring-closing metathesis chemistry from the corresponding diene amides. A cursory examination of the biological properties of the library validates the relevance and significance of these structures.

  18. Bidirectional cross metathesis and ring-closing metathesis/ring opening of a C2-symmetric building block: a strategy for the synthesis of decanolide natural products

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    Bernd Schmidt

    2013-11-01

    Full Text Available Starting from the conveniently available ex-chiral pool building block (R,R-hexa-1,5-diene-3,4-diol, the ten-membered ring lactones stagonolide E and curvulide A were synthesized using a bidirectional olefin-metathesis functionalization of the terminal double bonds. Key steps are (i a site-selective cross metathesis, (ii a highly diastereoselective extended tethered RCM to furnish a (Z,E-configured dienyl carboxylic acid and (iii a Ru–lipase-catalyzed dynamic kinetic resolution to establish the desired configuration at C9. Ring closure was accomplished by macrolactonization. Curvulide A was synthesized from stagonolide E through Sharpless epoxidation.

  19. Bidirectional cross metathesis and ring-closing metathesis/ring opening of a C 2-symmetric building block: a strategy for the synthesis of decanolide natural products.

    Science.gov (United States)

    Schmidt, Bernd; Kunz, Oliver

    2013-01-01

    Starting from the conveniently available ex-chiral pool building block (R,R)-hexa-1,5-diene-3,4-diol, the ten-membered ring lactones stagonolide E and curvulide A were synthesized using a bidirectional olefin-metathesis functionalization of the terminal double bonds. Key steps are (i) a site-selective cross metathesis, (ii) a highly diastereoselective extended tethered RCM to furnish a (Z,E)-configured dienyl carboxylic acid and (iii) a Ru-lipase-catalyzed dynamic kinetic resolution to establish the desired configuration at C9. Ring closure was accomplished by macrolactonization. Curvulide A was synthesized from stagonolide E through Sharpless epoxidation.

  20. Stereoselective synthesis of functionalized cyclic amino acid derivatives via a [2,3]-Stevens rearrangement and ring-closing metathesis.

    Science.gov (United States)

    Nash, Aaron; Soheili, Arash; Tambar, Uttam K

    2013-09-20

    Unnatural cyclic amino acids are valuable tools in biomedical research and drug discovery. A two-step stereoselective strategy for converting simple glycine-derived aminoesters into unnatural cyclic amino acid derivatives has been developed. The process includes a palladium-catalyzed tandem allylic amination/[2,3]-Stevens rearrangement followed by a ruthenium-catalyzed ring-closing metathesis. The [2,3]-rearrangement proceeds with high diastereoselectivity through an exo transition state. Oppolzer's chiral auxiliary was utilized to access an enantiopure cyclic amino acid by this approach, which will enable future biological applications.

  1. Tandem ring-closing metathesis/isomerization reactions for the total synthesis of violacein

    DEFF Research Database (Denmark)

    Petersen, Mette Terp; Nielsen, Thomas Eiland

    2013-01-01

    A series of 5-substituted 2-pyrrolidinones was synthesized through a one-pot ruthenium alkylidene-catalyzed tandem RCM/isomerization/nucleophilic addition sequence. The intermediates resulting from RCM/isomerization showed reactivity toward electrophiles in aldol condensation reactions which...

  2. Benzoylureas as removable cis amide inducers: synthesis of cyclic amides via ring closing metathesis (RCM).

    Science.gov (United States)

    Brady, Ryan M; Khakham, Yelena; Lessene, Guillaume; Baell, Jonathan B

    2011-02-07

    Rapid and high yielding synthesis of medium ring lactams was made possible through the use of a benzoylurea auxiliary that serves to stabilize a cisoid amide conformation, facilitating cyclization. The auxiliary is released after activation under the mild conditions required to deprotect a primary amine, such as acidolysis of a Boc group in the examples given here. This methodology is a promising tool for the synthesis of medium ring lactams, macrocyclic natural products and peptides.

  3. Synthesis of the EF-ring of ciguatoxin 3C based on the [2,3]-Wittig rearrangement and ring-closing olefin metathesis.

    Science.gov (United States)

    Goto, Akiyoshi; Fujiwara, Kenshu; Kawai, Ayako; Kawai, Hidetoshi; Suzuki, Takanori

    2007-12-20

    The EF-ring segment of ciguatoxin 3C, a causative toxin of ciguatera fish poisoning, was synthesized in three major steps: 1,4-addition for the C20O-C27 bond connection, chirality transferring anti selective [2,3]-Wittig rearrangement for the construction of the anti-2-hydroxyalkyl ether part, and ring-closing olefin metathesis for the F-ring formation.

  4. Recent applications of ring-rearrangement metathesis in organic synthesis

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    Sambasivarao Kotha

    2015-10-01

    Full Text Available Ring-rearrangement metathesis (RRM involves multiple metathesis processes such as ring-opening metathesis (ROM/ring-closing metathesis (RCM in a one-pot operation to generate complex targets. RRM delivers complex frameworks that are difficult to assemble by conventional methods. The noteworthy point about this type of protocol is multi-bond formation and it is an atom economic process. In this review, we have covered literature that appeared during the last seven years (2008–2014.

  5. Olefin metathesis in nano-sized systems

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    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.

  6. Synthesis of anti-tumour phosphatidylinositol analogues from glucose by the use of ring-closing olefin metathesis

    DEFF Research Database (Denmark)

    Andresen, Thomas Lars; Skytte, Dorthe M.; Madsen, Robert

    2004-01-01

    A divergent strategy is described for synthesis of the novel phosphatidylinositols 1-3. The synthetic approach commences from benzyl-protected methyl 6-iodo-6-deoxy-a-D-glucopyranoside, which undergoes zinc-mediated reductive fragmentation followed by vinyl Grignard addition and ring-closing meta...

  7. The right computational recipe for olefin metathesis with ru-based catalysts: The whole mechanism of ring-closing olefin metathesis

    KAUST Repository

    Poater, Albert

    2014-10-14

    The initiation mechanism of ruthenium methylidene complexes was studied detailing mechanistic insights of all involved reaction steps within a classical olefin metathesis pathway. Computational studies reached a good agreement with the rarely available experimental data and even enabled to complement them. As a result, a highly accurate computational and rather cheap recipe is presented; M06/TZVP//BP86/SVP (PCM, P = 1354 atm).

  8. The right computational recipe for olefin metathesis with ru-based catalysts: The whole mechanism of ring-closing olefin metathesis

    KAUST Repository

    Poater, Albert; Pump, Eva; Vummaleti, Sai V. C.; Cavallo, Luigi

    2014-01-01

    The initiation mechanism of ruthenium methylidene complexes was studied detailing mechanistic insights of all involved reaction steps within a classical olefin metathesis pathway. Computational studies reached a good agreement with the rarely available experimental data and even enabled to complement them. As a result, a highly accurate computational and rather cheap recipe is presented; M06/TZVP//BP86/SVP (PCM, P = 1354 atm).

  9. Nitro-Grela-type complexes containing iodides – robust and selective catalysts for olefin metathesis under challenging conditions

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    Andrzej Tracz

    2015-10-01

    Full Text Available Iodide-containing nitro-Grela-type catalysts have been synthesized and applied to ring closing metathesis (RCM and cross metathesis (CM reactions. These new catalysts have exhibited improved efficiency in the transformation of sterically, non-demanding alkenes. Additional steric hindrance in the vicinity of ruthenium related to the presence of iodides ensures enhanced catalyst stability. The benefits are most apparent under challenging conditions, such as very low reaction concentrations, protic solvents or with the occurrence of impurities.

  10. Olefin metathesis and metathesis polymerization

    CERN Document Server

    Ivin, K J

    1997-01-01

    This book is a follow-up to Ivins Olefin Metathesis, (Academic Press, 1983). Bringing the standard text in the field up to date, this Second Edition is a result of rapid growth in the field, sparked by the discovery of numerous well-defined metal carbene complexes that can act as very efficient initiators of all types of olefin metathesis reaction, including ring-closing metathesis of acyclic dienes, enynes, and dienynes; ring-opening metathesis polymerizationof cycloalkenes, acyclic diene metathesis polymerization; and polymerization of alkynes, as well as simple olefin metathesis. Olefin Metathesis and Metathesis Polymerization provides a broad, up-to-date account of the subject from its beginnings in 1957 to the latest applications in organic synthesis. The book follows the same format as the original, making it useful toteachers and to researchers, and will be of particular interest to those working in the fields of organic chemistry, polymer chemistry, organometallic chemistry, catalysis, materials scien...

  11. A Modular Approach to Aryl-C-ribonucleosides via the Allylic Substitution and Ring-Closing Metathesis Sequence. A Stereocontrolled Synthesis of All Four alpha-/beta- and D-/L-C-Nucleoside Stereoisomers

    Czech Academy of Sciences Publication Activity Database

    Štambaský, J.; Kapras, V.; Štefko, Martin; Kysilka, O.; Hocek, Michal; Malkov, A. V.; Kočovský, P.

    2011-01-01

    Roč. 76, č. 19 (2011), s. 7781-7803 ISSN 0022-3263 R&D Projects: GA MŠk LC512; GA AV ČR IAA400550902 Institutional research plan: CEZ:AV0Z40550506 Keywords : C-nucleosides * allylic substitution * metathesis * dihydroxylation Subject RIV: CC - Organic Chemistry Impact factor: 4.450, year: 2011

  12. Alkane Metathesis

    KAUST Repository

    Basset, Jean-Marie; Callens, Emmanuel; Riache, Nassima

    2015-01-01

    metal for alkane (de)hydrogenation and another for olefin metathesis in which the activity of these catalysts is essentially driven by the performance of the (de)hydrogenation steps. In this book chapter, we would focus on the evolution of these two

  13. Alkane Metathesis

    KAUST Repository

    Basset, Jean-Marie

    2015-03-29

    Catalytic activation of alkanes which directly transforms light alkanes into higher homologs is a major area in organometallic chemistry and petrochemical chemistry. This transformation is a chemical challenge considering the inertness of the sp3 carbon-hydrogen bond. It is generally accepted that this catalytic process involves the formation of olefins. This reaction is defined as alkane metathesis. To date, two catalytic systems of alkane metathesis exist: (i) a single catalytic system prepared by surface organometallic chemistry, acting as multifunctional-supported catalyst which transforms any alkanes into a mixture of their lower and higher homologs and (ii) the other catalytic systems employing a tandem strategy with two different metals, one metal for alkane (de)hydrogenation and another for olefin metathesis in which the activity of these catalysts is essentially driven by the performance of the (de)hydrogenation steps. In this book chapter, we would focus on the evolution of these two classes of catalysts by looking at their specific reactivity of the catalysts towards alkanes, comparing their performances and studying the mechanism.

  14. Hexacoordinate Ru-based olefin metathesis catalysts with pH-responsive N-heterocyclic carbene (NHC and N-donor ligands for ROMP reactions in non-aqueous, aqueous and emulsion conditions

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    Shawna L. Balof

    2015-10-01

    Full Text Available Three new ruthenium alkylidene complexes (PCy3Cl2(H2ITapRu=CHSPh (9, (DMAP2Cl2(H2ITapRu=CHPh (11 and (DMAP2Cl2(H2ITapRu=CHSPh (12 have been synthesized bearing the pH-responsive H2ITap ligand (H2ITap = 1,3-bis(2’,6’-dimethyl-4’-dimethylaminophenyl-4,5-dihydroimidazol-2-ylidene. Catalysts 11 and 12 are additionally ligated by two pH-responsive DMAP ligands. The crystal structure was solved for complex 12 by X-ray diffraction. In organic, neutral solution, the catalysts are capable of performing standard ring-opening metathesis polymerization (ROMP and ring closing metathesis (RCM reactions with standard substrates. The ROMP with complex 11 is accelerated in the presence of two equiv of H3PO4, but is reduced as soon as the acid amount increased. The metathesis of phenylthiomethylidene catalysts 9 and 12 is sluggish at room temperature, but their ROMP can be dramatically accelerated at 60 °C. Complexes 11 and 12 are soluble in aqueous acid. They display the ability to perform RCM of diallylmalonic acid (DAMA, however, their conversions are very low amounting only to few turnovers before decomposition. However, both catalysts exhibit outstanding performance in the ROMP of dicyclopentadiene (DCPD and mixtures of DCPD with cyclooctene (COE in acidic aqueous microemulsion. With loadings as low as 180 ppm, the catalysts afforded mostly quantitative conversions of these monomers while maintaining the size and shape of the droplets throughout the polymerization process. Furthermore, the coagulate content for all experiments stayed <2%. This represents an unprecedented efficiency in emulsion ROMP based on hydrophilic ruthenium alkylidene complexes.

  15. Carbohydrate carbocyclization by a zinc-mediated tandem reaction and ring-closing enyne metathesis

    DEFF Research Database (Denmark)

    Poulsen, Carina Storm; Madsen, Robert

    2002-01-01

    reaction, an amino group can be introduced in the 1,7-enyne products. Addition of 2-TMS-ethynylcerium(III) chloride after the reductive ring-opening produces the corresponding 1,6-enynes. Further annulation of the product 1,3-dienes can be achieved through a Diels-Alder reaction with good control of stereo...

  16. Synthesis of Calystegine A(3) from Glucose by the Use of Ring-Closing Metathesis

    DEFF Research Database (Denmark)

    Monrad, Rune Nygaard; Pipper, Charlotte Bressen; Madsen, Robert

    2009-01-01

    A synthesis of the nortropane alkaloid calystegine A(3) is described from D-glucose. The key step employs a zinc-mediated tandem reaction where a benzyl-protected methyl 6-iodo glucoside is fragmented to give an unsaturated aldehyde, which is then transformed into the corresponding benzylimine...... affords calystegine A(3). The synthesis uses a total of 13 steps from glucose and confirms the absolute configuration of the natural product....

  17. The metathesis of alkynes

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    H. C. M. Vosloo

    1991-07-01

    Full Text Available The alkyne metathesis reaction is a direct result of the known and intensively studied alkene or olefin metathesis reaction. Unfortunately this reaction was never studied as intensively as the alkene metathesis reaction, mainly because of a lack of active catalytic systems. In the alkyn metathesis reaction the carbon-carbon triple bonds are broken and rearranged to give a redistribution of alkylidyne groups.

  18. Synthesis of 7-Deoxypancratistatin from Carbohydrates by the Use of Olefin Metathesis

    DEFF Research Database (Denmark)

    Håkansson, Anders Eckart; Palmelund, Anders; Holm, H.

    2006-01-01

    from D-xylose and piperonal. The former is converted into ribofuranoside 28, which is coupled with bromide 7 in the presence of zinc, and this is followed by ring-closing olefin metathesis. Subsequent Overman rearrangement, dihydroxylation, and deprotection then affords the natural product....

  19. Synthetic Strategies for Converting Carbohydrates into Carbocycles by the Use of Olefin Metathesis

    DEFF Research Database (Denmark)

    Madsen, Robert

    2007-01-01

    This microreview covers recent advances in the use of ring-closing metathesis for the synthesis of carbocycles from carbohydrates. Various strategies for the synthesis of a,w-dienes from carbohydrates are presented, which give rise to a large variety of dienes with different stereochemistry, prot...

  20. Synthesis of Heavy Fluorous Ruthenium Metathesis Catalysts Using the Stereoselective Addition of Polyfluoroalkyllithium to Sterically Hindered Diimines

    Czech Academy of Sciences Publication Activity Database

    Hošek, J.; Rybáčková, M.; Čejka, J.; Cvačka, Josef; Kvíčala, J.

    2015-01-01

    Roč. 34, č. 13 (2015), s. 3327 -3334 ISSN 0276-7333 Institutional support: RVO:61388963 Keywords : ring-closing metathesis * form tetrasubstituted olefins * N-heterocyclic carbene Subject RIV: CC - Organic Chemistry Impact factor: 4.186, year: 2015

  1. Synthesis of Heterocycles through a Ruthenium‐Catalyzed Tandem Ring‐Closing Metathesis/Isomerization/N‐Acyliminium Cyclization Sequence

    DEFF Research Database (Denmark)

    Ascic, Erhad; Jensen, Jakob Feldthusen; Nielsen, Thomas Eiland

    2011-01-01

    Tandem bicycle: In the title reaction double bonds created during ring-closing metathesis isomerize to generate reactive iminium intermediates that undergo intramolecular cyclization reactions with tethered heteroatom and carbon nucleophiles. In this way, a series of biologically interesting hete...... heterocyclic compounds can be made, including a known precursor for the total synthesis of the antiparasitic natural product harmicine....

  2. Maintenance optimization after RCM

    International Nuclear Information System (INIS)

    Doyle, E.K.; Lee, C.-G.; Cho, D.

    2005-01-01

    Variant forms of RCM (Reliability Centered Maintenance) have been the maintenance optimizing tools of choice in industry for the last 20 years. Several such optimization techniques have been implemented at the Bruce Nuclear Station. Further cost refinement of the Station preventive maintenance strategy whereby decisions are based on statistical analysis of historical failure data are now being evaluated. The evaluation includes a requirement to demonstrate that earlier optimization projects have long term positive impacts. This proved to be a significant challenge. Eventually a methodology was developed using Crowe/AMSAA (Army Materials Systems Analysis Activity) plots to justify expenditures on further optimization efforts. (authors)

  3. Alkene Metathesis Catalysis: A Key for Transformations of Unsaturated Plant Oils and Renewable Derivatives

    Directory of Open Access Journals (Sweden)

    Dixneuf Pierre H.

    2016-03-01

    Full Text Available This account presents the importance of ruthenium-catalysed alkene cross-metathesis for the catalytic transformations of biomass derivatives into useful intermediates, especially those developed by the authors in the Rennes (France catalysis team in cooperation with chemical industry. The cross-metathesis of a variety of functional alkenes arising from plant oils, with acrylonitrile and fumaronitrile and followed by catalytic tandem hydrogenation, will be shown to afford linear amino acid derivatives, the precursors of polyamides. The exploration of cross-metathesis of bio-sourced unsaturated nitriles with acrylate with further catalytic hydrogenation has led to offer an excellent route to α,ω-amino acid derivatives. That of fatty aldehydes has led to bifunctional long chain aldehydes and saturated diols. Two ways of access to functional dienes by ruthenium-catalyzed ene-yne cross-metathesis of plant oil alkene derivatives with alkynes and by cross-metathesis of bio-sourced alkenes with allylic chloride followed by catalytic dehydrohalogenation, are reported. Ricinoleate derivatives offer a direct access to chiral dihydropyrans and tetrahydropyrans via ring closing metathesis. Cross-metathesis giving value to terpenes and eugenol for the straightforward synthesis of artificial terpenes and functional eugenol derivatives without C=C bond isomerization are described.

  4. RCM and component evaluation logic

    International Nuclear Information System (INIS)

    Davis, B.; Anderson, J.

    1991-01-01

    This paper reports on the prevention maintenance program at Palo Verde Nuclear Generating Station (PVNGS), initially developed based on recommendations found in vendor technical manuals and accepted industry standards. The method was used until there was sufficient operating history to justify changes. The Reliability Centered Maintenance (RCM) project was started to provide another approach to the implementation of preventive maintenance. RCM evaluations were performed on nine systems. RCM was then suspended since it was found during implementation that additional documentation was necessary. RCM was selected as a preventive maintenance development process because it provides a documented analytical approach to establishing a preventive maintenance program. It is also being developed throughout the industry as a standard approach to preventive maintenance. PVNGS became interested in performing RCM analyses primarily to ensure that system and component reliability is maintained at the highest level possible and that hidden or rare failures are addressed by appropriate and effective maintenance. A secondary reason was to save maintenance expenditures

  5. 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.

  6. RCM: the Bruce B experience

    International Nuclear Information System (INIS)

    Hill, Earl S.; Doyle, E.K.

    1995-01-01

    The use of RCM techniques have begun to change maintenance practice at Bruce B. This paper identifies the status of the program at Bruce B, and examines a new methodology for completing system analysis studies by incorporating lessons learned and results from Bruce A. (author)

  7. Synthesis of interlocked molecules by olefin metathesis

    Science.gov (United States)

    Clark, Paul Gregory

    A large body of work in the Grubbs group has focused on the development of functional-group tolerant ruthenium alkylidene catalysts that perform a number of olefin metathesis reactions. These catalysts have seen application in a wide range of fields, including classic total synthesis as well as polymer and materials chemistry. One particular family of compounds, interlocked molecules, has benefitted greatly from these advances in catalyst stability and activity. This thesis describes several elusive and challenging interlocked architectures whose syntheses have been realized through the utilization of different types of ruthenium-catalyzed olefin metathesis reactions. Ring-closing olefin metathesis has enabled the synthesis of a [c2]daisy-chain dimer with the ammonium binding site near the cap of the dimer. A deprotonated DCD possessing such a structural attribute will more forcefully seek to restore coordinating interactions upon reprotonation, enhancing its utility as a synthetic molecular actuator. Dimer functionalization facilitated incorporation into linear polymers, with a 48% size increase of an unbound, extended analogue of the polymer demonstrating slippage of the dimer units. Ongoing work is directed at further materials studies, in particular, exploring the synthesis of macroscopic networks containing the DCD units and analyzing the correlation between molecular-scale extension-contraction manipulations and resulting macro-scale changes. A "clipping" approach to a polycatenated cyclic polymer, a structure that resembles a molecular "charm bracelet", has been described. The use of ring-opening metathesis polymerization of a carbamate monomer in the presence of a chain transfer agent allowed for the synthesis of a linear polymer that was subsequently functionalized and cyclized to the corresponding cyclic analogue. This cyclic polymer was characterized through a variety of techniques, and subjected to further functionalization reactions, affording a cyclic

  8. Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

    KAUST Repository

    Żukowska, Karolina

    2015-08-20

    Two ruthenium olefin metathesis initiators featuring electronically modified quinoline-based chelating carbene ligands are introduced. Their reactivity in RCM and ROMP reactions was tested and the results were compared to those obtained with the parent unsubstituted compound. The studied complexes are very stable at high temperatures up to 140 °C. The placement of an electron-withdrawing functionality translates into an enhanced activity in RCM. While electronically modified precatalysts, which exist predominantly in the trans-dichloro configuration, gave mostly the RCM and a minor amount of the cycloisomerization product, the unmodified congener, which preferentially exists as its cis-dichloro isomer, shows a switched reactivity. The position of the equilibrium between the cis- and the trans-dichloro species was found to be the crucial factor governing the reactivity of the complexes.

  9. Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

    KAUST Repository

    Żukowska, Karolina; Pump, Eva; Pazio, Aleksandra E; Woźniak, Krzysztof; Cavallo, Luigi; Slugovc, Christian

    2015-01-01

    Two ruthenium olefin metathesis initiators featuring electronically modified quinoline-based chelating carbene ligands are introduced. Their reactivity in RCM and ROMP reactions was tested and the results were compared to those obtained with the parent unsubstituted compound. The studied complexes are very stable at high temperatures up to 140 °C. The placement of an electron-withdrawing functionality translates into an enhanced activity in RCM. While electronically modified precatalysts, which exist predominantly in the trans-dichloro configuration, gave mostly the RCM and a minor amount of the cycloisomerization product, the unmodified congener, which preferentially exists as its cis-dichloro isomer, shows a switched reactivity. The position of the equilibrium between the cis- and the trans-dichloro species was found to be the crucial factor governing the reactivity of the complexes.

  10. Asymmetric Catalytic Aza-Diels-Alder/Ring-Closing Cascade Reaction Forming Bicyclic Azaheterocycles by Trienamine Catalysis.

    Science.gov (United States)

    Li, Yang; Barløse, Casper; Jørgensen, Julie; Carlsen, Bjørn Dreiø; Jørgensen, Karl Anker

    2017-01-01

    An asymmetric catalytic aza-Diels-Alder/ring-closing cascade reaction between acylhydrazones and in situ formed trienamines is presented. The reaction proceeds through a formal aza-Diels-Alder cycloaddition, followed by a ring-closing reaction forming the hemiaminal ring leading to chiral bicyclic azaheterocycles in moderate to good yield (up to 71 %), good enantio- (up to 92 % ee) and diastereoselectivity (up to >20:1 d.r.). Furthermore, transformations are presented to show the potential application of the formed product. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. cis-Apa: a practical linker for the microwave-assisted preparation of cyclic pseudopeptides via RCM cyclative cleavage.

    Science.gov (United States)

    Baron, Alice; Verdié, Pascal; Martinez, Jean; Lamaty, Frédéric

    2011-02-04

    A new linker cis-5-aminopent-3-enoic acid (cis-Apa) was prepared for the synthesis of cyclic pseudopeptides by cyclization-cleavage by using ring-closing methatesis (RCM). We developed a new synthetic pathway for the preparation of the cis-Apa linker that was tested in the cyclization-cleavage process of different RGD peptide sequences. Different macrocyclic peptidomimetics were prepared by using this integrated microwave-assisted method, showing that the readily available cis-Apa amino acid is well adapted as a linker in the cyclization-cleavage process.

  12. Experimental adoption of RCM in EDF substations

    International Nuclear Information System (INIS)

    Heroin, G.; Aupied, J.; Sanchis, G.

    1995-12-01

    EDF, after testing Reliability Centred Maintenance (RCM) on systems used in nuclear power plants, has now successfully extended RCM to all of its nuclear power plants. In the light of this experience, EDF has committed itself to a pilot study on a line bay of a 400 kV substation in 1992. The RCM method as applied benefited from EDF's policy of maintenance, introduced five years ago on all substations, which has enhanced prospects of reliability. The original feature in the selection of maintenance tasks was that it brought into play two criteria for failure assessment: frequency and seriousness, and two criteria for maintenance task selection: efficiency and facility. (author)

  13. Cationic bis-N-heterocyclic carbene (NHC) ruthenium complex: Structure and application as latent catalyst in olefin metathesis

    KAUST Repository

    Rouen, Mathieu

    2014-09-11

    An unexpected cationic bis-N-heterocyclic carbene (NHC) benzylidene ether based ruthenium complex (2 a) was prepared through the double incorporation of an unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligand that bore an N-substituted cyclododecyl side chain. The isolation and full characterization (including X-ray diffraction studies) of key synthetic intermediates along with theoretical calculations allowed us to understand the mechanism of the overall cationization process. Finally, the newly developed complex 2 a displayed interesting latent behavior during ring-closing metathesis, which could be "switched on" under acidic conditions.

  14. RCM vs. traditional maintenance practice: Some problems when RCM is introduced for the first time

    International Nuclear Information System (INIS)

    Shishkova, I.V.

    2000-01-01

    The presentation is focused on some problems which arise when RCM is introduced for first time. These problems were identified from EQE-Bulgaria experience when RCM meters were discussed for first time at number of plants and organizations. Mainly the following problem areas are covered: The first group of problems arise from the nature of RCM. The RCM is referred to as a 'new concept', 'new philosophy', 'new maintenance system', etc. On the other hand, RCM has nothing new - it is a structure of established maintenance techniques. It leads to some difficulties to explain what exactly is the 'new' to a managerial body and to a staff of a plant which has its own established maintenance system running for years. This group of problems covers in particular the following points: RCM definition vs. 'Traditional' Maintenance definition; The understanding about the relationship between inherent reliability and the desired performance of an asset; Difficulties to prove the advantages of RCM and the benefits of its implementation in case RCM is not a country-wide practice. The second problem area is the terminology. The RCM concept is developed and described mainly in reference documents written in English. The direct translation into a certain language introduces some misunderstanding especially if there is no established terminology in the corresponding national language. The first major task is to get clear understanding about relationship between RCM terminology and the terms used in the current maintenance practice defined in the national standards. The next problem area is the availability or unavailability of relevant reliability plant specific data. We found that people tend to trust more the 'numerical' (quantitative) results rather than the qualitative ones. So efforts should be spent to explain and even to prove the advantages and disadvantages of both qualitative and quantitative approaches as well as to show clearly the relation between qualitative and

  15. Preserving SSC Design Function Using RCM Principles

    International Nuclear Information System (INIS)

    Mohammadi, K.

    2009-01-01

    Reliability-Centered Maintenance (RCM) can be defined as an approach that employs preventive, predictive, proactive, and reactive maintenance practices and strategies in an integrated manner to increase the probability that a Structure, System, or Component (SSC) will function as designed over its life cycle with optimum maintenance. The goal of RCM is to preserve the SSC intended design function at the lowest cost by developing a maintenance strategy that is supported by sound technical and economic justification. RCM has been used extensively by the aircraft, space, defense, power generation, and manufacturing industries where functional failures of SSCs can have the potential to compromise worker or public safety, cause adverse environmental impact, cause loss of production, and/or result in excessive damage to critical SSCs. This paper provides a framework for performing an RCM analysis in support of DOE Order 430.1A (Life Cycle Asset Management) and DOE Order 420.1B (Facility Safety). The influence of RCM on the various aspects of the maintenance program including the work control process is also discussed

  16. Dependency of the regio- and stereoselectivity of intramolecular, ring-closing glycosylations upon the ring size

    Directory of Open Access Journals (Sweden)

    Patrick Claude

    2011-12-01

    Full Text Available Phenyl 3,4,6-tri-O-benzyl-2-O-(3-carboxypropionyl-1-thio-β-D-galactopyranoside (1 was condensed via its pentafluorophenyl ester 2 with 5-aminopentyl (4a, 4-aminobutyl (4b, 3-aminopropyl (4c and 2-aminoethyl 4,6-O-benzylidene-β-D-glucopyranoside (4d, prepared from the corresponding N-Cbz protected glucosides 3a–d, to give the corresponding 2-[3-(alkylcarbamoylpropionyl] tethered saccharides 5a–d. Intramolecular, ring closing glycosylation of the saccharides with NIS and TMSOTf afforded the tethered β(1→3 linked disaccharides 6a–c, the α(1→3 linked disaccharides 7a–d and the α(1→2 linked disaccharide 8d in ratios depending upon the ring size formed during glycosylation. No β(1→2 linked disaccharides were formed. Molecular modeling of saccharides 6–8 revealed that a strong aromatic stacking interaction between the aromatic parts of the benzyl and benzylidene protecting groups in the galactosyl and glucosyl moieties was mainly responsible for the observed regioselectivity and anomeric selectivity of the ring-closing glycosylation step.

  17. Enyne Metathesis Catalyzed by Ruthenium Carbene Complexes

    DEFF Research Database (Denmark)

    Poulsen, Carina Storm; Madsen, Robert

    2003-01-01

    Enyne metathesis combines an alkene and an alkyne into a 1,3-diene. The first enyne metathesis reaction catalyzed by a ruthenium carbene complex was reported in 1994. This review covers the advances in this transformation during the last eight years with particular emphasis on methodology...

  18. Build/Couple/Pair Strategy Combining the Petasis 3-Component Reaction with Ru-Catalyzed Ring-Closing Metathesis and Isomerization

    DEFF Research Database (Denmark)

    Ascic, Erhad; Le Quement, Sebastian Thordal; Ishøy, Mette

    2012-01-01

    A “build/couple/pair” pathway for the systematic synthesis of structurally diverse small molecules is presented. The Petasis 3-component reaction was used to synthesize anti-amino alcohols displaying pairwise reactive combinations of alkene moieties. Upon treatment with a ruthenium alkylidene...

  19. 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.

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

    KAUST Repository

    Merle, Nicolas; Le Qué mé ner, Fré dé ric; Barman, Samir; Samantaray, Manoja; Szeto, Kai C.; De Mallmann, Aimery; Taoufik, Mostafa; Basset, Jean-Marie

    2017-01-01

    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.

  1. Metathesis: A "Change-Your-Partners" Dance

    Indian Academy of Sciences (India)

    Organic chemistry, the chemistry of carbon compounds, is a fascinating subject. ... In general, a chemical reaction is referred to as 'metathesis' or exchange reaction, if it is of .... pounds (alcohols, ketones, aldehydes, etc.), but is stable for long.

  2. by a solid-state metathesis approach

    Indian Academy of Sciences (India)

    Wintec

    Department of Mechanical Engineering,. † ... A solid-state metathesis approach initiated by microwave energy has been successfully applied for ... and chemical properties of synthesized powders are determined by powder X-ray diffraction, ...

  3. Metathesis of alkanes and related reactions

    KAUST Repository

    Basset, Jean-Marie

    2010-02-16

    (Figure Presented) The transformation of alkanes remains a difficult challenge because of the relative inertness of the C-H and C-C bonds. The rewards for asserting synthetic control over unfunctionalized, saturated hydrocarbons are considerable, however, because converting short alkanes into longer chain analogues is usually a value-adding process. Alkane metathesis is a novel catalytic and direct transformation of two molecules of a given alkane into its lower and higher homologues; moreover, the process proceeds at relatively low temperature (ambient conditions or higher). It was discovered through the use of a silica-supported tantalum hydride, (=SiO)2TaH, a multifunctional catalyst with a single site of action. This reaction completes the story of the metathesis reactions discovered over the past 40 years: olefin metathesis, alkyne metathesis, and ene-yne cyclizations. In this Account, we examine the fundamental mechanistic aspects of alkane metathesis as well as the novel reactions that have been derived from its study. The silica-supported tantalum hydride catalyst was developed as the result of systematic and meticulous studies of the interaction between oxide supports and organometallic complexes, a field of study denoted surface organometallic chemistry (SOMC). A careful examination of this surface-supported tantalum hydride led to the later discovery of aluminasupported tungsten hydride, W(H)3/Al 2O3, which proved to be an even better catalyst for alkane metathesis. Supported tantalum and tungsten hydrides are highly unsaturated, electron-deficient species that are very reactive toward the C-H and C-C bonds of alkanes. They show a great versatility in various other reactions, such as cross-metathesis between methane and alkanes, cross-metathesis between toluene and ethane, or even methane nonoxidative coupling. Moreover, tungsten hydride exhibits a specific ability in the transformation of isobutane into 2,3-dimethylbutane as well as in the metathesis of

  4. Metathesis of alkanes and related reactions.

    Science.gov (United States)

    Basset, Jean-Marie; Copéret, Christophe; Soulivong, Daravong; Taoufik, Mostafa; Cazat, Jean Thivolle

    2010-02-16

    The transformation of alkanes remains a difficult challenge because of the relative inertness of the C-H and C-C bonds. The rewards for asserting synthetic control over unfunctionalized, saturated hydrocarbons are considerable, however, because converting short alkanes into longer chain analogues is usually a value-adding process. Alkane metathesis is a novel catalytic and direct transformation of two molecules of a given alkane into its lower and higher homologues; moreover, the process proceeds at relatively low temperature (ambient conditions or higher). It was discovered through the use of a silica-supported tantalum hydride, ([triple bond]SiO)(2)TaH, a multifunctional catalyst with a single site of action. This reaction completes the story of the metathesis reactions discovered over the past 40 years: olefin metathesis, alkyne metathesis, and ene-yne cyclizations. In this Account, we examine the fundamental mechanistic aspects of alkane metathesis as well as the novel reactions that have been derived from its study. The silica-supported tantalum hydride catalyst was developed as the result of systematic and meticulous studies of the interaction between oxide supports and organometallic complexes, a field of study denoted surface organometallic chemistry (SOMC). A careful examination of this surface-supported tantalum hydride led to the later discovery of alumina-supported tungsten hydride, W(H)(3)/Al(2)O(3), which proved to be an even better catalyst for alkane metathesis. Supported tantalum and tungsten hydrides are highly unsaturated, electron-deficient species that are very reactive toward the C-H and C-C bonds of alkanes. They show a great versatility in various other reactions, such as cross-metathesis between methane and alkanes, cross-metathesis between toluene and ethane, or even methane nonoxidative coupling. Moreover, tungsten hydride exhibits a specific ability in the transformation of isobutane into 2,3-dimethylbutane as well as in the metathesis

  5. Innovations in RCM at Bruce B

    International Nuclear Information System (INIS)

    Hill, E.S.; Doyle, E.K.

    1996-01-01

    The use of RCM techniques have begun to change maintenance practice at Bruce B. This paper discusses innovative practices begun recently. Bruce B has decided to evaluate plant systems using different methods based on the effects of system failure. This approach reduces costs, by using a streamlined method, while maintaining the accuracy of analysis. In addition, the approach increases the likelihood that program recommendations will be implemented by the maintenance department by providing maintenance craft with input to the process. Bruce B has also developed techniques to accelerate the analysis process by evaluating analyses performed at other units. These innovations have been successful piloted at the station

  6. Reliability centered Maintenance (RCM) program for Chashma NPP (CHASNUPP)

    International Nuclear Information System (INIS)

    Khalid, S.; Khan, S.A.

    2000-01-01

    This paper describes the proposed Reliability Centered Maintenance (RCM) program for Chashma Nuclear Power Plant (CHASNUPP). Major steps are the identification of risk critical components and the implementation of RCM procedures. Identification of risk critical components is based upon the CHASNUPP level 1 PSA results (performed under IAEA TC Project PAK/9/019) which is near completion. The other requirements for implementation of RCM program is the qualitative analysis to be performed for identifying the dominant potential failure modes of each risk critical component and determination of the necessary maintenance activities, required to ensure reliable operation of the identified risk critical components. Implementation of RCM program for these components will lead to improvement in plant availability and safety together with reduction in the maintenance cost. Development - implementation of RCM program at this stage will help the CHASNUPP Maintenance department who is now developing the maintenance program - procedures for CHASNUPP. (author)

  7. Latent ruthenium–indenylidene catalysts bearing a N-heterocyclic carbene and a bidentate picolinate ligand

    Directory of Open Access Journals (Sweden)

    Thibault E. Schmid

    2015-09-01

    Full Text Available A silver-free methodology was developed for the synthesis of unprecedented N-heterocyclic carbene ruthenium indenylidene complexes bearing a bidentate picolinate ligand. The highly stable (SIPr(picolinateRuCl(indenylidene complex 4a (SIPr = 1,3-bis(2-6-diisopropylphenylimidazolidin-2-ylidene demonstrated excellent latent behaviour in ring closing metathesis (RCM reaction and could be activated in the presence of a Brønsted acid. The versatility of the catalyst 4a was subsequently demonstrated in RCM, cross-metathesis (CM and enyne metathesis reactions.

  8. A tandem Mannich addition–palladium catalyzed ring-closing route toward 4-substituted-3(2H-furanones

    Directory of Open Access Journals (Sweden)

    Jubi John

    2014-06-01

    Full Text Available A facile route towards highly functionalized 3(2H-furanones via a sequential Mannich addition–palladium catalyzed ring closing has been elaborated. The reaction of 4-chloroacetoacetate esters with imines derived from aliphatic and aromatic aldehydes under palladium catalysis afforded 4-substituted furanones in good to excellent yields. 4-Hydrazino-3(2H-furanones could also be synthesized from diazo esters in excellent yields by utilising the developed strategy. We could also efficiently transform the substituted furanones to aza-prostaglandin analogues.

  9. Perencanaan Kegiatan Maintenance Dengan Metode Reability Centered Maintenance (Rcm) II

    OpenAIRE

    Rachmad Hidayat; Nachnul Ansori; Ali Imron

    2010-01-01

    Maintenance Activity Planning by Reability Centered Maintenance (RCM) II Method. This research discussmaintenance activity by using RCM II method to determine failure function risk at compresor screw. Calculation isgiven to magnitude optimum time maintenance interval by considering the cost maintenance and the cost reparation.From the research results with RPN points out that critical component that needs to get main priority in givemaintenance on compresor screw are bust logistic on timeworn...

  10. Guide for generic application of Reliability Centered Maintenance (RCM) recommendations

    International Nuclear Information System (INIS)

    Schwan, C.A.; Toomey, G.E.; Morgan, T.A.; Darling, S.S.

    1991-02-01

    Previously completed reliability centered maintenance (RCM) studies form the basis for developing or refining a preventive maintenance program. This report describes a generic methodology that will help utilities optimize nuclear plant maintenance programs using RCM techniques. This guide addresses the following areas: history of the generic methodology development process, and use of the generic methodology for conducting system-to-system and component-to-component evaluations. 2 refs., 2 figs., 5 tabs

  11. Guidelines for implementation of RCM on safety systems

    International Nuclear Information System (INIS)

    Kim, Tae Woon; Brijendra Singh.

    1996-04-01

    Reliability Centered Maintenance (RCM) methodology was originally developed by the commercial airlines industry in the early 1960s for identifying applicable and effective preventive maintenance tasks and as currently used in nuclear power industry. Effective maintenance of the systems at a nuclear power plant (NPP) is essential for its safe and reliable operation. Reliability Centered Maintenance at NPP is the program to assure that plant systems remain within an original design criteria and are not adversely affected during the plant life time. The aim of this report is to provide the guidelines to implement the RCM approach on NPP safety systems. Safety systems are usually standby and therefore, we need to periodically detect and repair failures that may have occurred since the previous activation or inspection the equipment. The RCM guidelines are intended to help identify the failure modes and related root causes and then decide the maintenance policies to achieve the high level of safety and reliability. The RCM is intended to improve or maintain high levels of system reliability and plant availability. Since the reliability of plant systems will be improved, the plant safety correspondingly will be increased. Another goal of RCM is to optimize the maintenance and surveillance tasks such that the overall level of resources required to accomplish essential tasks is kept to minimum. RCM also strives to eliminate unnecessary corrective maintenance and to select yet most cost-effective approach to maintenance, testing and inspection for system components. 9 refs. (Author) .new

  12. Methods for treating a metathesis feedstock with metal alkoxides

    Science.gov (United States)

    Cohen, Steven A.; Anderson, Donde R.; Wang, Zhe; Champagne, Timothy M.; Ung, Thay A.

    2018-04-17

    Various methods are provided for treating and reacting a metathesis feedstock. In one embodiment, the method includes providing a feedstock comprising a natural oil, chemically treating the feedstock with a metal alkoxide under conditions sufficient to diminish catalyst poisons in the feedstock, and, following the treating, combining a metathesis catalyst with the feedstock under conditions sufficient to metathesize the feedstock.

  13. The Synthesis of cis- and trans-Fused Bicyclic Sugar Amino Acids

    NARCIS (Netherlands)

    Risseeuw, Martijn D.P.; Grotenbreg, Gijsbert M.; Witte, Martin D.; Tuin, Adriaan W.; Leeuwenburgh, Michiel A.; Marel, Gijsbert A. van der; Overkleeft, Herman S.; Overhand, Mark

    2006-01-01

    Four isomeric bicyclic sugar amino acids (SAAs) were prepared from an α-acetylenic-C-glucoside by employing a Petasis olefination and a ring-closing metathesis (RCM) as key steps. The applicability of the resulting SAAs in solid-phase peptide synthesis was demonstrated by the synthesis of a

  14. Rapid synthesis of the A-E fragment of ciguatoxin CTX3C.

    Science.gov (United States)

    Clark, J Stephen; Conroy, Joanne; Blake, Alexander J

    2007-05-24

    The A-E fragment of the marine natural product CTX3C has been prepared in an efficient manner by using a strategy in which two-directional and iterative ring-closing metathesis (RCM) reactions were employed for ring construction.

  15. Application of RCM to a medium scale industry

    International Nuclear Information System (INIS)

    Deshpande, V.S.; Modak, J.P.

    2002-01-01

    The factors which are assuming considerable importance in cost effective decision making of operation of any industrial enterprise are in the order of significance liability, safety and environmental conditions. Hence, preventive maintenance (PM) optimisation is providing wide opportunities and challenges to everyone involved in all aspects of operation of industrial enterprise. Reliability centred maintenance (RCM) methodology offers the best available strategy for PM optimisation. It incorporates a new understanding of the ways in which equipment fails. In this paper, the concept of RCM has been applied to steel melting shop of a medium scale steel industry. By systematically applying the RCM methodology, failures, failure causes and effects on the system are analysed. To preserve the system function, PM categories are suggested for various failure modes in the components such as (1) time directed (2) condition directed (3) failure finding (4) run to failure. Features of predictive maintenance of a medium scale steel industry are deduced through this paper in a rather generalised form

  16. Analisis Perawatan Mesin dengan Pendekatan RCM dan MVSM

    Directory of Open Access Journals (Sweden)

    Dwi Agustina Kurniawati

    2017-10-01

    Full Text Available Maintenance system at UMKM ED Aluminum Yogyakarta is using preventive and corrective maintenance program, but the implementation of this program still have many problems. The problem occurs because there is no maintenance system program and the company doesn’t have Standard Operational Procedure (SOP in maintenance to overcome machine failures resulted in the increase of the downtime value. To cope the problems,  in this paper we used application of SOP and appropriate task maintenance selection using Maintenance Value Stream Map (MVSM method supported by Reliability Centered Maintenance (RCM. Beside task selected among all products that have been produced, there is one machine that gives the biggest profit to the company. The product is feet infusion. Kondia milling machine is one of machines produces the feet infusion that has the longest downtime which was 17,75 hour during January 2016 until October 2016. RCM consist of Failure Mode Effect Analysis (FMEA, Pareto diagram, decision worksheet RCM, whereas the MVSM describes the maintenance activity. Based on Pareto analysis, the critical components on the Kondia milling machine were the magnetic contactor, relay, fuse, cutter, dynamo and bearing. The result of RCM decision worksheet proposed the appropriate action for the critical components cares. The Standard Operational Procedure (SOP for the maintenance system on the operation of Kondia milling machine are suggested to the company for getting more significant outcome.

  17. SAPS simulation with GITM/UCLA-RCM coupled model

    Science.gov (United States)

    Lu, Y.; Deng, Y.; Guo, J.; Zhang, D.; Wang, C. P.; Sheng, C.

    2017-12-01

    Abstract: SAPS simulation with GITM/UCLA-RCM coupled model Author: Yang Lu, Yue Deng, Jiapeng Guo, Donghe Zhang, Chih-Ping Wang, Cheng Sheng Ion velocity in the Sub Aurora region observed by Satellites in storm time often shows a significant westward component. The high speed westward stream is distinguished with convection pattern. These kind of events are called Sub Aurora Polarization Stream (SAPS). In March 17th 2013 storm, DMSP F18 satellite observed several SAPS cases when crossing Sub Aurora region. In this study, Global Ionosphere Thermosphere Model (GITM) has been coupled to UCLA-RCM model to simulate the impact of SAPS during March 2013 event on the ionosphere/thermosphere. The particle precipitation and electric field from RCM has been used to drive GITM. The conductance calculated from GITM has feedback to RCM to make the coupling to be self-consistent. The comparison of GITM simulations with different SAPS specifications will be conducted. The neutral wind from simulation will be compared with GOCE satellite. The comparison between runs with SAPS and without SAPS will separate the effect of SAPS from others and illustrate the impact on the TIDS/TADS propagating to both poleward and equatorward directions.

  18. Derivation of the human embryonic stem cell line RCM1

    Directory of Open Access Journals (Sweden)

    P.A. De Sousa

    2016-03-01

    Full Text Available The human embryonic stem cell line RCM-1 was derived from a failed to fertilise egg undergoing parthenogenetic stimulation. The cell line shows normal pluripotency marker expression and differentiation to three germ layers in vitro and in vivo. It has a normal 46XX female karyotype and microsatellite PCR identity, HLA and blood group typing data is available.

  19. A tandem cross-metathesis/semipinacol rearrangement reaction.

    Science.gov (United States)

    Plummer, Christopher W; Soheili, Arash; Leighton, James L

    2012-05-18

    An efficient and (E)-selective synthesis of a 6-alkylidenebicyclo[3.2.1]octan-8-one has been developed. The key step is a tandem cross-metathesis/semipinacol rearrangement reaction, wherein the Hoveyda-Grubbs II catalyst, or more likely a derivative thereof, serves as the Lewis acid for the rearrangement. Despite the fact that both the starting alkene and the cross-metathesis product are viable rearrangement substrates, only the latter rearranges, suggesting that the Lewis acidic species is generated only after the cross-metathesis reaction is complete.

  20. A Sociolinguistic Analysis of Metathesis in Azeri Language

    Directory of Open Access Journals (Sweden)

    Biook Behnam

    2012-07-01

    Full Text Available This study tries to investigate the correlation between sociolinguistic parameters such as sex, age, and social class and the use of metathesis in Azeri. There have been few studies from a sociolinguistic perspective on the use of metathesis. Through studying the stigmatized forms of speech in Azeri, the present study indicates that a significant relationship exists between extralinguistic variables and metathesis as a phonological process. The subjects of the study were Azeri speakers living in different districts of Tabriz categorized by three socioeconomically different groups. The statistical analyses of data indicate that there is an intimate and reciprocal relationship between linguistic behavior and social structure.

  1. 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.

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

    KAUST Repository

    Poater, Albert; Pump, Eva; Vummaleti, Sai V. C.; Cavallo, Luigi

    2014-01-01

    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.

  3. Revisiting the metathesis of 13C-monolabeled ethane

    KAUST Repository

    Maury, Olivier; Lefort, Laurent; Vidal, Vé ronique; Thivolle-Cazat, Jean; Basset, Jean-Marie

    2010-01-01

    The metathesis of 13C-monolabeled ethane leads to the parallel occurrence of degenerate and productive reactions, affording the statistical distribution of the various product isotopomers, which can be rationalized in terms of a mechanistic reaction

  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. PERENCANAAN PEMELIHARAAN MESIN BALLMILL DENGAN BASIS RCM (RELIABILITY CENTERED MAINTENANCE

    Directory of Open Access Journals (Sweden)

    Ahmad Kholid Alghofari

    2006-12-01

    Full Text Available Aktifitas produksi sering mengalami hambatan dikarenakan tidak berfungsinya mesin-mesin produksi yang dalam industri manufaktur merupakan komponen utama. Kegagalan beroperasi mesin mengakibatkan downtime yang ujung-ujungnya menurunkan produktifitas perusahaan. Oleh karenanya diperlukan sebuah sistem perencanaan pemeliharaan agar menghasilkan availability (ketersediaan mesin yang optimal. Perusahaan yang dijadikan proyek penelitian adalah PT. Sici Multi IndoMarmer yang merupakan perusahaan yang bergerak dalam bidang produksi keramik (kloset jongkok, kloset duduk, washtafel, tempat sabun dimana sistem pemeliharaan mesin, khususnya mesin ballmill yang telah dilakukan masih bersifat corrective maintenance. Tujuan dari penelitian ini adalah implementasi RCM (reliability centered maintenance untuk dapat menentukan pemeliharan yang optimal serta dapat memprediksikan langkah untuk mengatasi kerusakan yang mungkin terjadi pada periode berikutnya berdasarkan data-data yang ada. Dari pengolahan data dan analisa diperoleh komponen-komponen yang paling sering mengalami kerusakan pada mesin ballmill , penyebab kegagalan, keputusan seleksi dan rekomendasi yang dianjurkan untuk sistem pemeliharaan dengan basis RCM.

  6. Research on Operating Procedure Development in View of RCM Theory

    International Nuclear Information System (INIS)

    Shi, J.

    2015-01-01

    The operation of NPPs (nuclear power plants) is closely related to SSCs (Structure, System and Component) function implementations and failure recoveries, and strictly follows operating procedure. The philosophy of RCM (Reliability Centered Maintenance) which is a widely-used systematic engineering approach in industry focusing on likewise facility functions and effectiveness of maintenance is accepted in relative analysis of NPPs operation in this paper. Based on the theory of RCM, the paper will discuss general logic of operating procedure development and framework optimization as well combining NPPs engineering design. Since the quality of operating procedures has a significant impact on the safe and reliable operation of NPPs, the paper provides a proposed operating procedure development logic diagramme for reference for the procedure optimization task ahead. (author)

  7. Implementation of the RCM approach at EDF NPPs: Current status

    International Nuclear Information System (INIS)

    Dubreuil-Chambardel, A.; Martin-Onraet, M.; Degrave, C.

    2001-01-01

    To ensure safest possible operation and to get best overall economic performance of its Nuclear Power Plants, 10 years ago Electricite de France launched a Reliability Centered Maintenance (RCM) project to optimize the preventive maintenance programs. The principles underlying the RCM approach are based on common sense: failures must be prevented by preventive maintenance operations in all cases when the repercussions for the installation could be serious or critical in term of safety, availability or maintenance costs. The approach is a 3-phases process: 1. Evaluation of the functional consequences of failures 2. Evaluation of performances based on the analysis of experience feedback 3. Optimization of the preventive maintenance tasks The new preventive maintenance programs are presently almost completed and progressively implemented. Here and now, the implementation of the RCM approach allows to emphasize some benefits: 1. Same or increased level of safety 2. Same or increased level of plant availability 3. ALARA principles better taken into account 4. Cost control 5. Positive change in maintenance culture. Some new studies are in progress, such as the development of a 'Risk Based In Service Inspection' for passive components. (author)

  8. Pilot RCM application to the Diablo Canyon main stream system

    International Nuclear Information System (INIS)

    Groff, C.R.; Beckham, P.E.; Bych, K.H.

    1988-01-01

    In 1986 Pacific Gas ampersand Electric Company (PG ampersand E) became extremely interested in reliability-centered maintenance (RCM) after the initial review of two successful Electric Power Research Institute sponsored projects. RCM was visualized as a methodology to common sensitize the burgeoning preventive maintenance (PM) program at the Diablo Canyon plant. RCM could further the uses of predictive and condition-monitoring techniques, as well as eliminate maintenance on components whose failures were noncritical. An extensive review of maintenance and operation experience data, in conjunction with plant staff recommendations and a prioritization according to maintenance expenditures and operational/safety significance, produced the selected system: the turbine main steam supply system (main steam). The pilot project segmented the main steam system into eight subsystems to aid in analysis: (a) main steam isolation valves, (b) auxiliary feedwater pump turbine, (c) overpressure protection (steam dump), (d) main feedwater pump turbines, (e) main steam, (f) main turbine, (g) steam blowdown, and (h) moisture separator reheaters. System analysis activities, including the preparation of functional failure analyses, failure modes and effects analyses, and logic model analyses, were conducted in parallel with corrective and preventive maintenance data-gathering activities to maximize project team personnel participation during the project. Results and lessons learned are summarized

  9. Unsaturated Fatty Acid Esters Metathesis Catalyzed by Silica Supported WMe5

    KAUST Repository

    Riache, Nassima; Callens, Emmanuel; Talbi, Karima; Basset, Jean-Marie

    2015-01-01

    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

  10. Guide for monitoring effectiveness of utility Reliability Centered Maintenance (RCM) programs

    International Nuclear Information System (INIS)

    Midgett, W.D.; Wilson, J.F.; Krochmal, D.F.; Owsenek, L.W.

    1991-02-01

    Reliability centered maintenance (RCM) programs help utilities optimize preventive maintenance efforts while improving plant safety and economy through increased dependability of plant components. The project team developed this guide and accompanying methodology based on status updates from the Ginna and San Onofre demonstration projects. These updates addressed areas ranging from system selection to the effectiveness of RCM program implementation. In addition, the team incorporated information from a 12-utility survey soliciting opinions on the need for a methodology to monitor RCM cost-effectiveness. An analysis of the 12-utility survey showed that no techniques had been developed to measure RCM program cost-effectiveness. Thus, this guide addresses two key areas: Pros and cons of various monitoring techniques available to assess the overall effectiveness of RCM and a methodology for specifically evaluating the cost-effectiveness of RCM programs. 1 fig

  11. Development of neutron shielding material using metathesis-polymer matrix

    Energy Technology Data Exchange (ETDEWEB)

    Sakurai, Yoshinori E-mail: ysakurai@rri.kyoto-u.ac.jp; Sasaki, Akira; Kobayashi, Tooru

    2004-04-21

    A neutron shielding material using a metathesis-polymer matrix, which is a thermosetting resin, was developed. This shielding material has characteristics that can be controlled for different mixing ratios of neutron absorbers and for formation in the laboratory. Additionally, the elastic modulus can be changed at the hardening process, from a flexible elastoma to a mechanically tough solid. Experiments were performed at the Kyoto University Research Reactor in order to determine the important characteristics of this metathesis-polymer shielding material, such as neutron shielding performance, secondary gamma-ray generation and activation. The metathesis-polymer shielding material was shown to be practical and as effective as the other available shielding materials, which mainly consist of thermoplastic resin.

  12. Development of RCM analysis software for Korean nuclear power plants

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young Ho; Choi, Kwang Hee; Jeong, Hyeong Jong [Korea Electric Power Research Institute, Taejon (Korea, Republic of)

    1999-12-31

    A software called KEPCO RCM workstation (KRCM) has been developed to optimize the maintenance strategies of Korean nuclear power plants. The program modules of the KRCM were designed in a manner that combines EPRI methodologies and KEPRI analysis technique. The KRCM is being applied to the three pilot system, chemical and volume control system, main steam system, and compressed air system of Yonggwang Units 1 and 2. In addition, the KRCM can be utilized as a tool to meet a part of the requirements of maintenance rule (MR) imposed by U.S. NRC. 3 refs., 4 figs. (Author)

  13. Development of RCM analysis software for Korean nuclear power plants

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young Ho; Choi, Kwang Hee; Jeong, Hyeong Jong [Korea Electric Power Research Institute, Taejon (Korea, Republic of)

    1998-12-31

    A software called KEPCO RCM workstation (KRCM) has been developed to optimize the maintenance strategies of Korean nuclear power plants. The program modules of the KRCM were designed in a manner that combines EPRI methodologies and KEPRI analysis technique. The KRCM is being applied to the three pilot system, chemical and volume control system, main steam system, and compressed air system of Yonggwang Units 1 and 2. In addition, the KRCM can be utilized as a tool to meet a part of the requirements of maintenance rule (MR) imposed by U.S. NRC. 3 refs., 4 figs. (Author)

  14. The safety monitor and RCM workstation as complementary tools in risk based maintenance optimization

    International Nuclear Information System (INIS)

    Rawson, P.D.

    2000-01-01

    Reliability Centred Maintenance (RCM) represents a proven technique for rendering maintenance activities safer, more effective, and less expensive, in terms of systems unavailability and resource management. However, it is believed that RCM can be enhanced by the additional consideration of operational plant risk. This paper discusses how two computer-based tools, i.e., the RCM Workstation and the Safety Monitor, can complement each other in helping to create a living preventive maintenance strategy. (author)

  15. Comparing Ru and Fe-catalyzed olefin metathesis

    KAUST Repository

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

    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.

  16. 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.

  17. Metathesis synthesis and characterization of complex metal fluoride ...

    Indian Academy of Sciences (India)

    Administrator

    V MANIVANNAN*, P PARHI and JONATHAN W KRAMER. Department of Mechanical Engineering, Campus Delivery 1374, Colorado State University, Fort Collins,. CO 80523, USA. MS received 30 April 2008. Abstract. Metathesis synthesis of complex metal fluorides using mechanochemical activation has been reported.

  18. Revisiting the metathesis of 13C-monolabeled ethane

    KAUST Repository

    Maury, Olivier

    2010-12-13

    The metathesis of 13C-monolabeled ethane leads to the parallel occurrence of degenerate and productive reactions, affording the statistical distribution of the various product isotopomers, which can be rationalized in terms of a mechanistic reaction scheme combining both processes. © 2010 American Chemical Society.

  19. Metathesis synthesis and characterization of complex metal fluoride ...

    Indian Academy of Sciences (India)

    Administrator

    Sivakumar et al 2004; Mandal and Gopalakrishnan 2005). Although metathesis reactions may initiate spontane- ously .... cal lithography are needed (Sahnoun et al 2005). KMF3 materials with perovskite structures are ... (Knox 1961; Machin et al 1963; Pari et al 1994) and shown in figure 5. The KMF3 compounds are anti-.

  20. 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)

  1. 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

  2. Synthesis of Mono(perfluoroalkyl) Cyclodextrins via Cross Metathesis

    Czech Academy of Sciences Publication Activity Database

    Řezanka, M.; Eignerová, Barbara; Jindřich, J.; Kotora, M.

    -, č. 32 (2010), s. 6256-6262 ISSN 1434-193X R&D Projects: GA AV ČR KAN200200651 Institutional research plan: CEZ:AV0Z40550506 Keywords : metathesis * cyclodextrins * fluorine * alkylation * amphiphiles Subject RIV: CC - Organic Chemistry Impact factor: 3.206, year: 2010

  3. Recent advances in the development of alkyne metathesis catalysts

    Directory of Open Access Journals (Sweden)

    Matthias Tamm

    2011-01-01

    Full Text Available The number of well-defined molybdenum and tungsten alkylidyne complexes that are able to catalyze alkyne metathesis reactions efficiently has been significantly expanded in recent years.The latest developments in this field featuring highly active imidazolin-2-iminato- and silanolate–alkylidyne complexes are outlined in this review.

  4. Mo-catalyzed cross-metathesis reaction of propynylferrocene

    Czech Academy of Sciences Publication Activity Database

    Bobula, T.; Hudlický, J.; Novák, P.; Gyepes, R.; Císařová, I.; Štěpnička, P.; Kotora, Martin

    -, č. 25 (2008), s. 3911-3920 ISSN 1434-1948 Grant - others:GA MŠk(CZ) LC06070 Program:LC Institutional research plan: CEZ:AV0Z40550506 Keywords : alkynes * metallocenes * metathesis * electrochemistry * X-ray diffraction Subject RIV: CC - Organic Chemistry Impact factor: 2.694, year: 2008

  5. Estimating the Mediterranean Sea Water Budget: impact of RCM design

    Science.gov (United States)

    Somot, S.; Elguindi, N.; Sanchez-Gomez, E.; Herrmann, M.; Déqué, M.

    2009-09-01

    scientific questions deal with the RCM design for the following points: Q1. the horizontal resolution Q2. the physics of the RCM Q3. the regional modelling technique (stretched-grid model, limited area model, spectral nudging technique) Q4. the regional air-sea-river coupling Q5. the RCM internal variability Up-to-date observation estimates of the various terms of the MSWB are used to sort out between the different configurations of the RCMs.

  6. Re-scan confocal microscopy (RCM) improves the resolution of confocal microscopy and increases the sensitivity

    NARCIS (Netherlands)

    de Luca, Giulia; Breedijk, Ronald; Hoebe, Ron; Stallinga, Sjoerd; Manders, Erik

    2017-01-01

    Re-scan confocal microscopy (RCM) is a new super-resolution technique based on a standard confocal microscope extended with a re-scan unit in the detection path that projects the emitted light onto a sensitive camera. In this paper the fundamental properties of RCM, lateral resolution, axial

  7. Re-scan confocal microscopy (RCM) improves the resolution of confocal microscopy and increases the sensitivity

    NARCIS (Netherlands)

    De Luca, G.; Breedijk, R.; Hoebe, R.; Stallinga, S.; Manders, E.

    Re-scan confocal microscopy (RCM) is a new super-resolution technique based on a standard confocal microscope extended with a re-scan unit in the detection path that projects the emitted light onto a sensitive camera. In this paper the fundamental properties of RCM, lateral resolution, axial

  8. Economic evaluation of reliability-centred maintenance (RCM): an electricity transmission industry perspective

    International Nuclear Information System (INIS)

    Bowler, D.J.; Primrose, P.L.; Leonard, R.

    1995-01-01

    Traditional approaches to appraising the introduction of reliability centred maintenance (RCM) are shown to exhibit severe limitations. In particular, the economic implications surrounding its adoption are repeatedly mis-stated, with the consequence that organisations may be investing in unprofitable RCM ventures. Previously quoted benefits are examined and, contrary to established opinion, it is shown that these 'generalised' statements, once redeemed, are able to be quantified. The paper then proceeds to describe a financial methodology, developed by NGC and UMIST, by which the introduction of RCM can be evaluated. Moreover, it shows that, by regarding RCM as an investment decision, rather than an 'act of faith', the economic viability of a potential application can be determined before vital resources are committed. Finally, it is demonstrated that when the methodology is applied within the context of the electricity transmission industry, the economic case underlying the adoption of RCM can be realistically appraised. (author)

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

    KAUST Repository

    Leitgeb, Anita; Abbas, Mudassar E.; Fischer, Roland C.; Poater, Albert; Cavallo, Luigi; Slugovc, Christian

    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.

  10. Exploiting Confinement Effects to Tune Selectivity in Cyclooctane Metathesis

    KAUST Repository

    Pump, Eva

    2017-08-24

    The mechanism of cyclooctane metathesis using confinement effect strategies in mesoporous silica nanoparticles (MSNs) is discussed by catalytic experiments and density functional theory (DFT) calculations. WMe6 was immobilized inside the pores of a series of MSNs having the same structure but different pore diameters (60, 30 and 25 Å). Experiments in cyclooctane metathesis suggest that confinement effects observed in smaller pores (30 and 25 Å) improve selectivity towards the dimeric cyclohexadecane. In contrast, in larger pores (60 Å) a broad product distribution dominated by ring contracted cycloalkanes was found. The catalytic cycle and potential side reactions occurring at [(≡SiO-)WMe5] were examined with DFT calculations. Analysis of the geometries for the key reaction intermediates allowed to rationalize the impact of a confined environment on the enhanced selectivity towards the dimeric product in smaller pores, while in large pores the ring contracted products are favored.

  11. Bimacrocyclic concave N-heterocyclic carbenes (NHCs): synthesis, structure, and application in catalyses

    OpenAIRE

    Lüning , Ulrich; Winkelmann , Ole

    2009-01-01

    Abstract Imidazolinium moieties have been incorporated into bimacrocycles to generate precursors for concave N-heterocyclic carbenes (NHCs). Starting from 2-nitroresorcinol and alkenols, symmetric concave imidazolinium salts 1 were obtained. Bimacrocyclization was achieved via ring closing metathesis (RCM). In an analogous fashion, axially chiral concave imidazolinium salts 2 were obtained by using a naphthalene bridgehead devoid of local C2-symmetry. The concave NHCs derived from ...

  12. A combined emitter threat assessment method based on ICW-RCM

    Science.gov (United States)

    Zhang, Ying; Wang, Hongwei; Guo, Xiaotao; Wang, Yubing

    2017-08-01

    Considering that the tradition al emitter threat assessment methods are difficult to intuitively reflect the degree of target threaten and the deficiency of real-time and complexity, on the basis of radar chart method(RCM), an algorithm of emitter combined threat assessment based on ICW-RCM (improved combination weighting method, ICW) is proposed. The coarse sorting is integrated with fine sorting in emitter combined threat assessment, sequencing the emitter threat level roughly accordance to radar operation mode, and reducing task priority of the low-threat emitter; On the basis of ICW-RCM, sequencing the same radar operation mode emitter roughly, finally, obtain the results of emitter threat assessment through coarse and fine sorting. Simulation analyses show the correctness and effectiveness of this algorithm. Comparing with classical method of emitter threat assessment based on CW-RCM, the algorithm is visual in image and can work quickly with lower complexity.

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

    Science.gov (United States)

    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. 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)

  15. Metathesis reactions for the synthesis of ring-fused carbazoles

    CSIR Research Space (South Africa)

    Pelly, SC

    2005-12-09

    Full Text Available stream_source_info pelly_2005.pdf.txt stream_content_type text/plain stream_size 48007 Content-Encoding ISO-8859-1 stream_name pelly_2005.pdf.txt Content-Type text/plain; charset=ISO-8859-1 Metathesis Reactions... (99). N,Nminute-Di-tert-butyldicarboxylate-2,2minute-biindolyl-3,3minute-divi- nyl 12. Into a 50-mL two-necked oven-dried flask, fitted with a dropping funnel, was placed MePPh3Br (533 mg, 1.49 mmol), and the contents of the flask were blanketed...

  16. NATO Advanced Study Institute on Ring-opening Metathesis Polymerization of Olefins and Polymerization of Alkynes

    CERN Document Server

    1998-01-01

    The first NATO Advanced Study Institute on Olefin Metathesis and Polymerization Catalysts was held on September 10-22, 1989 in Akcay, Turkey. Based on the fundamental research of RRSchrock, RGrubbs and K.B.Wagener in the field of ring opening metathesis polymerization (ROMP), acyclic diene metathesis (ADMET) and alkyne polymerization, these areas gained growing interest within the last years. Therefore the second NATO-ASI held on metathesis reactions was on Ring Opening Metathesis Po­ lymerization of Olefins and Polymerization of Alkynes on September 3-16, 1995 in Akcay, Turkey. The course joined inorganic, organic and polymer chemists to exchange their knowledge in this field. This volume contains the main and short lectures held in Akcay. To include ADMET reactions better into the title of this volume we changed it into: Metathesis Polymerization of Olefins and Alkyne Polymerization. This volume is addressed to research scientists, but also to those who start to work in the area of olefin metathesis and al...

  17. Optimization of maintenance programme at Daya Bay Nuclear Power Station based on RCM analysis results

    International Nuclear Information System (INIS)

    Liu Min

    2003-01-01

    This paper begins with an introduction to Guangdong Daya Bay Nuclear Power Station (GNPS) and gives a simple introduction to the operations and maintenance documentation system at GNPS. It then will review the maintenance program guidelines base and the associated problems prior to the application of reliability centered maintenance (RCM). How RCM was implemented at GNPS, how the results of RCM analysis were used to optimize the maintenance program and test program, and what is the interface between RCM and the existing maintenance program will be shown. Next, it will show the successful implementation of RCM at GNPS resulted in the following changes: A new understanding of equipment failure challenges operations and maintenance beliefs, maintenance concepts undergo a large change, maintenance program and periodic testing program are continuously modified and optimized, new on-condition maintenance technologies are introduced, non-productive scheduled overhauls are discarded, maintenance costs are effectively controlled, maintenance appropriateness has improved, management of hidden failures is more effective and timely. It will show the benefit of greater equipment reliability brought about by all of these changes, which in turn increases the reliability and safety of the entire power station. (author)

  18. Reliability Centered Maintenance (RCM) Methodology and Application to the Shutdown Cooling System for APR-1400 Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Faragalla, Mohamed M.; Emmanuel, Efenji; Alhammadi, Ibrahim; Awwal, Arigi M.; Lee, Yong Kwan [KEPCO International Nuclear Graduate School, Ulsan (Korea, Republic of)

    2016-10-15

    Shutdown Cooling System (SCS) is a safety-related system that is used in conjunction with the Main Steam and Main or Auxiliary Feedwater Systems to reduce the temperature of the Reactor Coolant System (RCS) in post shutdown periods from the hot shutdown operating temperature to the refueling temperature. In this paper RCM methodology is applied to (SCS). RCM analysis is performed based on evaluation of Failure Modes Effects and Criticality Analysis (FME and CA) on the component, system and plant. The Logic Tree Analysis (LTA) is used to determine the optimum maintenance tasks. The main objectives of RCM is the safety, preserve the System function, the cost-effective maintenance of the plant components and increase the reliability and availability value. The RCM methodology is useful for improving the equipment reliability by strengthening the management of equipment condition, and leads to a significant decrease in the number of periodical maintenance, extended maintenance cycle, longer useful life of equipment, and decrease in overall maintenance cost. It also focuses on the safety of the system by assigning criticality index to the various components and further selecting maintenance activities based on the risk of failure involved. Therefore, it can be said that RCM introduces a maintenance plan designed for maximum safety in an economical manner and making the system more reliable. For the SCP, increasing the number of condition monitoring tasks will improve the availability of the SCP. It is recommended to reduce the number of periodic maintenance activities.

  19. Rare-earth-metal nitridophosphates through high-pressure metathesis

    International Nuclear Information System (INIS)

    Kloss, Simon David; Schnick, Wolfgang

    2015-01-01

    Developing a synthetic method to target an broad spectrum of unknown phases can lead to fascinating discoveries. The preparation of the first rare-earth-metal nitridophosphate LiNdP_4N_8 is reported. High-pressure solid-state metathesis between LiPN_2 and NdF_3 was employed to yield a highly crystalline product. The in situ formed LiF is believed to act both as the thermodynamic driving force and as a flux to aiding single-crystal formation in dimensions suitable for crystal structure analysis. Magnetic properties stemming from Nd"3"+ ions were measured by SQUID magnetometry. LiNdP_4N_8 serves as a model system for the exploration of rare-earth-metal nitridophosphates that may even be expanded to transition metals. High-pressure metathesis enables the systematic study of these uncharted regions of nitride-based materials with unprecedented properties. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  20. Well-defined silica-supported zirconium–imido complexes mediated heterogeneous imine metathesis

    KAUST Repository

    Hamzaoui, Bilel

    2016-02-15

    Upon prolonged thermal exposure under vacuum, a well-defined single-site surface species [(≡Si-O-)Zr(NEt2)3] (1) evolves into an ethylimido complex [(≡Si-O-)Zr(=NEt)NEt2] (2). Reactions of 2 with an imine substrate result in imido/imine (=NRi, R: Et, Ph) exchange (metathesis) with the formation of [(≡Si-O-)Zr(=NPh)NEt2] (3). Compounds 2 and 3 effectively catalyze imine/imine cross-metathesis and are thus considered as the first heterogeneous catalysts active for imine metathesis. © The Royal Society of Chemistry 2016.

  1. Well-defined silica-supported zirconium–imido complexes mediated heterogeneous imine metathesis

    KAUST Repository

    Hamzaoui, Bilel; Pelletier, Jeremie; Abou-Hamad, Edy; Basset, Jean-Marie

    2016-01-01

    Upon prolonged thermal exposure under vacuum, a well-defined single-site surface species [(≡Si-O-)Zr(NEt2)3] (1) evolves into an ethylimido complex [(≡Si-O-)Zr(=NEt)NEt2] (2). Reactions of 2 with an imine substrate result in imido/imine (=NRi, R: Et, Ph) exchange (metathesis) with the formation of [(≡Si-O-)Zr(=NPh)NEt2] (3). Compounds 2 and 3 effectively catalyze imine/imine cross-metathesis and are thus considered as the first heterogeneous catalysts active for imine metathesis. © The Royal Society of Chemistry 2016.

  2. Synthetic studies on taxanes: A domino-enyne metathesis/Diels ...

    Indian Academy of Sciences (India)

    Abstract. A domino enyne cross-metathesis/intramolecular Diels-Alder reaction has been successfully used to synthesize a bicyclo[5.3.1] undecene, corresponding to AB-ring of taxol without the gem dimethyl group.

  3. A cross-metathesis approach to the stereocontrolled synthesis of the AB ring segment of ciguatoxin

    OpenAIRE

    Kadota, Isao; Abe, Takashi; Uni, Miyuki; Takamura, Hiroyoshi; Yamamoto, Yoshinori

    2008-01-01

    Synthesis of the AB ring segments of ciguatoxin is described. The present synthesis includes a Lewis acid mediated cyclization of allylstannane with aldehyde, cross-metathesis reaction introducing the side chain, and Grieco-Nishizawa dehydration on the A ring.

  4. Selective conversion of butane into liquid hydrocarbon fuels on alkane metathesis catalysts

    KAUST Repository

    Szeto, Kaï Chung; Hardou, Lucie; Merle, Nicolas; Basset, Jean-Marie; Thivolle-Cazat, Jean; Papaioannou, Charalambos; Taoufik, Mostafa

    2012-01-01

    We report a selective direct conversion of n-butane into higher molecular weight alkanes (C 5+) by alkane metathesis reaction catalysed by silica-alumina supported tungsten or tantalum hydrides at moderate temperature and pressure. The product

  5. Development of RCM methodology and tools for EDF nuclear power plants

    International Nuclear Information System (INIS)

    Jacquot, J.P.; Bouchet, J.L.; Despujols, A.; Dewailly, J.; Martin-Mattei, C.

    1992-06-01

    This paper outlines the development of Reliability-Centered Maintenance procedures in the nuclear power industry. It presents the pilot study undertaken by EDF in the overall framework of its 'OMF' (RCM) project, as well as the potential for further improving and enriching analytical methods. Lastly, it gives the prospects for the future design of an 'OMF' workstation

  6. Configurations of the Re-scan Confocal Microscope (RCM) for biomedical applications

    NARCIS (Netherlands)

    de Luca, G. M. R.; Desclos, E.; Breedijk, R. M. P.; Dolz-Edo, L.; Smits, G. J.; Bielefeld, P.; Picavet, L.; Fitzsimons, C. P.; Hoebe, R.; Manders, E. M. M.

    2017-01-01

    The new high-sensitive and high-resolution technique, Re-scan Confocal Microscopy (RCM), is based on a standard confocal microscope extended with a re-scan detection unit. The re-scan unit includes a pair of re-scanning mirrors that project the emission light onto a camera in a scanning manner. The

  7. Impact of spectral nudging and domain size in studies of RCM response to parameter modification

    Energy Technology Data Exchange (ETDEWEB)

    Separovic, Leo; Laprise, Rene [Universite du Quebec a Montreal, Centre pour l' Etude et la Simulation du Climat a l' Echelle Regionale (ESCER), Montreal, QC (Canada); Universite du Quebec a Montreal (UQAM), Montreal, QC (Canada); Elia, Ramon de [Universite du Quebec a Montreal, Centre pour l' Etude et la Simulation du Climat a l' Echelle Regionale (ESCER), Montreal, QC (Canada); Consortium Ouranos, Montreal, QC (Canada)

    2012-04-15

    The paper aims at finding an RCM configuration that facilitates studies devoted to quantifying RCM response to parameter modification. When using short integration times, the response of the time-averaged variables to RCM modification tend to be blurred by the noise originating in the lack of predictability of the instantaneous atmospheric states. Two ways of enhancing the signal-to-noise ratio are studied in this work: spectral nudging and reduction of the computational domain size. The approach followed consists in the analysis of the sensitivity of RCM-simulated seasonal averages to perturbations of two parameters controlling deep convection and stratiform condensation, perturbed one at a time. Sensitivity is analyzed within different simulation configurations obtained by varying domain size and using the spectral nudging option. For each combination of these factors multiple members of identical simulations that differ exclusively in initial conditions are also generated to provide robust estimates of the sensitivities (the signal) and sample the noise. Results show that the noise magnitude is decreased both by reduction of domain size and the spectral nudging. However, the reduction of domain size alters some sensitivity signals. When spectral nudging is used significant alterations of the signal are not found. (orig.)

  8. Influence of the applied voltage on the Rapid Chloride Migration (RCM) test

    NARCIS (Netherlands)

    Spiesz, P.R.; Brouwers, H.J.H.

    2012-01-01

    This study addresses the influence of the applied voltage (electrical field) on the value of the chloride migration coefficient, as determined with the Rapid Chloride Migration (RCM) test, and on other properties of cement based mortars. It is shown that in the investigated ranges of applied

  9. Study on the chloride migration coefficient obtained following different Rapid Chloride Migration (RCM) test guidelines

    NARCIS (Netherlands)

    Spiesz, P.R.; Brouwers, H.J.H.; Uzoegbo, H.C.; Schmidt, W.

    2013-01-01

    This work presents the differences in the available Rapid Chloride Migration (RCM) test guidelines, and their influence on the values of the chloride migration coefficients DRCM, obtained following these guidelines. It is shown that the differences between the guidelines are significant and concern

  10. Configurations of the Re-scan Confocal Microscope (RCM) for biomedical applications

    NARCIS (Netherlands)

    De Luca, G.M.R.; Desclos, E.; Breedijk, R.M.P.; Dolz-Edo, L.; Smits, G.J.; Nahidiazar, L.; Bielefeld, P.; Picavet, L.; Fitzsimons, C.P.; Hoebe, R.; Manders, E.M.M.

    The new high-sensitive and high-resolution technique, Re-scan Confocal Microscopy (RCM), is based on a standard confocal microscope extended with a re-scan detection unit. The re-scan unit includes a pair of re-scanning mirrors that project the emission light onto a camera in a scanning manner. The

  11. Metallacyclobutane substitution and its effect on alkene metathesis for propylene production over W-H/Al2O3: Case of isobutene/2-butene cross-metathesis

    KAUST Repository

    Szeto, Kaï Chung

    2013-09-06

    Cross metathesis between 2-butenes and isobutene yielding the valuable products propylene and 2-methyl-2-butene has been investigated at low pressure and temperature using WH3/Al2O3, a highly active and selective catalyst. Two parallel catalytic cycles for this reaction have been proposed where the cycle involving the less sterically hindered tungstacyclobutane intermediates is most likely favored. Moreover, it has been found that the arrangement of substituents on the least thermodynamically favored tungstacyclobutane governs the conversion rate of the cross metathesis reaction for propylene production from butenes and/or ethylene. © 2013 American Chemical Society.

  12. Metallacyclobutane substitution and its effect on alkene metathesis for propylene production over W-H/Al2O3: Case of isobutene/2-butene cross-metathesis

    KAUST Repository

    Szeto, Kaï Chung; Mazoyer, Etienne; Merle, Nicolas; Norsic, Sé bastien; Basset, Jean-Marie; Nicholas, Christopher P.; Taoufik, Mostafa

    2013-01-01

    Cross metathesis between 2-butenes and isobutene yielding the valuable products propylene and 2-methyl-2-butene has been investigated at low pressure and temperature using WH3/Al2O3, a highly active and selective catalyst. Two parallel catalytic cycles for this reaction have been proposed where the cycle involving the less sterically hindered tungstacyclobutane intermediates is most likely favored. Moreover, it has been found that the arrangement of substituents on the least thermodynamically favored tungstacyclobutane governs the conversion rate of the cross metathesis reaction for propylene production from butenes and/or ethylene. © 2013 American Chemical Society.

  13. Studi Implementasi RCM untuk Peningkatan Produktivitas Dok Apung (Studi Kasus: PT.Dok dan Perkapalan Surabaya

    Directory of Open Access Journals (Sweden)

    Nurlaily Mufarikhah

    2017-01-01

    Full Text Available Dok apung merupakan salah satu fasilitas galangan yang ada di PT.Dok dan Perkapalan Surabaya, yang terdiri dari dok I,II,IV dan V. Dok apung mempunyai peran yang sangat penting dalam kegiatan reparasi kapal. Oleh karena itu, PT.Dok dan Perkapalan Surabaya melakukan tindakan perawatan untuk menjaga kinerja dok apung. Mengingat begitu pentingnya peran dok apung, maka dilakukan penelitian tindakan dan rencana perawatan yang tepat untuk meningkatkan produktivitas dok apung dengan menggunakan metode RCM. Penelitian dengan metode RCM (Reliability Centered Maintenance secara umum dibagi menjadi 2 yaitu, secara kualitatif dan secara kuantitatif. Analisa kualitatif terdiri dari FMEA (Failure Mode and Effect Analysis, FTA (Fault Tree Analysis, dan LTA (Logic Tree Analysis. Sedangkan analisa kuantitatif terdiri dari perhitungan MTTF (Mean Time to Failure, MTTR (Mean Time to Repair, penentuan reliability, dan failure rate dengan menggunakan software weibull 6++. Dari hasil analisa kualitatif terdapat 4 komponen MSI (Maintenance Significant Item, yaitu capstan, ponton, crane dan pompa. Dari hasil analisa kuantitatif didapatkan komponen yang memengaruhi reliability dok apung. Reliability yang paling rendah yaitu ponton, pompa, capstan dan crane. Penilaian reliability didasarkan pada akibat yang ditimbulkan dari kerusakan atau kegagalan komponen terhadap sistem, sedangkan nilai MTTF (Mean Time to Failure paling rendah pada crane dan pompa yaitu 120 dan 150 hari. Secara teoritis, penerapan RCM (Reliability Centered Maintennace akan meningkatkan keandalan komponen. Tindakan dan rencana perawatan yang disarankan berdasarkan metode RCM (Reliability Centered Maintenance yaitu melakukan pengecekan secara rutin serta melakukan training pada bagian maintenance mengenai konsep perawatan. Interval maintenance pada crane dan ponton  dilakukan setiap 1 bulan sekali, sedangkan interval maintenance pada capstan dan pompa dilakukan setiap 2 bulan sekali.

  14. A comprehensive approach to RCM-based preventive maintenance program development

    International Nuclear Information System (INIS)

    Hall, B.E.; Davis, T.; Pennington, A.J.

    1988-01-01

    In late 1986, Public Service Electric and Gas Company (PSE ampersand G) concluded that to support its vision and strategic planning it would be necessary to develop a consistent approach to maintenance for all nuclear units at the artificial island. General Physics Corporation was selected to lead a consultant team to support full-scale development of a preventive maintenance (PM) program for Salem and Hope Creek generating stations based on a reliability-centered maintenance (RCM) approach. RCM was selected because it represents a systematic approach to developing a PM program that provides a logical, consistent, and traceable methodology and produces a well-documented engineering basis for the program. Early in 1987, primary objectives for the PM program were defined. The Phase I tasks addressed key programmatic areas such as maintenance philosophy, procedures, condition monitoring, performance trending, equipment failure data base, ogranization, PM program effectiveness evaluation, RCM process, reliability/availability modeling, information management, training, spare parts, software/hardware, and commitments. Phase I of the PM program development project was completed in January 1988. Highlights of the Phase I work and the PM program manual are described

  15. 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.

  16. ANALISIS MODA KEGAGALAN DENGAN PENDEKATAN RELIABILITY CENTERED MAINTENANCE (RCM (Studi kasus Baking Section Mesin Imfori PT Nissin Biskuit Indonesia

    Directory of Open Access Journals (Sweden)

    Sri Hartini

    2012-02-01

    Full Text Available Reliability Centered Maintenance (RCM adalah suatu pendekatan perawatan yang berbasis pada upaya menjamin keandalan mesin. Dengan pendekatan ini, perawatan ditujukan untuk menjamin agar asset terus menerus mencapai kemampuan dasarnya. Dalam penelitian dilakukan analisis fungsi sistem yang tepat terhadap Baking Section mesin Imaforni PT Nissin Biskuit Indonesia melalui pendekatan RCM untuk mengetahui moda kegagalan yang dapat menyebabkan sistem kehilangan fungsinya. Kata Kunci : Fungsi Sistem,Moda Kegagalan,Reliability Centered Maintenance.

  17. Ultrasound-assisted self-metathesis reactions of monounsaturated fatty acids

    Directory of Open Access Journals (Sweden)

    Elmkaddem Mohammed Kamal

    2016-09-01

    Full Text Available An efficient protocol for the self-metathesis of oleic acid, using ruthenium catalysts is described. The self-metathesis reaction under ultrasonic activation allows the conversion of monoenic fatty acids such as oleic acid, elaidic acid and erucic acid into diacids and olefins with very short reaction times in the presence of Grubbs ruthenium catalysts. These yields and selectivity towards the desired products are influenced by the nature of solvents. This study demonstrated that metathesis reaction carried out in DCM or 1-butanol showed promising results, since it produced a variety of products, like n-alkenes and diacids with good yields (45–75% and high selectivities (75–95%.

  18. Well-Defined Silica Grafted Molybdenum Bis(imido) Catalysts for Imine Metathesis Reactions

    KAUST Repository

    Barman, Samir

    2017-04-06

    Novel site-isolated tetracoordinated molybdenum complexes possessing bis(imido) ligands, [(≡Si–O)2Mo(═NR)2] (R = t-Bu, 2,6-C6H3-i-Pr2), were immobilized on partially dehydroxylated silica (SiO2-200) by a rigorous surface organometallic chemistry protocol. The newly developed materials adorned with bis(imido) functional units, which were previously exploited mainly as spectator ligands on silica-supported olefin metathesis molybdenum catalysts, are found to be efficient heterogeneous catalytic systems for imine cross metathesis under mild conditions.

  19. Well-Defined Silica Grafted Molybdenum Bis(imido) Catalysts for Imine Metathesis Reactions

    KAUST Repository

    Barman, Samir; Merle, Nicolas; Minenkov, Yury; De Mallmann, Aimery; Samantaray, Manoja; Le Qué mé ner, Fré dé ric; Szeto, Kai C.; Abou-Hamad, Edy; Cavallo, Luigi; Taoufik, Mostafa; Basset, Jean-Marie

    2017-01-01

    Novel site-isolated tetracoordinated molybdenum complexes possessing bis(imido) ligands, [(≡Si–O)2Mo(═NR)2] (R = t-Bu, 2,6-C6H3-i-Pr2), were immobilized on partially dehydroxylated silica (SiO2-200) by a rigorous surface organometallic chemistry protocol. The newly developed materials adorned with bis(imido) functional units, which were previously exploited mainly as spectator ligands on silica-supported olefin metathesis molybdenum catalysts, are found to be efficient heterogeneous catalytic systems for imine cross metathesis under mild conditions.

  20. Developing RCM Strategy for Hydrogen Fuel Cells Utilizing On Line E-Condition Monitoring

    International Nuclear Information System (INIS)

    Baglee, D; Knowles, M J

    2012-01-01

    Fuel cell vehicles are considered to be a viable solution to problems such as carbon emissions and fuel shortages for road transport. Proton Exchange Membrane (PEM) Fuel Cells are mainly used in this purpose because they can run at low temperatures and have a simple structure. Yet high maintenance costs and the inherent dangers of maintaining equipment using hydrogen are two main issues which need to be addressed. The development of appropriate and efficient strategies is currently lacking with regard to fuel cell maintenance. A Reliability Centered Maintenance (RCM) approach offers considerable benefit to the management of fuel cell maintenance since it includes an identification and consideration of the impact of critical components. Technological developments in e-maintenance systems, radio-frequency identification (RFID) and personal digital assistants (PDAs) have proven to satisfy the increasing demand for improved reliability, efficiency and safety. RFID technology is used to store and remotely retrieve electronic maintenance data in order to provide instant access to up-to-date, accurate and detailed information. The aim is to support fuel cell maintenance decisions by developing and applying a blend of leading-edge communications and sensor technology including RFID. The purpose of this paper is to review and present the state of the art in fuel cell condition monitoring and maintenance utilizing RCM and RFID technologies. Using an RCM analysis critical components and fault modes are identified. RFID tags are used to store the critical information, possible faults and their cause and effect. The relationship between causes, faults, symptoms and long term implications of fault conditions are summarized. Finally conclusions are drawn regarding suggested maintenance strategies and the optimal structure for an integrated, cost effective condition monitoring and maintenance management system.

  1. Developing RCM Strategy for Hydrogen Fuel Cells Utilizing On Line E-Condition Monitoring

    Science.gov (United States)

    Baglee, D.; Knowles, M. J.

    2012-05-01

    Fuel cell vehicles are considered to be a viable solution to problems such as carbon emissions and fuel shortages for road transport. Proton Exchange Membrane (PEM) Fuel Cells are mainly used in this purpose because they can run at low temperatures and have a simple structure. Yet high maintenance costs and the inherent dangers of maintaining equipment using hydrogen are two main issues which need to be addressed. The development of appropriate and efficient strategies is currently lacking with regard to fuel cell maintenance. A Reliability Centered Maintenance (RCM) approach offers considerable benefit to the management of fuel cell maintenance since it includes an identification and consideration of the impact of critical components. Technological developments in e-maintenance systems, radio-frequency identification (RFID) and personal digital assistants (PDAs) have proven to satisfy the increasing demand for improved reliability, efficiency and safety. RFID technology is used to store and remotely retrieve electronic maintenance data in order to provide instant access to up-to-date, accurate and detailed information. The aim is to support fuel cell maintenance decisions by developing and applying a blend of leading-edge communications and sensor technology including RFID. The purpose of this paper is to review and present the state of the art in fuel cell condition monitoring and maintenance utilizing RCM and RFID technologies. Using an RCM analysis critical components and fault modes are identified. RFID tags are used to store the critical information, possible faults and their cause and effect. The relationship between causes, faults, symptoms and long term implications of fault conditions are summarized. Finally conclusions are drawn regarding suggested maintenance strategies and the optimal structure for an integrated, cost effective condition monitoring and maintenance management system.

  2. Exploring new generations of ruthenium olefin metathesis catalysts: The reactivity of a bis-ylidene ruthenium complex by DFT

    KAUST Repository

    Poater, Albert; Credendino, Raffaele; Slugovc, Christian; Cavallo, Luigi

    2013-01-01

    Density functional theory calculations were used to predict the behaviour of a potential novel architecture of olefin metathesis catalysts, in which one of the neutral ligands of classical Ru-based catalysts, e.g. a phosphine or an N-heterocyclic carbene, is replaced by an alkylidene group. Introduction of a second alkylidene ligand favors dissociation of the remaining phosphine and the overall energy profile for the metathesis using ethylene as the probe substrate reveals that the proposed bis-alkylidene complexes might match the requirements of a good performing olefin metathesis catalyst. © 2013 The Royal Society of Chemistry.

  3. Metathesis of cardanol over Ru catalysts supported on mesoporousmolecular sieve SBA-15

    Czech Academy of Sciences Publication Activity Database

    Shinde, Tushar; Varga, Vojtěch; Polášek, Miroslav; Horáček, Michal; Žilková, Naděžda; Balcar, Hynek

    2014-01-01

    Roč. 478, MAY 2014 (2014), s. 138-145 ISSN 0926-860X R&D Projects: GA ČR(CZ) GAP106/12/0189 Institutional support: RVO:61388955 Keywords : cardanol * metathesis * supported catalysts Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.942, year: 2014

  4. 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

  5. Regioselective Wacker Oxidation of Internal Alkenes: Rapid Access to Functionalized Ketones Facilitated by Cross-Metathesis

    KAUST Repository

    Morandi, Bill

    2013-07-26

    Wacka wacka: The title reaction makes use of a wide range of directing groups (DG) to enable the highly regioselective oxidation of alkenes, and occurs predictably at the distal position. Both E and Z alkenes afford valuable functionalized ketones and cross-metathesis was shown to facilitate the preparation of the starting materials. BQ=benzoquinone.

  6. Efforts toward rapid construction of the cortistatin A carbocyclic core via enyne-ene metathesis

    KAUST Repository

    Baumgartner, Corinne

    2010-01-01

    Our efforts toward the construction of the carbocylic core of cortistatin A via an enyne-ene metathesis are disclosed. Interestingly, an attempted S N2 inversion of a secondary mesylate in our five-membered D-ring piece gave a product with retention of stereochemistry. © 2010 The Royal Society of Chemistry.

  7. Regioselective Wacker Oxidation of Internal Alkenes: Rapid Access to Functionalized Ketones Facilitated by Cross-Metathesis

    KAUST Repository

    Morandi, Bill; Wickens, Zachary K.; Grubbs, Robert H.

    2013-01-01

    Wacka wacka: The title reaction makes use of a wide range of directing groups (DG) to enable the highly regioselective oxidation of alkenes, and occurs predictably at the distal position. Both E and Z alkenes afford valuable functionalized ketones and cross-metathesis was shown to facilitate the preparation of the starting materials. BQ=benzoquinone.

  8. Hoveyda-Grubbs type metathesis catalyst immobilized on mesoporous molecular sieves MCM-41 and SBA-15

    Czech Academy of Sciences Publication Activity Database

    Balcar, Hynek; Shinde, Tushar; Žilková, Naděžda; Bastl, Zdeněk

    2011-01-01

    Roč. 7, January (2011), s. 22-28 ISSN 1860-5397 R&D Projects: GA AV ČR IAA400400805; GA AV ČR KAN100400701 Institutional research plan: CEZ:AV0Z40400503 Keywords : alkene metathesis * catalyst immobilization * hybrid catalysis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.517, year: 2011

  9. Efforts toward rapid construction of the cortistatin A carbocyclic core via enyne-ene metathesis

    KAUST Repository

    Baumgartner, Corinne; Ma, Sandy; Liu, Qi; Stoltz, Brian M.

    2010-01-01

    Our efforts toward the construction of the carbocylic core of cortistatin A via an enyne-ene metathesis are disclosed. Interestingly, an attempted S N2 inversion of a secondary mesylate in our five-membered D-ring piece gave a product with retention

  10. Omega-functionalized fatty acids, alcohols, and ethers via olefin metathesis

    Science.gov (United States)

    Methyl 17-hydroxy stearate was converted to methyl octadec-16-enoate using copper sulfate adsorbed on silica gel. This compound, possessing unsaturation at the opposite end of the chain from the carboxylate, served as a useful substrate for the olefin metathesis reaction. As a result, several fatt...

  11. Selective conversion of butane into liquid hydrocarbon fuels on alkane metathesis catalysts

    KAUST Repository

    Szeto, Kaï Chung

    2012-01-01

    We report a selective direct conversion of n-butane into higher molecular weight alkanes (C 5+) by alkane metathesis reaction catalysed by silica-alumina supported tungsten or tantalum hydrides at moderate temperature and pressure. The product is unprecedented, asymmetrically distributed towards heavier alkanes. This journal is © 2012 The Royal Society of Chemistry.

  12. Using climate derivatives for assessment of meteorological parameter relationships in RCM and observations

    Science.gov (United States)

    Timuhins, Andrejs; Bethers, Uldis; Bethers, Peteris; Klints, Ilze; Sennikovs, Juris; Frishfelds, Vilnis

    2017-04-01

    In a changing climate it is essential to estimate its impacts on different economic fields. In our study we tried to create a framework for climate change assessment and climate change impact estimation for the territory of Latvia and to create results which are also understandable for non-scientists (stakeholder, media and public). This approach allowed us to more carefully assess the presentation and interpretation of results and their validation, for public viewing. For the presentation of our work a website was created (www.modlab.lv/klimats) containing two types of documents in a unified framework, meteorological parameter analysis of different easily interpretable derivative values. Both of these include analysis of the current situation as well as illustrate the projection for future time periods. Derivate values are calculated using two data sources: the bias corrected regional climate data and meteorological observation data. Derivative documents contain description of derived value, some interesting facts and conclusions. Additionally, all results may be viewed in temporal and spatial graphs and maps, for different time periods as well as different seasons. Bias correction (Sennikovs and Bethers, 2009) for the control period 1961-1990 is applied to RCM data series. Meteorological observation data of the Latvian Environment, Geology, and Meteorology Agency and ENSEMBLES project daily data of 13 RCM runs for the period 1960-2100 are used. All the documents are prepared in python notebooks, which allow for flexible changes. At the moment following derivative values have been published: forest fire risk index, wind energy, phenology (Degree days), road condition (friction, ice conditions), daily minimal meteorological visibility, headache occurrence rate, firs snow date and meteorological parameter analysis: temperature, precipitation, wind speed, relative humidity, and cloudiness. While creating these products RCM ability to represent the actual climate was

  13. RCM [reliability-centered maintenance] at Ginna: Preventive maintenance program optimization at year 20

    International Nuclear Information System (INIS)

    Edgar, E.C.

    1989-01-01

    The reliability-centered maintenance (RCM) program at Rochester Gas ampersand Electric Company's Ginna station is entering its second year. Of the 20 systems originally selected for evaluation, 10 are in various stages of completion, and recommendations resulting from the earliest systems studied are now being implemented. As expected, few major discoveries have been made in terms of preventive maintenance program failings or excesses. The performance of the now 20-yr-old plant has been excellent in recent years, and objectives focus more on ensuring continued high standards of safety, reliability, and economy than on maintenance program cost reduction

  14. Correcting Spatial Variance of RCM for GEO SAR Imaging Based on Time-Frequency Scaling

    Science.gov (United States)

    Yu, Ze; Lin, Peng; Xiao, Peng; Kang, Lihong; Li, Chunsheng

    2016-01-01

    Compared with low-Earth orbit synthetic aperture radar (SAR), a geosynchronous (GEO) SAR can have a shorter revisit period and vaster coverage. However, relative motion between this SAR and targets is more complicated, which makes range cell migration (RCM) spatially variant along both range and azimuth. As a result, efficient and precise imaging becomes difficult. This paper analyzes and models spatial variance for GEO SAR in the time and frequency domains. A novel algorithm for GEO SAR imaging with a resolution of 2 m in both the ground cross-range and range directions is proposed, which is composed of five steps. The first is to eliminate linear azimuth variance through the first azimuth time scaling. The second is to achieve RCM correction and range compression. The third is to correct residual azimuth variance by the second azimuth time-frequency scaling. The fourth and final steps are to accomplish azimuth focusing and correct geometric distortion. The most important innovation of this algorithm is implementation of the time-frequency scaling to correct high-order azimuth variance. As demonstrated by simulation results, this algorithm can accomplish GEO SAR imaging with good and uniform imaging quality over the entire swath. PMID:27428974

  15. Reliability Centred Maintenance (RCM) Analysis of Laser Machine in Filling Lithos at PT X

    Science.gov (United States)

    Suryono, M. A. E.; Rosyidi, C. N.

    2018-03-01

    PT. X used automated machines which work for sixteen hours per day. Therefore, the machines should be maintained to keep the availability of the machines. The aim of this research is to determine maintenance tasks according to the cause of component’s failure using Reliability Centred Maintenance (RCM) and determine the amount of optimal inspection frequency which must be performed to the machine at filling lithos process. In this research, RCM is used as an analysis tool to determine the critical component and find optimal inspection frequencies to maximize machine’s reliability. From the analysis, we found that the critical machine in filling lithos process is laser machine in Line 2. Then we proceed to determine the cause of machine’s failure. Lastube component has the highest Risk Priority Number (RPN) among other components such as power supply, lens, chiller, laser siren, encoder, conveyor, and mirror galvo. Most of the components have operational consequences and the others have hidden failure consequences and safety consequences. Time-directed life-renewal task, failure finding task, and servicing task can be used to overcome these consequences. The results of data analysis show that the inspection must be performed once a month for laser machine in the form of preventive maintenance to lowering the downtime.

  16. Poisoning Experiments Aimed at Discriminating Active and Less-Active Sites of Silica-Supported Tantalum Hydride for Alkane Metathesis

    KAUST Repository

    Saggio, Guillaume; Taoufik, Mostafa; Basset, Jean-Marie; Thivolle-Cazat, Jean

    2010-01-01

    Only 50% of the silica-supported tantalum hydride sites are active in the metathesis of propane. Indeed, more than 45% of the tantalum hydride can be eliminated by a selective oxygen poisoning of inactive sites with no significant decrease

  17. Evaluation of an olefin metathesis pre-catalyst with a bulky and electron-rich N-heterocyclic carbene

    KAUST Repository

    Manzini, Simone

    2015-03-01

    The commercially-available metathesis pre-catalyst M23 has been evaluated alongside new complex [RuCl2((3-phenyl)indenylidene)(PPh3)(SIPrOMe)] (1), which bears a para-methoxy-substituted N-heterocyclic carbene ligand. Several model metathesis reactions could be conducted using only parts-per-million levels of ruthenium catalyst. The effects of the different NHC ligands on reactivity have been explored.

  18. Evaluation of an olefin metathesis pre-catalyst with a bulky and electron-rich N-heterocyclic carbene

    KAUST Repository

    Manzini, Simone; Urbina Blanco, Cé sar A.; Nelson, David J.; Poater, Albert; Lebl, Tomas; Meiries, Sé bastien; Slawin, Alexandra M.Z.; Falivene, Laura; Cavallo, Luigi; Nolan, Steven P.

    2015-01-01

    The commercially-available metathesis pre-catalyst M23 has been evaluated alongside new complex [RuCl2((3-phenyl)indenylidene)(PPh3)(SIPrOMe)] (1), which bears a para-methoxy-substituted N-heterocyclic carbene ligand. Several model metathesis reactions could be conducted using only parts-per-million levels of ruthenium catalyst. The effects of the different NHC ligands on reactivity have been explored.

  19. Divergent Synthesis of Revised Apratoxin E, 30-epi-Apratoxin E, and 30S/30R-Oxoapratoxin E.

    Science.gov (United States)

    Mao, Zhuo-Ya; Si, Chang-Mei; Liu, Yi-Wen; Dong, Han-Qing; Wei, Bang-Guo; Lin, Guo-Qiang

    2017-10-20

    In this report, originally proposed apratoxin E (30S-7), revised apratoxin E (30R-7), and (30S)/(30R)-oxoapratoxin E (30S)-38/(30R)-38 were efficiently prepared by two synthetic methods. The chiral lactone 10, recycled from the degradation of saponin glycosides, was utilized to prepare the key nonpeptide fragment 9. Our alternative convergent assembly strategy was applied to the divergent synthesis of revised apratoxin E and its three analogues. Moreover, ring-closing metathesis (RCM) was for the first time found to be an efficient strategy for the macrocyclization of apratoxins.

  20. Can limited area NWP and/or RCM models improve on large scales inside their domain?

    Science.gov (United States)

    Mesinger, Fedor; Veljovic, Katarina

    2017-04-01

    In a paper in press in Meteorology and Atmospheric Physics at the time this abstract is being written, Mesinger and Veljovic point out four requirements that need to be fulfilled by a limited area model (LAM), be it in NWP or RCM environment, to improve on large scales inside its domain. First, NWP/RCM model needs to be run on a relatively large domain. Note that domain size in quite inexpensive compared to resolution. Second, NWP/RCM model should not use more forcing at its boundaries than required by the mathematics of the problem. That means prescribing lateral boundary conditions only at its outside boundary, with one less prognostic variable prescribed at the outflow than at the inflow parts of the boundary. Next, nudging towards the large scales of the driver model must not be used, as it would obviously be nudging in the wrong direction if the nested model can improve on large scales inside its domain. And finally, the NWP/RCM model must have features that enable development of large scales improved compared to those of the driver model. This would typically include higher resolution, but obviously does not have to. Integrations showing improvements in large scales by LAM ensemble members are summarized in the mentioned paper in press. Ensemble members referred to are run using the Eta model, and are driven by ECMWF 32-day ensemble members, initialized 0000 UTC 4 October 2012. The Eta model used is the so-called "upgraded Eta," or "sloping steps Eta," which is free of the Gallus-Klemp problem of weak flow in the lee of the bell-shaped topography, seemed to many as suggesting the eta coordinate to be ill suited for high resolution models. The "sloping steps" in fact represent a simple version of the cut cell scheme. Accuracy of forecasting the position of jet stream winds, chosen to be those of speeds greater than 45 m/s at 250 hPa, expressed by Equitable Threat (or Gilbert) skill scores adjusted to unit bias (ETSa) was taken to show the skill at large scales

  1. Use of RCM simulations to assess the impact of climate change on wind energy availability

    DEFF Research Database (Denmark)

    Pryor, S.C.; Barthelmie, Rebecca Jane

    2004-01-01

    There is considerable interest in the potential impact of climate change on the feasibility and predictability of renewable energy sources including wind energy. This report presents an application and evaluation of physical (dynamical) downscaling toolsfor examining the impact of climate change...... on near-surface flow and hence wind energy density across northern Europe. It is shown that: - Simulated wind fields using the Rossby Centre coupled Regional Climate Model (RCM) (RCAO) during the control period(1961-1990) exhibit reasonable and realistic features as documented in in situ observations...... and reanalysis data products. - The differences between near-surface wind speed and direction calculated for the control run (January 1, 1961 – December 30, 1990)based on boundary conditions derived from two Global Climate Models (GCM): HadAM3H and ECHAM4/OPYC3 are comparable to changes in the climate change...

  2. Controlling of degradation effects in radiation processing of polymers. Second RCM report

    International Nuclear Information System (INIS)

    2005-08-01

    The research and development works carried out by the participants of the CRP (Coordinated Research Project) dealt with natural polymers, synthetic polymers and new techniques for better understanding of radiation degradation of polymers. It includes progress in radiation degradation of polysaccharides from agricultural products (including sodium alginate, carrageenans, chitosan and gum acacia); use of radiation-degradation for doping of conductive polymers; controlling degradation processes in artificial joint implants, surface treatment of materials and food packaging; stabilizer additives for radiation environments; surface treatment of materials; and application of specialized analytical techniques (positron annihilation spectroscopy, ESR, RBS, ERDA, NMR/isotopic-labeling) to gain improved understanding of radiation degradation effects and mechanisms. Projects within the RCM group span the spectrum from fundamental studies through specific technological applications. Participants from Czech Republic, Spain and Turkey benefited from scientific collaboration with Bulgaria on PAS

  3. 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.

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

    KAUST Repository

    Urbina-Blanco, Cé sar A.; Poater, Albert; Lé bl, Tomá š; Manzini, Simone; Slawin, Alexandra M. Z.; Cavallo, Luigi; Nolan, Steven P.

    2013-01-01

    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.

  5. Ring Opening Metathesis Polymerization of Cyclopentene Using a Ruthenium Catalyst Confined by a Branched Polymer Architecture

    KAUST Repository

    Mugemana, Clement; Bukhriakov, Konstantin; Bertrand, Olivier; Vu, Khanh B.; Gohy, Jean-Francois; Hadjichristidis, Nikolaos; Rodionov, Valentin

    2016-01-01

    Multi-arm polystyrene stars functionalized with Grubbs-type catalysts in their cores were synthesized and used for the ring-opening metathesis polymerization (ROMP) of cyclopentene. The spatial confinement of the catalytic sites and the nanoscale phase separation between polystyrene and the growing polypentenamer chains lead to a dramatic inhibition of the ROMP termination and chain transfer steps. Consequently, cyclopentene polymerizations proceeded fast and with a high degree of conversion even in air. The Grubbs second generation catalyst was oxidatively inactivated under the same conditions. In contrast to conventional small-molecule catalysts, the ultimate degree of conversion of cyclopentene monomer and the polydispersity of the product polypentenamer are not affected by the temperature. This indicates that spatial confinement of the catalyst resulted in a significant change in the activation parameters for the alkene metathesis ring-opening.

  6. Ring Opening Metathesis Polymerization of Cyclopentene Using a Ruthenium Catalyst Confined by a Branched Polymer Architecture

    KAUST Repository

    Mugemana, Clement

    2016-03-22

    Multi-arm polystyrene stars functionalized with Grubbs-type catalysts in their cores were synthesized and used for the ring-opening metathesis polymerization (ROMP) of cyclopentene. The spatial confinement of the catalytic sites and the nanoscale phase separation between polystyrene and the growing polypentenamer chains lead to a dramatic inhibition of the ROMP termination and chain transfer steps. Consequently, cyclopentene polymerizations proceeded fast and with a high degree of conversion even in air. The Grubbs second generation catalyst was oxidatively inactivated under the same conditions. In contrast to conventional small-molecule catalysts, the ultimate degree of conversion of cyclopentene monomer and the polydispersity of the product polypentenamer are not affected by the temperature. This indicates that spatial confinement of the catalyst resulted in a significant change in the activation parameters for the alkene metathesis ring-opening.

  7. Evolution of Storm-time Subauroral Electric Fields: RCM Event Simulations

    Science.gov (United States)

    Sazykin, S.; Spiro, R. W.; Wolf, R. A.; Toffoletto, F.; Baker, J.; Ruohoniemi, J. M.

    2012-12-01

    Subauroral polarization streams (SAPS) are regions of strongly-enhanced westward ExB plasma drift (poleward-directed electric fields) located just equatorward of the evening auroral oval. Several recently -installed HF (coherent scatter) radars in the SuperDARN chain at mid-latitudes present a novel opportunity for obtaining two-dimensional maps of ionospheric ExB flows at F-region altitudes that span several hours of the evening and nighttime subauroral ionosphere. These new and exciting observations of SAPS provide an opportunity and a challenge to coupled magnetosphere-ionosphere models. In this paper, we use the Rice Convection Model (RCM) to simulate several events where SAPS were observed by the mid-latitude SuperDARN chain. RCM frequently predicts the occurrence of SAPS in the subauroral evening MLT sector; the mechanism is essentially current closure on the dusk side where downward Birkeland currents (associated with the ion plasma sheet inner edge) map to a region of reduced ionospheric conductance just equatorward of the diffuse auroral precipitation (associated with the electron plasma sheet inner edge). We present detailed comparisons of model-computed ionospheric convection patterns with observations, with two goals in mind: (1) to analyze to what extent the observed appearance and time evolution of SAPS structures are driven by time variations of the cross polar cap potential drop (or, equivalently, the z-component of the interplanetary magnetic field), and (2) to evaluate the ability of the model to reproduce the spatial extent and magnitude of SAPS structures.

  8. Scaling a Convection-Resolving RCM to Near-Global Scales

    Science.gov (United States)

    Leutwyler, D.; Fuhrer, O.; Chadha, T.; Kwasniewski, G.; Hoefler, T.; Lapillonne, X.; Lüthi, D.; Osuna, C.; Schar, C.; Schulthess, T. C.; Vogt, H.

    2017-12-01

    In the recent years, first decade-long kilometer-scale resolution RCM simulations have been performed on continental-scale computational domains. However, the size of the planet Earth is still an order of magnitude larger and thus the computational implications of performing global climate simulations at this resolution are challenging. We explore the gap between the currently established RCM simulations and global simulations by scaling the GPU accelerated version of the COSMO model to a near-global computational domain. To this end, the evolution of an idealized moist baroclinic wave has been simulated over the course of 10 days with a grid spacing of up to 930 m. The computational mesh employs 36'000 x 16'001 x 60 grid points and covers 98.4% of the planet's surface. The code shows perfect weak scaling up to 4'888 Nodes of the Piz Daint supercomputer and yields 0.043 simulated years per day (SYPD) which is approximately one seventh of the 0.2-0.3 SYPD required to conduct AMIP-type simulations. However, at half the resolution (1.9 km) we've observed 0.23 SYPD. Besides formation of frontal precipitating systems containing embedded explicitly-resolved convective motions, the simulations reveal a secondary instability that leads to cut-off warm-core cyclonic vortices in the cyclone's core, once the grid spacing is refined to the kilometer scale. The explicit representation of embedded moist convection and the representation of the previously unresolved instabilities exhibit a physically different behavior in comparison to coarser-resolution simulations. The study demonstrates that global climate simulations using kilometer-scale resolution are imminent and serves as a baseline benchmark for global climate model applications and future exascale supercomputing systems.

  9. Synthesis of novel aryl brassinosteroids through alkene cross-metathesis and preliminary biological study

    Czech Academy of Sciences Publication Activity Database

    Kořínková, Petra; Bazgier, V.; Oklešťková, Jana; Rárová, L.; Strnad, Miroslav; Kvasnica, Miroslav

    2017-01-01

    Roč. 127, NOV (2017), s. 46-55 ISSN 0039-128X R&D Projects: GA ČR GJ15-08202Y; GA MŠk(CZ) LO1204 Institutional support: RVO:61389030 Keywords : Brassinosteroids * BRI1 receptor kinase * Cross-metathesis * Molecular docking * Organic synthesis * Plant bioassays Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 2.282, year: 2016

  10. C-84 Selective Porphyrin Macrocycle with an Adaptable Cavity Constructed Through Alkyne Metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, C. X.; Long, H.; Zhang, W.

    2012-06-21

    A bisporphyrin macrocycle was constructed from a porphyrin-based diyne monomer in one step through alkyne metathesis. The fullerene binding studies (C{sub 60}, C{sub 70} and C{sub 84}) showed the highest binding affinity of the macrocycle for C{sub 84}, which is in great contrast to its bisporphyrin four-armed cage analogue that showed the strongest binding with C{sub 70}.

  11. From ruthenium olefin metathesis catalyst to (η5-3- phenylindenyl)hydrido complex via alcoholysis

    KAUST Repository

    Manzini, Simone; Nelson, David J.; Lé bl, Tomá š; Poater, Albert; Cavallo, Luigi; Slawin, Alexandra M. Z.; Nolan, Steven P.

    2014-01-01

    The synthesis and characterisation of [Ru(H)(η5-3- phenylindenyl)(iBu-Phoban)2] 4 is reported ( iBu-Phoban = 9-isobutyl-9-phosphabicyclo-[3.3.1]-nonane). 4 is obtained via alcoholysis of metathesis pre-catalyst M11, in a process that was previously thought to be limited to analogous complex [RuCl 2(PPh3)2(3-phenylindenylidene)] (M 10). This journal is © The Royal Society of Chemistry.

  12. Well-defined polyethylene molecular brushes by polyhomologation and ring opening metathesis polymerization

    KAUST Repository

    Zhang, Hefeng; Gnanou, Yves; Hadjichristidis, Nikolaos

    2014-01-01

    A novel strategy using polyhomologation and ring opening metathesis polymerization (ROMP) has been developed for the synthesis of well-defined polyethylene (PE) molecular brushes. Polyhomologation was used to afford an OH-terminated PE, which after transformation to the norbornyl PE macromonomer was subjected to ROMP. Kinetics of ROMP of the PE macromonomer was studied by in situ1H NMR monitoring. The brush structure was proved from HT-GPC, 1H NMR and DSC results.

  13. Synthesis of E- and Z-trisubstituted alkenes by catalytic cross-metathesis

    Science.gov (United States)

    Nguyen, Thach T.; Koh, Ming Joo; Mann, Tyler J.; Schrock, Richard R.; Hoveyda, Amir H.

    2017-12-01

    Catalytic cross-metathesis is a central transformation in chemistry, yet corresponding methods for the stereoselective generation of acyclic trisubstituted alkenes in either the E or the Z isomeric forms are not known. The key problems are a lack of chemoselectivity—namely, the preponderance of side reactions involving only the less hindered starting alkene, resulting in homo-metathesis by-products—and the formation of short-lived methylidene complexes. By contrast, in catalytic cross-coupling, substrates are more distinct and homocoupling is less of a problem. Here we show that through cross-metathesis reactions involving E- or Z-trisubstituted alkenes, which are easily prepared from commercially available starting materials by cross-coupling reactions, many desirable and otherwise difficult-to-access linear E- or Z-trisubstituted alkenes can be synthesized efficiently and in exceptional stereoisomeric purity (up to 98 per cent E or 95 per cent Z). The utility of the strategy is demonstrated by the concise stereoselective syntheses of biologically active compounds, such as the antifungal indiacen B and the anti-inflammatory coibacin D.

  14. Assessing the importance of spatio-temporal RCM resolution when estimating sub-daily extreme precipitation under current and future climate conditions

    DEFF Research Database (Denmark)

    Sunyer Pinya, Maria Antonia; Luchner, J.; Onof, C.

    2017-01-01

    extreme precipitation over Denmark generated by the regional climate model (RCM) HIRHAM-ECEARTH at different spatial resolutions (8, 12, 25 and 50km), three RCM from the RiskChange project at 8km resolution and three RCMs from ENSEMBLES at 25km resolution at temporal aggregations from 1 to 48h...... are more skewed than the observational dataset, which leads to an overestimation by the higher spatial resolution simulations. Nevertheless, in general, under current conditions RCM simulations at high spatial resolution represent extreme events and high-order moments better. The changes projected...

  15. Ruthenium-catalyzed intramolecular metathesis of dienes and its application in the synthesis of bridged and spiro azabicycles

    Science.gov (United States)

    Kuznetsov, N. Yu; Bubnov, Yu N.

    2015-07-01

    The review presents a historical excursion into catalytic alkene metathesis, covering the problems of history of the discovery of this process, as well as investigations on the properties, structure and reactivity of the most popular ruthenium catalysts for metathesis, mechanism of their action and decomposition. The main part covers studies devoted to the syntheses of bridged azabicyclic and 1-azaspirocyclic compounds comprising the intramolecular metathesis of dienes as the key step. The formation of a bicyclic skeleton of a series of natural bridged (cocaine, ferruginine, calystegines, and anatoxin-a) and spiro (pinnaic acids, halichlorine, hystrionicotoxin, and cephalotaxine) azabicycles, as well as their analogues and compounds with larger rings is demonstrated. The methods for the synthesis of diene precursors and the conditions for final assembling of the bicyclic compounds are considered in detail. The generalization of the literature data allows one to efficiently carry out the mentioned process taking into account the most important features. The bibliography includes 129 references.

  16. Ruthenium-catalyzed intramolecular metathesis of dienes and its application in the synthesis of bridged and spiro azabicycles

    International Nuclear Information System (INIS)

    Kuznetsov, N Yu; Bubnov, Yu N

    2015-01-01

    The review presents a historical excursion into catalytic alkene metathesis, covering the problems of history of the discovery of this process, as well as investigations on the properties, structure and reactivity of the most popular ruthenium catalysts for metathesis, mechanism of their action and decomposition. The main part covers studies devoted to the syntheses of bridged azabicyclic and 1-azaspirocyclic compounds comprising the intramolecular metathesis of dienes as the key step. The formation of a bicyclic skeleton of a series of natural bridged (cocaine, ferruginine, calystegines, and anatoxin-a) and spiro (pinnaic acids, halichlorine, hystrionicotoxin, and cephalotaxine) azabicycles, as well as their analogues and compounds with larger rings is demonstrated. The methods for the synthesis of diene precursors and the conditions for final assembling of the bicyclic compounds are considered in detail. The generalization of the literature data allows one to efficiently carry out the mentioned process taking into account the most important features. The bibliography includes 129 references

  17. Metathesis Polymerization Reactions Induced by the Bimetallic Complex (Ph4P2[W2(μ-Br3Br6

    Directory of Open Access Journals (Sweden)

    Despoina Chriti

    2015-12-01

    Full Text Available The reactivity of the bimetallic complex (Ph4P2[W2(μ-Br3Br6] ({W 2.5 W}7+, a′2e3 towards ring opening metathesis polymerization (ROMP of norbornene (NBE and some of its derivatives, as well as the mechanistically related metathesis polymerization of phenylacetylene (PA, is presented. Our results show that addition of a silver salt (AgBF4 is necessary for the activation of the ditungsten complex. Polymerization of PA proceeds smoothly in tetrahydrofuran (THF producing polyphenylacetylene (PPA in high yields. On the other hand, the ROMP of NBE and its derivatives is more efficient in CH2Cl2, providing high yields of polymers. 13C Cross Polarization Magic Angle Spinning (CPMAS spectra of insoluble polynorbornadiene (PNBD and polydicyclopentadiene (PDCPD revealed the operation of two mechanisms (metathetic and radical for cross-linking, with the metathesis pathway prevailing.

  18. Development of RCM methodology and tools for EDF nuclear power plants

    International Nuclear Information System (INIS)

    Jacquot, J.P.; Bouchet, J.L.; Despujols, A.; Dewailly, J.; Martin-Mattei, C.

    1995-01-01

    In 1990, EDF launched a Reliability-Centered Maintenance project for its nuclear plants. This 'OMF' project aims at developing methods and tools for analysis and in the first phase, applying these to one initial system (the pilot study). The results of the pilot study have confirmed the advantages of the 'OMF' analytical method: the prospects for the approach on an industrial scale are extremely promising. It should be noted that the precision of our 'OMF' analysis is not doubt superior to that common in other industrial domains (MSG/RCM analysis). The particular approach implies analysis of systems and components and, most importantly, integration of operation feedback, with a view to developing a rigorous maintenance program which can constantly be updated. In addition to the defining and implementing the method, the review of designing software aids has begun. The pilot study clearly pointed up the need for such aids in handling the necessary volume of information and assisting experts in their analysis. The EDF 'OMF' workstation (and its environment) will be used not only in preparing the 'initial' maintenance program but also in updating it during the 'living' program phase. (author)

  19. Analysis of impacts on hydrometeorological extremes in the Senegal River Basin from REMO RCM

    Energy Technology Data Exchange (ETDEWEB)

    Galiano, Sandra Garcia; Osorio, Juan Diego Giraldo [Technical Univ. of Cartagena, Dept. of Thermal Engineering and Fluids, Cartagena (Spain)

    2010-06-15

    West Africa is highly vulnerable to climate variability. The precipitation latitudinal gradient determines agricultural activities. The cultivated area of the Sahel is a densely populated region, whereas flood recession agriculture is practiced in the Senegal River Valley. The present study analyses both spatial-temporal rainfall patterns of the REMO Regional Climate Model (RCM) and observed rainfall data, focusing in particular on extreme hydro-meteorological phenomena. An analysis of simulated daily rainfall data was performed to determine the frequency and magnitude of length of dry spells, as well as the extreme rainfall events. A projected annual decrease in rainfall on horizon 2050 could be explained by two factors: the decrease in the percentage of rainy days on both west and north sides of the basin, and the decrease of precipitation amount for rainy days in the southern basin. Finally, an increase in the frequency of dry spell in the monsoon season by 2050 is projected. Such findings are significant in a framework of strategies for water resources management and planning at basin scale, in order to build adaptive capacity. (orig.)

  20. Development of RCM methodology and tools for EDF nuclear power plants

    Energy Technology Data Exchange (ETDEWEB)

    Jacquot, J.P.; Bouchet, J.L.; Despujols, A.; Dewailly, J.; Martin-Mattei, C. [Electricite de France, 78 - Chatou (France)

    1995-12-31

    In 1990, EDF launched a Reliability-Centered Maintenance project for its nuclear plants. This `OMF` project aims at developing methods and tools for analysis and in the first phase, applying these to one initial system (the pilot study). The results of the pilot study have confirmed the advantages of the `OMF` analytical method: the prospects for the approach on an industrial scale are extremely promising. It should be noted that the precision of our `OMF` analysis is not doubt superior to that common in other industrial domains (MSG/RCM analysis). The particular approach implies analysis of systems and components and, most importantly, integration of operation feedback, with a view to developing a rigorous maintenance program which can constantly be updated. In addition to the defining and implementing the method, the review of designing software aids has begun. The pilot study clearly pointed up the need for such aids in handling the necessary volume of information and assisting experts in their analysis. The EDF `OMF` workstation (and its environment) will be used not only in preparing the `initial` maintenance program but also in updating it during the `living` program phase. (author) 4 refs.

  1. Climate and climate change sensitivity to model configuration in the Canadian RCM over North America

    Energy Technology Data Exchange (ETDEWEB)

    De Elia, Ramon [Ouranos Consortium on Regional Climate and Adaptation to Climate Change, Montreal (Canada); Centre ESCER, Univ. du Quebec a Montreal (Canada); Cote, Helene [Ouranos Consortium on Regional Climate and Adaptation to Climate Change, Montreal (Canada)

    2010-06-15

    Climate simulations performed with Regional Climate Models (RCMs) have been found to show sensitivity to parameter settings. The origin, consequences and interpretations of this sensitivity are varied, but it is generally accepted that sensitivity studies are very important for a better understanding and a more cautious manipulation of RCM results. In this work we present sensitivity experiments performed on the simulated climate produced by the Canadian Regional Climate Model (CRCM). In addition to climate sensitivity to parameter variation, we analyse the impact of the sensitivity on the climate change signal simulated by the CRCM. These studies are performed on 30-year long simulated present and future seasonal climates, and we have analysed the effect of seven kinds of configuration modifications: CRCM initial conditions, lateral boundary condition (LBC), nesting update interval, driving Global Climate Model (GCM), driving GCM member, large-scale spectral nudging, CRCM version, and domain size. Results show that large changes in both the driving model and the CRCM physics seem to be the main sources of sensitivity for the simulated climate and the climate change. Their effects dominate those of configuration issues, such as the use or not of large-scale nudging, domain size, or LBC update interval. Results suggest that in most cases, differences between simulated climates for different CRCM configurations are not transferred to the estimated climate change signal: in general, these tend to cancel each other out. (orig.)

  2. Effect of Support on Metathesis of n-Decane: Drastic Improvement in Alkane Metathesis with WMe5 Linked to Silica-Alumina

    KAUST Repository

    Samantaray, Manoja

    2015-03-11

    [WMe6] (1) supported on the surface of SiO2-Al2O3(500) (2) has been extensively characterized by solid-state NMR spectroscopy, elemental analysis, and gas quantification, which clearly reveal the formation of a mixture of monopodal and bipodal species with the migration of methyl from W to Al. The supported species SiO2-Al2O3(500) (2) transformed at 120°C into two types of carbynic centers, one of which is cationic and the other neutral. These species are very efficient for the metathesis of n-decane. Comparison with already-synthesized neutral bipodal tungsten indicates that the high increase in activity is due to the cationic character of the grafted tungsten.

  3. Effect of Support on Metathesis of n-Decane: Drastic Improvement in Alkane Metathesis with WMe5 Linked to Silica-Alumina

    KAUST Repository

    Samantaray, Manoja; Dey, Raju; Abou-Hamad, Edy; Hamieh, Ali Imad Ali; Basset, Jean-Marie

    2015-01-01

    [WMe6] (1) supported on the surface of SiO2-Al2O3(500) (2) has been extensively characterized by solid-state NMR spectroscopy, elemental analysis, and gas quantification, which clearly reveal the formation of a mixture of monopodal and bipodal species with the migration of methyl from W to Al. The supported species SiO2-Al2O3(500) (2) transformed at 120°C into two types of carbynic centers, one of which is cationic and the other neutral. These species are very efficient for the metathesis of n-decane. Comparison with already-synthesized neutral bipodal tungsten indicates that the high increase in activity is due to the cationic character of the grafted tungsten.

  4. Características de los sistemas TPM y RCM en la ingeniería del mantenimiento

    OpenAIRE

    Cárcel Carrasco, Francisco Javier

    2016-01-01

    [EN] There are multiple organizational systems in industrial maintenance engineering. Total productive maintenance (TPM) and reliability centered maintenance (RCM), are the most documented and known within the technical and scientific literature in relation to the management of physical assets. In this article, are analyzed in a basic way the fundamental aspects of these two organizational systems and characteristics that underlie them that have made reference in the systems us...

  5. Simple activation by acid of latent Ru-NHC-based metathesis initiators bearing 8-quinolinolate co-ligands

    KAUST Repository

    Wappel, Julia

    2016-01-28

    A straightforward synthesis utilizing the ring-opening metathesis polymerization (ROMP) reaction is described for acid-triggered N,O-chelating ruthenium-based pre-catalysts bearing one or two 8-quinolinolate ligands. The innovative pre-catalysts were tested regarding their behavior in ROMP and especially for their use in the synthesis of poly(dicyclopentadiene) (pDCPD). Bearing either the common phosphine leaving ligand in the first and second Grubbs olefin metathesis catalysts, or the Ru–O bond cleavage for the next Hoveyda-type catalysts, this work is a step forward towards the control of polymer functionalization and living or switchable polymerizations.

  6. Synthesis and Ring-Opening Metathesis Polymerization of Second-Generation Dendronized Poly(ether Monomers Initiated by Ruthenium Carbenes

    Directory of Open Access Journals (Sweden)

    Guzmán Pablo E.

    2016-03-01

    Full Text Available The Ring-Opening Metathesis Polymerization (ROMP of second-generation dendronized monomers is described. Using the highly active and fast-initiating third-generation ruthenium complex [(H2IMes(pyr2Cl2RuCHPh], moderate to high molecular weight polymers (430-2230 kDa are efficiently synthesized with low dispersities (Ð = 1.01-1.17. This study highlights the power of the metathesis approach toward polymer synthesis in a context where monomer structure can significantly impede polymerization.

  7. 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.

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

    KAUST Repository

    Dey, Raju; Samantaray, Manoja; Callens, Emmanuel; Hamieh, Ali Imad Ali; Emwas, Abdul-Hamid M.; Abou-Hamad, Edy; Kavitake, Santosh Giridhar; Basset, Jean-Marie

    2016-01-01

    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.

  9. Simple activation by acid of latent Ru-NHC-based metathesis initiators bearing 8-quinolinolate co-ligands

    KAUST Repository

    Wappel, Julia; Fischer, Roland C; Cavallo, Luigi; Slugovc, Christian; Poater, Albert

    2016-01-01

    A straightforward synthesis utilizing the ring-opening metathesis polymerization (ROMP) reaction is described for acid-triggered N,O-chelating ruthenium-based pre-catalysts bearing one or two 8-quinolinolate ligands. The innovative pre-catalysts were tested regarding their behavior in ROMP and especially for their use in the synthesis of poly(dicyclopentadiene) (pDCPD). Bearing either the common phosphine leaving ligand in the first and second Grubbs olefin metathesis catalysts, or the Ru–O bond cleavage for the next Hoveyda-type catalysts, this work is a step forward towards the control of polymer functionalization and living or switchable polymerizations.

  10. Perancangan Sistem Pemeliharaan Menggunakan Metode Reliability Centered Maintenance (RCM Pada Pulverizer (Studi Kasus: PLTU Paiton Unit 3

    Directory of Open Access Journals (Sweden)

    RATNA BHAKTI PUSPITA SARI

    2017-03-01

    Full Text Available PLTU Paiton Unit 3 merupakan perusahaan yang bergerak di bidang produksi listrik menggunakan bahan baku batubara yang terletak di Paiton, Probolinggo. Untuk mencapai target, proses produksi dilakukan 24 jam selama 1 tahun tanpa henti. Program pemeliharaan mesin sangat penting untuk kelancaran proses produksi. Dalam rangka mencapai target tersebut dituntut adanya kelancaran batubara dari silo hingga surface burner menggunakan pulverizer. Data dari Departemen Engineering menunjukkan bahwa beberapa subsistem pulverizer sering mengalami kerusakan yang dapat menimbulkan kegagalan pada sistem tersebut. Penelitian tugas akhir ini menggunakan metode Reliability Centered Maintenance (RCM untuk menurunkan tingkat breakdown mesin dan downtime produksi. Data historis kerusakan pulverizer dianalisa. Kemudian kegagalan dari suatu komponen yang dapat menyebabkan kegagalan fungsi dari sistem diidentifikasi menggunakan metode Failure Mode and Effect Analysis (FMEA. Selanjutnya menggunakan RCM Decision Worksheet untuk mengetahui bagian dari sistem yang gagal dan perlu dilakukan tindakan perbaikan dan pencegahan berdasarkan kegagalan yang ada agar kejadian yang sama tidak terulang dan menentukan kegiatan perancang perawatan yang tepat pada setiap komponen Berdasarkan analisis data secara Reliability Centered Maintenance (RCM terdapat 12 failure mode yang terjadi pada pulverizer. 3 failure mode dapat dicegah dengan scheduled restoration task, 8 failure mode dapat dicegah dengan scheduled discard task, dan 1 failure mode dapat dicegah dengan redesign. Analisis kuantitatif menggunakan distribusi kegagalan dengan perangkat lunak Weibull++6 didapatkan MTBF grinding roller 2880,66 jam, MTBF hydraulic pump 5075,06 jam, MTBF gearbox 5381,65 jam dan MTBF coal feeder 525,17 jam.

  11. Metathesis in the generation of low-temperature gas in marine shales

    Directory of Open Access Journals (Sweden)

    Jarvie Daniel M

    2010-01-01

    Full Text Available Abstract The recent report of low-temperature catalytic gas from marine shales took on additional significance with the subsequent disclosure of natural gas and low-temperature gas at or near thermodynamic equilibrium in methane, ethane, and propane. It is important because thermal cracking, the presumed source of natural gas, cannot generate these hydrocarbons at equilibrium nor can it bring them to equilibrium over geologic time. The source of equilibrium and the source of natural gas are either the same (generation under equilibrium control or closely associated. Here we report the catalytic interconversion of hydrocarbons (metathesis as the source of equilibrium in experiments with Cretaceous Mowry shale at 100°C. Focus was on two metathetic equilibria: methane, ethane, and propane, reported earlier, Q (K = [(C1*(C3]/[(C22], and between these hydrocarbons and n-butane, Q* (K = [(C1*(n-C4]/[(C2*(C3], reported here for the first time. Two observations stand out. Initial hydrocarbon products are near equilibrium and have maximum average molecular weights (AMW. Over time, products fall from equilibrium and AMW in concert. It is consistent with metathesis splitting olefin intermediates [Cn] to smaller intermediates (fission as gas generation creates open catalytic sites ([ ]: [Cn] + [ ] → [Cn-m] + [Cm]. Fission rates increasing exponentially with olefin molecular weight could contribute to these effects. AMW would fall over time, and selective fission of [C3] and [n-C4] would draw Q and Q* from equilibrium. The results support metathesis as the source of thermodynamic equilibrium in natural gas.

  12. CRED Recording Current Meter (RCM); AMSM, TUT; Long: -170.75830, Lat: -14.37498 (WGS84); Sensor Depth: 22.00m; Data Range: 20020303-20040224.

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Data from Coral Reef Ecosystem Division (CRED), NOAA Pacific Islands Fisheries Science Center (PIFSC) Recording Current Meters (RCM) provide a time series of water...

  13. CRED Recording Current Meter (RCM); PRIA, KIN; Long: -162.35925, Lat: 06.38263 (WGS84); Sensor Depth: 7.60m; Data Range: 20020318-20040402.

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Data from Coral Reef Ecosystem Division (CRED), NOAA Pacific Islands Fisheries Science Center (PIFSC) Recording Current Meters (RCM) provide a time series of water...

  14. Cis/trans Coordination in olefin metathesis by static and molecular dynamic DFT calculations

    KAUST Repository

    Poater, Albert

    2014-05-25

    In regard to [(N-heterocyclic carbene)Ru]-based catalysts, it is still a matter of debate if the substrate binding is preferentially cis or trans to the N-heterocyclic carbene ligand. By means of static and molecular dynamic DFT calculations, a simple olefin, like ethylene, is shown to be prone to the trans binding. Bearing in mind the higher reactivity of trans isomers in olefin metathesis, this insight helps to construct small alkene substrates with increased reactivity. © 2014 Springer Science+Business Media New York.

  15. Energetics of the ruthenium-halide bond in olefin metathesis (pre)catalysts

    KAUST Repository

    Falivene, Laura; Poater, Albert; Cazin, Catherine S J; Slugovc, Christian; Cavallo, Luigi

    2013-01-01

    A DFT analysis of the strength of the Ru-halide bond in a series of typical olefin metathesis (pre)catalysts is presented. The calculated Ru-halide bond energies span the rather broad window of 25-43 kcal mol-1. This indicates that in many systems dissociation of the Ru-halide bond is possible and is actually competitive with dissociation of the labile ligand generating the 14e active species. Consequently, formation of cationic Ru species in solution should be considered as a possible event. © 2013 The Royal Society of Chemistry.

  16. Cis/trans Coordination in olefin metathesis by static and molecular dynamic DFT calculations

    KAUST Repository

    Poater, Albert; Correa, Andrea; Pump, Eva; Cavallo, Luigi

    2014-01-01

    In regard to [(N-heterocyclic carbene)Ru]-based catalysts, it is still a matter of debate if the substrate binding is preferentially cis or trans to the N-heterocyclic carbene ligand. By means of static and molecular dynamic DFT calculations, a simple olefin, like ethylene, is shown to be prone to the trans binding. Bearing in mind the higher reactivity of trans isomers in olefin metathesis, this insight helps to construct small alkene substrates with increased reactivity. © 2014 Springer Science+Business Media New York.

  17. Understanding the Hydro-metathesis Reaction of 1-decene by Using Well-defined Silica Supported W, Mo, Ta Carbene/Carbyne Complexes

    KAUST Repository

    Saidi, Aya

    2017-12-21

    Direct conversion of 1-decene to petroleum range alkanes was obtained using hydro-metathesis reaction. To understand this reaction we employed three different well-defined single site catalysts precursors; [(≡Si-O-)W(CH3)5] 1, [(≡Si-O-)Mo(≡CtBu)(CH2tBu)2] 2 and [(≡Si-O)Ta(=CHtBu)(CH2tBu)2] 3. We witnessed that in our conditions olefin metathesis/isomerization of 1-decene occurs much faster followed by reduction of the newly formed olefins rather than reduction of the 1-decene to decane, followed by metathesis of decane. We found that Mo-based catalyst favors 2+2 cycloaddition of 1-decene forming metallocarbene, followed by reduction of the newly formed olefins to alkanes. However, in the case of W and Ta-based catalysts, a rapid isomerization (migration) of the double bond followed by olefin metathesis and reduction of the newly formed olefins were observed. We witnessed that silica supported W catalyst precursor 1 and Mo catalyst precursor 2 are better catalysts for hydro-metathesis reaction with TONs of 818 and 808 than Ta-based catalyst 3 (TON of 334). This comparison of the catalysts provides us a better understanding that, if a catalyst is efficient in olefin metathesis reaction it would be a better catalyst for hydro-metathesis reaction.

  18. Use of RCM simulations to assess the impact of climate change on wind energy availability

    Energy Technology Data Exchange (ETDEWEB)

    Pryor, S.C.; Barthelmie, R.J.

    2004-08-01

    There is considerable interest in the potential impact of climate change on the feasibility and predictability of renewable energy sources including wind energy. This report presents an application and evaluation of physical (dynamical) downscaling tools for examining the impact of climate change on near-surface flow and hence wind energy density across northern Europe. It is shown that: Simulated wind fields using the Rossby Centre coupled Regional Climate Model (RCM) (RCAO) during the control period (1961-1990) exhibit reasonable and realistic features as documented in in situ observations and reanalysis data products. The differences between near-surface wind speed and direction calculated for the control run (January 1, 1961 December 30, 1990) based on boundary conditions derived from two Global Climate Models (GCM): HadAM3H and ECHAM4/OPYC3 are comparable to changes in the climate change projection period (January 1, 2071 December 30, 2100) for two emission scenarios (SRES A2 and B2). These differences are also of similar magnitude to differences between the RCAO fields in the control period and the NCEP/NCAR reanalysis data. The RCAO simulations for the 2071-2100 period indicate evidence for a small increase in the annual wind energy resource over northern Europe between the control run (January 1, 1961 December 30, 1990) and climate change projection period (January 1, 2071 December 30, 2100), and for more substantial increases in mean wind speed and energy density during the winter season (December February), but the uncertainty of these prognoses remains high. (au)

  19. Iron based superconductors and related compounds synthesized by solid state metathesis and high temperature reactions

    International Nuclear Information System (INIS)

    Frankovsky, Rainer

    2013-01-01

    The results of this thesis can be divided into three major topics, which can also be seen as different approaches of solid state chemistry to reveal interesting features of known and unknown compounds and to develop alternative synthesis routes. Firstly, known compounds with related structural motifs to the superconducting iron-arsenides were investigated regarding their structural and physical properties. In case of La 3 Pd 4 Ge 4 the influence of Fe doping on the properties was studied, whereas in the series ZrMAs (M=Ti,V) the physical properties have not yet been reported at all and were investigated for the first time. Secondly, an alternative synthesis route has been developed for the synthesis of superconducting LaFeAsO 1-x F x . This solid state metathesis reaction distinctly increased the quality of the samples compared to conventionally prepared products. Furthermore, the reaction pathway was investigated and clarified, which helps to understand the processes during high temperature solid state metathesis reactions in general. Thirdly, this alternative synthesis route was expanded to other systems and new compounds like co-substituted LaFe 1-x Mn x AsO 1-y F y were prepared and thoroughly investigated. This led to a complex study of the interplay of magnetism, electronic and structural conditions and the occurrence of superconducting properties. The investigation and understanding of such complex coherences will probably be decisive for the further understanding of the superconducting mechanism in iron based superconductors.

  20. Dynamic behaviour of tantalum hydride supported on silica or MCM-41 in the metathesis of alkanes

    KAUST Repository

    Soignier, Sophie

    2014-01-01

    The metathesis of ethane and propane catalysed by tantalum hydride supported on silica or MCM-41 was studied under static and dynamic conditions. During the reaction, the rate decreased over time, indicating deactivation of the catalyst. The evolution of the catalytic system and surface species over time was monitored by various physico-chemical methods: FTIR, 13C NMR spectroscopy, elemental analysis and chemical reactivity. A carbonaceous deposit composed of unsaturated hydrocarbyl species was observed by 13C NMR. This deposit was responsible for poisoning of the catalyst. The deactivation of the catalyst proved more severe at higher temperatures and under static rather than dynamic conditions. A partial regeneration of the catalyst could be achieved during a series of repeated runs. Mechanistically, the deconvolution of the products\\' distribution over time indicated the occurrence of hydrogenolysis in the early stages of the reaction, while pure metathesis dominated later on. The hydrogen was supplied by the dehydrogenation of hydrocarbyl surface species involved in the deactivation process. © 2014 The Royal Society of Chemistry.

  1. Developing new methods for the mono-end functionalization of living ring opening metathesis polymers.

    Science.gov (United States)

    Kilbinger, Andreas F M

    2012-01-01

    In this article we present a review of our recent results in one area of research we are involved in. All research efforts in our group focus on functional polymers and new ways of gaining higher levels of control with regard to the placement of functional groups within these polymers. Here, the living ring opening metathesis polymerization (ROMP) will be reviewed for which end-functionalization methods had been rare until very recently. Polymers carrying particular functional groups only at the chain-ends are, however, very interesting for a variety of industrial and academic applications. Polymeric surfactants and polymer-protein conjugates are two examples for the former and polymer-β-sheet-peptide conjugates one example for the latter. The functionalization of macroscopic or nanoscopic surfaces often relies on mono-end functional polymers. Complex macromolecular architectures are often constructed from macromolecules carrying exactly one functional group at their chain- end. The ring opening metathesis polymerization is particularly interesting in this context as it is one of the most functional group tolerant polymerization methods known. Additionally, high molecular weight polymers are readily accessible with this technique, a feature that living radical polymerizations often struggle to achieve. Finding new ways of functionalizing the polymer chain-end of ROMP polymers has therefore been a task long overdue. Here, we present our contribution to this area of research.

  2. Dynamic behaviour of tantalum hydride supported on silica or MCM-41 in the metathesis of alkanes

    KAUST Repository

    Soignier, Sophie; Saggio, Guillaume; Taoufik, Mostafa; Basset, Jean-Marie; Thivolle-Cazat, Jean

    2014-01-01

    The metathesis of ethane and propane catalysed by tantalum hydride supported on silica or MCM-41 was studied under static and dynamic conditions. During the reaction, the rate decreased over time, indicating deactivation of the catalyst. The evolution of the catalytic system and surface species over time was monitored by various physico-chemical methods: FTIR, 13C NMR spectroscopy, elemental analysis and chemical reactivity. A carbonaceous deposit composed of unsaturated hydrocarbyl species was observed by 13C NMR. This deposit was responsible for poisoning of the catalyst. The deactivation of the catalyst proved more severe at higher temperatures and under static rather than dynamic conditions. A partial regeneration of the catalyst could be achieved during a series of repeated runs. Mechanistically, the deconvolution of the products' distribution over time indicated the occurrence of hydrogenolysis in the early stages of the reaction, while pure metathesis dominated later on. The hydrogen was supplied by the dehydrogenation of hydrocarbyl surface species involved in the deactivation process. © 2014 The Royal Society of Chemistry.

  3. 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.

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

    KAUST Repository

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

    2017-01-01

    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.

  5. Design and synthesis of fused polycycles via Diels-Alder reaction and ring-rearrangement metathesis as key steps.

    Science.gov (United States)

    Kotha, Sambasivarao; Ravikumar, Ongolu

    2015-01-01

    Atom efficient processes such as the Diels-Alder reaction (DA) and the ring-rearrangement metathesis (RRM) have been used to design new polycycles. In this regard, ruthenium alkylidene catalysts are effective in realizing the RRM of bis-norbornene derivatives prepared by DA reaction and Grignard addition. Here, fused polycycles are assembled which are difficult to produce by conventional synthetic routes.

  6. Metathesis of 2-pentene over Mo and W supported mesoporous molecular sieves MCM-41 and SBA-15

    Czech Academy of Sciences Publication Activity Database

    Ibrahim, M. A.; Akhtar, M. N.; Čejka, Jiří; Montanari, E.; Balcar, Hynek; Kubů, Martin; Al-Khattaf, S. S.

    2017-01-01

    Roč. 53, SEP 2017 (2017), s. 119-126 ISSN 1226-086X R&D Projects: GA ČR(CZ) GAP106/12/0189 Institutional support: RVO:61388955 Keywords : metathesis * MCM-41 * SBA-15 Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 4.421, year: 2016

  7. Divergent Synthesis of Diastereomeric Sphingosines from a Chiral Aziridine

    Energy Technology Data Exchange (ETDEWEB)

    Kang, On-Yu; Shin, Mi-Ri; Kang, Han-Young [Chungbuk National University, Gongju (Korea, Republic of)

    2016-07-15

    All four stereoisomers of sphingosines were synthesized starting from a single intermediate, chiral aziridine (2), which was efficiently prepared by enzymatic desymmetrization in an enatiopure form. Aziridine (2) was converted to 3, which was used for the synthesis of 4. Both the advanced key intermediates, vinylaziridines 3 and 4, were successfully converted to threo-sphingosines 1a and 1b, respectively. Ring-closing metathesis (RCM) using the Grubbs II catalyst was the key reaction in the synthesis. Two erythro-sphingosines 1c and 1d were synthesized by the ring-expansion reactions of vinylaziridines 3 and 4, followed by RCM reactions. The successful divergent synthesis confirmed that chiral vinylaziridine 2 can be used as a key intermediate for the synthesis of sphingosine-related natural products.

  8. Comparison of different statistical downscaling methods to estimate changes in hourly extreme precipitation using RCM projections from ENSEMBLES

    DEFF Research Database (Denmark)

    Sunyer Pinya, Maria Antonia; Gregersen, Ida Bülow; Rosbjerg, Dan

    2015-01-01

    change method for extreme events, a weather generator combined with a disaggregation method and a climate analogue method. All three methods rely on different assumptions and use different outputs from the regional climate models (RCMs). The results of the three methods point towards an increase...... in extreme precipitation but the magnitude of the change varies depending on the RCM used and the spatial location. In general, a similar mean change is obtained for the three methods. This adds confidence in the results as each method uses different information from the RCMs. The results of this study...

  9. Olefin cross metathesis based de novo synthesis of a partially protected L-amicetose and a fully protected L-cinerulose derivative

    Directory of Open Access Journals (Sweden)

    Bernd Schmidt

    2014-05-01

    Full Text Available Cross metathesis of a lactate derived allylic alcohol and acrolein is the entry point to a de novo synthesis of 4-benzoate protected L-amicetose and a cinerulose derivative protected at C5 and C1.

  10. Probing Stereoselectivity in Ring-Opening Metathesis Polymerization Mediated by Cyclometalated Ruthenium-Based Catalysts: A Combined Experimental and Computational Study

    OpenAIRE

    Rosebrugh, L. E.; Ahmed, T. S.; Marx, V. M.; Hartung, J.; Liu, P.; López, J. G.; Houk, K. N.; Grubbs, R. H.

    2016-01-01

    The microstructures of polymers produced by ring-opening metathesis polymerization (ROMP) with cyclometalated Ru-carbene metathesis catalysts were investigated. A strong bias for a cis,syndiotactic microstructure with minimal head-to-tail bias was observed. In instances where trans errors were introduced, it was determined that these regions were also syndiotactic. Furthermore, hypothetical reaction intermediates and transition structures were analyzed computationally. Combined experimental a...

  11. Low-temperature synthesis of actinide tetraborides by solid-state metathesis reactions

    Science.gov (United States)

    Lupinetti, Anthony J [Los Alamos, NM; Garcia, Eduardo [Los Alamos, NM; Abney, Kent D [Los Alamos, NM

    2004-12-14

    The synthesis of actinide tetraborides including uranium tetraboride (UB.sub.4), plutonium tetraboride (PuB.sub.4) and thorium tetraboride (ThB.sub.4) by a solid-state metathesis reaction are demonstrated. The present method significantly lowers the temperature required to .ltoreq.850.degree. C. As an example, when UCl.sub.4 is reacted with an excess of MgB.sub.2, at 850.degree. C., crystalline UB.sub.4 is formed. Powder X-ray diffraction and ICP-AES data support the reduction of UCl.sub.3 as the initial step in the reaction. The UB.sub.4 product is purified by washing water and drying.

  12. Selective Metathesis of α-Olefins from Bio-Sourced Fischer–Tropsch Feeds

    KAUST Repository

    Rouen, Mathieu; Queval, Pierre; Borre, Etienne; Falivene, Laura; Poater, Albert; Berthod, Mikael; Hugues, Francois; Cavallo, Luigi; Basle, Olivier; Olivier-Bourbigou, Helene; Mauduit, Marc

    2016-01-01

    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.

  13. About the activity and selectivity of less well-known metathesis catalysts during ADMET polymerizations

    Directory of Open Access Journals (Sweden)

    Hatice Mutlu

    2010-12-01

    Full Text Available We report on the catalytic activity of commercially available Ru-indenylidene and “boomerang” complexes C1, C2 and C3 in acyclic diene metathesis (ADMET polymerization of a fully renewable α,ω-diene. A high activity of these catalysts was observed for the synthesis of the desired renewable polyesters with molecular weights of up to 17000 Da, which is considerably higher than molecular weights obtained using the same monomer with previously studied catalysts. Moreover, olefin isomerization side reactions that occur during the ADMET polymerizations were studied in detail. The isomerization reactions were investigated by degradation of the prepared polyesters via transesterification with methanol, yielding diesters. These diesters, representing the repeat units of the polyesters, were then quantified by GC-MS.

  14. 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.

  15. 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.

  16. Synthesis of amide-functionalized cellulose esters by olefin cross-metathesis.

    Science.gov (United States)

    Meng, Xiangtao; Edgar, Kevin J

    2015-11-05

    Cellulose esters with amide functionalities were synthesized by cross-metathesis (CM) reaction of terminally olefinic esters with different acrylamides, catalyzed by Hoveyda-Grubbs 2nd generation catalyst. Chelation by amides of the catalyst ruthenium center caused low conversions using conventional solvents. The effects of both solvent and structure of acrylamide on reaction conversion were investigated. While the inherent tendency of acrylamides to chelate Ru is governed by the acrylamide N-substituents, employing acetic acid as a solvent significantly improved the conversion of certain acrylamides, from 50% to up to 99%. Homogeneous hydrogenation using p-toluenesulfonyl hydrazide successfully eliminated the α,β-unsaturation of the CM products to give stable amide-functionalized cellulose esters. The amide-functionalized product showed higher Tg than its starting terminally olefinic counterpart, which may have resulted from strong hydrogen bonding interactions of the amide functional groups. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

    KAUST Repository

    Maity, Niladri; Barman, Samir; Minenkov, Yury; Ould-Chikh, Samy; Abou-Hamad, Edy; Ma, Tao; Qureshi, Ziyauddin; Cavallo, Luigi; D'Elia, Valerio; Gates, Bruce C.; Basset, Jean-Marie

    2018-01-01

    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.

  18. Striking difference between alkane and olefin metathesis using the well-defined precursor [≡Si-O-WMe5]: Indirect evidence in favour of a bifunctional catalyst W alkylidene-hydride

    KAUST Repository

    Riache, Nassima; Callens, Emmanuel; Espinas, Jeff; Dé ry, Alexandre; Samantaray, Manoja; Dey, Raju; Basset, Jean-Marie

    2015-01-01

    Metathesis of linear alkanes catalyzed by the well-defined precursor (≡Si-O-WMe5) affords a wide distribution of linear alkanes from methane up to triacontane. Olefin metathesis using the same catalyst and under the same reaction conditions gives a very striking different distribution of linear α-olefins and internal olefins. This shows that olefin and alkane metathesis processes occur via very different pathways.

  19. On the development of a coupled regional climate-vegetation model RCM-CLM-CN-DV and its validation in Tropical Africa

    Science.gov (United States)

    Wang, Guiling; Yu, Miao; Pal, Jeremy S.; Mei, Rui; Bonan, Gordon B.; Levis, Samuel; Thornton, Peter E.

    2016-01-01

    This paper presents a regional climate system model RCM-CLM-CN-DV and its validation over Tropical Africa. The model development involves the initial coupling between the ICTP regional climate model RegCM4.3.4 (RCM) and the Community Land Model version 4 (CLM4) including models of carbon-nitrogen dynamics (CN) and vegetation dynamics (DV), and further improvements of the models. Model improvements derive from the new parameterization from CLM4.5 that addresses the well documented overestimation of gross primary production (GPP), a refinement of stress deciduous phenology scheme in CN that addresses a spurious LAI fluctuation for drought-deciduous plants, and the incorporation of a survival rule into the DV model to prevent tropical broadleaf evergreens trees from growing in areas with a prolonged drought season. The impact of the modifications on model results is documented based on numerical experiments using various subcomponents of the model. The performance of the coupled model is then validated against observational data based on three configurations with increasing capacity: RCM-CLM with prescribed leaf area index and fractional coverage of different plant functional types (PFTs); RCM-CLM-CN with prescribed PFTs coverage but prognostic plant phenology; RCM-CLM-CN-DV in which both the plant phenology and PFTs coverage are simulated by the model. Results from these three models are compared against the FLUXNET up-scaled GPP and ET data, LAI and PFT coverages from remote sensing data including MODIS and GIMMS, University of Delaware precipitation and temperature data, and surface radiation data from MVIRI and SRB. Our results indicate that the models perform well in reproducing the physical climate and surface radiative budgets in the domain of interest. However, PFTs coverage is significantly underestimated by the model over arid and semi-arid regions of Tropical Africa, caused by an underestimation of LAI in these regions by the CN model that gets exacerbated

  20. Ene-yne Cross-Metathesis for the Preparation of 2,3-Diaryl-1,3-dienes

    Directory of Open Access Journals (Sweden)

    Meriem K. Abderrezak

    2017-11-01

    Full Text Available Ene-yne cross-metathesis from alkynes and ethylene is a useful method to produce substituted conjugated butadiene derivatives. If this method has been used with aliphatic alkynes, it has however never been used starting from diarylacetylenes as internal alkynes. We show that the ene-yne cross-metathesis catalyzed by the second generation Hoveyda ruthenium catalyst provides the 2,3-diarylbuta-1,3-dienes under 3 atm of ethylene at 100 °C. The scope and limitations of the reaction have been evaluated starting from unsymmetrical functionalized diarylacetylene derivatives hence leading to unsymmetrical 2,3-diarylbuta-1,3-dienes in a straightforward and environmentally acceptable manner.

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

    KAUST Repository

    Merle, Nicolas; Le Qué mé ner, Fré dé ric; Bouhoute, Yassine; Szeto, Kai C.; De Mallmann, Aimery; Barman, Samir; Samantaray, Manoja; Delevoye, Laurent; Gauvin, Ré gis M.; Taoufik, Mostafa; Basset, Jean-Marie

    2016-01-01

    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.

  2. 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.

  3. Acyclic Diene Metathesis (ADMET Polymerization for Precise Synthesis of Defect-Free Conjugated Polymers with Well-Defined Chain Ends

    Directory of Open Access Journals (Sweden)

    Tahmina Haque

    2015-03-01

    Full Text Available This accounts introduces unique characteristics by adopting the acyclic diene metathesis (ADMET polymerization for synthesis of conjugated polymers, poly(arylene vinylenes, known as promising molecular electronics. The method is more suitable than the other methods in terms of atom efficiency affording defect-free, stereo-regular (exclusive trans polymers with well-defined chain ends; the resultant polymers possess better property than those prepared by the conventional methods. The chain ends (vinyl group in the resultant polymer prepared by ruthenium-carbene catalyst(s can be modified by treating with molybdenum-alkylidene complex (olefin metathesis followed by addition of various aldehyde (Wittig type cleavage, affording the end-functionalized polymers exclusively. An introduction of initiating fragment, the other conjugated segment, and one-pot synthesis of end-functionalized block copolymers, star shape polymers can be achieved by adopting this methodology.

  4. Pharmacophore mapping in the laulimalide series: total synthesis of a vinylogue for a late-stage metathesis diversification strategy.

    Science.gov (United States)

    Wender, Paul A; Hilinski, Michael K; Skaanderup, Philip R; Soldermann, Nicolas G; Mooberry, Susan L

    2006-08-31

    An efficient synthesis of the macrocyclic core of laulimalide with a pendant vinyl group at C20 is described, allowing for late-stage introduction of various side chains through a selective and efficient cross metathesis diversification step. Representative analogues reported herein are the first to contain modifications to only the side chain dihydropyran of laulimalide and des-epoxy laulimalide. This step-economical strategy enables the rapid synthesis of new analogues using alkenes as an inexpensive, abundantly available diversification feedstock.

  5. Tandem cross enyne metathesis (CEYM)-intramolecular Diels-Alder reaction (IMDAR). An easy entry to linear bicyclic scaffolds.

    Science.gov (United States)

    Miró, Javier; Sánchez-Roselló, María; Sanz, Álvaro; Rabasa, Fernando; Del Pozo, Carlos; Fustero, Santos

    2015-01-01

    A new tandem cross enyne metathesis (CEYM)-intramolecular Diels-Alder reaction (IMDAR) has been carried out. It involves conjugated ketones, esters or amides bearing a remote olefin and aromatic alkynes as the starting materials. The overall process enables the preparation of a small family of linear bicyclic scaffolds in a very simple manner with moderate to good levels of diastereoselectivity. This methodology constitutes one of the few examples that employ olefins differently than ethylene in tandem CEYM-IMDAR protocols.

  6. Design and synthesis of fused polycycles via Diels–Alder reaction and ring-rearrangement metathesis as key steps

    Directory of Open Access Journals (Sweden)

    Sambasivarao Kotha

    2015-07-01

    Full Text Available Atom efficient processes such as the Diels–Alder reaction (DA and the ring-rearrangement metathesis (RRM have been used to design new polycycles. In this regard, ruthenium alkylidene catalysts are effective in realizing the RRM of bis-norbornene derivatives prepared by DA reaction and Grignard addition. Here, fused polycycles are assembled which are difficult to produce by conventional synthetic routes.

  7. Design and synthesis of polycyclic sulfones via Diels-Alder reaction and ring-rearrangement metathesis as key steps.

    Science.gov (United States)

    Kotha, Sambasivarao; Gunta, Rama

    2015-01-01

    Here, we describe a new and simple synthetic strategy to various polycyclic sulfones via Diels-Alder reaction and ring-rearrangement metathesis (RRM) as the key steps. This approach delivers tri- and tetracyclic sulfones with six (n = 1), seven (n = 2) or eight-membered (n = 3) fused-ring systems containing trans-ring junctions unlike the conventional all cis-ring junctions generally obtained during the RRM sequence. Interestingly the starting materials used are simple and commercially available.

  8. In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes

    KAUST Repository

    Martínez, Juan Pablo

    2016-04-10

    Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes

    KAUST Repository

    Martí nez, Juan Pablo; Vummaleti, Sai V. C.; Falivene, Laura; Nolan, Steven P.; Cavallo, Luigi; Solà , Miquel; Poater, Albert

    2016-01-01

    Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Report of the 2nd RCM on nanoscale radiation engineering of advanced materials for potential biomedical applications

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2010-07-01

    There are critical needs for advanced materials in the area of biomaterial engineering, primarily in generating biomaterials of enhanced specific functionalities, improved biocompatibility, and minimal natural rejection but with enhanced interfacial adhesion. These can be achieved by introduction of proper functionalities at the nanoscale dimensions for which, due to their characteristics, radiation techniques are uniquely suited. Accordingly, many of the IAEA Member States (MS) have interest in creating advanced materials for various health-care applications using a wide array of radiation sources and their broad expertise. In seeking new knowledge to advance the field and tackle this specific problem, to collaborate to enhance the quality of the scientific research and improve their efficiency and effectiveness, MS had requested the support of the IAEA for such collaboration. Based on these requests, and the conclusions and recommendations of the Consultant's meeting on Advanced Materials on the Nano-scale Synthesized by Radiation-Induced Processes, held on 10-14 December 2007, the present CRP was formulated and started in 2009. The first RCM was held in 30 March – 3 April 2009, in Vienna, where the work plan for both individual participants and collaborations were discussed and accepted, as reported in the Meeting Report published as IAEA Working Material (http://www-naweb.iaea.org/napc/iachem/working{sub m}aterials.html). The second RCM was held on 15-19 November 2010, Paris, France, and was attended by 17 participants (chief scientific investigators or team members) and one cost-free observer from Brazil. The participants presented their research achievements since the first RCM, centred on the main expected outputs of this CRP: a. Methodologies to prepare and characterize nanogels; nanoparticles and nanoporous membranes, as well as to synthesize and modify nanoparticle surfaces by attaching organic ligands by radiation; b. Methodologies to radiation

  11. Report of the 2nd RCM on nanoscale radiation engineering of advanced materials for potential biomedical applications

    International Nuclear Information System (INIS)

    2010-01-01

    There are critical needs for advanced materials in the area of biomaterial engineering, primarily in generating biomaterials of enhanced specific functionalities, improved biocompatibility, and minimal natural rejection but with enhanced interfacial adhesion. These can be achieved by introduction of proper functionalities at the nanoscale dimensions for which, due to their characteristics, radiation techniques are uniquely suited. Accordingly, many of the IAEA Member States (MS) have interest in creating advanced materials for various health-care applications using a wide array of radiation sources and their broad expertise. In seeking new knowledge to advance the field and tackle this specific problem, to collaborate to enhance the quality of the scientific research and improve their efficiency and effectiveness, MS had requested the support of the IAEA for such collaboration. Based on these requests, and the conclusions and recommendations of the Consultant's meeting on Advanced Materials on the Nano-scale Synthesized by Radiation-Induced Processes, held on 10-14 December 2007, the present CRP was formulated and started in 2009. The first RCM was held in 30 March – 3 April 2009, in Vienna, where the work plan for both individual participants and collaborations were discussed and accepted, as reported in the Meeting Report published as IAEA Working Material (http://www-naweb.iaea.org/napc/iachem/working_materials.html). The second RCM was held on 15-19 November 2010, Paris, France, and was attended by 17 participants (chief scientific investigators or team members) and one cost-free observer from Brazil. The participants presented their research achievements since the first RCM, centred on the main expected outputs of this CRP: a. Methodologies to prepare and characterize nanogels; nanoparticles and nanoporous membranes, as well as to synthesize and modify nanoparticle surfaces by attaching organic ligands by radiation; b. Methodologies to radiation synthesize

  12. Metodologies d’anulació en substrats heterocíclics: Reaccions de RCM i ciclacions de Heck

    OpenAIRE

    Alonso Serrano, Sandra

    2010-01-01

    [cat] La present Tesi Doctoral es situa en el context de l’estudi d’estratègies sintètiques per a la formació d’anells en l’àrea heterocíclica. En particular, s’han avaluat les possibilitats sintètiques de la combinació de dues reaccions d’eficàcia prou reconeguda per a la formació d’enllaços carboni-carboni, la reacció de RCM i la reacció intramolecular de Heck d’halurs vinílics, per a la construcció de les estructures policíliques amb pont característiques dels alcaloides ervitsina i apari...

  13. Multimodel GCM-RCM Ensemble-Based Projections of Temperature and Precipitation over West Africa for the Early 21st Century

    Directory of Open Access Journals (Sweden)

    I. Diallo

    2012-01-01

    Full Text Available Reliable climate change scenarios are critical for West Africa, whose economy relies mostly on agriculture and, in this regard, multimodel ensembles are believed to provide the most robust climate change information. Toward this end, we analyze and intercompare the performance of a set of four regional climate models (RCMs driven by two global climate models (GCMs (for a total of 4 different GCM-RCM pairs in simulating present day and future climate over West Africa. The results show that the individual RCM members as well as their ensemble employing the same driving fields exhibit different biases and show mixed results in terms of outperforming the GCM simulation of seasonal temperature and precipitation, indicating a substantial sensitivity of RCMs to regional and local processes. These biases are reduced and GCM simulations improved upon by averaging all four RCM simulations, suggesting that multi-model RCM ensembles based on different driving GCMs help to compensate systematic errors from both the nested and the driving models. This confirms the importance of the multi-model approach for improving robustness of climate change projections. Illustrative examples of such ensemble reveal that the western Sahel undergoes substantial drying in future climate projections mostly due to a decrease in peak monsoon rainfall.

  14. Diastereoselective Synthesis of Novel Heterocyclic Scaffolds through Tandem Petasis 3-Component/Intramolecular Diels-Alder and ROM-RCM Reactions

    DEFF Research Database (Denmark)

    Ishøy, Mette; Petersen, Rico; Petersen, Michael Åxman

    2017-01-01

    A high-yielding, stereoselective and extraordinarily complexity generatingPetasis 3-component/intramolecular Diels-Alderreaction has been developed. In combination with ROM-RCM, rapid access to complex sp3-rich heterocyclic scaffolds amenableto subsequent functionalization and library synthesis...

  15. Capability of the SMHI-RCA4 RCM driven by the ERA-Interim reanalysis to simulate heat waves in Argentina

    Czech Academy of Sciences Publication Activity Database

    Collazo, S.; Lhotka, Ondřej; Rusticucci, M.; Kyselý, J.

    2017-01-01

    Roč. 38, č. 1 (2017), s. 483-496 ISSN 0899-8418 Institutional support: RVO:67179843 Keywords : heat waves * RCM * maximum temperature * ENSO * Argentina * extreme events Subject RIV: DG - Athmosphere Sciences, Meteorology OBOR OECD: Environmental sciences (social aspects to be 5.7) Impact factor: 3.760, year: 2016

  16. Alteration of light-dependent gene regulation by the absence of the RCO-1/RCM-1 repressor complex in the fungus Neurospora crassa.

    Directory of Open Access Journals (Sweden)

    Carmen Ruger-Herreros

    Full Text Available The activation of transcription by light in the fungus Neurospora crassa requires the White Collar Complex (WCC, a photoreceptor and transcription factor complex. After light reception two WCCs interact and bind the promoters of light-regulated genes to activate transcription. This process is regulated by VVD, a small photoreceptor that disrupts the interaction between WCCs and leads to a reduction in transcription after long exposures to light. The N. crassa RCO-1/RCM-1 repressor complex is the homolog of the Tup1-Ssn6 repressor complex in yeast, and its absence modifies photoadaptation. We show that the absence of the RCO-1/RCM-1 repressor complex leads to several alterations in transcription that are gene-specific: an increase in the accumulation of mRNAs in the dark, a repression of transcription, and a derepression of transcription after long exposures to light. The absence of the RCO-1/RCM-1 repressor complex leads to lower VVD levels that are available for the regulation of the activity of the WCC. The reduction in the amount of VVD results in increased WCC binding to the promoters of light-regulated genes in the dark and after long exposures to light, leading to the modification of photoadaptation that has been observed in rco-1 and rcm-1 mutants. Our results show that the photoadaptation phenotype of mutants in the RCO-1/RCM-1 repressor complex is, at least in part, an indirect consequence of the reduction of vvd transcription, and the resulting modification in the regulation of transcription by the WCC.

  17. Applicability of ranked Regional Climate Models (RCM) to assess the impact of climate change on Ganges: A case study.

    Science.gov (United States)

    Anand, Jatin; Devak, Manjula; Gosain, Ashvani Kumar; Khosa, Rakesh; Dhanya, Ct

    2017-04-01

    The negative impact of climate change is felt over wide range of spatial scales, ranging from small basins to large watershed area, which can possibly outweighs the benefits of natural water system. General Circulation Models (GCMs) has been widely used as an input to a hydrological models (HMs), to simulate different hydrological components of a river basin. However, the coarser scale of GCMs and spatio-temporal biases, restricted its use at finer resolution. If downscaled, adds one more level of uncertainty i.e., downscaling uncertainty together with model and scenario uncertainty. The outputs computed from Regional Climate Models (RCM) may aid the uncertainties arising from GCMs, as the RCMs are the miniatures of GCMs. However, the RCMs do have some inherent systematic biases, hence bias correction is a prerequisite process before it is fed to HMs. RCMs, together with the input from GCMs at later boundaries also takes topography of the area into account. Hence, RCMs need to be ranked a priori. In this study, impact of climate change on the Ganga basin, India, is assessed using the ranked RCMs. Firstly, bias correction of 14 RCM models are done using Quantile-Quantile mapping and Equidistant cumulative distribution method, for historic (1990-2004) and future scenario (2021-2100), respectively. The runoff simulations from Soil Water Assessment Tool (SWAT), for historic scenario is used for ranking of RCMs. Entropy and PROMETHEE-2 method is employed to rank the RCMs based on five performance indicators namely, Nash-Sutcliffe efficiency (NSE), coefficient of determination (R2), normalised root mean square error (NRMSE), absolute normalised mean bias error (ANMBE) and average absolute relative error (AARE). The results illustrated that each of the performance indicators behaves differently for different RCMs. RCA 4 (CNRM-CERFACS) is found as the best model with the highest value of  (0.85), followed by RCA4 (MIROC) and RCA4 (ICHEC) with  values of 0.80 and 0

  18. Simple addition of silica to an alkane solution of Wilkinson WMe6 or Schrock W alkylidyne complex give active complex for saturated and unsaturated hydrocarbons metathesis

    KAUST Repository

    Callens, Emmanuel

    2015-08-24

    Addition of PDA silica to a solution of the Wilkinson WMe6 as well as the Schrock W neopentilidyne tris neopentyl complex catalyzes linear or cyclic alkanes to produce respectively a distribution of linear alkanes from methane up to triacontane or a mixture of cyclic and macrocyclic hydrocarbons. This single catalytic system transforms also linear α-olefins into higher and lower homologues via isomerization/metathesis mechanism (ISOMET). This complex is also efficient towards functionalized olefins. Unsaturated fatty acid esters (FAEs) are converted into diesters corresponding to self-metathesis products.

  19. Effect of support on hydro-metathesis of propene: A comparative study of W(CH 3 ) 6 anchored to silica vs. silica-alumina

    KAUST Repository

    Tretiakov, Mykyta

    2018-03-27

    Hydro-metathesis of propene was carried out by using well-defined W(CH3)6 supported on silica and silica-alumina. It was observed that W(CH3)6 supported silica-alumina catalyst is much better (TON 4577) than the silica supported catalyst (TON 2104). We demonstrated that the present catalysts are much better than the previously reported (tantalum hydride/KCC-1, TON 786) catalyst. For the first time, we observed the formation of n-decane from propene, which enables us to think of using cheaper raw materials and converting them to petroleum range alkanes using hydro-metathesis reaction.

  20. 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

  1. Biofuel by isomerizing metathesis of rapeseed oil esters with (bio)ethylene for use in contemporary diesel engines.

    Science.gov (United States)

    Pfister, Kai F; Baader, Sabrina; Baader, Mathias; Berndt, Silvia; Goossen, Lukas J

    2017-06-01

    Rapeseed oil methyl ester (RME) and (bio)ethylene are converted into biofuel with an evenly rising boiling point curve, which fulfills the strict boiling specifications prescribed by the fuel standard EN 590 for modern (petro)diesel engines. Catalyzed by a Pd/Ru system, RME undergoes isomerizing metathesis in a stream of ethylene gas, leading to a defined olefin, monoester, and diester blend. This innovative refining concept requires negligible energy input (60°C) and no solvents and does not produce waste. It demonstrates that the pressing challenge of increasing the fraction of renewables in engine fuel may be addressed purely chemically rather than by motor engineering.

  2. Tandem cross enyne metathesis (CEYM–intramolecular Diels–Alder reaction (IMDAR. An easy entry to linear bicyclic scaffolds

    Directory of Open Access Journals (Sweden)

    Javier Miró

    2015-08-01

    Full Text Available A new tandem cross enyne metathesis (CEYM–intramolecular Diels–Alder reaction (IMDAR has been carried out. It involves conjugated ketones, esters or amides bearing a remote olefin and aromatic alkynes as the starting materials. The overall process enables the preparation of a small family of linear bicyclic scaffolds in a very simple manner with moderate to good levels of diastereoselectivity. This methodology constitutes one of the few examples that employ olefins differently than ethylene in tandem CEYM–IMDAR protocols.

  3. Truncated borrelidin analogues: synthesis by sequential cross metathesis/olefination for the southern fragment and biological evaluation.

    Science.gov (United States)

    Gündemir-Durmaz, Tülay; Schmid, Fabian; El Baz, Yana; Häusser, Annette; Schneider, Carmen; Bilitewski, Ursula; Rauhut, Guntram; Garnier, Delphine; Baro, Angelika; Laschat, Sabine

    2016-09-21

    The construction of novel borrelidin analogues is reported in which the northern fragment is truncated to a simple hydroxyundecanecarboxylate and the original cyclopentanecarboxylic acid in the southern fragment is replaced with different six-membered rings. The required precursors were prepared by cross metathesis of the appropriate carbocycle-based homoallylic alcohol with crotonaldehyde followed by HWE olefination of the resulting enal with bromocyanophosphonate. The key aldehyde for intramolecular cross coupling was accessible by oxidation of the hydroxy group of the linked undecanecarboxylate unit. Grignard mediated macrocyclization finally yielded the borrelidin related products. The investigation is complemented by SAR studies and quantum-chemical calculations.

  4. Cycloalkyl-based unsymmetrical unsaturated (U2)-NHC ligands: Flexibility and dissymmetry in ruthenium-catalysed olefin metathesis

    KAUST Repository

    Rouen, Mathieu

    2014-01-01

    Air-stable Ru-indenylidene and Hoveyda-type complexes bearing new unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands combining a mesityl unit and a flexible cycloalkyl moiety as N-substituents were synthesised. Structural features, chemical stabilities and catalytic profiles in olefin metathesis of this new library of cycloalkyl-based U2-NHC Ru complexes were studied and compared with their unsymmetrical saturated NHC-Ru homologues as well as a set of commercially available Ru-catalysts bearing either symmetrical SIMes or IMes NHC ligands. © 2014 the Partner Organisations.

  5. Cyclooctane metathesis catalyzed by silica-supported tungsten pentamethyl [(ΞSiO)W(Me)5]: Distribution of macrocyclic alkanes

    KAUST Repository

    Riache, Nassima

    2014-10-03

    Metathesis of cyclic alkanes catalyzed by the new surface complex [(ΞSiO)W(Me)5] affords a wide distribution of cyclic and macrocyclic alkanes. The major products with the formula CnH2n are the result of either a ring contraction or ring expansion of cyclooctane leading to lower unsubstituted cyclic alkanes (5≤n≤7) and to an unprecedented distribution of unsubstituted macrocyclic alkanes (12≤n≤40), respectively, identified by GC/MS and by NMR spectroscopies.

  6. Non-aqueous metathesis as a general approach to prepare nanodispersed materials: Case study of scheelites

    International Nuclear Information System (INIS)

    Afanasiev, Pavel

    2015-01-01

    A general approach to the preparation of inorganic nanoparticles is proposed, using metathesis of precursor salts in non-aqueous liquids. Nanoparticles of scheelites AMO 4 (A=Ba, Sr, Ca; M=Mo, W), were obtained with a quantitative yield. Precipitations in formamide, N-methylformamide, propylene carbonate, DMSO and polyols often provide narrow particle size distributions. Advantageous morphology was explained by strong ionic association in non-aqueous solvents, leading to slow nucleation and negligible Ostwald ripening. Mean particle size below 10 nm and high specific surface areas were obtained for several Ca(Sr)Mo(W)O 4 materials, making them promising for applications as adsorbents or catalysts. Zeta-potential of scheelites in aqueous suspensions showed negative values in a wide range of pH. Systematic study of optical properties demonstrated variation of optical gap in the sequences W>Mo and Ba>Sr>Ca. The observed trends were reproduced by DFT calculations. No quantum confinement effect was observed for small particles, though the surface states induce low-energy features in the optical spectra. - Graphical abstract: Scheelites AMO 4 (A=Ca, Sr, Ba; M=Mo, W) were prepared in various non-aqueous liquids with high specific surface areas and narrow size distributions. The optical gap of scheelites changes in the series Ca

  7. In situ crosslinking of surface-initiated ring opening metathesis polymerization of polynorbornene for improved stability.

    Science.gov (United States)

    Fursule, Ishan A; Abtahi, Ashkan; Watkins, Charles B; Graham, Kenneth R; Berron, Brad J

    2018-01-15

    In situ crosslinking is expected to increase the solvent stability of coatings formed by surface-initiated ring opening metathesis polymerization (SI ROMP). Solvent-associated degradation limits the utility of SI ROMP coatings. SI ROMP coatings have a unique capacity for post-functionalization through reaction of the unsaturated site on the polymer backbone. Any post-reaction scheme which requires a liquid solvent has the potential to degrade the coating and lower the thickness of the resulting film. We designed a macromolecular crosslinking group based on PEG dinorbornene. The PEG length is tailored to the expected mean chain to chain distance during surface-initiated polymerization. This crosslinking macromer is randomly copolymerized with norbornene through SI ROMP on a gold coated substrate. The solvent stability of polynorbornene coatings with and without PEG dinorbornene is quantitatively determined, and the mechanism of degradation is further supported through XPS and AFM analyses. The addition of the 0.25mol% PEG dinorbornene significantly increases the solvent stability of the SI ROMP coatings. The crosslinker presence in the more stable films is supported with observable PEG absorbances by FTIR and an increase in contact angle hysteresis when compared to non-crosslinked coatings. The oxidation of the SI ROMP coatings is supported by the observation of carbonyl oxygen in the polynorbornene coatings. The rapid loss of the non-crosslinked SI ROMP coating corresponds to nanoscale pitting across the surface and micron-scale regions of widespread film loss. The crosslinked coatings have uniform nanoscale pitting, but the crosslinked films show no evidence of micron-scale film damage. In all, the incorporation of minimal crosslinking content is a simple strategy for improving the solvent stability of SI ROMP coatings. Copyright © 2017 Elsevier Inc. All rights reserved.

  8. The Selection Method of RCM in the Primary Cooling System of RSG GA. Siwabessy Related to Functions as the Primary Cooling Reactor RSG GA. Siwabessy

    International Nuclear Information System (INIS)

    Mohammad Tahril Azis; Salman Suprawhardana, M.; Teguh Pudji Purwanto

    2010-01-01

    Reactor RSG GA. Siwabessy to ensure the temperature inside the reactor core and reflectors within the limits of allowable operations during reactor operation. The primary cooling system components must refer to the thermal power reactors and to minimize failure probability of components to operate the reactor in safe and secure. The RCM Method Development (Reliability Centered Maintenance) with a web-based Free Open Source Software (FOSS)/GPL (General Public License), will assist the maintenance support information system that can work in the intranet / internet. Free Open Source Software (FOSS) is software that can provide assurance to the user to perform the development, sharing and make changes if necessary, especially users feel confident that the software actually legal and free (free software). The RCM method recommends maintenance types of 52 task selection to be applied in the primary cooling system with details time directed (td) 35% (18 tasks), condition directed (cd) 63% (33 tasks) and 1% failure finding (1 task). (author)

  9. Capability of the SMHI-RCA4 RCM driven by the ERA-Interim reanalysis to simulate heat waves in Argentina

    Czech Academy of Sciences Publication Activity Database

    Collazo, S.; Lhotka, Ondřej; Rusticucci, M.; Kyselý, Jan

    2018-01-01

    Roč. 38, č. 1 (2018), s. 483-496 ISSN 0899-8418 R&D Projects: GA MŠk 7AMB15AR001; GA ČR(CZ) GA16-22000S Institutional support: RVO:68378289 Keywords : Argentina * ENSO * extreme events * heat waves * maximum temperature * RCM Subject RIV: DG - Athmosphere Sciences, Meteorology OBOR OECD: Meteorology and atmospheric sciences Impact factor: 3.760, year: 2016 http://onlinelibrary.wiley.com/doi/10.1002/joc.5190/full

  10. The fifth research coordination meeting (RCM) on 'Updated codes and methods to reduce the calculational uncertainties of liquid metal fast reactors reactivity effects'. Working material

    International Nuclear Information System (INIS)

    2004-01-01

    The general objective of the CRP is to validate, verify and improve methodologies and computer codes used for the calculation of reactivity coefficients in fast reactors aiming at enhancing the utilization of plutonium and minor actinides. The objectives of the fifth RCM were: to review the progress achieved since the 4th RCM; to review and finalize the draft synthesis report on BN-600 MOX Fueled Core Benchmark Analysis (Phase 4); to compare the results of Phase 5 (BFS Benchmark Analysis); to agree on the work scope of Phase 6 (BN-Full MOX Minor Actinide Core Benchmark); to discuss the preparation of the final report. In this context, review and related discussions were made on the following items: summary review of Actions and results since the 4th RCM; finalization of the draft synthesis report on BN-600 full MOX-fueled core benchmark analysis (Phase 4); presentation of individual results for Phase 5 by Member States; preliminary inter-comparison analysis of the results for Phase 5; definition of the benchmark model and work scope to be performed for Phase 6; details of the work scope and future CRP timetable for preparing a final report

  11. Access to unusual polycyclic spiro-enones from 2,2'-bis(allyloxy)-1,1'-binaphthyls using Grubbs' catalysts: an unprecedented one-pot RCM/Claisen sequence.

    Science.gov (United States)

    Piedra, Estefanía; Francos, Javier; Nebra, Noel; Suárez, Francisco J; Díez, Josefina; Cadierno, Victorio

    2011-07-21

    Treatment of 2,2'-bis(allyloxy)-1,1'-binaphthyls with the first-generation Grubbs' carbene under MW-irradiation results in the formation of new polycyclic spiro-enones through an unprecedented RCM/Claisen sequence.

  12. Understanding the Hydro-metathesis Reaction of 1-decene by Using Well-defined Silica Supported W, Mo, Ta Carbene/Carbyne Complexes

    KAUST Repository

    Saidi, Aya; Samantaray, Manoja; Tretiakov, Mykyta; Kavitake, Santosh Giridhar; Basset, Jean-Marie

    2017-01-01

    Direct conversion of 1-decene to petroleum range alkanes was obtained using hydro-metathesis reaction. To understand this reaction we employed three different well-defined single site catalysts precursors; [(≡Si-O-)W(CH3)5] 1, [(≡Si-O-)Mo(≡CtBu)(CH2

  13. Effect of support on hydro-metathesis of propene: A comparative study of W(CH 3 ) 6 anchored to silica vs. silica-alumina

    KAUST Repository

    Tretiakov, Mykyta; Samantaray, Manoja; Saidi, Aya; Basset, Jean-Marie

    2018-01-01

    Hydro-metathesis of propene was carried out by using well-defined W(CH3)6 supported on silica and silica-alumina. It was observed that W(CH3)6 supported silica-alumina catalyst is much better (TON 4577) than the silica supported catalyst (TON 2104

  14. Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane

    KAUST Repository

    Samantaray, Manoja; Kavitake, Santosh Giridhar; Morlanes, Natalia Sanchez; Abou-Hamad, Edy; Hamieh, Ali Imad Ali; Dey, Raju; Basset, Jean-Marie

    2017-01-01

    Two compatible organometallic complexes, W(Me)(6) (1) and TiNp4 (2), were successively anchored on a highly dehydroxylated single silica support (SiO2-700) to synthesize the well-defined bimetallic precatalyst [(equivalent to Si-O-)W(Me)(5)(equivalent to Si-O-)Ti(Np)(3)] (4). Precatalyst 4 was characterized at the molecular level using advanced surface organometallic chemistry (SOMC) characterization techniques. The strong autocorrelation observed between methyl of W and Ti in H-1-H-1 multiple-quantum NMR spectra demonstrates that W and Ti species are in close proximity to each other. The bimetallic precatalyst 4, with a turnover number (TON) of 9784, proved to be significantly more efficient than the silica-supported monometallic catalyst [(equivalent to Si-O-)W(Me)(5)] (3), with a TON of 98, for propane metathesis at 150 degrees C in a flow reactor. The dramatic improvement in the activity signifies the cooperativity between Ti and W and indicates that the key step of alkane metathesis (C-H bond activation followed by beta-H elimination) occurs on Ti, followed by olefin metathesis, which occurs on W. We have demonstrated the influence and importance of proximity of Ti to W for achieving such a significantly high activity. This is the first report demonstrating the considerably high activity (TON = 9784) in propane metathesis at moderate temperature (150 degrees C) using a well-defined bimetallic system prepared via the SOMC approach.

  15. Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane

    KAUST Repository

    Samantaray, Manoja

    2017-02-10

    Two compatible organometallic complexes, W(Me)(6) (1) and TiNp4 (2), were successively anchored on a highly dehydroxylated single silica support (SiO2-700) to synthesize the well-defined bimetallic precatalyst [(equivalent to Si-O-)W(Me)(5)(equivalent to Si-O-)Ti(Np)(3)] (4). Precatalyst 4 was characterized at the molecular level using advanced surface organometallic chemistry (SOMC) characterization techniques. The strong autocorrelation observed between methyl of W and Ti in H-1-H-1 multiple-quantum NMR spectra demonstrates that W and Ti species are in close proximity to each other. The bimetallic precatalyst 4, with a turnover number (TON) of 9784, proved to be significantly more efficient than the silica-supported monometallic catalyst [(equivalent to Si-O-)W(Me)(5)] (3), with a TON of 98, for propane metathesis at 150 degrees C in a flow reactor. The dramatic improvement in the activity signifies the cooperativity between Ti and W and indicates that the key step of alkane metathesis (C-H bond activation followed by beta-H elimination) occurs on Ti, followed by olefin metathesis, which occurs on W. We have demonstrated the influence and importance of proximity of Ti to W for achieving such a significantly high activity. This is the first report demonstrating the considerably high activity (TON = 9784) in propane metathesis at moderate temperature (150 degrees C) using a well-defined bimetallic system prepared via the SOMC approach.

  16. Deep learning based classification of morphological patterns in RCM to guide noninvasive diagnosis of melanocytic lesions (Conference Presentation)

    Science.gov (United States)

    Kose, Kivanc; Bozkurt, Alican; Ariafar, Setareh; Alessi-Fox, Christi A.; Gill, Melissa; Dy, Jennifer G.; Brooks, Dana H.; Rajadhyaksha, Milind

    2017-02-01

    In this study we present a deep learning based classification algorithm for discriminating morphological patterns that appear in RCM mosaics of melanocytic lesions collected at the dermal epidermal junction (DEJ). These patterns are classified into 6 distinct types in the literature: background, meshwork, ring, clod, mixed, and aspecific. Clinicians typically identify these morphological patterns by examination of their textural appearance at 10X magnification. To mimic this process we divided mosaics into smaller regions, which we call tiles, and classify each tile in a deep learning framework. We used previously acquired DEJ mosaics of lesions deemed clinically suspicious, from 20 different patients, which were then labelled according to those 6 types by 2 expert users. We tried three different approaches for classification, all starting with a publicly available convolutional neural network (CNN) trained on natural image, consisting of a series of convolutional layers followed by a series of fully connected layers: (1) We fine-tuned this network using training data from the dataset. (2) Instead, we added an additional fully connected layer before the output layer network and then re-trained only last two layers, (3) We used only the CNN convolutional layers as a feature extractor, encoded the features using a bag of words model, and trained a support vector machine (SVM) classifier. Sensitivity and specificity were generally comparable across the three methods, and in the same ranges as our previous work using SURF features with SVM . Approach (3) was less computationally intensive to train but more sensitive to unbalanced representation of the 6 classes in the training data. However we expect CNN performance to improve as we add more training data because both the features and the classifier are learned jointly from the data. *First two authors share first authorship.

  17. Study of ethylene/2-butene cross-metathesis over W-H/Al2O 3 for propylene production: Effect of the temperature and reactant ratios on the productivity and deactivation

    KAUST Repository

    Mazoyer, Etienne; Szeto, Kaï Chung; Merle, Nicolas; Norsic, Sé bastien; Boyron, Olivier; Basset, Jean-Marie; Taoufik, Mostafa; Nicholas, Christopher P.

    2013-01-01

    A highly active and selective catalyst based on supported tungsten hydride for the cross-metathesis between ethylene and 2-butenes yielding propylene has been investigated at low pressure with various temperatures and feed ratios. At low temperature

  18. Microwave-Assisted Syntheses of Bioactive Seven-Membered, Macro-Sized Heterocycles and Their Fused Derivatives

    Directory of Open Access Journals (Sweden)

    Mohsine Driowya

    2016-08-01

    Full Text Available This review describes the recent advances in the microwave-assisted synthesis of 7-membered and larger heterocyclic compounds. Several types of reaction for the cyclization step are discussed: Ring Closing Metathesis (RCM, Heck and Sonogashira reactions, Suzuki-Miyaura cross-coupling, dipolar cycloadditions, multi-component reactions (Ugi, Passerini, etc. Green syntheses and solvent-free procedures have been introduced whenever possible. The syntheses discussed herein have been selected to illustrate the huge potential of microwave in the synthesis of highly functionalized molecules with potential therapeutic applications, in high yields, enhanced reaction rates and increased chemoselectivity, compared to conventional methods. More than 100 references from the recent literature are listed in this review.

  19. Poisoning Experiments Aimed at Discriminating Active and Less-Active Sites of Silica-Supported Tantalum Hydride for Alkane Metathesis

    KAUST Repository

    Saggio, Guillaume

    2010-10-04

    Only 50% of the silica-supported tantalum hydride sites are active in the metathesis of propane. Indeed, more than 45% of the tantalum hydride can be eliminated by a selective oxygen poisoning of inactive sites with no significant decrease in the global turnover. Conversely, cyclopentane induces no such selective poisoning. Hence, the active tantalum hydride sites that show greater resistance to oxygen poisoning correspond to the νTa-H bands of higher wavenumbers, particularly that at 1860cm-1. These active tantalum hydride sites should correspond to tris- or monohydride species relatively far from silica surface oxygen atoms. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Function-oriented synthesis: biological evaluation of laulimalide analogues derived from a last step cross metathesis diversification strategy.

    Science.gov (United States)

    Mooberry, Susan L; Hilinski, Michael K; Clark, Erin A; Wender, Paul A

    2008-01-01

    Laulimalide is a potent microtubule stabilizing agent and a promising anticancer therapeutic lead. The identification of stable, efficacious and accessible analogues is critical to clinically exploiting this novel lead. To determine which structural features of laulimalide are required for beneficial function and thus for accessing superior clinical candidates, a series of side chain analogues were prepared through a last step cross metathesis diversification strategy and their biological activities were evaluated. Five analogues, differing in potency from 233 nM to 7.9 muM, effectively inhibit cancer cell proliferation. Like laulimalide, they retain activity against multidrug resistant cells, stabilize microtubules and cause the formation of aberrant mitotic spindles, mitotic accumulation, Bcl-2 phosphorylation and initiation of apoptosis. Structural modifications in the C 23-C 27 dihydropyran side chain can be made without changing the overall mechanism of action, but it is clear that this subunit has more than a bystander role.

  1. 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.

  2. Rapid synthesis of graphitic carbon nitride powders by metathesis reaction between CaCN2 and C2Cl6

    International Nuclear Information System (INIS)

    Pang Linlin; Bi Jianqiang; Bai Yujun; Qi Yongxin; Zhu Huiling; Wang Chengguo; Wu Jiwei; Lu Chengwei

    2008-01-01

    Carbon nitride powders were rapidly synthesized at low temperature via the chemical metathesis reaction between CaCN 2 and C 2 Cl 6 . X-ray diffraction results confirm the formation of crystalline graphitic carbon nitride. Besides the dominant morphology of nanoparticles, flakes, nanorods, hollow and solid spheres can be observed by transmission electron microscopy. The absorption peaks of C-N, C=N and s-triazine rings, as well as the absence of C≡N peak in the infrared spectra, further verify the formation of graphite-like sp 2 -bonded structure with planar networks. Elemental analysis gives an atomic ratio of N/C around 0.3. X-ray photoelectron spectra exhibit the existence of chemical bonding between C and N

  3. Moving from Classical Ru-NHC to Neutral or Charged Rh-NHC Based Catalysts in Olefin Metathesis

    Directory of Open Access Journals (Sweden)

    Albert Poater

    2016-01-01

    Full Text Available Considering the versatility of oxidation states of rhodium together with the successful background of ruthenium-N-heterocyclic carbene based catalysts in olefin metathesis, it is envisaged the exchange of the ruthenium of the latter catalysts by rhodium, bearing an open-shell neutral rhodium center, or a +1 charged one. In the framework of in silico experiments, density functional theory (DFT calculations have been used to plot the first catalytic cycle that as a first step includes the release of the phosphine. DFT is, in this case, the tool that allows the discovery of the less endergonic reaction profile from the precatalytic species for the neutral catalyst with respect to the corresponding ruthenium one; increasing the endergonic character when dealing with the charged system.

  4. Mechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis

    KAUST Repository

    Pump, Eva

    2015-06-30

    The intramolecular allenylidene RuCl2(PR3)2(C═C═CPh2) to indenylidene RuCl2(PR3)2(Ind) rearrangement that occurs during the synthesis of Ru-based precatalysts for olefin metathesis is presented. In the absence of acid, the ring closure via C–H activation was shown to be unfavored for energy barriers up to 70 kcal/mol. Thus, it turned out to be HCl (or other acid) that plays a crucial role during formation of the indenylidene, as the upper energy barrier decreases to a reasonable 35 kcal/mol. Moreover, we proved computationally that depending on the nature of the phosphine the intramolecular rearrangement is either facilitated (PPh3) or slightly hampered (PCy3), which is in line with experimental results.

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

    KAUST Repository

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

    2016-01-01

    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. Mechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis

    KAUST Repository

    Pump, Eva; Slugovc, Christian; Cavallo, Luigi; Poater, Albert

    2015-01-01

    The intramolecular allenylidene RuCl2(PR3)2(C═C═CPh2) to indenylidene RuCl2(PR3)2(Ind) rearrangement that occurs during the synthesis of Ru-based precatalysts for olefin metathesis is presented. In the absence of acid, the ring closure via C–H activation was shown to be unfavored for energy barriers up to 70 kcal/mol. Thus, it turned out to be HCl (or other acid) that plays a crucial role during formation of the indenylidene, as the upper energy barrier decreases to a reasonable 35 kcal/mol. Moreover, we proved computationally that depending on the nature of the phosphine the intramolecular rearrangement is either facilitated (PPh3) or slightly hampered (PCy3), which is in line with experimental results.

  7. Report of the 1st RCM on ''Nanoscale radiation engineering of advanced materials for potential biomedical applications''. Working document

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2009-07-01

    There are critical needs for advanced materials in the area of biomaterial engineering, primarily in generating biomaterials of enhanced specific functionalities, improved biocompatibility, and minimal natural rejection but with enhanced interfacial adhesion. These can be achieved by introduction of proper functionalities at the nanoscale dimensions and radiation techniques are uniquely suited for such a task, due to their favorable characteristics, and in most cases, not possible by other methods of synthesis. Accordingly, many of the developing and developed Member States have an interest in creating advanced materials for various health-care applications using a wide array of radiation sources and their broad expertise. The proposal for this CRP was formulated based on the requests and information received from the member states and the conclusions and recommendations of the Consultant’s meeting on “Advanced Materials on the Nano-scale Synthesized by Radiation-Induced Processes”, held on 10-14 December 2007, in Vienna. Based on these conclusions, this CRP aims to support MS to develop methodologies for the use of radiation in the synthesis, modification, and characterization of nanomaterials - nanogels, nanoparticles, nanovehicles, nanoporous membranes, and surfaces with enhanced biocompatibility for potential biomedical applications, such as cell-sheet engineering and artificial tissue construction; diagnostics and imaging; and drug delivery. Additionally, this CRP facilitates networking between radiation technologists and biomedical scientists for the development of such applications. The CRP generated a huge interest, but due to funding constrains, many good proposals had to be rejected. The first RCM of the CRP was convened in Vienna on 30 March - 03 April 2009. It was attended by 14 representatives and two observers. The participants presented and discussed the status of the field, the needs for further research, and various application possibilities

  8. Report of the 1st RCM on ''Nanoscale radiation engineering of advanced materials for potential biomedical applications''. Working document

    International Nuclear Information System (INIS)

    2009-01-01

    There are critical needs for advanced materials in the area of biomaterial engineering, primarily in generating biomaterials of enhanced specific functionalities, improved biocompatibility, and minimal natural rejection but with enhanced interfacial adhesion. These can be achieved by introduction of proper functionalities at the nanoscale dimensions and radiation techniques are uniquely suited for such a task, due to their favorable characteristics, and in most cases, not possible by other methods of synthesis. Accordingly, many of the developing and developed Member States have an interest in creating advanced materials for various health-care applications using a wide array of radiation sources and their broad expertise. The proposal for this CRP was formulated based on the requests and information received from the member states and the conclusions and recommendations of the Consultant’s meeting on “Advanced Materials on the Nano-scale Synthesized by Radiation-Induced Processes”, held on 10-14 December 2007, in Vienna. Based on these conclusions, this CRP aims to support MS to develop methodologies for the use of radiation in the synthesis, modification, and characterization of nanomaterials - nanogels, nanoparticles, nanovehicles, nanoporous membranes, and surfaces with enhanced biocompatibility for potential biomedical applications, such as cell-sheet engineering and artificial tissue construction; diagnostics and imaging; and drug delivery. Additionally, this CRP facilitates networking between radiation technologists and biomedical scientists for the development of such applications. The CRP generated a huge interest, but due to funding constrains, many good proposals had to be rejected. The first RCM of the CRP was convened in Vienna on 30 March - 03 April 2009. It was attended by 14 representatives and two observers. The participants presented and discussed the status of the field, the needs for further research, and various application possibilities

  9. Effect of ethanol/water blends addition on diesel fuel combustion in RCM and DI diesel engine

    International Nuclear Information System (INIS)

    Nour, Mohamed; Kosaka, Hidenori; Sato, Susumu; Bady, Mahmoud; Abdel-Rahman, Ali K.; Uchida, Kenta

    2017-01-01

    Highlights: • Effect of ethanol/water addition on diesel combustion studied using optical diagnostics. • The addition of water to ethanol improves engine combustion and soot oxidation. • Ethanol/water injection into exhaust manifold eliminates their endothermic effect. • Ethanol with high water content is recommended for better engine combustion. • Soot concentration reduced by 50% and NO x emissions reduced by 88%. - Abstract: The effect of ethanol/water blends addition on diesel fuel combustion and emissions is investigated experimentally in this study using optical diagnostics. Basic study is performed using rapid compression machine (RCM) under CI conditions. The tested ethanol energy fractions varied in the range of 10–40% of the total added fuel energy, while water volume ratios varied in the range of 10–40% of the injected ethanol. Ethanol and water were evaporated before entering the combustion chamber to eliminate their endothermic effect. Results reveal that addition of ethanol/water blends to diesel fuel results in longer ignition delay and promote the apparent heat release rate (AHRR) at the premixed combustion phase compared to absolute ethanol addition. Additionally, soot and NO x emissions are reduced with ethanol/water addition compared to absolute ethanol addition and neat diesel combustion. The basic study is then extended to investigate the effect ethanol/water blends addition on diesel fuel combustion using single cylinder diesel engine. Waste heat in exhaust manifold is utilized to vaporize ethanol/water blends before combustion. Results reveal that ethanol/water blends injection leads to increase in peak cylinder pressure, indicated mean effective pressure (IMEP), and AHRR at premixed combustion phase. Additionally, the ignition delay increased with ethanol/water addition. NO x emission is decreased up to 88% along with a reduction in soot by 50%. The lower ethanol to water volume ratios show better combustion efficiency, IMEP

  10. Regulation of glycogen metabolism by the CRE-1, RCO-1 and RCM-1 proteins in Neurospora crassa. The role of CRE-1 as the central transcriptional regulator.

    Science.gov (United States)

    Cupertino, Fernanda Barbosa; Virgilio, Stela; Freitas, Fernanda Zanolli; Candido, Thiago de Souza; Bertolini, Maria Célia

    2015-04-01

    The transcription factor CreA/Mig1/CRE-1 is a repressor protein that regulates the use of alternative carbon sources via a mechanism known as Carbon Catabolite Repression (CCR). In Saccharomyces cerevisiae, Mig1 recruits the complex Ssn6-Tup1, the Neurospora crassa RCM-1 and RCO-1 orthologous proteins, respectively, to bind to promoters of glucose-repressible genes. We have been studying the regulation of glycogen metabolism in N. crassa and the identification of the RCO-1 corepressor as a regulator led us to investigate the regulatory role of CRE-1 in this process. Glycogen content is misregulated in the rco-1(KO), rcm-1(RIP) and cre-1(KO) strains, and the glycogen synthase phosphorylation is decreased in all strains, showing that CRE-1, RCO-1 and RCM-1 proteins are involved in glycogen accumulation and in the regulation of GSN activity by phosphorylation. We also confirmed the regulatory role of CRE-1 in CCR and its nuclear localization under repressing condition in N. crassa. The expression of all glycogenic genes is misregulated in the cre-1(KO) strain, suggesting that CRE-1 also controls glycogen metabolism by regulating gene expression. The existence of a high number of the Aspergillus nidulans CreA motif (5'-SYGGRG-3') in the glycogenic gene promoters led us to analyze the binding of CRE-1 to some DNA motifs both in vitro by DNA gel shift and in vivo by ChIP-qPCR analysis. CRE-1 bound in vivo to all motifs analyzed demonstrating that it down-regulates glycogen metabolism by controlling gene expression and GSN phosphorylation. Copyright © 2015 Elsevier Inc. All rights reserved.

  11. Surface mass balance and runoff modeling using HIRHAM4 RCM at Kangerlussuaq (Søndre Strømfjord), West Greenland, 1950-2080

    DEFF Research Database (Denmark)

    Mernild, Sebastian H.; Liston, Glen E.; Hiemstra, Christopher A.

    2011-01-01

    A regional atmospheric model, the HIRHAM4 regional climate model (RCM) using boundary conditions from the ECHAM5 atmosphere-ocean general circulation model (AOGCM), was downscaled to a 500-m gridcell increment using SnowModel to simulate 131 yr (1950-2080) of hydrologic cycle evolution in west...... Greenland's Kangerlussuaq drainage. Projected changes in the Greenland Ice Sheet (GrIS) surface mass balance (SMB) and runoff are relevant for potential hydropower production and prediction of ecosystem changes in sensitive Kangerlussuaq Fjord systems. Mean annual surface air temperatures and precipitation...

  12. Aplicación del modelo Reliability-Centred Maintenance (RCM) en líneas de distribución de Alta Tensión

    OpenAIRE

    Vizcarro Pedret, Laia

    2009-01-01

    El objetivo de este proyecto es definir gamas de mantenimiento para cables subterráneos de Alta Tensión, basándose en la metodología RCM (Mantenimiento Basado en la Fiabilidad); establecer niveles iniciales de alerta, para los cuales el cable presenta riesgos de fallo; realizar un estudio técnico-económico de diferentes modos de diagnóstico y analizar la viabilidad de implantar sistemas de monitorización OFF-LINE u ON-LINE. El proyecto establece los criterios y pasos a seguir p...

  13. Synergy between Two Metal Catalysts: A Highly Active Silica Supported Bimetallic W/Zr Catalyst for Metathesis of n-Decane

    KAUST Repository

    Samantaray, Manoja

    2016-06-01

    A well-defined, silica supported, bimetallic precatalyst [≡Si-O-W(Me)5 ≡Si-O-Zr(Np)3](4) has been synthesized for the first time via successively grafting two organometallic complexes [W(CH3)6 (1) followed by ZrNp4 (2)] on a single silica support. Surprisingly, multiple quantum NMR characterization demonstrates that W and Zr species are in close proximity to each other. Hydrogenation of this bimetallic catalyst at room temperature showed the easy formation of Zirconium hydride, probably facilitated by tungsten hydride which was formed at this temperature. This bimetallic W/Zr hydride precatalyst proved to be more efficient (TON: 1436) than the monometallic W hydride (TON: 650) in metathesis of n-decane at 150 0C. This synergy between Zr and W suggests that the slow step of alkane metathesis is the C-H bond activation which occurs on Zr. The produced olefin resulting from a ß–H elimination undergoes easy metathesis on W.

  14. In Situ Generated Ruthenium-Arene Catalyst for Photoactivated Ring-Opening Metathesis Polymerization through Photolatent N-Heterocyclic Carbene Ligand.

    Science.gov (United States)

    Pinaud, Julien; Trinh, Thi Kim Hoang; Sauvanier, David; Placet, Emeline; Songsee, Sriprapai; Lacroix-Desmazes, Patrick; Becht, Jean-Michel; Tarablsi, Bassam; Lalevée, Jacques; Pichavant, Loïc; Héroguez, Valérie; Chemtob, Abraham

    2018-01-09

    1,3-Bis(mesityl)imidazolium tetraphenylborate (IMesH + BPh 4 - ) can be synthesized in one step by anion metathesis between the corresponding imidazolium chloride and sodium tetraphenylborate. In the presence of 2-isopropylthioxanthone (sensitizer), an IMes N-heterocyclic carbene (NHC) ligand can be photogenerated under irradiation at 365 nm through coupled electron/proton transfer reactions. By combining this tandem NHC photogenerator system with metathesis inactive [RuCl 2 (p-cymene)] 2 precatalyst, the highly active RuCl 2 (p-cymene)(IMes) complex can be formed in situ, enabling a complete ring-opening metathesis polymerization (ROMP) of norbornene in the matter of minutes at room temperature. To the best of our knowledge, this is the first example of a photogenerated NHC. Its exploitation in photoROMP has resulted in a simplified process compared to current photocatalysts, because only stable commercial or easily synthesized reagents are required. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Accuracy of a new ring-opening metathesis elastomeric dental impression material with spray and immersion disinfection.

    Science.gov (United States)

    Kronström, Mats H; Johnson, Glen H; Hompesch, Richard W

    2010-01-01

    A new elastomeric impression material has been formulated with a ring-opening metathesis chemistry. In addition to other properties of clinical significance, the impression accuracy must be confirmed. The purpose of this study was to compare the accuracy of the new elastomeric impression material with vinyl polysiloxane and polyether following both spray and immersion disinfection. Impressions of a modified dentoform with a stainless steel crown preparation in the lower right quadrant were made, and type IV gypsum working casts and dies were formed. Anteroposterior (AP), cross-arch (CA), buccolingual (BL), mesiodistal (MD), occlusogingivobuccal (OGB), and occlusogingivolingual (OGL) dimensions were measured using a microscope. Working cast and die dimensions were compared to those of the master model. The impression materials were a newly formulated, ring-opening metathesis-polymerization impression material (ROMP Cartridge Tray and ROMP Volume Wash), vinyl polysiloxane (VPS, Aquasil Ultra Monophase/LV), and a polyether (PE, Impregum Penta Soft/Permadyne Garant L). Fifteen impressions with each material were made, of which 5 were disinfected by spray for 10 minutes (CaviCide), 5 were disinfected by immersion for 90 minutes (ProCide D), and 5 were not disinfected. There were significant cross-product interactions with a 2-way ANOVA, so a 1-way ANOVA and Dunnett's T3 multiple comparison test were used to compare the dimensional changes of the 3 impression materials, by disinfection status and for each location (alpha=.05). For ROMP, there were no significant differences from the master, for any dimension, when comparing the control and 2 disinfectant conditions. No significant differences were detected among the 3 impression materials for CA, BL, and MD. The working die dimensions of OGB and OGL for VPS with immersion disinfection were significantly shorter than with PE and ROMP (P<.05). Overall, the AP dimension was more accurate than CA, and the BL of working dies

  16. Antiperovskite nitridophosphate oxide Ho{sub 3}[PN{sub 4}]O by high-pressure metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Kloss, Simon D.; Weidmann, Niels; Schnick, Wolfgang [Department of Chemistry, University of Munich (LMU), Butenandtstrasse 5-13, 81377, Munich (Germany)

    2017-04-03

    Rare-earth nitridophosphates are a recently discovered class of materials, which are accessible by high-pressure metathesis. Antiperovskite-type Ho{sub 3}[PN{sub 4}]O was synthesized from HoF{sub 3}, LiPN{sub 2}, Li{sub 3}N, and Li{sub 2}O at 5 GPa and ca. 1025 C by this method and the multianvil technique. Ho{sub 3}[PN{sub 4}]O contains rarely observed isolated PN{sub 4} tetrahedra and can be derived by the hierarchical substitution of the ABX{sub 3} perovskite, in which Ho occupies the X positions, O occupies the B position, and the PN{sub 4} tetrahedra occupy the A position. The structure was refined on the basis of powder diffraction data [I4/mcm, a = 6.36112(3), c = 10.5571(1) Aa, Z = 4, R{sub wp} = 0.04, R{sub Bragg} = 0.01, χ{sup 2} = 2.275] starting from the structural model of isotypic Gd{sub 3}[SiN{sub 3}O]O. To characterize Ho{sub 3}[PN{sub 4}]O, elemental analyses were performed through energy-dispersive X-ray spectroscopy (EDX) and inductively coupled plasma optical emission spectroscopy (ICP-OES). Ho{sub 3}[PN{sub 4}]O is paramagnetic down to low temperatures with μ{sub eff} = 10.43(1) μ{sub B} and a Curie temperature (Θ) of 0.11(4) K. It shows the optical characteristics of Ho{sup 3+} ions and vibrations corresponding to isolated PN{sub 4} tetrahedra. On the basis of DFT calculations [generalized gradient approximation (GGA)], Ho{sub 3}[PN{sub 4}]O has an indirect band gap of 1.87 eV. We demonstrate the versatility of high-pressure metathesis by attaining the low end of the P/N atomic ratio κ = 1/4. This confirms the previous assumption that rare-earth nitridophosphates with κ = 1/2 to 1/4 are feasible by this method. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. Report of the 2nd RCM on development of radiation-processed products of natural polymers for application in agriculture, healthcare, industry and environment. Working Material

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2010-07-01

    Radiation processing offers a clean and additive-free method for preparation of value-added novel materials based on renewable, non-toxic and biodegradable natural polymers and natural polymer waste. The results of research work showed that depending on the irradiation conditions, natural polysaccharides (alginate, chitin/chitosan, carrageeneans, carboxylmethylcellulose, etc.) could be either degraded or crosslinked by radiation. This paved the way for development of many successful applications; some of them commercialized, for use in agriculture, health care and environmental protection. The inputs for the formulation of this CRP and the key issues that need to be addressed were provided by the Consultant’s Meeting on “Radiation Processing of Natural Polymers for Development of Finished Products for Health Care, Agriculture and Environment” held in Kuala Lumpur, Malaysia from 26 – 30 March 2007. The main objective was defined as wide-spread promotion and general application of radiation processed natural materials, by coupling radiation technology and end-users to derive additional benefits from these value-added natural materials. The first RCM of the CRP was convened in Vienna on 21-25 April 2008. The participants presented and discussed the status of the field, the needs for further research, and various application possibilities. The work plan formulated during the meeting focused on harmonization of procedures for characterization of irradiated polymers, and protocols for investigation of the functional properties of degraded natural polymer products and their field testing. A network for collaboration was also proposed. The Meeting Report was published and is available for all Member States. The second RCM of this CRP was held in Reims, France, on 12–16 October 2009. The meeting was attended by 14 participants who reported their individual research results obtained since the first RCM, as well as their further plans. This meeting report contains

  18. Report of the 2nd RCM on development of radiation-processed products of natural polymers for application in agriculture, healthcare, industry and environment. Working Material

    International Nuclear Information System (INIS)

    2010-01-01

    Radiation processing offers a clean and additive-free method for preparation of value-added novel materials based on renewable, non-toxic and biodegradable natural polymers and natural polymer waste. The results of research work showed that depending on the irradiation conditions, natural polysaccharides (alginate, chitin/chitosan, carrageeneans, carboxylmethylcellulose, etc.) could be either degraded or crosslinked by radiation. This paved the way for development of many successful applications; some of them commercialized, for use in agriculture, health care and environmental protection. The inputs for the formulation of this CRP and the key issues that need to be addressed were provided by the Consultant’s Meeting on “Radiation Processing of Natural Polymers for Development of Finished Products for Health Care, Agriculture and Environment” held in Kuala Lumpur, Malaysia from 26 – 30 March 2007. The main objective was defined as wide-spread promotion and general application of radiation processed natural materials, by coupling radiation technology and end-users to derive additional benefits from these value-added natural materials. The first RCM of the CRP was convened in Vienna on 21-25 April 2008. The participants presented and discussed the status of the field, the needs for further research, and various application possibilities. The work plan formulated during the meeting focused on harmonization of procedures for characterization of irradiated polymers, and protocols for investigation of the functional properties of degraded natural polymer products and their field testing. A network for collaboration was also proposed. The Meeting Report was published and is available for all Member States. The second RCM of this CRP was held in Reims, France, on 12–16 October 2009. The meeting was attended by 14 participants who reported their individual research results obtained since the first RCM, as well as their further plans. This meeting report contains

  19. Product Distribution from Precursor Bite Angle Variation in Multitopic Alkyne Metathesis: Evidence for a Putative Kinetic Bottleneck.

    Science.gov (United States)

    Moneypenny, Timothy P; Yang, Anna; Walter, Nathan P; Woods, Toby J; Gray, Danielle L; Zhang, Yang; Moore, Jeffrey S

    2018-05-02

    In the dynamic synthesis of covalent organic frameworks and molecular cages, the typical synthetic approach involves heuristic methods of discovery. While this approach has yielded many remarkable products, the ability to predict the structural outcome of subjecting a multitopic precursor to dynamic covalent chemistry (DCC) remains a challenge in the field. The synthesis of covalent organic cages is a prime example of this phenomenon, where precursors designed with the intention of affording a specific product may deviate dramatically when the DCC synthesis is attempted. As such, rational design principles are needed to accelerate discovery in cage synthesis using DCC. Herein, we test the hypothesis that precursor bite angle contributes significantly to the energy landscape and product distribution in multitopic alkyne metathesis (AM). By subjecting a series of precursors with varying bite angles to AM, we experimentally demonstrate that the product distribution, and convergence toward product formation, is strongly dependent on this geometric attribute. Surprisingly, we discovered that precursors with the ideal bite angle (60°) do not afford the most efficient pathway to the product. The systematic study reported here illustrates how seemingly minor adjustments in precursor geometry greatly affect the outcome of DCC systems. This research illustrates the importance of fine-tuning precursor geometric parameters in order to successfully realize desirable targets.

  20. All-Polymer Photovoltaic Devices of Poly(3-(4- n -octyl)-phenylthiophene) from Grignard Metathesis (GRIM) Polymerization

    KAUST Repository

    Holcombe, Thomas W.

    2009-10-14

    (Graph Presented) The synthesis of poly[3-(4-n-octyl)-phenylthiophene] (POPT) from Grignard Metathesis (GRIM) is reported. GRIM POPT is found to have favorable electronic, optical, and processing properties for organic photovoltaics (OPVs). Space-charge limited current and field effect transistor measurements for POPT yielded hole mobilities of 1 × 10-4 cm2/(V s) and 0.05 cm2/(V s), respectively. Spincasting GRIM POPT from chlorobenzene yields a thin film with a 1.8 eV band gap, and PC61BM:POPT bulk heterojection devices provide a peak performance of 3.1%. Additionally, an efficiency of 2.0% is achieved in an all-polymer, bilayer OPV using poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-(1-cyanovinylene) phenylene] (CNPPV) as an acceptor. This state-of-the-art all-polymer device is analyzed in comparison to the analogous poly(3-hexylthiophene) (P3HT)/CNPPV device. Counter to expectations based on more favorable energy level alignment, greater active layer light absorption, and similar hole mobility, P3HT/CNPPV devices perform less well than POPT/CNPPV devices with a peak efficiency of 0.93%. © 2009 American Chemical Society.

  1. Olefin Metathesis with Ru-Based Catalysts Exchanging the Typical N-Heterocyclic Carbenes by a Phosphine–Phosphonium Ylide

    Directory of Open Access Journals (Sweden)

    Laia Arnedo

    2017-03-01

    Full Text Available Density functional theory (DFT calculations have been used to describe the first turnover of an olefin metathesis reaction calling for a new in silico family of homogenous Ru-based catalysts bearing a phosphine–phosphonium ylide ligand, with ethylene as a substrate. Equal to conventional Ru-based catalysts bearing an N-heterocyclic carbene (NHC ligand, the activation of these congeners occurs through a dissociative mechanism, with a more exothermic first phosphine dissociation step. In spite of a stronger electron-donating ability of a phosphonium ylide C-ligand with respect to a diaminocarbene analogue, upper energy barriers were calculated to be on average ca. 5 kcal/mol higher than those of Ru–NHC standards. Overall, the study also highlights advantages of bidentate ligands over classical monodentate NHC and phosphine ligands, with a particular preference for the cis attack of the olefin. The new generation of catalysts is constituted by cationic complexes potentially soluble in water, to be compared with the typical neutral Ru–NHC ones.

  2. All-Polymer Photovoltaic Devices of Poly(3-(4- n -octyl)-phenylthiophene) from Grignard Metathesis (GRIM) Polymerization

    KAUST Repository

    Holcombe, Thomas W.; Woo, Claire H.; Kavulak, David F.J.; Thompson, Barry C.; Fréchet, Jean M. J.

    2009-01-01

    (Graph Presented) The synthesis of poly[3-(4-n-octyl)-phenylthiophene] (POPT) from Grignard Metathesis (GRIM) is reported. GRIM POPT is found to have favorable electronic, optical, and processing properties for organic photovoltaics (OPVs). Space-charge limited current and field effect transistor measurements for POPT yielded hole mobilities of 1 × 10-4 cm2/(V s) and 0.05 cm2/(V s), respectively. Spincasting GRIM POPT from chlorobenzene yields a thin film with a 1.8 eV band gap, and PC61BM:POPT bulk heterojection devices provide a peak performance of 3.1%. Additionally, an efficiency of 2.0% is achieved in an all-polymer, bilayer OPV using poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-(1-cyanovinylene) phenylene] (CNPPV) as an acceptor. This state-of-the-art all-polymer device is analyzed in comparison to the analogous poly(3-hexylthiophene) (P3HT)/CNPPV device. Counter to expectations based on more favorable energy level alignment, greater active layer light absorption, and similar hole mobility, P3HT/CNPPV devices perform less well than POPT/CNPPV devices with a peak efficiency of 0.93%. © 2009 American Chemical Society.

  3. 3. Research Coordination Meeting (RCM) of the Coordinated Research Project (CRP) on 'Studies of advanced reactor technology options for effective incineration of radioactive waste'. Working material

    International Nuclear Information System (INIS)

    2007-01-01

    To meet expressed Member States' needs, the IAEA has initiated a Coordinated Research Project (CRP) on 'Studies of Advanced Reactor Technology Options for Effective Incineration of Radioactive Waste'. The final goal of the CRP is to deepen the understanding of the dynamics of transmutation systems, e.g. the accelerator driven system, especially systems with deteriorated safety parameters, qualify the available methods, specify the range of validity of methods, and formulate requirements for future theoretical developments. Should transient experiments be available, the CRP will pursue experimental benchmarking work. In any case, based on the results, the CRP will conclude on the potential need of transient experiments and make appropriate proposals for experimental programs. The Technical Meeting in Chennai was the 3rd Research Coordination Meeting (RCM) of the CRP The man objectives of the RCM were to: - Discuss and perform inter-comparisons of the various benchmark results; - Prepare the first draft of the final CRP Report Status of the analyses and inter-comparisons of the results. The main objective of the CRP was to study innovative technology options for incinerating/utilizing radioactive wastes. The CRP's benchmarking exercises focused on eight innovative transmutation 'Domains', which correspond to different critical and sub-critical concepts or groups of concepts: I. Critical fast reactor, solid fuel, with fertile; II. Critical fast reactor, solid fuel, fertile-free; III. ADS, solid fuel, with fertile; IV. ADS, solid fuel, fertile-free; V. Critical reactor and ADS, molten salt fuel, with fertile; VI. Critical reactor and ADS, molten salt fuel, fertile-free; VII. Critical fast reactor and ADS, gas cooled; VIII. Fusion/fission hybrid system. For each of these Domains, the discussions and inter-comparisons considered the following issues: - Reactor-models; - Scenarios/phenomena; - Static analyses; - Dynamic analyses; - Methods; - Codes; - Neutronic data base

  4. The fourth research co-ordination meeting (RCM) on 'Updated codes and methods to reduce the calculational uncertainties of liquid metal fast reactors reactivity effects'. Working material

    International Nuclear Information System (INIS)

    2003-01-01

    The fourth Research Co-ordination Meeting (RCM) of the Co-ordinated Research Project (CRP) on 'Updated Codes and Methods to Reduce the Calculational Uncertainties of the LMFR Reactivity Effect' was held during 19-23 May, 2003 in Obninsk, Russian Federation. The general objective of the CRP is to validate, verify and improve methodologies and computer codes used for the calculation of reactivity coefficients in fast reactors aiming at enhancing the utilization of plutonium and minor actinides. The first RCM took place in Vienna on 24 - 26 November 1999. The meeting was attended by 19 participants from 7 Member States and one from an international organization (France, Germany, India, Japan, Rep. of Korea, Russian Federation, the United Kingdom, and IAEA). The participants from two Member States (China and the U.S.A.) provided their results and presentation materials even though being absent at the meeting. The results for several relevant reactivity parameters obtained by the participants with their own state-of-the-art basic data and codes, were compared in terms of calculational uncertainty, and their effects on the ULOF transient behavior of the hybrid BN- 600 core were evaluated. Contributions of the participants in the benchmark analyses is shown. This report first addresses the benchmark definitions and specifications given for each Phase and briefly introduces the basic data, computer codes, and methodologies applied to the benchmark analyses by various participants. Then, the results obtained by the participants in terms of calculational uncertainty and their effect on the core transient behavior are intercompared. Finally it addresses some conclusions drawn in the benchmarks

  5. Influence of alkene substituent in dictating the reaction course to ...

    Indian Academy of Sciences (India)

    RITABRATA DATTA

    2017-11-06

    Nov 6, 2017 ... form carbocycles or oxacycles during ring closing metathesis of ... Electronic supplementary material: The online version of this article (https:// doi.org/ ...... tific and Industrial Research for a Senior Research Fellowship.

  6. Synthesis of LaO1-xFxFeAs (x=0-0.15) via solid state metathesis reaction

    Science.gov (United States)

    Frankovsky, Rainer; Marchuk, Alexey; Pobel, Roman; Johrendt, Dirk

    2012-04-01

    LaOFeAs and superconducting LaO1-xFxFeAs have been synthesized via salt metathesis reactions and characterized by X-ray powder diffraction and magnetic susceptibility measurements. The process uses LaOCl and NaFeAs as precursors and yielded very pure samples. Superconductivity was confirmed in samples with x=0.05, 0.10 and 0.15 at critical temperatures of 11 K, 26 K and 9 K, respectively. According to temperature-dependent X-ray diffraction data, the reaction pathway is not topotactic in contrast to earlier suggestions.

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

    DEFF Research Database (Denmark)

    Hyldtoft, Lene; Madsen, Robert

    1999-01-01

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

  8. Report of the 2nd RCM on Radiation Treatment of Wastewater for Reuse with Particular Focus on Wastewaters Containing Organic Pollutants. Working Material

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2012-07-01

    compounds using validated analytical methods and develop guidelines for selection of areas where the radiation treatment has high potential for rendering treated wastewater suitable for industrial and irrigation purposes. The first Research Coordination Meeting (RCM) of the CRP was held at the Agency’s Headquarters in Vienna, during 2-6 May, 2011. The meeting summarized the current status of investigations in this field and discussed the ways to meet the CRP goals. All participants were encouraged to make use of the available material of the CRP participant and work plan, networking and sub-groups activities were defined to enhance cooperation among the participants. The second RCM, held in Republic of Korea from 29 October 29 to 2 November, 2012 reported on the progress achieved since the first meeting, critically evaluated the results obtained by different groups and formulated the work programme and networking activities for the next period.

  9. Report of the 2nd RCM on Radiation Treatment of Wastewater for Reuse with Particular Focus on Wastewaters Containing Organic Pollutants. Working Material

    International Nuclear Information System (INIS)

    2012-01-01

    compounds using validated analytical methods and develop guidelines for selection of areas where the radiation treatment has high potential for rendering treated wastewater suitable for industrial and irrigation purposes. The first Research Coordination Meeting (RCM) of the CRP was held at the Agency’s Headquarters in Vienna, during 2-6 May, 2011. The meeting summarized the current status of investigations in this field and discussed the ways to meet the CRP goals. All participants were encouraged to make use of the available material of the CRP participant and work plan, networking and sub-groups activities were defined to enhance cooperation among the participants. The second RCM, held in Republic of Korea from 29 October 29 to 2 November, 2012 reported on the progress achieved since the first meeting, critically evaluated the results obtained by different groups and formulated the work programme and networking activities for the next period

  10. Surface-initiated ring-opening metathesis polymerization (SI-ROMP) to attach a tethered organic corona onto CdSe/ZnS core/shell quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Vatansever, Fatma, E-mail: vatansever.fatma@mgh.harvard.edu; Hamblin, Michael R., E-mail: hamblin@helix.mgh.harvard.edu [Massachusetts General Hospital, Wellman Center for Photomedicine (United States)

    2016-10-15

    Core–shell CdSe/ZnS quantum dots (QDs) are useful as tunable photostable fluorophores for multiple applications in industry, biology, and medicine. However, to achieve the optimum optical properties, the surface of the QDs must be passivated to remove charged sites that might bind extraneous substances and allow aggregation. Here we describe a method of growing an organic polymer corona onto the QD surface using the bottom-up approach of surface-initiated ring-opening metathesis polymerization (SI-ROMP) with Grubbs catalyst. CdSe/ZnS QDs were first coated with mercaptopropionic acid by displacing the original tri-octylphosphine oxide layer, and then reacted with 7-octenyl dimethyl chlorosilane. The resulting octenyl double bonds allowed the attachment of ruthenium alkylidene groups as a catalyst. A subsequent metathesis reaction with strained bicyclic monomers (norbornene-dicarbonyl chloride (NDC), and a mixture of NDC and norbornenylethylisobutyl-polyhedral oligomeric silsesquioxane (norbornoPOSS)) allowed the construction of tethered organic homo-polymer or co-polymer layers onto the QD. Compounds were characterized by FT-IR, 1H-NMR, X-ray photoelectron spectroscopy, differential scanning calorimetry, and transmission electron microscopy. Atomic force microscopy showed that the coated QDs were separate and non-aggregated with a range of diameter of 48–53 nm.

  11. 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; Merle, Nicolas; Mallmann, Aimery De; Basset, Jean-Marie; Berrier, Elise; Delevoye, Laurent; Paul, Jean Franois; Nicholas, Christopher P.; Gauvin, Ré gis M.; Taoufik, Mostafa

    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.

  12. Optimal Hydrophobicity in Ring-Opening Metathesis Polymerization-Based Protein Mimics Required for siRNA Internalization.

    Science.gov (United States)

    deRonde, Brittany M; Posey, Nicholas D; Otter, Ronja; Caffrey, Leah M; Minter, Lisa M; Tew, Gregory N

    2016-06-13

    Exploring the role of polymer structure for the internalization of biologically relevant cargo, specifically siRNA, is of critical importance to the development of improved delivery reagents. Herein, we report guanidinium-rich protein transduction domain mimics (PTDMs) based on a ring-opening metathesis polymerization scaffold containing tunable hydrophobic moieties that promote siRNA internalization. Structure-activity relationships using Jurkat T cells and HeLa cells were explored to determine how the length of the hydrophobic block and the hydrophobic side chain compositions of these PTDMs impacted siRNA internalization. To explore the hydrophobic block length, two different series of diblock copolymers were synthesized: one series with symmetric block lengths and one with asymmetric block lengths. At similar cationic block lengths, asymmetric and symmetric PTDMs promoted siRNA internalization in the same percentages of the cell population regardless of the hydrophobic block length; however, with 20 repeat units of cationic charge, the asymmetric block length had greater siRNA internalization, highlighting the nontrivial relationships between hydrophobicity and overall cationic charge. To further probe how the hydrophobic side chains impacted siRNA internalization, an additional series of asymmetric PTDMs was synthesized that featured a fixed hydrophobic block length of five repeat units that contained either dimethyl (dMe), methyl phenyl (MePh), or diphenyl (dPh) side chains and varied cationic block lengths. This series was further expanded to incorporate hydrophobic blocks consisting of diethyl (dEt), diisobutyl (diBu), and dicyclohexyl (dCy) based repeat units to better define the hydrophobic window for which our PTDMs had optimal activity. High-performance liquid chromatography retention times quantified the relative hydrophobicities of the noncationic building blocks. PTDMs containing the MePh, diBu, and dPh hydrophobic blocks were shown to have superior

  13. Exceptionally Stable and Efficient Solid Supported Hoveyda-Type Catalyst

    Czech Academy of Sciences Publication Activity Database

    Skowerski, K.; Pastva, J.; Czarnocki, S. J.; Janošcová, Jana

    2015-01-01

    Roč. 19, č. 7 (2015), s. 872-877 ISSN 1083-6160 Institutional support: RVO:61388955 Keywords : OLEFIN-METATHESIS CATALYSTS * RING-CLOSING METATHESIS * N-HETEROCYCLIC CARBENES Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.922, year: 2015

  14. The Effect of Nitrogen Surface Ligands on Propane Metathesis: Design and Characterizations of N-modified SBA15-Supported Schrock-type Tungsten Alkylidyne

    KAUST Repository

    Eid, Ahmed A.

    2014-04-01

    Catalysis, which is primarily a molecular phenomenon, is an important field of chemistry because it requires the chemical conversion of molecules into other molecules. It also has an effect on many fields, including, but not limited to, industry, environment and life Science[1]. Surface Organometallic Chemistry is an effective methodology for Catalysis as it imports the concept and mechanism of organometallic chemistry, to surface science and heterogeneous catalysis. So, it bridges the gap between homogenous and heterogeneous catalysis[1]. The aim of the present research work is to study the effect of Nitrogen surface ligands on the activity of Alkane, Propane in particular, metathesis. Our approach is based on the preparation of selectively well-defined group (VI) transition metal complexes supported onto mesoporous materials, SBA15 and bearing amido and/or imido ligands. We choose nitrogen ligands because, according to the literature, they showed in some cases better catalytic properties in homogenous catalysis in comparison with their oxygen counterparts[2]. The first section covers the modification of a highly dehydroxylated SBA15 surface using a controlled ammonia treatment. These will result in the preparation of two kind of Nitrogen surface ligands: -\\tOne with vicinal silylamine/silanol, (≡SiNH2)(≡SiOH), noted [N,O]SBA15 and, -\\tAnother\\tone\\twith\\tvicinal\\tbis-silylamine moieties (≡SiNH2)2, noted [N,N]SBA15[3]. The second section covers the reaction of Schrock type Tungsten Carbyne [W(≡C- tBu)(CH2-tBu)3] with those N-surface ligands and their characterizations by FT-IR, multiple quantum solid state NMR (1H, 13C), elemental analysis and gas phase analysis. The third section covers the generation of the active site, tungsten hydride species. Their performance toward propane metathesis reaction using the dynamic reactor technique PID compared toward previous well-known catalysts supported on silica oxide or mesoporous materials[4]. A fairly good

  15. Production of diesel fuels from vegetable oils by means of homogenous catalysed metathesis of methyl oleate; Gewinnung von dieselartigen Kraftstoffen aus Pflanzenoelen mittels homogen katalysierter Metathese von Methyloleat

    Energy Technology Data Exchange (ETDEWEB)

    Erben, Friedrich; Paetzold, Eckhard [Rostock Univ. (Germany). Leibniz-Institut fuer Katalyse; Schuemann, Ulrike; Wichmann, Volker; Fluegge, Evelyn; Berndt, Silvia; Harndorf, Horst [Rostock Univ. (Germany). Lehrstuhl fuer Kolbenmaschinen und Verbrennungsmotoren; Kragl, Udo [Rostock Univ. (Germany). Leibniz-Institut fuer Katalyse; Rostock Univ. (Germany). Inst. fuer Chemie

    2013-10-01

    Due to the increasing shortage of fossil combustibles renewable resources like oils and fats have great potential for the production of diesel-like fuels. A key step in adapting the properties of biogenic fuels to those from fossil sources is cracking or isomerisation of linear hydrocarbon chains. This is necessary for optimal cold flow properties and a continuously rising boiling curve. The present work describes the potential of metathesis for this purpose. By formal exchange of parts of molecules of a small number of starting materials a variety of products is formed which exhibit a fuel-like composition. Ethenolysis as well as hexenolysis is examined, whereat hexenolysis owns the greater potential for production of diesel-like fuels out of unsaturated fatty acid esters. (orig.)

  16. Rapid synthesis of graphitic carbon nitride powders by metathesis reaction between CaCN{sub 2} and C{sub 2}Cl{sub 6}

    Energy Technology Data Exchange (ETDEWEB)

    Pang Linlin [Key Laboratory of Liquid Structure and Heredity of Materials, Ministry of Education, Shandong University, Jinan, 250061 (China); Carbon Fiber Engineering Research Center of Shandong Province, Shandong University, Jinan 250061 (China); Bi Jianqiang [Key Laboratory of Liquid Structure and Heredity of Materials, Ministry of Education, Shandong University, Jinan, 250061 (China); Bai Yujun [Key Laboratory of Liquid Structure and Heredity of Materials, Ministry of Education, Shandong University, Jinan, 250061 (China) and Carbon Fiber Engineering Research Center of Shandong Province, Shandong University, Jinan 250061 (China)], E-mail: byj97@126.com; Qi Yongxin [Carbon Fiber Engineering Research Center of Shandong Province, Shandong University, Jinan 250061 (China); Zhu Huiling [Key Laboratory of Liquid Structure and Heredity of Materials, Ministry of Education, Shandong University, Jinan, 250061 (China); Carbon Fiber Engineering Research Center of Shandong Province, Shandong University, Jinan 250061 (China); Wang Chengguo; Wu Jiwei [Carbon Fiber Engineering Research Center of Shandong Province, Shandong University, Jinan 250061 (China); Lu Chengwei [Department of Equipment, Shandong University of Science and Technology, Jinan 250031 (China)

    2008-12-20

    Carbon nitride powders were rapidly synthesized at low temperature via the chemical metathesis reaction between CaCN{sub 2} and C{sub 2}Cl{sub 6}. X-ray diffraction results confirm the formation of crystalline graphitic carbon nitride. Besides the dominant morphology of nanoparticles, flakes, nanorods, hollow and solid spheres can be observed by transmission electron microscopy. The absorption peaks of C-N, C=N and s-triazine rings, as well as the absence of C{identical_to}N peak in the infrared spectra, further verify the formation of graphite-like sp{sup 2}-bonded structure with planar networks. Elemental analysis gives an atomic ratio of N/C around 0.3. X-ray photoelectron spectra exhibit the existence of chemical bonding between C and N.

  17. How does the addition of steric hindrance to a typical N-heterocyclic carbene ligand affect catalytic activity in olefin metathesis?

    KAUST Repository

    Poater, Albert; Falivene, Laura; Urbina-Blanco, Cé sar A.; Manzini, Simone; Nolan, Steven P.; Cavallo, Luigi

    2013-01-01

    Density functional theory (DFT) calculations were used to predict and rationalize the effect of the modification of the structure of the prototype 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) N-heterocyclic carbene (NHC) ligand. The modification consists in the substitution of the methyl groups of ortho isopropyl substituent with phenyl groups, and here we plan to describe how such significant changes affect the metal environment and therefore the related catalytic behaviour. Bearing in mind that there is a significant structural difference between both ligands in different olefin metathesis reactions, here by means of DFT we characterize where the NHC ligand plays a more active role and where it is a simple spectator, or at least its modification does not significantly change its catalytic role/performance. © 2013 The Royal Society of Chemistry.

  18. Impact of electronic modification of the chelating benzylidene ligand in cis-dichloro-configured second-generation olefin metathesis catalysts on their activity

    KAUST Repository

    Pump, Eva; Poater, Albert; Zirngast, Michaela; Torvisco, Ana; Fischer, Roland C.; Cavallo, Luigi; Slugovc, Christian

    2014-01-01

    A series of electronically modified second-generation cis-dichloro ruthenium ester chelating benzylidene complexes was prepared, characterized, and benchmarked in a typical ring-opening metathesis polymerization (ROMP) experiment. The electronic tuning of the parent chelating benzylidene ligand (2-ethyl ester benzylidene) was achieved by substitution at the 4- and 5-positions with electron-withdrawing nitro or electron-donating methoxy groups. The effect of the electronic tuning on the cis-trans isomerization process was studied experimentally and theoretically. Density functional theory calculations clearly revealed the influence of electronic modification on the relative stability between the cis and trans isomers, which is decisive for the activity of the studied compounds as initiators in ROMP. © 2014 American Chemical Society.

  19. Impact of electronic modification of the chelating benzylidene ligand in cis-dichloro-configured second-generation olefin metathesis catalysts on their activity

    KAUST Repository

    Pump, Eva

    2014-06-09

    A series of electronically modified second-generation cis-dichloro ruthenium ester chelating benzylidene complexes was prepared, characterized, and benchmarked in a typical ring-opening metathesis polymerization (ROMP) experiment. The electronic tuning of the parent chelating benzylidene ligand (2-ethyl ester benzylidene) was achieved by substitution at the 4- and 5-positions with electron-withdrawing nitro or electron-donating methoxy groups. The effect of the electronic tuning on the cis-trans isomerization process was studied experimentally and theoretically. Density functional theory calculations clearly revealed the influence of electronic modification on the relative stability between the cis and trans isomers, which is decisive for the activity of the studied compounds as initiators in ROMP. © 2014 American Chemical Society.

  20. Alkane metathesis with the tantalum methylidene [(≡SiO)Ta(=CH2)Me2]/[(≡SiO)2Ta(=CH2)Me] generated from well-defined surface organometallic complex [(≡SiO)TaVMe4

    KAUST Repository

    Chen, Yin; Abou-Hamad, Edy; Hamieh, Ali Imad Ali; Hamzaoui, Bilel; Emsley, Lyndon; Basset, Jean-Marie

    2015-01-01

    By grafting TaMe5 on Aerosil700, a stable, well-defined, silica-supported tetramethyl tantalum(V) complex, [(≡SiO)TaMe4], is obtained on the silica surface. After thermal treatment at 150 °C, the complex is transformed into two surface tantalum methylidenes, [(≡SiO)2Ta(=CH2)Me] and [(≡SiO)Ta(=CH2)Me2], which are active in alkane metathesis and comparable to the previously reported [(≡SiO)2TaHx]. Here we present the first experimental study to isolate and identify a surface tantalum carbene as the intermediate in alkane metathesis. A systematic experimental study reveals a new reasonable pathway for this reaction.

  1. Alkane metathesis with the tantalum methylidene [(≡SiO)Ta(=CH2)Me2]/[(≡SiO)2Ta(=CH2)Me] generated from well-defined surface organometallic complex [(≡SiO)TaVMe4

    KAUST Repository

    Chen, Yin

    2015-01-21

    By grafting TaMe5 on Aerosil700, a stable, well-defined, silica-supported tetramethyl tantalum(V) complex, [(≡SiO)TaMe4], is obtained on the silica surface. After thermal treatment at 150 °C, the complex is transformed into two surface tantalum methylidenes, [(≡SiO)2Ta(=CH2)Me] and [(≡SiO)Ta(=CH2)Me2], which are active in alkane metathesis and comparable to the previously reported [(≡SiO)2TaHx]. Here we present the first experimental study to isolate and identify a surface tantalum carbene as the intermediate in alkane metathesis. A systematic experimental study reveals a new reasonable pathway for this reaction.

  2. Transforming n=1 members of the Ruddlesden-Popper phases to a n=3 member through metathesis: synthesis of a new layered perovskite, Ca2La2CuTi2O10

    International Nuclear Information System (INIS)

    Sivakumar, T.; Lofland, S.E.; Ramanujachary, K.V.; Ramesha, K.; Subbanna, G.N.; Gopalakrishnan, J.

    2004-01-01

    We report the formation of a new n=3 Ruddlesden-Popper (R-P) layered perovskite oxide, Ca 2 La 2 CuTi 2 O 10 (I), in the metathesis reaction between NaLaTiO 4 and Ca 2 CuO 2 Cl 2 (n=1 R-P phases) at 700 deg. C in air. Rietveld refinement of powder XRD data shows that I is isostructural with Sr 4 Ti 3 O 10 (space group I4/mmm; a=3.8837(5), c=27.727(6) A), consisting of triple perovskite CuTi 2 O 10 sheets wherein Cu and Ti are ordered at the central and terminal octahedral sites, respectively. Magnetization data provide support for the presence of strong antiferromagnetically coupled CuO 2 sheets in the structure. I is metastable decomposing at higher temperatures (∼950 deg. C) to a mixture of perovskite-like CaLa 2 CuTi 2 O 9 and CaO. Interestingly, the reaction between NaLaTiO 4 and Sr 2 CuO 2 Cl 2 follows a different metathesis route, 2NaLaTiO 4 +Sr 2 CuO 2 Cl 2 →La 2 CuO 4 +2SrTiO 3 +2NaCl, revealing multiplicity of reaction pathways for solid-state metathesis reactions

  3. Extrudate versus Powder Silica Alumina as Support for Re2O7 Catalyst in the Metathesis of Seed Oil-Derivatives – A Comparison

    Directory of Open Access Journals (Sweden)

    Bassie B. Marvey

    2009-01-01

    Full Text Available Self- and cross-metathesis of fatty acid methyl esters (FAMEs was investigated using a silica alumina supported Re2O7 catalyst. Although a 3 wt% Re2O7/SiO2-Al2O3/SnBu4 is already active for the metathesis of unsaturated FAMEs, the results have shown that particle size of silica alumina support has a profound influence on its activity and selectivity. Consequently, high substrate conversions coupled with improved product yields (for mono- and diesters and reaction rates were obtained upon using powder, as opposed to extrudate silica alumina as the support material. Diesters are platform compounds for the synthesis of polymers and fragrances. In this paper a comparative outline of the influence of particle size of silica alumina (extrudate versus powder on catalytic performance of a 3 wt% Re2O7/SiO2-Al2O3/SnBu4 for self- and cross-metathesis of FAMEs is made. Low surface area and diffusion constraints associated with extrudates were identified as some of the factors leading to low catalytic activity and selectivity.

  4. Combination of in situ metathesis reaction with a novel "magnetic effervescent tablet-assisted ionic liquid dispersive microextraction" for the determination of endogenous steroids in human fluids.

    Science.gov (United States)

    Wu, Jia; Xu, Zilin; Pan, Yixuan; Shi, Yi; Bao, Xiujie; Li, Jun; Tong, Yu; Tang, Han; Ma, Shuyan; Wang, Xuedong; Lyu, Jianxin

    2018-05-01

    Herein, a novel magnetic effervescence tablet-assisted microextraction coupled to in situ metathesis reaction of ionic liquid (IS-META-ILDM) is presented for the determination of four endogenous steroids in human urine, pregnant women's blood, and fetal umbilical cord blood. The magnetic effervescent tablets, which were composed of Fe 3 O 4 nanoparticles, sodium carbonate (alkaline source), and tartaric acid (acidic source), were used to disperse the extractant and for convenient magnetic separation. After the effervescent reaction, in situ reaction between NH 4 PF 6 and [C 6 MIM]BF 4 was adopted to change hydrophilic ionic liquid to hydrophobic liquid, which could be separated from the aqueous phase. The newly developed method has three obvious advantages: (1) combination of effervescent dispersion and magnetic nanoparticles' retrieval is cost-effective and the dispersion and collection of the extractant can be completed almost simultaneously; (2) as compared to temperature-controlled ionic liquid dispersive microextraction and cold-induced solidified microextraction, this method avoids a heating and cooling process which significantly reduces the extraction time and energy cost; and (3) the combination of adsorption by magnetic nanoparticles with extraction by in situ metathesis reaction easily produces high recoveries for target analytes. The optimized composition of effervescent tablet and experimental parameters are as follows: 0.64 g mixture of sodium carbonate and tartaric acid, 7 mg of Fe 3 O 4 (20 nm) as magnetic sorbents, 40 μL of [C 6 MIM]BF 4 as the extraction solvent, 0.15 g NH 4 PF 6 , and 300 μL of elution solvent. Under the optimized conditions, the newly developed method provided high extraction recoveries (90.0-118.5%) and low LODs (0.14-0.17 μg L -1 ) in urine and blood samples. In total, this IS-META-ILDM method provided high extraction efficiency, fast and convenient separation, and underutilization of any organic solvent, and thus

  5. Report of the 1st RCM on Radiation Curing of Composites for Enhancing the Features and Utility in Health Care and Industry. Working Material

    International Nuclear Information System (INIS)

    2011-01-01

    Radiation Processing of Composites for Enhancing their Function and Utility in Healthcare and Industry” held on 22-26 February 2010, in Vienna. The CRP aims to support MS to develop methodologies and protocols for new abrasion resistant coating formulations, radiation curable nano-composites from natural polymers, new biodegradable packaging materials suitable for radiation sterilization, and new methods to modify surface characteristic of nano-sized materials to enhance polymer fillers interaction. This CRP provides a forum for knowledge and technology transfer among the participating institutions, as well as promotes early involvement of developing countries in knowledge-intensive R&D programs to enhance their level of competence and confidence and promote the local spin-off initiatives. The first RCM of the CRP was convened in Vienna on 18-22 July 2011. The 14 participants presented and discussed the status of the field, the needs for further research, and various application possibilities. The Participants agreed on the work plan for the next 18 months and indicated possible collaborations. One day of the meeting was devoted to presentations by cost-free participants, members of the EU 7th Framework COST ACTION MP0701 “Polymer nanocomposites with novel structural and functional properties”. This meeting report contains these information, in a summarized way in the Executive Summary part, and with full details in the individual reports of the participants

  6. Report of the 1st RCM on Radiation Curing of Composites for Enhancing the Features and Utility in Health Care and Industry. Working Material

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2011-07-01

    Radiation Processing of Composites for Enhancing their Function and Utility in Healthcare and Industry” held on 22-26 February 2010, in Vienna. The CRP aims to support MS to develop methodologies and protocols for new abrasion resistant coating formulations, radiation curable nano-composites from natural polymers, new biodegradable packaging materials suitable for radiation sterilization, and new methods to modify surface characteristic of nano-sized materials to enhance polymer fillers interaction. This CRP provides a forum for knowledge and technology transfer among the participating institutions, as well as promotes early involvement of developing countries in knowledge-intensive R&D programs to enhance their level of competence and confidence and promote the local spin-off initiatives. The first RCM of the CRP was convened in Vienna on 18-22 July 2011. The 14 participants presented and discussed the status of the field, the needs for further research, and various application possibilities. The Participants agreed on the work plan for the next 18 months and indicated possible collaborations. One day of the meeting was devoted to presentations by cost-free participants, members of the EU 7th Framework COST ACTION MP0701 “Polymer nanocomposites with novel structural and functional properties”. This meeting report contains these information, in a summarized way in the Executive Summary part, and with full details in the individual reports of the participants.

  7. Investigation of Surface Alkylation Strategy in SOMC: In Situ Generation of a Silica-Supported Tungsten Methyl Catalyst for Cyclooctane Metathesis

    KAUST Repository

    Hamieh, Ali Imad Ali

    2016-07-28

    An efficient and potentially scalable method is described for the synthesis of the silica-supported complexes [(≡Si-O-)WMe5] and [(≡Si-O-)WMe2(≡CH)] obtained by in situ alkylation of the surface-grafted tungsten chloride [(≡Si-O-)WCl5] (1). [(≡Si-O-)WCl5] can be readily prepared by the reaction of commercially available and stable tungsten hexachloride WCl6 with partially dehydroxylated silica at 700 °C (SiO2-700). Further reaction with ZnMe2 at room temperature rapidly forms a mixture of surface-alkylated tungsten complexes. They were fully characterized by microanalysis, FTIR, mass balance, and solid-state NMR (1H, 13C, 1H-13C HETCOR, 1H-1H double quantum and triple quantum) and identified as [(≡Si-O-)WMe5] and another product, [(≡Si-O-)WMe2(≡CH)]. The latter might have been generated by partial decomposition of the tungsten methyl chloride compound, which is formed during the stepwise alkylation of [(≡Si-O-)WCl5]. DFT calculations were carried out to check the relative stability of the tungsten methyl chloride intermediates and the feasibility of the reaction and corroborate the experimental results. This tungsten complex and its derivative were found to be active catalysts for the metathesis of cyclooctane. © 2016 American Chemical Society.

  8. Preparation of Bottlebrush Polymers via a One-Pot Ring-Opening Polymerization (ROP) and Ring-Opening Metathesis Polymerization (ROMP) Grafting-Through Strategy.

    Science.gov (United States)

    Radzinski, Scott C; Foster, Jeffrey C; Matson, John B

    2016-04-01

    Bottlebrush polymers are synthesized using a tandem ring-opening polymerization (ROP) and ring-opening metathesis polymerization (ROMP) strategy. For the first time, ROP and ROMP are conducted sequentially in the same pot to yield well-defined bottlebrush polymers with molecular weights in excess of 10(6) Da. The first step of this process involves the synthesis of a polylactide macromonomer (MM) via ROP of d,l-lactide initiated by an alcohol-functionalized norbornene. ROMP grafting-through is then carried out in the same pot to produce the bottlebrush polymer. The applicability of this methodology is evaluated for different MM molecular weights and bottlebrush backbone degrees of polymerization. Size-exclusion chromatographic and (1)H NMR spectroscopic analyses confirm excellent control over both polymerization steps. In addition, bottlebrush polymers are imaged using atomic force microscopy and stain-free transmission electron microscopy on graphene oxide. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Investigation of Surface Alkylation Strategy in SOMC: In Situ Generation of a Silica-Supported Tungsten Methyl Catalyst for Cyclooctane Metathesis

    KAUST Repository

    Hamieh, Ali Imad Ali; Dey, Raju; Samantaray, Manoja; Abdel-Azeim, Safwat; Abou-Hamad, Edy; Chen, Yin; Pelletier, Jeremie; Cavallo, Luigi; Basset, Jean-Marie

    2016-01-01

    An efficient and potentially scalable method is described for the synthesis of the silica-supported complexes [(≡Si-O-)WMe5] and [(≡Si-O-)WMe2(≡CH)] obtained by in situ alkylation of the surface-grafted tungsten chloride [(≡Si-O-)WCl5] (1). [(≡Si-O-)WCl5] can be readily prepared by the reaction of commercially available and stable tungsten hexachloride WCl6 with partially dehydroxylated silica at 700 °C (SiO2-700). Further reaction with ZnMe2 at room temperature rapidly forms a mixture of surface-alkylated tungsten complexes. They were fully characterized by microanalysis, FTIR, mass balance, and solid-state NMR (1H, 13C, 1H-13C HETCOR, 1H-1H double quantum and triple quantum) and identified as [(≡Si-O-)WMe5] and another product, [(≡Si-O-)WMe2(≡CH)]. The latter might have been generated by partial decomposition of the tungsten methyl chloride compound, which is formed during the stepwise alkylation of [(≡Si-O-)WCl5]. DFT calculations were carried out to check the relative stability of the tungsten methyl chloride intermediates and the feasibility of the reaction and corroborate the experimental results. This tungsten complex and its derivative were found to be active catalysts for the metathesis of cyclooctane. © 2016 American Chemical Society.

  10. Melhoria do pilar "manutenção planejada" da TPM através da utilização do RCM para nortear as estratégias de manutenção

    OpenAIRE

    Fábio Januário de Souza

    2004-01-01

    O atual ambiente competitivo, onde baixo custo, alta qualidade e um grau crescente de customização são exigências para a sobrevivência das empresas, tem influenciado as ações dos profissionais de manutenção com vistas ao aprimoramento das políticas de manutenção. Como resultado, tem-se na área de manutenção industrial, uma grande quantidade de métodos, software, modelos e ferramentas de gestão disponíveis. Dentre eles, dois métodos se destacam: o RCM (Reliability Centered Maintenance ou Manut...

  11. WMe6 tamed by silica: Si-O-WMe5 as an efficient, well-defined species for alkane metathesis, leading to the observation of a supported W-methyl/methylidyne species

    KAUST Repository

    Samantaray, Manoja

    2014-01-22

    The synthesis and full characterization of a well-defined silica-supported ≡Si-O-W(Me)5 species is reported. Under an inert atmosphere, it is a stable material at moderate temperature, whereas the homoleptic parent complex decomposes above -20 °C, demonstrating the stabilizing effect of immobilization of the molecular complex. Above 70 °C the grafted complex converts into the two methylidyne surface complexes [(≡SiO-)W(≡CH) Me2] and [(≡SiO-)2W(≡CH)Me]. All of these silica-supported complexes are active precursors for propane metathesis reactions. © 2013 American Chemical Society.

  12. WMe6 tamed by silica: Si-O-WMe5 as an efficient, well-defined species for alkane metathesis, leading to the observation of a supported W-methyl/methylidyne species

    KAUST Repository

    Samantaray, Manoja; Callens, Emmanuel; Abou-Hamad, Edy; Rossini, Aaron J.; Widdifield, Cory M.; Dey, Raju; Emsley, Lyndon; Basset, Jean-Marie

    2014-01-01

    The synthesis and full characterization of a well-defined silica-supported ≡Si-O-W(Me)5 species is reported. Under an inert atmosphere, it is a stable material at moderate temperature, whereas the homoleptic parent complex decomposes above -20 °C, demonstrating the stabilizing effect of immobilization of the molecular complex. Above 70 °C the grafted complex converts into the two methylidyne surface complexes [(≡SiO-)W(≡CH) Me2] and [(≡SiO-)2W(≡CH)Me]. All of these silica-supported complexes are active precursors for propane metathesis reactions. © 2013 American Chemical Society.

  13. Molecular and Silica-Supported Molybdenum Alkyne Metathesis Catalysts: Influence of Electronics and Dynamics on Activity Revealed by Kinetics, Solid-State NMR, and Chemical Shift Analysis.

    Science.gov (United States)

    Estes, Deven P; Gordon, Christopher P; Fedorov, Alexey; Liao, Wei-Chih; Ehrhorn, Henrike; Bittner, Celine; Zier, Manuel Luca; Bockfeld, Dirk; Chan, Ka Wing; Eisenstein, Odile; Raynaud, Christophe; Tamm, Matthias; Copéret, Christophe

    2017-12-06

    Molybdenum-based molecular alkylidyne complexes of the type [MesC≡Mo{OC(CH 3 ) 3-x (CF 3 ) x } 3 ] (MoF 0 , x = 0; MoF 3 , x = 1; MoF 6 , x = 2; MoF 9 , x = 3; Mes = 2,4,6-trimethylphenyl) and their silica-supported analogues are prepared and characterized at the molecular level, in particular by solid-state NMR, and their alkyne metathesis catalytic activity is evaluated. The 13 C NMR chemical shift of the alkylidyne carbon increases with increasing number of fluorine atoms on the alkoxide ligands for both molecular and supported catalysts but with more shielded values for the supported complexes. The activity of these catalysts increases in the order MoF 0 molecular and supported species. Detailed solid-state NMR analysis of molecular and silica-supported metal alkylidyne catalysts coupled with DFT/ZORA calculations rationalize the NMR spectroscopic signatures and discernible activity trends at the frontier orbital level: (1) increasing the number of fluorine atoms lowers the energy of the π*(M≡C) orbital, explaining the more deshielded chemical shift values; it also leads to an increased electrophilicity and higher reactivity for catalysts up to MoF 6 , prior to a sharp decrease in reactivity for MoF 9 due to the formation of stable metallacyclobutadiene intermediates; (2) the silica-supported catalysts are less active than their molecular analogues because they are less electrophilic and dynamic, as revealed by their 13 C NMR chemical shift tensors.

  14. Study of ethylene/2-butene cross-metathesis over W-H/Al2O 3 for propylene production: Effect of the temperature and reactant ratios on the productivity and deactivation

    KAUST Repository

    Mazoyer, Etienne

    2013-05-01

    A highly active and selective catalyst based on supported tungsten hydride for the cross-metathesis between ethylene and 2-butenes yielding propylene has been investigated at low pressure with various temperatures and feed ratios. At low temperature (120 °C), the catalyst deactivates notably with time on stream. This phenomenon was extensively examined by DRIFTS, TGA, DSC, and solid-state NMR techniques. It was found that a large amount of carbonaceous species were formed due to a side-reaction such as olefin polymerization which took place simultaneously with the metathesis reaction. However, at 150 °C, the catalyst was stable with time and thereby gave a high productivity in propylene. Importantly, the slight increase in temperature clearly disfavored the side reaction. The ratio of ethylene to trans-2-butene was also studied, and surprisingly, the W-H/Al2O3 catalyst is stable and highly selective to propylene even at substoichiometric ethylene ratios. © 2013 Elsevier Inc. All rights reserved.

  15. Metal-mediated gem-Difluoroallylation of N-Acylhydrazones: Highly Efficient Synthesis of a,a-Difluorohomoallylic Amines

    Institute of Scientific and Technical Information of China (English)

    YUE Xuyi; QIU Xiaolong; QING Fengling

    2009-01-01

    Indium-mediated gem-difluoroallylation of aldehyde-derived N-acylhydrazones 1a-1q and 4a-4g with 3-bromo-3,3-difluoropropene 2 afforded a,a-difluorohomoallylic hydrazides 3a-3q and 5a-5g in high yields, re-spectively. Functional groups such as nitro, phenolic hydroxyl, benzyloxy and even C=C bonds of a,fl-unsaturated aldehydes were compatible under this mild and operationally simple gem-difluoroallylic reaction condition. By means of substitution of Zn powder for indium, gem-difluoroallylation of ketone-derived N-acylhydrazones 6a-6d also provided the corresponding a,a-difluorohomoallylic hydrazides 7a-7d in medium yields. The N-N bond cleavage of the hydrazide 3a proceeded smoothly to give the corresponding primary gem-difluorohomoallylic amine 8, which could be converted to gem-difluoro-δ-substituted α,β-unsaturated lactam 11 via acryloylation fol-lowed by ring closing metathesis (RCM) reaction.

  16. Variation of the Sterical Properties of the N-Heterocyclic Carbene Coligand in Thermally Triggerable Ruthenium-Based Olefin Metathesis Precatalysts/Initiators

    KAUST Repository

    Pump, Eva

    2015-11-09

    A series of ruthenium complexes based on the κ(C,N)-(2-(benzo[h]quinolin-10-yl)methylidene ruthenium dichloride fragment featuring different neutral coligands L (L = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr), 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene (SIMes), 1,3-bis(2,4-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene (SIXyl), and 1,3-bis(2-methylphenyl)-4,5-dihydroimidazol-2-ylidene (SITol)) was prepared, characterized, and tested in the thermally induced ring-opening metathesis polymerization of dicyclopentadiene. In addition, the corresponding tricyclohexylphosphine derivative was investigated for comparison. All compounds were isolated as their trans-dichloro isomers. NMR spectroscopic features as well as structural features are, particularly within the NHC-bearing complexes, very similar, but their polymerization activity at elevated temperatures is distinctly different. While the SIMes derivative shows the desired properties, i.e., latency at room temperature and pronounced polymerization activity at elevated temperature, all other preinitiators do not. The preinitiator featuring the SIPr coligand is the most latent one, needing temperatures > 140 °C to show moderate activity in the polymerization of dicyclopentadiene. Compounds bearing the smaller N-heterocyclic carbene congeners are stable and latent at room temperature, but decompose upon heating, diminishing the polymerization activity at elevated temperatures. Density functional calculations show that the SIMes derivative is the easiest to activate and yields the most stable 14-electron intermediate. Finally calculations reveal a distinct influence of the nature of the N-heterocyclic carbene ligand on the position of the equilibrium of cis- and trans-dichloro isomers of the complexes. While the SIPr and the SIMes derivatives prefer the cis-configuration, all other derivatives favor, at least in solvents with low dielectric constants, the trans

  17. A general enantioselective route to the chamigrene natural product family

    KAUST Repository

    White, David E.

    2010-06-01

    Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.

  18. A general enantioselective route to the chamigrene natural product family

    KAUST Repository

    White, David E.; Stewart, Ian C.; Seashore-Ludlow, Brinton A.; Grubbs, Robert H.; Stoltz, Brian M.

    2010-01-01

    Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.

  19. Short syntheses of enantiopure calystegine B-2, B-3, and B-4

    DEFF Research Database (Denmark)

    Skaanderup, Philip Robert; Madsen, Robert

    2001-01-01

    Calystegine B-2 B-3, and B-4 have been prepared in 5 steps from the benzyl protected methyl 6-iodoglycopyranosides of glucose, galactose and mannose, respectively, by using a zinc-mediated domino reaction followed by ring-closing olefin metathesis as the key steps.......Calystegine B-2 B-3, and B-4 have been prepared in 5 steps from the benzyl protected methyl 6-iodoglycopyranosides of glucose, galactose and mannose, respectively, by using a zinc-mediated domino reaction followed by ring-closing olefin metathesis as the key steps....

  20. A Concise Synthesis of Castanospermine by the Use of a Transannular Cyclization

    DEFF Research Database (Denmark)

    Jensen, Thomas; Mikkelsen, Mette; Lauritsen, Anne

    2009-01-01

    A nine-step synthesis of (+)-castanospermine has been accomplished in 22% overall yield from methyl alpha-D-glucopyranoside. The key transformations involve a zinc-mediated fragmentation of benzyl-protected methyl 6-iodoglucopyranoside, ring-closing olefin metathesis, and strain-release transannu......A nine-step synthesis of (+)-castanospermine has been accomplished in 22% overall yield from methyl alpha-D-glucopyranoside. The key transformations involve a zinc-mediated fragmentation of benzyl-protected methyl 6-iodoglucopyranoside, ring-closing olefin metathesis, and strain...

  1. Build/Couple/Pair and Multifunctional Catalysis Strategies for the Synthesis of Heterocycles from Simple Starting Materials

    DEFF Research Database (Denmark)

    Ascic, Erhad

    . Multifunctional Catalysis: Synthesis of Heterocycles from Simple Starting Materials A multifunctional catalysis approach, involving a ruthenium-catalyzed tandem ringclosing metathesis/isomerization/N-acyliminium cyclization sequence, is described. Double bonds created during ring-closing metathesis isomerize......, a series of interesting indolizidinones are formed in good yields with excellent diastereoselectivities, including a formal total synthesis of the antiparasitic natural product harmicine and the first total synthesis of mescalotam. Furthermore, preliminary asymmetric variants of the tandem process have...

  2. Test Case RCM-3 Using CPS

    Science.gov (United States)

    2001-03-01

    influence We observe an important variation of the flame length with the ratio gas / liquid injected (Figure 6 and Figure 7). The flame length increases with...fraction, the flame length increases (Figure 7). This is due to the increase of the oxygen injection speed to obtain the correct amount of oxygen...influence of C, with have made calculation with an arbitrary value for a witch is 10-6 N / m. The flame length decrease with the surface tension

  3. The enantioselective total synthesis of (+)-clusianone.

    Science.gov (United States)

    Horeischi, Fiene; Guttroff, Claudia; Plietker, Bernd

    2015-02-11

    (+)-Clusianone, an exo-type B PPAP with reported anti-HIV and chemoprotective activities, was synthesized in eleven steps with 97% ee starting from acetylacetone. An enantioselective decarboxylative Tsuji-Trost-allylation and a Ru-catalyzed ring-closing metathesis-decarboxylative allylation were used to control both diastereo- and enantioselectivity.

  4. Synthesis of 5/7-, 5/8- and 5/9-bicyclic lactam templates as constraints for external beta-turns.

    Science.gov (United States)

    Duggan, Heather M E; Hitchcock, Peter B; Young, Douglas W

    2005-06-21

    The 5/7-, 5/8- and 5/9-bicyclic lactams 3, 17, 5 and 6 have been synthesised as single diastereoisomers by a route involving ring closing olefin metathesis. The X-ray crystal structure of the amino acid hydrochloride has been carried out and compared to that of the saturated external beta-turn constraint 18.

  5. Control of alpha/beta Anomer Formation by a 2',5' Bridge: Toward Nucleoside Derivatives Locked in the South Conformation

    Czech Academy of Sciences Publication Activity Database

    Hřebabecký, Hubert; Dračínský, Martin; Procházková, Eliška; Šála, Michal; Mackman, R.; Nencka, Radim

    2017-01-01

    Roč. 82, č. 21 (2017), s. 11337-11347 ISSN 0022-3263 R&D Projects: GA ČR(CZ) GA16-20054S Institutional support: RVO:61388963 Keywords : borne encephalitis virus * ring closing metathesis * nucleotide analogs Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 4.849, year: 2016

  6. South African Journal of Chemistry - Vol 60 (2007)

    African Journals Online (AJOL)

    The Synthesis of 5-, 6-, 7- and 8-Membered Oxygen-containing Benzo-fused Rings using Alkene Isomerization and Ring-closing Metathesis Reactions · EMAIL FREE FULL TEXT EMAIL FREE FULL TEXT DOWNLOAD FULL TEXT DOWNLOAD FULL TEXT. R Pathak, J Panayides, TD Jeftic, CB de Koning, WAL van Otterlo ...

  7. Convergent synthesis of the HIJKLM ring system of ciguatoxin CTX3C.

    Science.gov (United States)

    Takamura, Hiroyoshi; Nishiuma, Naoki; Abe, Takashi; Kadota, Isao

    2011-09-02

    The HIJKLM ring system of ciguatoxin CTX3C was synthesized in a convergent manner. The key steps were a conjugate addition/alkylation sequence, spiroacetalization, intramolecular allylation, ring-closing metathesis, and hydrogenation to form the 36-α-methyl substituent.

  8. Convergent Synthesis of Pancratistatin from Piperonal and Xylose

    DEFF Research Database (Denmark)

    Dam, Johan Hygum; Madsen, Robert

    2009-01-01

    to afford a highly functionalised 1,7-diene, which is then converted into the corresponding cyclohexene by ring-closing olefin metathesis. Subsequent Overman rearrangement, dihydroxylation and deprotection afford the natural product in a total of 25 steps from the two starting materials. The longest linear...

  9. A simple approach to the construction of the core structure present

    Indian Academy of Sciences (India)

    A convenient route for the synthesis of oxacyclobutapentalene, the tricyclic bridged core structure present in bioactive marine diterpene bielschowskysin and the polyketide hippolachnin A, is reported. The key steps involve ring closing metathesis of a triene derived from D-mannitol to produce selectively the dihydrofuran ...

  10. Well-Defined Surface Species [(≡Si - O -)W(=O)Me3] Prepared by Direct Methylation of [(≡Si - O -)W(=O)Cl3], a Catalyst for Cycloalkane Metathesis and Transformation of Ethylene to Propylene

    KAUST Repository

    Hamieh, Ali Imad Ali

    2015-04-03

    The silica-supported tungsten oxo-trimethyl complex [(≡Si - O -)W(=O)Me3] was synthesized using a novel SOMC synthetic approach. By grafting the inexpensive stable compound WOCl4 on the surface of silica, partially dehydroxylated at 700 °C (SiO2-700), a well-defined monopodal surface complex [(≡Si - O -)W(=O)Cl3] was produced. The supported complex directly methylated with ZnMe2 and transformed into [(≡Si - O -)W(=O)Me3], which we fully characterized by microanalysis, IR, mass balance and SS NMR (1H, 13C, 1H-13C HETCOR, 1H-1H DQ and TQ). [(≡Si - O)W(=O)Me3] has two conformational isomers on the surface at room temperature. The conversion of one to the other was observed at 318 K by variable-temperature 13C CP/MAS and 1H spin echo MAS solid-state NMR; this was also confirmed by NMR and DFT calculations. [(≡Si - O)W(=O)Me3] was found to be active in cyclooctane metathesis and to have a wide distribution range in ring-contracted and ring-expanded products. In addition, [(≡Si - O)W(=O)Me3] proved to be highly active for selective transformation of ethylene to propylene compared to other silica-supported organometallic complexes. (Chemical Equation Presented). © 2015 American Chemical Society.

  11. Well-Defined Surface Species [(≡Si - O -)W(=O)Me3] Prepared by Direct Methylation of [(≡Si - O -)W(=O)Cl3], a Catalyst for Cycloalkane Metathesis and Transformation of Ethylene to Propylene

    KAUST Repository

    Hamieh, Ali Imad Ali; Chen, Yin; Abdel-Azeim, Safwat; Abou-Hamad, Edy; Goh, Li Min Serena; Samantaray, Manoja; Dey, Raju; Cavallo, Luigi; Basset, Jean-Marie

    2015-01-01

    The silica-supported tungsten oxo-trimethyl complex [(≡Si - O -)W(=O)Me3] was synthesized using a novel SOMC synthetic approach. By grafting the inexpensive stable compound WOCl4 on the surface of silica, partially dehydroxylated at 700 °C (SiO2-700), a well-defined monopodal surface complex [(≡Si - O -)W(=O)Cl3] was produced. The supported complex directly methylated with ZnMe2 and transformed into [(≡Si - O -)W(=O)Me3], which we fully characterized by microanalysis, IR, mass balance and SS NMR (1H, 13C, 1H-13C HETCOR, 1H-1H DQ and TQ). [(≡Si - O)W(=O)Me3] has two conformational isomers on the surface at room temperature. The conversion of one to the other was observed at 318 K by variable-temperature 13C CP/MAS and 1H spin echo MAS solid-state NMR; this was also confirmed by NMR and DFT calculations. [(≡Si - O)W(=O)Me3] was found to be active in cyclooctane metathesis and to have a wide distribution range in ring-contracted and ring-expanded products. In addition, [(≡Si - O)W(=O)Me3] proved to be highly active for selective transformation of ethylene to propylene compared to other silica-supported organometallic complexes. (Chemical Equation Presented). © 2015 American Chemical Society.

  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. On the Dehydrocoupling of Alkenylacetylenes Mediated by Various Samarocene Complexes: A Charming Story of Metal Cooperativity Revealing a Novel Dual Metal σ-Bond Metathesis Type of Mechanism (DM|σ-BM

    Directory of Open Access Journals (Sweden)

    Christos E. Kefalidis

    2015-12-01

    Full Text Available The prevailing reductive chemistry of Sm(II has been accessed and explored mostly by the use of samarocene precursors. The highly reducing character of these congeners, along with their Lewis acidity and predominantly ionic bonding, allows for the relatively facile activation of C–H bonds, as well as peculiar transformations of unsaturated substrates (e.g., C–C couplings. Among other important C–C coupling reactions, the reaction of phenylacetylene with different mono- or bimetallic samarocene complexes affords trienediyl complexes of the type {[(C5Me52Sm]2(µ-η2:η2-PhC4Ph}. In contrast, when t-butylacetylene is used, uncoupled monomers of the type (C5Me52Sm(C≡C–tBu were obtained. Although this type of reactivity may appear to be simple, the mechanism underlying these transformations is complex. This conclusion is drawn from the density functional theory (DFT mechanistic studies presented herein. The operating mechanistic paths consist of: (i the oxidation of each samarium center and the concomitant double reduction of the alkyne to afford a binuclear intermediate; (ii the C–H scission of the acetylinic bond that lies in between the two metals; (iii a dual metal σ-bond metathesis (DM|σ-SBM process that releases H2; and eventually (iv the C–C coupling of the two bridged μ-alkynides to give the final bimetallic trienediyl complexes. For the latter mechanistic route, the experimentally used phenylacetylene was considered first as well as the aliphatic hex-1-yne. More interestingly, we shed light into the formation of the mono(alkynide complex, being the final experimental product of the reaction with t-butylacetylene.

  14. 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)

  15. Detailed structural characterization of the grafting of [Ta(=CHtBu)(CH2tBu)3] and [Cp*TaMe4] on silica partially dehydroxylated at 700 C and the activity of the grafted complexes toward alkane metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Le Roux, Erwan; Chabanas, Mathieu; Baudouin, Anne; de Mallmann, Aimery; Coperet, Christophe; Quadrelli, E. Allesandra; Thivolle-Cazat, Jean; Basset, Jean-Marie; Lukens, Wayne; Lesage, Anne; Emsley, Lyndon; Sunley, Glenn J.

    2004-08-30

    The reaction of [Ta({double_bond}CHtBu)(CH{sub 2}tBu){sub 3}] or [Cp*Ta(CH{sub 3}){sub 4}] with a silica partially dehydroxylated at 700 C gives the corresponding monosiloxy surface complexes [({triple_bond}SiO)Ta({double_bond}CHtBu)(CH{sub 2}tBu){sub 2}] and [({triple_bond}SiO)Ta(CH{sub 3}){sub 3}Cp*] by eliminating a {sigma}-bonded ligand as the corresponding alkane (H-CH{sub 2}tBu or H-CH{sub 3}). EXAFS data show that an adjacent siloxane bridge of the surface plays the role of an extra surface ligand, which most likely stabilizes these complexes as in [({triple_bond}SiO)Ta({double_bond}CHtBu)(CH{sub 2}tBu){sub 2}({triple_bond}SiOSi{triple_bond})] (1a') and [({triple_bond}SiO)Ta(CH{sub 3}){sub 3}Cp*({triple_bond}SiOSi{triple_bond})] (2a'). In the case of [({triple_bond}SiO)Ta({double_bond}CHtBu)(CH{sub 2}tBu){sub 2}({triple_bond}SiOSi{triple_bond})], the structure is further stabilized by an additional interaction: a C-H agostic bond as evidenced by the small J coupling constant for the carbenic C-H (H{sub C-H} = 80 Hz), which was measured by J-resolved 2D solid-state NMR spectroscopy. The product selectivity in propane metathesis in the presence of [({triple_bond}SiO)Ta({double_bond}CHtBu)-(CH{sub 2}tBu){sub 2}({triple_bond}SiOSi{triple_bond})] (1a') as a catalyst precursor and the inactivity of the surface complex [({triple_bond}SiO)Ta-(CH{sub 3}){sub 3}Cp*({triple_bond}SiOSi{triple_bond})] (2a') show that the active site is required to be highly electrophilic and probably involves a metallacyclobutane intermediate.

  16. Ruthenium catalysts bearing a benzimidazolylidene ligand for the metathetical ring-closure of tetrasubstituted cycloolefins

    KAUST Repository

    Borguet, Yannick

    2015-01-01

    © The Royal Society of Chemistry. Deprotonation of 1,3-di(2-tolyl)benzimidazolium tetrafluoroborate with a strong base afforded 1,3-di(2-tolyl)benzimidazol-2-ylidene (BTol), which dimerized progressively into the corresponding dibenzotetraazafulvalene. The complexes [RhCl(COD)(BTol)] (COD is 1,5-cyclooctadiene) and cis-[RhCl(CO)2(BTol)] were synthesized to probe the steric and electronic parameters of BTol. Comparison of the percentage of buried volume (%VBur) and of the Tolman electronic parameter (TEP) of BTol with those determined previously for 1,3-dimesitylbenzimidazol-2-ylidene (BMes) revealed that the two N-heterocyclic carbenes displayed similar electron donicities, yet the 2-tolyl substituents took a slightly greater share of the rhodium coordination sphere than the mesityl groups, due to a more pronounced tilt. The anti,anti conformation adopted by BTol in the molecular structure of [RhCl(COD)(BTol)] ensured nonetheless a remarkably unhindered access to the metal center, as evidenced by steric maps. Second-generation ruthenium-benzylidene and isopropoxybenzylidene complexes featuring the BTol ligand were obtained via phosphine exchange from the first generation Grubbs and Hoveyda-Grubbs catalysts, respectively. The atropisomerism of the 2-tolyl substituents within [RuCl2(=CHPh)(PCy3)(BTol)] was investigated by using variable temperature NMR spectroscopy, and the molecular structures of all four possible rotamers of [RuCl2(=CH-o-OiPrC6H4)(BTol)] were determined by X-ray crystallography. Both complexes were highly active at promoting the ring-closing metathesis (RCM) of model α,ω-dienes. The replacement of BMes with BTol was particularly beneficial to achieve the ring-closure of tetrasubstituted cycloalkenes. More specifically, the stable isopropoxybenzylidene chelate enabled an almost quantitative RCM of two challenging substrates, viz., diethyl 2,2-bis(2-methylallyl)malonate and N,N-bis(2-methylallyl)tosylamide, within a few hours at 60°C.

  17. Metathesis of alkanes and related reactions

    KAUST Repository

    Basset, Jean-Marie; Copé ret, Christophe; Soulivong, Daravong; Taoufik, Mostafa; Thivolle-Cazat, Jean

    2010-01-01

    , the process proceeds at relatively low temperature (ambient conditions or higher). It was discovered through the use of a silica-supported tantalum hydride, (=SiO)2TaH, a multifunctional catalyst with a single site of action. This reaction completes the story

  18. Novel phosphanucleoside analogs of dideoxynucleosides

    Czech Academy of Sciences Publication Activity Database

    Páv, Ondřej; Buděšínský, Miloš; Rosenberg, Ivan

    2017-01-01

    Roč. 73, č. 34 (2017), s. 5220-5228 ISSN 0040-4020 R&D Projects: GA ČR(CZ) GA17-12703S; GA ČR GA13-26526S; GA MZd NV15-31604A Institutional support: RVO:61388963 Keywords : phosphanucleoside * nucleoside analog * ring-closing metathesis * stereoselective hydroboration * chiral resolution Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 2.651, year: 2016

  19. Analisis Pemeliharaan Mesin Blowmould Dengan Metode RCM Di PT. CCAI

    Directory of Open Access Journals (Sweden)

    Nur Yulianti Hidayah

    2017-10-01

    Full Text Available PT. Coca-Cola Amatil Indonesia is a company that produces carbonated beverages. Most of the production activity uses automatic machines. The problem faced is the damage that often occurs suddenly on the blowmould machine so that corrective maintenance must be done. The purpose of this research is to know the cause of the damage and to propose the action plan to minimize downtime. The method used is Reliability Centered Maintenance to determine the selection of action and time interval of replacement for critical components on the blowmould machine. From the FMEA analysis, it is known that the critical components of each blowmould machine subsystem are bearing roller feed, mandrel, seal gasket, and fitting. The results of LTA analysis are the category of failure (outage problem and economic problem and the selection of action for the critical component (time directed. From the calculation of Total Minimum Downtime, known that the replacement schedule for critical component are 23 days for bearing roller feed, 9 days for mandrel, 8 days for seal gasket, and 8 days for fitting, that is resulting in decreased downtime of 1.56% with a value of 99.63% availability

  20. Using Ring Strain to Control 4π-Electrocyclization Reactions: Torquoselectivity in Ring Closing of Medium-Ring Dienes and Ring Opening of Bicyclic Cyclobutenes.

    Science.gov (United States)

    Boon, Byron A; Green, Aaron G; Liu, Peng; Houk, K N; Merlic, Craig A

    2017-05-05

    Syntheses of strained cyclic dienes were accomplished via palladium(II)-catalyzed oxidative cyclizations of terminal bis(vinylboronate esters). The reactions generate strained (E,E)-1,3-dienes that undergo spontaneous 4π-electrocyclizations to form bicyclic cyclobutenes. Formation of the cyclobutenes is driven by the strain in the medium-ring (E,E)-1,3-diene intermediate. Thermal ring openings of the cyclobutenes give (Z,Z)-1,3-diene products, again for thermodynamic reasons. DFT calculations verified the thermodynamic versus kinetic control of the reactions, and kinetic studies are in excellent agreement with the calculated energy changes. An extension of the tandem coupling/4π-electrocyclization pathway was demonstrated by a palladium(II)-catalyzed oxidative homocoupling/8π-electrocyclization cascade.

  1. Liposomal Drug Delivery of Anticancer Agents

    DEFF Research Database (Denmark)

    Pedersen, Palle Jacob

    and retention (EPR) effect. The liposomes consists of sPLA2 IIA sensitive phospholipids having anticancer drugs covalently attached to the sn-2 position of the glycerol backbone in the phospholipids, hence drug leakage is avoided from the carrier system. Various known anticancer agents, like chlorambucil, all......) based strategy using a limited number of reaction types. Upon coupling of unsaturated building blocks ring closing metathesis cascades were used to “reprogram” the molecular scaffold and highly diverse structures were obtained. In total 20 novel compounds with a broad structural diversity were prepared...

  2. Total Syntheses of Cyanthiwigins B, F, and G

    KAUST Repository

    Enquist, John A.

    2011-07-18

    A concise and versatile approach toward the preparation of the cyanthiwigin family of cyathane natural products is described. By leveraging a unique double asymmetric catalytic alkylation procedure it is possible to quickly establish two of the most critical stereocenters of the cyanthiwigin framework with high levels of selectivity and expediency. The synthetic route additionally employs both a tandem ring-closing cross-metathesis reaction, and an aldehyde-olefin radical cyclization process, in order to rapidly arrive at the tricyclic cyathane core of the cyanthiwigin molecules. From this unifying intermediate, the preparations of cyanthiwigins B, F, and G are attained swiftly and without the need for protecting groups.

  3. A Short Synthetic Route to the Calystegine Alkaloids

    DEFF Research Database (Denmark)

    Skaanderup, Philip Robert; Madsen, Robert

    2003-01-01

    An efficient strategy is described for the synthesis of enantiopure calystegine alkaloids. The key step employs a zinc-mediated fragmentation of benzyl-protected methyl 6-iodo-glycosides followed by in situ formation of the benzyl imine and Barbier-type allylation with zinc, magnesium, or indium...... metal. Stereochemistry in the pivotal allylation is controlled by the choice of the metal. The functionalized 1,8-nonadienes, thus formed, are converted into cycloheptenes by ring-closing metathesis. Regioselective hydroboration and oxidation give the corresponding cycloheptanones, which are deprotected...

  4. Practical route to the left wing of CTX1B and total syntheses of CTX1B and 54-deoxyCTX1B.

    Science.gov (United States)

    Yamashita, Shuji; Takeuchi, Katsutoshi; Koyama, Takuya; Inoue, Masayuki; Hayashi, Yujiro; Hirama, Masahiro

    2015-02-02

    Ciguatoxins, the principal causative agents of ciguatera seafood poisoning, are extremely large polycyclic ethers. We report herein a reliable route for constructing the left wing of CTX1B, which possesses the acid/base/oxidant-sensitive bisallylic ether moiety, by a 6-exo radical cyclization/ring-closing metathesis strategy. This new route enabled us to achieve the second-generation total synthesis of CTX1B and the first synthesis of 54-deoxyCTX1B. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Total Syntheses of Cyanthiwigins B, F, and G

    KAUST Repository

    Enquist, John A.; Virgil, Scott C.; Stoltz, Brian M.

    2011-01-01

    A concise and versatile approach toward the preparation of the cyanthiwigin family of cyathane natural products is described. By leveraging a unique double asymmetric catalytic alkylation procedure it is possible to quickly establish two of the most critical stereocenters of the cyanthiwigin framework with high levels of selectivity and expediency. The synthetic route additionally employs both a tandem ring-closing cross-metathesis reaction, and an aldehyde-olefin radical cyclization process, in order to rapidly arrive at the tricyclic cyathane core of the cyanthiwigin molecules. From this unifying intermediate, the preparations of cyanthiwigins B, F, and G are attained swiftly and without the need for protecting groups.

  6. A Short Synthesis of (+)-Cyclophellitol

    DEFF Research Database (Denmark)

    Hansen, Flemming Gundorph; Bundgaard, Eva; Madsen, Robert

    2005-01-01

    A new synthesis of (+)-cyclophellitol, a potent b-glucosidase inhibitor, has been completed in nine steps from D-xylose. The key transformations involve a zinc-mediated fragmentation of benzyl-protected methyl 5-deoxy-5-iodo-xylofuranoside followed by a highly diastereoselective indium-mediated c......-mediated coupling with ethyl 4-bromocrotonate. Subsequent ring-closing olefin metathesis, ester reduction, olefin epoxidation, and deprotection then afford the natural product. This constitutes the shortest synthesis of (+)-cyclophellitol reported to date....

  7. Exploiting Confinement Effects to Tune Selectivity in Cyclooctane Metathesis

    KAUST Repository

    Pump, Eva; Cao, Zhen; Samantaray, Manoja K; Bendjeriou-Sedjerari, Anissa; Cavallo, Luigi; Basset, Jean-Marie

    2017-01-01

    . In contrast, in larger pores (60 Å) a broad product distribution dominated by ring contracted cycloalkanes was found. The catalytic cycle and potential side reactions occurring at [(≡SiO-)WMe5] were examined with DFT calculations. Analysis of the geometries

  8. Thermoset polymers via ring opening metathesis polymerization of functionalized oils

    Science.gov (United States)

    Larock, Richard C; Henna, Phillip H; Kessier, Michael R

    2012-11-27

    The invention provides a method for producing a thermosetting resin from renewable oils, the method comprising supplying renewable oil molecules containing strained ring alkene moieties; reacting the alkene moieties with cyclic alkenes to create a polymer; and repeating the above two steps until the resin having desired characteristics are obtained. Also provided is a thermoset resin comprising functionalized renewable oil polymerized with a co-monomer.

  9. Insights into the decomposition of olefin metathesis precatalysts

    KAUST Repository

    Manzini, Simone

    2014-06-02

    The decomposition of a series of benzylidene, methylidene, and 3-phenylindenylidene complexes has been probed in alcohol solution in the presence of base. Tricyclohexylphosphane-containing precatalysts are shown to yield [RuCl(H)(H2)(PCy3)2] in isopropyl alcohol solutions, while 3-phenylindenylidene complexes lead to η5-(3- phenyl)indenyl products. The potential-energy surfaces for the formation of the latter species have been probed using density functional theory studies. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Factors influencing ring closure through olefin metathesis – A ...

    Indian Academy of Sciences (India)

    Unknown

    the substituents/functional groups present on the alkenes as well as at the allylic position. This article presents an overview of these ... med and (4) functional groups/substituents present in the substrate. The past several years have ..... Ackermann I, Tom D E and Furstner A 2000 Tetra- hedron 56 2196. 13. Holder S and ...

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

    Science.gov (United States)

    2006-08-01

    organic, and biochemistry, lectured in chemistry of weapons, and researched on ionic liquids and nucleic acid derivatives. She discovered her joy of...Products from oligomerization of the dimer scaffold or olefin isomerization are excluded from these projected numbers.97,98 The number of...Figure 3-8). This is excluding any olefin isomerization products or oligomerization of the cyclic scaffold. If stereoisomers are considered, then

  12. Insights into the decomposition of olefin metathesis precatalysts

    KAUST Repository

    Manzini, Simone; Poater, Albert; Nelson, David J.; Cavallo, Luigi; Slawin, Alexandra M. Z.; Nolan, Steven P.

    2014-01-01

    The decomposition of a series of benzylidene, methylidene, and 3-phenylindenylidene complexes has been probed in alcohol solution in the presence of base. Tricyclohexylphosphane-containing precatalysts are shown to yield [RuCl(H)(H2)(PCy3)2] in isopropyl alcohol solutions, while 3-phenylindenylidene complexes lead to η5-(3- phenyl)indenyl products. The potential-energy surfaces for the formation of the latter species have been probed using density functional theory studies. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Catalysts and methods for ring opening metathesis polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Schrock, Richard Royce; Autenrieth, Benjamin

    2018-04-03

    The present invention, among other things, provides highly syndiotactic poly(dicyclopentadiene) and/or hydrogenated poly(dicyclopentadiene), compositions thereof, and compounds and methods for preparing the same. In some embodiments, a provided compound is a compound of formula I, II or III. In some embodiments, a provided method comprises providing a compound of formula I, II or III.

  14. Hydrological simulations driven by RCM climate scenarios at basin scale in the Po River, Italy

    Directory of Open Access Journals (Sweden)

    R. Vezzoli

    2014-09-01

    Full Text Available River discharges are the main expression of the hydrological cycle and are the results of climate natural variability. The signal of climate changes occurrence raises the question of how it will impact on river flows and on their extreme manifestations: floods and droughts. This question can be addressed through numerical simulations spanning from the past (1971 to future (2100 under different climate change scenarios. This work addresses the capability of a modelling chain to reproduce the observed discharge of the Po River over the period 1971–2000. The modelling chain includes climate and hydrological/hydraulic models and its performance is evaluated through indices based on the flow duration curve. The climate datasets used for the 1971–2000 period are (a a high resolution observed climate dataset, and COSMO-CLM regional climate model outputs with (b perfect boundary condition, ERA40 Reanalysis, and (c suboptimal boundary conditions provided by the global climate model CMCC–CM. The aim of the different simulations is to evaluate how the uncertainties introduced by the choice of the regional and/or global climate models propagate in the simulated discharges. This point is relevant to interpret the results of the simulated discharges when scenarios for the future are considered. The hydrological/hydraulic components are simulated through a physically-based distributed model (TOPKAPI and a water balance model at the basin scale (RIBASIM. The aim of these first simulations is to quantify the uncertainties introduced by each component of the modelling chain and their propagation. Estimation of the overall uncertainty is relevant to correctly understand the future river flow regimes. The results show how bias correction algorithms can help in reducing the overall uncertainty associated to the different stages of the modelling chain.

  15. The application of RCM to ASME code requirements for in-service testing

    International Nuclear Information System (INIS)

    Rowley, C.W.

    1990-01-01

    This paper reports that the high reliability of nuclear power plant systems and components is highly important for both nuclear safety and electrical power production economics. The optimum operating performance of these plant systems and components is heavily dependent on the original or modified design for its inherent reliability and the appropriate trade-off in preventive and corrective maintenance for its developed reliability. In developing this optimum operating performance goal, the plant staff could rely solely on the experience of its personnel. However using this internal subjective approach, the average nuclear power availability has been far less than 80%. Obviously the production economics of a nuclear power plant is the province of the owner-operator, but the safety system and component performance impacts the entire industry. Hence the nuclear industry needs to have in-service testing requirements that maintain the necessary safety standards. Historically the ASME Inservice Testing Code has been a vehicle for defining some of those necessary safety standards, such as inservice testing of pumps, valves, and snubbers. The nuclear industry needs to expand the code testing to include all the systems that affect these necessary safety standards

  16. Diagnostic budget study of the internal variability in ensemble simulations of the Canadian RCM

    Energy Technology Data Exchange (ETDEWEB)

    Nikiema, Oumarou; Laprise, Rene [UQAM, Canadian Network for Regional Climate Modelling and Diagnostics, Centre ESCER, Departement des Sciences de la Terre et de l' Atmosphere, B.P. 8888, Montreal, QC (Canada)

    2011-06-15

    Due to the chaotic and nonlinear nature of the atmospheric dynamics, it is known that small differences in the initial conditions (IC) of models can grow and affect the simulation evolution. In this study, we perform a quantitative diagnostic budget calculation of the various diabatic and dynamical contributions to the time evolution and spatial distribution of internal variability (IV) in simulations with the nested Canadian Regional Climate Model. We establish prognostic budget equations of the IV for the potential temperature and the relative vorticity fields. For both of these variables, the IV equations present similar terms, notably terms relating to the transport of IV by ensemble-mean flow and to the covariance of fluctuations acting on the gradient of the ensemble-mean state. We show the skill of these equations to diagnose the IV that took place in an ensemble of 20 3-month (summer season) simulations that differed only in their IC. Our study suggests that the dominant terms responsible for the large increase of IV are either the covariance term involving the potential temperature fluctuations and diabatic heating fluctuations, or the covariance of inter-member fluctuations acting upon ensemble-mean gradients. Our results also show that, on average, the third-order terms are negligible, but they can become important when the IV is large. (orig.)

  17. Highly Efficient Synthesis of the Natural Spiro-Terpenoid ( ± )-Andirolactone via RCM Reaction

    Institute of Scientific and Technical Information of China (English)

    ZHANG Tao; YANG Li-Ting; LIU Hua-Wei; LI Yu-Lin

    2003-01-01

    @@ Andirolactone 1 as the dextro enantiomer is a sesquiterpenoid with structure of spirocyclic butenolide, isolated from the wood of cedar ( Cedrus libanotica ), which is a needle-leaf tree that grows in southern Turkey and Libanon.The tar, which is obtained from its wood, is used to cure various diseases. [1

  18. RCM optimization of a system under both preventive and corrective maintenance

    International Nuclear Information System (INIS)

    Bris, R.; Cepin, M.

    2005-01-01

    Testing and maintenance activities of power electrical equipment are an important potential for both risk and cost reduction. A multi-objective maintenance optimization method is presented based on the Genetic Algorithms (GA) technique. The method determines the optimal schedule of preventive maintenance actions based on minimization both selected risk measure and cost. Applied cost model takes into account both preventive and corrective maintenance. This paper also presents application of the methodology to optimize maintenance of a real distribution network 22 kV. Conclusions and recommendations for practice are made on the basis of obtained results. (author)

  19. Electron beam treatment of organic pollutants contained in gaseous streams. 1. RCM report

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2005-07-01

    Volatile Organic Compounds (VOC) and Polyaromatic Hydrocarbons (PAH) are emitted in different processes, mostly combustion-based ones applied in power, chemical and metallurgical industries, municipal wastes incineration, etc. Many of them are persistent in environment, so called Persistent Organic Pollutants (POPs). They are responsible for ozone layer depletion, ground level and photochemical smog formation, contribute to the greenhouse effect, most of them being carcinogenic or/and mutagenic. Some tests performed in different countries have shown that electron beam technology can be a promising technique in these applications. Good removing efficiency for chlorohydrocarbons, dioxins and PAH was demonstrated in the laboratory scale. Different hybrid techniques like eb/absorption or eb/catalysis were studied as well. However, due to the different product formation, this technique should be studied carefully further concerning process mechanism, analyses of products and possible technical solution applications. The present CRP aiming at development of laboratory and pilot plant methodologies for comparative evaluation of degradation effects of organic pollutants in gaseous phase. Theoretical and experimental investigations of the mechanisms of the processes are part of the research work. Limitation of formation of toxic byproducts, modification of physical and chemical properties, application of hybrid processes (eb/catalytist) are important topics for further development under the CRP. The CRP has been launched with the objectives of developing analytical techniques for better understanding of degradation effects of organic pollutants in gaseous phase and technologies (processing conditions) to control these emissions. It is anticipated that through collaborative and cooperative research efforts of the participants, new analytical methods to study the process and strategies to apply electron beam to address these emissions will be developed. The executive summary provides background information followed by information on health risks associated with volatile organic compounds (VOCS), areas of development, laboratory and pilot scale research work, electron beam fuel gas purification technology - up-scaling and development, CRP overall objective, network collaboration and the workplan. The executive summary ends with conclusions and recommendations followed by 13 individual reports of participating countries. They are indexed separately.

  20. Electron beam treatment of organic pollutants contained in gaseous streams. 1. RCM report

    International Nuclear Information System (INIS)

    2005-01-01

    Volatile Organic Compounds (VOC) and Polyaromatic Hydrocarbons (PAH) are emitted in different processes, mostly combustion-based ones applied in power, chemical and metallurgical industries, municipal wastes incineration, etc. Many of them are persistent in environment, so called Persistent Organic Pollutants (POPs). They are responsible for ozone layer depletion, ground level and photochemical smog formation, contribute to the greenhouse effect, most of them being carcinogenic or/and mutagenic. Some tests performed in different countries have shown that electron beam technology can be a promising technique in these applications. Good removing efficiency for chlorohydrocarbons, dioxins and PAH was demonstrated in the laboratory scale. Different hybrid techniques like eb/absorption or eb/catalysis were studied as well. However, due to the different product formation, this technique should be studied carefully further concerning process mechanism, analyses of products and possible technical solution applications. The present CRP aiming at development of laboratory and pilot plant methodologies for comparative evaluation of degradation effects of organic pollutants in gaseous phase. Theoretical and experimental investigations of the mechanisms of the processes are part of the research work. Limitation of formation of toxic byproducts, modification of physical and chemical properties, application of hybrid processes (eb/catalytist) are important topics for further development under the CRP. The CRP has been launched with the objectives of developing analytical techniques for better understanding of degradation effects of organic pollutants in gaseous phase and technologies (processing conditions) to control these emissions. It is anticipated that through collaborative and cooperative research efforts of the participants, new analytical methods to study the process and strategies to apply electron beam to address these emissions will be developed. The executive summary provides background information followed by information on health risks associated with volatile organic compounds (VOCS), areas of development, laboratory and pilot scale research work, electron beam fuel gas purification technology - up-scaling and development, CRP overall objective, network collaboration and the workplan. The executive summary ends with conclusions and recommendations followed by 13 individual reports of participating countries. They are indexed separately

  1. Implementing Reliability Centered Maintenance (RCM) with State of the Art PT&I Technologies

    Science.gov (United States)

    Hollis, Sean; Sasser, Chase

    2016-01-01

    Building on the work that was started two decades ago, Jacobs Space Operations Group has utilized state of the art PTI technologies to assess the current condition of the assets they manage under the Test and Operations Support Contract (TOSC). Specifically, the Asset Management department leveraged the benefits of ultrasound technology to quantify a motor issue in the Liquid Oxygen Storage Area, and troubleshoot the sources prior to loading the tank to perform Verification and Validation (VV) activities. This technology was efficient, easy to implement, and provided system engineers with data on a possible source of the problem. In situations where legacy motors are exhibiting unexpected noises, it may seem easier to remove and refurbish the motor and replace the bearings because that solution resolves most of the common causes of the noise. However, that solution would have involved additional spending and may not have solved issues stemming from the foundation, if those existed. By utilizing the ultrasound equipment provided by UE Systems, the sound profiles allowed Jacobs TOSC team to determine that the issue resembled a faulty bearing. After replacing the bearing, the unexpected noise ceased.

  2. Identifying climate analogues for precipitation extremes for Denmark based on RCM simulations from the ENSEMBLES database

    DEFF Research Database (Denmark)

    Arnbjerg-Nielsen, Karsten; Funder, S. G.; Madsen, H.

    2015-01-01

    Climate analogues, also denoted Space-For-Time, may be used to identify regions where the present climatic conditions resemble conditions of a past or future state of another location or region based on robust climate variable statistics in combination with projections of how these statistics cha...

  3. Performance of a multi-RCM ensemble for South Eastern South America

    Energy Technology Data Exchange (ETDEWEB)

    Carril, A.F.; Menendez, C.G.; Salio, P. [Ciudad Universitaria, Ciudad Autonoma de Buenos Aires, Centro de Investigaciones del Mar y la Atmosfera (CIMA), CONICET-UBA, Buenos Aires (Argentina); Universidad de Buenos Aires, Departamento de Ciencias de la Atmosfera y los Oceanos (DCAO), FCEN, Buenos Aires (Argentina); UMI IFAECI/CNRS, Buenos Aires (Argentina); Remedio, A.R.C.; Jacob, D.; Pfeifer, S. [Max Planck Institute for Meteorology (MPI-M), Hamburg (Germany); Robledo, F.; Tencer, B. [Universidad de Buenos Aires, Departamento de Ciencias de la Atmosfera y los Oceanos (DCAO), FCEN, Buenos Aires (Argentina); Soerensson, A.; Zaninelli, P. [Ciudad Universitaria, Ciudad Autonoma de Buenos Aires, Centro de Investigaciones del Mar y la Atmosfera (CIMA), CONICET-UBA, Buenos Aires (Argentina); UMI IFAECI/CNRS, Buenos Aires (Argentina); Boulanger, J.P. [LOCEAN, UMR CNRS/IRD/UPMC, Paris (France); Castro, M. de; Sanchez, E. [Universidad de Castilla-La Mancha (UCLM), Toledo (Spain); Le Treut, H.; Li, L.Z.X. [Sciences de l' Environnement en Ile de France, Laboratoire de Meteorologie Dynamique (LMD), Institut-Pierre-Simon-Laplace et Ecole Doctorale, Paris (France); Penalba, O.; Rusticucci, M. [Universidad de Buenos Aires, Departamento de Ciencias de la Atmosfera y los Oceanos (DCAO), FCEN, Buenos Aires (Argentina); UMI IFAECI/CNRS, Buenos Aires (Argentina); Samuelsson, P. [Swedish Meteorological and Hydrological Institute (SMHI), Norrkoeping (Sweden)

    2012-12-15

    The ability of four regional climate models to reproduce the present-day South American climate is examined with emphasis on La Plata Basin. Models were integrated for the period 1991-2000 with initial and lateral boundary conditions from ERA-40 Reanalysis. The ensemble sea level pressure, maximum and minimum temperatures and precipitation are evaluated in terms of seasonal means and extreme indices based on a percentile approach. Dispersion among the individual models and uncertainties when comparing the ensemble mean with different climatologies are also discussed. The ensemble mean is warmer than the observations in South Eastern South America (SESA), especially for minimum winter temperatures with errors increasing in magnitude towards the tails of the distributions. The ensemble mean reproduces the broad spatial pattern of precipitation, but overestimates the convective precipitation in the tropics and the orographic precipitation along the Andes and over the Brazilian Highlands, and underestimates the precipitation near the monsoon core region. The models overestimate the number of wet days and underestimate the daily intensity of rainfall for both seasons suggesting a premature triggering of convection. The skill of models to simulate the intensity of convective precipitation in summer in SESA and the variability associated with heavy precipitation events (the upper quartile daily precipitation) is far from satisfactory. Owing to the sparseness of the observing network, ensemble and observations uncertainties in seasonal means are comparable for some regions and seasons. (orig.)

  4. The influence of air in mortar on the results of the RCM test

    NARCIS (Netherlands)

    Taher, A.; Hofstede, J.M.; van der Zanden, A.J.J.; Brouwers, H.J.H.; Bilek, V.; Kersner, Z.

    2014-01-01

    Chloride penetration into concrete structures reduces their service life. When chloride reaches the steel rebar, it may corrode which eventually leads to concrete deterioration. Hence, it is important to test concrete on chloride penetration resistance. Such testing often takes a long time, because

  5. Identifying climate analogues for precipitation extremes for Denmark based on RCM simulations from the ENSEMBLES database.

    Science.gov (United States)

    Arnbjerg-Nielsen, K; Funder, S G; Madsen, H

    2015-01-01

    Climate analogues, also denoted Space-For-Time, may be used to identify regions where the present climatic conditions resemble conditions of a past or future state of another location or region based on robust climate variable statistics in combination with projections of how these statistics change over time. The study focuses on assessing climate analogues for Denmark based on current climate data set (E-OBS) observations as well as the ENSEMBLES database of future climates with the aim of projecting future precipitation extremes. The local present precipitation extremes are assessed by means of intensity-duration-frequency curves for urban drainage design for the relevant locations being France, the Netherlands, Belgium, Germany, the United Kingdom, and Denmark. Based on this approach projected increases of extreme precipitation by 2100 of 9 and 21% are expected for 2 and 10 year return periods, respectively. The results should be interpreted with caution as the best region to represent future conditions for Denmark is the coastal areas of Northern France, for which only little information is available with respect to present precipitation extremes.

  6. Valorisation de la coupe C4 de vapocraquage via l'hydrogénation du butadiène, l'isomérisation des butènes et la métathèse, en MTBE ou en propylène Upgrading the C4 Cut from Steam Cracking via the Hydrogenation of Butadiene, the Isomerization of Butenes and Metathesis Into Mtbe Or Propylene

    Directory of Open Access Journals (Sweden)

    Chaumette S.

    2006-11-01

    of the cut can be transformed into MTBE by implementing the new n-butene isomerization process. Another upgrading scheme consits in transforming isobutene into MTBE and n-butenes into propylene by metathesis with ethylene. These new route may find competition in the transformation of butenes into alkylates, for automotive gasoline, with or without MTBE production. After a brief review of the different markets for the products involved, a technico-economic study serves to classify the different upgrading routes of the C4 cut from steam cracking, by comparing both the minimum profitable selling prices for a discounting rate of 12% and the discounted cash-flow rate of return for fixed selling prices. Calculations are performed within a context in which the C4 cut is devalorized in relation to naphtha with a price of $152/t. When butadiene no longer finds any outlets, and when its price is at a very low level such as $270/t, its extraction is hardly profitable, and propylene production by methatesis proves to be more advantageous. However, if the steam cracker is integrated in a refinery, butenes may also be advantageously transformed into alkylates or MTBE, more especially to meet a demand for octane or oxygenated products for fuels. These different routes for upgrading MTBE are more advantageous than MTBE production from butanes, requiring heavy investments for the separation of butanes, the isomerization of n-butane and the dehydrogenation of isobutane. Likewise, the transformation of butenes into propylene is more profitable than obtaining propylene by the dehydrogenation of proprane. A sensitivity study, for the price of butadiene and also for the price of other products, enables isoprofitability curves to be plotted, which delimite price zones favorable to one or the other of the products considered, taken two by two.

  7. Synthesis of Ophiocerins from Non-Carbohydrate Sources

    International Nuclear Information System (INIS)

    Hong, Hui Jeong; Lee, Dong Min; Kang, Han Young

    2010-01-01

    Direct and unified synthetic routes to ophiocerin A, B, C, and D have been successfully developed. These syntheses are based on ring-closing metathesis and non-carbohydrate starting materials and are simpler and more efficient than the previous syntheses, as demonstrated in the case of ophiocerin B (2) (eleven steps from methyl α-D-glucopyranoside vs. four steps from 4-penten-2-ol) and ophiocerin A (1) (twelve steps from methyl α-D-glucopyranoside vs. three steps from 4-penten-2-ol). These routes will be useful for the practical synthesis of related natural products. Ophiocerins are comprised of four compounds isolated from the aqueous fungi Ophioceras venezuelense, each bearing a tetrahydropyran ring with an interesting array of substituents (Figure 1). Since substituted tetrahydropyran rings are found in many biologically important natural products, ophiocerins have attracted the attention of synthetic chemists

  8. Synthesis of (+)-dumetorine and congeners by using flow chemistry technologies.

    Science.gov (United States)

    Riva, Elena; Rencurosi, Anna; Gagliardi, Stefania; Passarella, Daniele; Martinelli, Marisa

    2011-05-23

    An efficient total synthesis of the natural alkaloid (+)-dumetorine by using flow technology is described. The process entailed five separate steps starting from the enantiopure (S)-2-(piperidin-2-yl)ethanol 4 with 29% overall yield. Most of the reactions were carried out by exploiting solvent superheating and by using packed columns of immobilized reagents or scavengers to minimize handling. New protocols for performing classical reactions under continuous flow are disclosed: the ring-closing metathesis reaction with a novel polyethylene glycol-supported Hoveyda catalyst and the unprecedented flow deprotection/Eschweiler-Clarke methylation sequence. The new protocols developed for the synthesis of (+)-dumetorine were applied to the synthesis of its simplified natural congeners (-)-sedamine and (+)-sedridine. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Synthesis of naturally occurring iminosugars from D-fructose by the use of a zinc-mediated fragmentation reaction

    DEFF Research Database (Denmark)

    Lauritsen, Anne; Madsen, Robert

    2006-01-01

    A short synthesis of 1,4-dideoxy-1,4-imino-D-arabinitol (DAB) and a formal synthesis of australine are described. In both cases, D-fructose is employed as the starting material and converted into a protected methyl 6-deoxy-6-iodo-furanoside. Zinc-mediated fragmentation produces an unsaturated...... ketone which serves as a key building block for both syntheses. Ozonolysis, reductive amination with benzylamine and deprotection affordfs 1,4-dideoxy-1,4-imino-D-arabinitol in only 7 steps and 11% overall yield from D-fructose. Alternatively, reductive amination with homoallylamine, ring......-closing metathesis and protecting group manipulations give rise to an intermediate which can be converted into australine in 3 steps. The intermediate is prepared by two different strategies both of which use a total of 9 steps. The first strategy utilizes benzyl ethers for protection of fructose while the second...

  10. Total synthesis of ciguatoxin and 51-hydroxyCTX3C.

    Science.gov (United States)

    Inoue, Masayuki; Miyazaki, Keisuke; Ishihara, Yuuki; Tatami, Atsushi; Ohnuma, Yuyu; Kawada, Yuuya; Komano, Kazuo; Yamashita, Shuji; Lee, Nayoung; Hirama, Masahiro

    2006-07-26

    Ciguatoxins, the principal causative toxins of ciguatera seafood poisoning, are large ladder-like polycyclic ethers with the 13 ether rings ranging from five- to nine-membered. In this paper, we describe the total synthesis of the two most toxic members of the ciguatoxin family, ciguatoxin 1 and 51-hydroxyCTX3C 2, based on a unified synthetic strategy. The key features in our syntheses were (i) direct construction of the O,S-acetal from the corresponding left and right wing fragments (3, 4, 14); (ii) stereo- and chemoselective radical reaction of the alpha-oxyradical with pentafluorophenyl acrylate to achieve cyclization of the seven-membered G-ring; (iii) ring-closing metathesis reaction to build the nine-membered F-ring; and (iv) an efficient protective group strategy using the oxidatively removable 2-naphthylmethyl groups.

  11. Synthesis and Evaluation of a 2,11-Cembranoid-Inspired Library.

    Science.gov (United States)

    Welford, Amanda J; Caldwell, John J; Liu, Manjuan; Richards, Meirion; Brown, Nathan; Lomas, Cara; Tizzard, Graham J; Pitak, Mateusz B; Coles, Simon J; Eccles, Suzanne A; Raynaud, Florence I; Collins, Ian

    2016-04-11

    The 2,11-cembranoid family of natural products has been used as inspiration for the synthesis of a structurally simplified, functionally diverse library of octahydroisobenzofuran-based compounds designed to augment a typical medicinal chemistry library screen. Ring-closing metathesis, lactonisation and SmI2 -mediated methods were exemplified and applied to the installation of a third ring to mimic the nine-membered ring of the 2,11-cembranoids. The library was assessed for aqueous solubility and permeability, with a chemical-space analysis performed for comparison to the family of cembranoid natural products and a sample set of a screening library. Preliminary investigations in cancer cells showed that the simpler scaffolds could recapitulate the reported anti-migratory activity of the natural products. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  12. Electrochemically Triggered Co-Conformational Switching in a [2]catenane Comprising a Non-Symmetric Calix[6]arene Wheel and a Two-Station Oriented Macrocycle

    Directory of Open Access Journals (Sweden)

    Valeria Zanichelli

    2018-05-01

    Full Text Available Catenanes with desymmetrized ring components can undergo co-conformational rearrangements upon external stimulation and can form the basis for the development of molecular rotary motors. We describe the design, synthesis and properties of a [2]catenane consisting of a macrocycle—the ‘track’ ring—endowed with two distinct recognition sites (a bipyridinium and an ammonium for a calix[6]arene—the ‘shuttle’ ring. By exploiting the ability of the calixarene to thread appropriate non-symmetric axles with directional selectivity, we assembled an oriented pseudorotaxane and converted it into the corresponding oriented catenane by intramolecular ring closing metathesis. Cyclic voltammetric experiments indicate that the calixarene wheel initially surrounds the bipyridinium site, moves away from it when it is reduced, and returns in the original position upon reoxidation. A comparison with appropriate model compounds shows that the presence of the ammonium station is necessary for the calixarene to leave the reduced bipyridinium site.

  13. Efficient synthetic methods for the installation of boron-nitrogen bonds in conjugated organic molecules.

    Science.gov (United States)

    Morgan, Matthew M; Piers, Warren E

    2016-04-14

    Polycyclic aromatic hydrocarbons in which one or more CC units have been replaced by isoelectronic BN units have attracted interest as potentially improved organic materials in various devices. This promise has been hampered by a lack of access to gram quantities of these materials. However, the exploitation of keystone reactions such as ring closing metathesis, borylative cyclization of amino styrenes and electrophilic borylation has lead to strategies for access to workable amounts of material. These strategies can be augmented by judicious postfunctionalization reactions to diversify the library of materials available. This Frontier article highlights some of the recent successes and shows that the long promised applications of BN-doped PAHs are beginning to be explored in a meaningful way.

  14. Nicholas reactions in the construction of cyclohepta[de]naphthalenes and cyclohepta[de]naphthalenones. The total synthesis of microstegiol.

    Science.gov (United States)

    Taj, Rafiq A; Green, James R

    2010-12-03

    The application of the Nicholas reaction chemistry of 2,7-dioxygenated naphthalenes in the synthesis of cyclohepta[de]napthalenes and in the synthesis of (±)-microstegiol (1) is presented. The substitution profile of Nicholas monosubstitution (predominantly C-1) and disubstitution reactions (predominantly 1,6-) on 2,7-dioxygenated napthalenes is reported. Application of a 1,8-dicondensation product and selected C-1 monocondensation products to the construction of cyclohepta[de]naphthalenes by way of ring closing metathesis and intramolecular Friedel-Crafts reactions, respectively, is described. Deprotection of the C-7 oxygen function to the corresponding naphthol allows tautomerization to cyclohepta[de]naphthalene-1-ones upon seven-membered-ring closure in most cases, and replacement of the C-2 oxygen function in the naphthalene by a methyl group ultimately allows the synthesis of (±)-microstegiol.

  15. Structural diversification of the aminobicyclo[4.3.0]nonane skeleton using alkynylsilyl-derived allylic trichloroacetimidates.

    Science.gov (United States)

    Mostafa, Mohamed A B; McMillan, Angus E; Sutherland, Andrew

    2017-04-05

    The amino substituted bicyclo[4.3.0]nonane is a molecular scaffold found in a wide range of natural products and medicinal agents. Despite this, synthetic methods for the general preparation of this structural motif are sparse. Here we evaluate a diastereoselective approach for the preparation of vinylsilyl derived aminobicyclo[4.3.0]nonanes using a one-pot multi-bond forming process involving a Pd(ii)-catalysed Overman rearrangement, a Ru(ii)-catalysed ring closing enyne metathesis reaction, followed by a hydrogen bonding directed Diels-Alder reaction. We show that a benzyldimethylsilyl-substituted alkene analogue is amenable to further functionalisation and the late stage generation of diverse sp 3 -rich, drug-like aminobicyclo[4.3.0]nonane scaffolds with up to six stereogenic centres.

  16. Identification, synthesis and mass spectrometry of a macrolide from the African reed frog Hyperolius cinnamomeoventris

    Directory of Open Access Journals (Sweden)

    Markus Menke

    2016-12-01

    Full Text Available The contents of the gular glands of the male African reed frog Hyperolius cinnamomeoventris consist of a mixture of aliphatic macrolides and sesquiterpenes. While the known macrolide gephyromantolide A was readily identified, the structure of another major component was suggested to be a tetradecen-13-olide. The synthesis of the two candidate compounds (Z-5- and (Z-9-tetradecen-13-olide revealed the former to be the naturally occurring compound. The synthesis used ring-closing metathesis as key step. While the Hoveyda–Grubbs catalyst furnished a broad range of isomeric products, the (Z-selective Grubbs catalyst lead to pure (Z-products. Analysis by chiral GC revealed the natural frog compound to be (5Z,13S-5-tetradecen-13-olide (1. This compound is also present in the secretion of other hyperoliid frogs as well as in femoral glands of male mantellid frogs such as Spinomantis aglavei. The mass spectra of the synthesized macrolides as well as their rearranged isomers obtained during ring-closing metathesis showed that it is possible to assign the location of the double bond in an unsaturated macrolide on the basis of its EI mass spectrum. The occurrence of characteristic ions can be explained by the fragmentation pathway proposed in the article. In contrast, the localization of a double bond in many aliphatic open-chain compounds like alkenes, alcohols or acetates, important structural classes of pheromones, is usually not possible from an EI mass spectrum. In the article, we present the synthesis and for the first time elucidate the structure of macrolides from the frog family Hyperoliidae.

  17. A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

    KAUST Repository

    Poater, Albert

    2015-09-29

    During a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC), depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate.

  18. Easy access to nucleophilic boron through diborane to magnesium boryl metathesis

    Science.gov (United States)

    Pécharman, Anne-Frédérique; Colebatch, Annie L.; Hill, Michael S.; McMullin, Claire L.; Mahon, Mary F.; Weetman, Catherine

    2017-04-01

    Organoboranes are some of the most synthetically valuable and widely used intermediates in organic and pharmaceutical chemistry. Their synthesis, however, is limited by the behaviour of common boron starting materials as archetypal Lewis acids such that common routes to organoboranes rely on the reactivity of boron as an electrophile. While the realization of convenient sources of nucleophilic boryl anions would open up a wealth of opportunity for the development of new routes to organoboranes, the synthesis of current candidates is generally limited by a need for highly reducing reaction conditions. Here, we report a simple synthesis of a magnesium boryl through the heterolytic activation of the B-B bond of bis(pinacolato)diboron, which is achieved by treatment of an easily generated magnesium diboranate complex with 4-dimethylaminopyridine. The magnesium boryl is shown to act as an unambiguous nucleophile through its reactions with iodomethane, benzophenone and N,N'-di-isopropyl carbodiimide and by density functional theory.

  19. A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

    KAUST Repository

    Poater, Albert; Cavallo, Luigi

    2015-01-01

    During a Ru-catalyzed reaction of an olefin with an alkylidene moiety that leads to a metallacycle intermediate, the cis insertion of the olefin can occur from two different directions, namely side and bottom with respect to the phosphine or N-heterocyclic ligand (NHC), depending on the first or second generation Grubbs catalyst. Here, DFT calculations unravel to which extent the bottom coordination of olefins with respect is favored over the side coordination through screening a wide range of catalysts, including first and second generation Grubbs catalysts as well as the subsequent Hoveyda derivatives. The equilibrium between bottom and side coordination is influenced by sterics, electronics, and polarity of the solvent. The side attack is favored for sterically less demanding NHC and/or alkylidene ligands. Moreover the generation of a 14-electron species is also discussed, with either pyridine or phosphine ligands to dissociate.

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

    Czech Academy of Sciences Publication Activity Database

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

    2015-01-01

    Roč. 11, NOV 2015 (2015), s. 2087-2096 ISSN 1860-5397 Institutional support: RVO:61388955 Keywords : Hoveyda-Grubbs type catalyst * hybrid catalysts * lamellar zeolites Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.697, year: 2015

  1. Metathesis of cardanol over ammonium tagged Hoveyda-Grubbs type catalyst supported on SBA-15

    Czech Academy of Sciences Publication Activity Database

    Balcar, Hynek; Žilková, Naděžda; Kubů, Martin; Polášek, Miroslav; Zedník, J.

    2018-01-01

    Roč. 304, APR 2018 (2018), s. 127-134 ISSN 0920-5861 R&D Projects: GA ČR GA17-01440S Institutional support: RVO:61388955 Keywords : Cardanol * Flow chemistry * Hoveyda-Grubbs type catalyst * Immobilized catalyst Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 4.636, year: 2016

  2. Worsening of Heat Stress Due To Global Warming in South Korea Based on Multi-RCM Ensemble Projections

    Science.gov (United States)

    Im, Eun-Soon; Choi, Yeon-Woo; Ahn, Joong-Bae

    2017-11-01

    This study assesses the future changes in summer (June-July-August; JJA) heat stress over South Korea under global warming. To better resolve the region-specific changes in terms of geographical patterns and severity of heat stress in the Korean peninsula, four regional climate models (RCMs) are used for dynamical downscaling of Hadley Centre Global Environmental Model version 2—Atmosphere and Ocean global projections forced by two Representative Concentration Pathway (RCP4.5 and RCP8.5) scenarios. Dynamically downscaled simulations (horizontal resolution of 12.5 km and output interval of 3 h) facilitate in-depth analysis of diurnal variation and extremes over South Korea, as well as focusing on the particular location, Daegu, that is characterized by high vulnerability to rising temperature. Both maximum temperature and heat stress indices such as wet bulb globe temperature and apparent temperature, which include the effect of humidity, are examined in order to comprehensively interpret the behaviors of heat stress in response to anthropogenic climate change. Ensemble projections reveal robust patterns of temperature and resultant humidity increases that are roughly constrained by the approximate 7%/K increase in the moisture holding capacity. The changes in temperature and humidity are directly transmitted to the heat stress indices, showing a significant increase. The heat stress is exacerbated in a differentiated way, with more intensification in diurnal variation at nighttime and in regional variation at low-elevation basins. Both RCP4.5 and RCP8.5 scenarios project the statistical likelihood of a notable increase of extreme heat stress indices, much stronger and more extended heat waves, and the emergence of a long period of consecutive tropical nights.

  3. Report of the 3{sup rd} RCM on Improved High Current Liquid and Gas Targets for Cyclotron Produced Radioisotopes

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2009-07-01

    The overall objective of this CRP was the development of new accelerator targetry technology including several target systems but focusing on the reliable production of carbon-11 and fluorine-18 in various chemical forms with a view to increasing production yields, specific activity, improving the economics of production and the availability of the radiotracers. Significant advances have been made under this CRP in the development and standardization of high power gas and liquid targets. This CRP has resulted in the development of methods which can be used in high power targets to increase Carbon-11, Fluorine-18, Nitrogen-13, Iodine-123 and Krypton-81m, specific activities (a least a two fold increase), chemical purities as well as ensuring reliability of the production of the radiopharmaceuticals derived from these radionuclides. More importantly, these advances have minimized the unnecessarily operator exposure to radiation. In addition, knowledge of recovery and characterization of enriched H{sub 2} {sup 18}O was also gained. Through this research the production capabilities with regard to [{sup 18}F]F{sup -}, [{sup 11}C]CO{sub 2} and [{sup 11}C]CH{sub 4} have increased 3 to 6 fold. A high current niobium target system has been designed, tested and put in service which could increase production capability of {sup 18}FDG by a factor of 2.5. A survey of target maintenance procedures has been carried out and the results of this survey are reported in this CRP. It was determined that the tritium introduced by the inevitable nuclear reactions does not pose any health physics problems either during the tracer manufacturer or during potential water reclamation. It was further determined that radionuclides produced in the metal foil during irradiation are found in the target water at very low concentrations. These impurities can be essentially eliminated by using noble metal plated foils. The radionuclides can also be reduced by the separation technology typically used for fluorine extraction from the O-18 water. In no case were the radionuclides produced in the foil found in the fluorine containing final product. However, in spite of these findings, there is still significant research required on these target systems and more importantly the knowledge that has been gained needs to be transferred to the countries and facilities where it will help to optimize the production of radionuclides used for PET. With regard to the latter, a book will be published focusing on two of the most widely used target systems and including both fundamental knowledge and practical advice on the operation of these target systems. In addition to this book, lectures have been planned to convey both the knowledge gained in this CRP and the problems identified by this expert panel to the wider radionuclide production community with the idea that further research on these problems will benefit all the Member States and the community in general.

  4. 1st RCM of IAEA CRP on Prediction of Axial and Radial Creep in HWR Pressure Tubes

    International Nuclear Information System (INIS)

    Choi, Jong-Ho

    2013-01-01

    Expected outcome: Improved understanding of pressure tube creep mechanism by studying the effect of intrinsic (material response) as well as extrinsic parameters (operating conditions). • Improvement of material characterization technology: many laboratories participating in this CRP will conduct the microstructure characterization for the first time. • Recommendation for manufacturing to achieve optimal PT performance: The database will enable the identification of best pressure tube performance by comparison of data. • Improvement in aging management procedure: (channel selection for PT deformation management, etc.). • Safety enhancement for operating HWRs by reducing the uncertainty in the prediction of PT deformation

  5. Establishment of a maintenance plan based on quantitative analysis in the context of RCM in a JIT production scenario

    International Nuclear Information System (INIS)

    Alebrant Mendes, Angélica; Duarte Ribeiro, José Luis

    2014-01-01

    This paper presents a quantitative method for supporting the preparation or review of an equipment maintenance plan in a Just-in-time production scenario. The proposed method includes the following steps: (i) identifying the parts that influence reliability; (ii) surveying the failure rates and times to repair the parts; (iii) classification of parts according to the effect of their failures; (iv) surveying the line occupation parameters; (v) identifying the probability distributions for time to failure, time to repair, and line occupation; (vi) simulating the production and maintenance using the Monte Carlo approach; (vii) conducting a sensitivity analysis concerning variations in demand, MTTF, and MTTR; and (viii) establishing optimized intervals for preventive maintenance. The method is illustrated through an application in a labeling and filling gallons line at a paints and dyes production company. This method allowed the identification of critical parts as it relates to the productive scenario in question. The results can support companies in their decision making regarding the need and/or type of maintenance investment that would best fit an expected demand scenario

  6. Report of the 3rd RCM on Improved High Current Liquid and Gas Targets for Cyclotron Produced Radioisotopes

    International Nuclear Information System (INIS)

    2009-01-01

    The overall objective of this CRP was the development of new accelerator targetry technology including several target systems but focusing on the reliable production of carbon-11 and fluorine-18 in various chemical forms with a view to increasing production yields, specific activity, improving the economics of production and the availability of the radiotracers. Significant advances have been made under this CRP in the development and standardization of high power gas and liquid targets. This CRP has resulted in the development of methods which can be used in high power targets to increase Carbon-11, Fluorine-18, Nitrogen-13, Iodine-123 and Krypton-81m, specific activities (a least a two fold increase), chemical purities as well as ensuring reliability of the production of the radiopharmaceuticals derived from these radionuclides. More importantly, these advances have minimized the unnecessarily operator exposure to radiation. In addition, knowledge of recovery and characterization of enriched H 2 18 O was also gained. Through this research the production capabilities with regard to [ 18 F]F - , [ 11 C]CO 2 and [ 11 C]CH 4 have increased 3 to 6 fold. A high current niobium target system has been designed, tested and put in service which could increase production capability of 18 FDG by a factor of 2.5. A survey of target maintenance procedures has been carried out and the results of this survey are reported in this CRP. It was determined that the tritium introduced by the inevitable nuclear reactions does not pose any health physics problems either during the tracer manufacturer or during potential water reclamation. It was further determined that radionuclides produced in the metal foil during irradiation are found in the target water at very low concentrations. These impurities can be essentially eliminated by using noble metal plated foils. The radionuclides can also be reduced by the separation technology typically used for fluorine extraction from the O-18 water. In no case were the radionuclides produced in the foil found in the fluorine containing final product. However, in spite of these findings, there is still significant research required on these target systems and more importantly the knowledge that has been gained needs to be transferred to the countries and facilities where it will help to optimize the production of radionuclides used for PET. With regard to the latter, a book will be published focusing on two of the most widely used target systems and including both fundamental knowledge and practical advice on the operation of these target systems. In addition to this book, lectures have been planned to convey both the knowledge gained in this CRP and the problems identified by this expert panel to the wider radionuclide production community with the idea that further research on these problems will benefit all the Member States and the community in general

  7. Voltage-assisted capillary LC of peptides using monolithic capillary columns prepared by ring-opening metathesis polymerization

    Czech Academy of Sciences Publication Activity Database

    Sedláková, Pavla; Mikšík, Ivan; Gatschelhofer, Ch.; Sinner, F. M.; Buchmeiser, M. R.

    2007-01-01

    Roč. 28, č. 13 (2007), s. 2219-2222 ISSN 0173-0835 R&D Projects: GA ČR GA203/05/2539; GA ČR GA203/06/1044; GA MŠk(CZ) 1M0510 Institutional research plan: CEZ:AV0Z50110509 Keywords : ROMP * voltage-assisted capillary LC Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.609, year: 2007

  8. A theoretical view on the thermodynamic cis-trans equilibrium of dihalo ruthenium olefin metathesis (pre-)catalysts

    KAUST Repository

    Pump, Eva

    2015-02-24

    Abstract: This work was conducted to provide an overview on the position of the thermodynamic cis–trans equilibrium of 85 conventional and X-chelated alkylidene-ruthenium complexes (X=O, S, Se, N, P, Cl, I, Br). The reported energies (ΔE) were obtained through single-point calculations with M06 functional and TZVP basis set from BP86/SVP-optimized cis- and trans-dichloro geometries and using the polarizable continuum model to simulate the influence of the solvent. Dichloromethane and toluene were selected as examples for solvents with high and low dielectric constants. The obtained relative stabilities of the cis- and trans-dihalo derivatives of the respective alkylidene complexes will serve for a better explanation of their catalytic activity as has been disclosed herein with selected examples.Graphical abstract: [Figure not available: see fulltext.

  9. Generation of Stoichiometric Ethylene and Isotopic Derivatives and Application in Transition Metal-Catalyzed Vinylation and Enyne Metathesis

    DEFF Research Database (Denmark)

    Min, Geanna; Bjerglund, Klaus Meier; Kramer, Søren

    2013-01-01

    Ethylene is one of the most important building blocks in industry for the production of polymers and commodity chemicals. 13C- and D-isotope-labeled ethylenes are also valuable reagents with applications ranging from polymer-structure determination, reaction-mechanism elucidation to the preparation...... of more complex isotopically labeled compounds. However, these isotopic derivatives are expensive, and are flammable gases, which are difficult to handle. We have developed a method for the controlled generation of ethylene and its isotopic variants including, for the first time, fully isotopically...... labeled ethylene, from simple alkene precursors by using Ru catalysis. Applying a two-chamber reactor allows both the synthesis of ethylene and its immediate consumption in a chemical transformation permitting reactions to be performed with only stoichiometric amounts of this two carbon olefin...

  10. A theoretical view on the thermodynamic cis-trans equilibrium of dihalo ruthenium olefin metathesis (pre-)catalysts

    KAUST Repository

    Pump, Eva; Cavallo, Luigi; Slugovc, Christian

    2015-01-01

    obtained through single-point calculations with M06 functional and TZVP basis set from BP86/SVP-optimized cis- and trans-dichloro geometries and using the polarizable continuum model to simulate the influence of the solvent. Dichloromethane and toluene were

  11. The effects of CO addition on the autoignition of H-2, CH4 and CH4/H-2 fuels at high pressure in an RCM

    NARCIS (Netherlands)

    Gersen, Sander; Darmeveil, Harry; Levinsky, Howard

    2012-01-01

    Autoignition delay times of stoichiometric and fuel-lean (phi = 0.5) H-2, H-2/CO, CH4, CH4/CO, CH4/H-2 and CH4/CO/H-2 mixtures have been measured in an Rapid Compression Machine at pressures ranging from 20 to 80 bar and in the temperature range 900-1100K. The effects of CO addition on the ignition

  12. Derivation of RCM-driven potential evapotranspiration for hydrological climate change impact analysis in Great Britain: a comparison of methods and associated uncertainty in future projections

    Directory of Open Access Journals (Sweden)

    C. Prudhomme

    2013-04-01

    Full Text Available Potential evapotranspiration (PET is the water that would be lost by plants through evaporation and transpiration if water was not limited in the soil, and it is commonly used in conceptual hydrological modelling in the calculation of runoff production and hence river discharge. Future changes of PET are likely to be as important as changes in precipitation patterns in determining changes in river flows. However PET is not calculated routinely by climate models so it must be derived independently when the impact of climate change on river flow is to be assessed. This paper compares PET estimates from 12 equations of different complexity, driven by the Hadley Centre's HadRM3-Q0 model outputs representative of 1961–1990, with MORECS PET, a product used as reference PET in Great Britain. The results show that the FAO56 version of the Penman–Monteith equations reproduces best the spatial and seasonal variability of MORECS PET across GB when driven by HadRM3-Q0 estimates of relative humidity, total cloud, wind speed and linearly bias-corrected mean surface temperature. This suggests that potential biases in HadRM3-Q0 climate do not result in significant biases when the physically based FAO56 equations are used. Percentage changes in PET between the 1961–1990 and 2041–2070 time slices were also calculated for each of the 12 PET equations from HadRM3-Q0. Results show a large variation in the magnitude (and sometimes direction of changes estimated from different PET equations, with Turc, Jensen–Haise and calibrated Blaney–Criddle methods systematically projecting the largest increases across GB for all months and Priestley–Taylor, Makkink, and Thornthwaite showing the smallest changes. We recommend the use of the FAO56 equation as, when driven by HadRM3-Q0 climate data, this best reproduces the reference MORECS PET across Great Britain for the reference period of 1961–1990. Further, the future changes of PET estimated by FAO56 are within the range of uncertainty defined by the ensemble of 12 PET equations. The changes show a clear northwest–southeast gradient of PET increase with largest (smallest changes in the northwest in January (July and October respectively. However, the range in magnitude of PET changes due to the choice of PET method shown in this study for Great Britain suggests that PET uncertainty is a challenge facing the assessment of climate change impact on hydrology mostly ignored up to now.

  13. 2nd RCM of the CRP on Benchmark Analyses of Sodium Natural Convection in the Upper Plenum of the Monju Reactor Vessel. Working Material

    International Nuclear Information System (INIS)

    2010-01-01

    The overall objective of the CRP is to improve the Member States’ analytical capabilities in the field of fast reactor in-vessel sodium thermal hydraulics. A necessary condition towards achieving this objective is a wide international validation effort of the data and codes currently employed for the simulation of the various physical effects involved in this field. Therefore, in providing the required wide international basis of interested Member States, each applying different methodologies, the CRP will contribute towards achieving the stated objective with the help of benchmark exercises focusing, in a first stage, on the numerical simulation of temperature stratification of sodium observed in the Monju reactor vessel at a turbine trip test conducted in December 1995 during the original start-up experiments, and with the help of a thorough assessment of the calculation versus measured data comparisons

  14. First- and second-generation total synthesis of ciguatoxin CTX3C.

    Science.gov (United States)

    Inoue, Masayuki; Miyazaki, Keisuke; Uehara, Hisatoshi; Maruyama, Megumi; Hirama, Masahiro

    2004-08-17

    More than 20,000 people suffer annually from ciguatera seafood poisoning in subtropical and tropical regions. The extremely low content of the causative neurotoxins, designated as ciguatoxins, in fish has hampered isolation, detailed biological studies, and preparation of anti-ciguatoxin antibodies for detecting these toxins. Furthermore, the large (3 nm in length) and complex molecular structure of ciguatoxins has impeded chemists from completing their total synthesis. In this article, the full details of studies leading to the total synthesis of ciguatoxin CTX3C are provided. The key elements of the first-generation approach include O,O-acetal formation from the right and left wing fragments, conversion from O,O-acetal to O,S-acetal, a radical reaction to cyclize the G ring, a ring-closing metathesis reaction to close the F ring, and final removal of the 2-naphtylmethyl protective groups. Subsequent studies provided a second-generation total synthesis, which is more concise and results in a higher yield. Second-generation synthesis was accomplished by using a direct method of constructing the key intermediate O,S-acetal from alpha-chlorosulfide and a secondary alcohol. These syntheses ensure a practical supply of ciguatoxin for biological applications.

  15. Synthesis and characterization of a new class of glycosylated porphyrins bearing the RGD moiety and their application in photodynamic therapy

    International Nuclear Information System (INIS)

    Chaleix, Vincent

    2003-01-01

    The use of porphyrins and analogues as photosensitisers together with visible light is a new treatment of tumors (photodynamic therapy, PDT). Carbohydrate-substituted porphyrins are in this domain very promising compounds. In addition, it is known that endothelial cells of the neo-vascularisation in tumors express αVβ3 integrin. Extracellular domains of this transmembrane glycoprotein are able to bind components of the extracellular matrix (ECM) and more precisely the sequence Arg-Gly-Asp. With the aim of their utilization in photodynamic therapy of cancers, we describe the synthesis and characterization (UV-Visible, mass, NMR) of new glucosylated porphyrins bearing the RGD moiety. The first synthesised compounds were derived from tritolyl and tri-glucosyl-aryl-porphyrins where the peptidic moiety is linked to the phenyl group by a spacer arm by means of a solid phase reaction.. The second series consists of glucosylated porphyrin derivatives bearing a cyclical unsaturated pentapeptide including RGD sequence, obtained by ring closing metathesis in solid phase. We have also synthesized a dimer in which the two glucosylated porphyrins are linked by the RGD sequence. These compounds produced 1 O 2 and photo-cyto-toxicities against K562 leukemia cell line were favourably compared to Photofrin II R . Due to their sensitising abilities, these compounds are of considerable interest for photodynamic therapy. (author) [fr

  16. New architectures for molecular materials

    International Nuclear Information System (INIS)

    Arico, Fabio

    2002-01-01

    synthesis of a novel ruthenium-based [2]-catenane by double ring-closing metathesis using Grubbs' catalyst. The photochemical behaviour of the novel catenane architecture was investigated both to confirm the proposed structure and to explore possible future applications of the catenane as a light-driven molecular machine. (author)

  17. Soluble, Highly Conjugated Derivatives of Polyacetylene from the Ring-Opening Metathesis Polymerization of Monosubstituted Cyclooctatetraenes: Synthesis and the Relationship Between Polymer Structure and Physical Properties

    Science.gov (United States)

    1993-01-15

    through a pad of Celite into a flask equipped with a sidearm stopcock and the volume of the solution was not adjusted. Neopentyl lithium was...The resonance at 2.5 ppm (A) was irradiated and both this resonance and the resonance at 2.8 ppm (B) were integrated. An ethylene glycol temperature...angles for different side groups in model compound S (MM2 results, C3 = cyclopropyl, Np = neopentyl ). Figure 14. Values of torsion angle el at 10 fs

  18. Variation of the Sterical Properties of the N-Heterocyclic Carbene Coligand in Thermally Triggerable Ruthenium-Based Olefin Metathesis Precatalysts/Initiators

    KAUST Repository

    Pump, Eva; Leitgeb, Anita; Kozłowska, Anna; Torvisco, Ana; Falivene, Laura; Cavallo, Luigi; Grela, Karol; Slugovc, Christian

    2015-01-01

    A series of ruthenium complexes based on the κ(C,N)-(2-(benzo[h]quinolin-10-yl)methylidene ruthenium dichloride fragment featuring different neutral coligands L (L = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr), 1,3-bis(2

  19. Ring opening metathesis polymerization-derived block copolymers bearing chelating ligands: synthesis, metal immobilization and use in hydroformylation under micellar conditions

    Directory of Open Access Journals (Sweden)

    Gajanan M. Pawar

    2010-03-01

    Full Text Available Norborn-5-ene-(N,N-dipyrid-2-ylcarbamide (M1 was copolymerized with exo,exo-[2-(3-ethoxycarbonyl-7-oxabicyclo[2.2.1]hept-5-en-2-carbonyloxyethyl]trimethylammonium iodide (M2 using the Schrock catalyst Mo(N-2,6-Me2-C6H3(CHCMe2Ph(OCMe(CF322 [Mo] to yield poly(M1-b-M2. In water, poly(M1-b-M2 forms micelles with a critical micelle-forming concentration (cmc of 2.8 × 10−6 mol L−1; Reaction of poly(M1-b-M2 with [Rh(CODCl]2 (COD = cycloocta-1,5-diene yields the Rh(I-loaded block copolymer poly(M1-b-M2-Rh containing 18 mg of Rh(I/g of block copolymer with a cmc of 2.2 × 10−6 mol L−1. The Rh-loaded polymer was used for the hydroformylation of 1-octene under micellar conditions. The data obtained were compared to those obtained with a monomeric analogue, i.e. CH3CON(Py2RhCl(COD (C1, Py = 2-pyridyl. Using the polymer-supported catalyst under micellar conditions, a significant increase in selectivity, i.e. an increase in the n:iso ratio was accomplished, which could be further enhanced by the addition of excess ligand, e.g., triphenylphosphite. Special features of the micellar catalytic set up are discussed.

  20. Highly recoverable pyridinium-tagged Hoveyda-Grubbs pre-catalyst for olefin metathesis. Design of the boomerang ligand toward the optimal compromise between activity and reusability.

    Science.gov (United States)

    Rix, Diane; Caïjo, Fréderic; Laurent, Isabelle; Gulajski, Lukasz; Grela, Karol; Mauduit, Marc

    2007-09-28

    Whereas the boomerang ligand of Hoveyda-Grubbs pre-catalysts can be modified by attachment of a pyridinium tag to its benzylidene moiety, a precise adjustment of the length of the spacer allows the optimum balance to be reached between the activity of the catalyst and its recoverability, exceeding 98% after 6 catalytic runs in the best case.

  1. 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.

  2. "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.

  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

    2016-01-01

    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

  4. "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; Thivolle-Cazat, Jean; Taoufik, Mostafa; Stoffelbach, Franç ois; Norsic, Sé bastien; Basset, Jean-Marie

    2011-01-01

    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.

  5. In Silico Switch from Second- to First-Row Transition Metals in Olefin Metathesis: From Ru to Fe and from Rh to Co

    Directory of Open Access Journals (Sweden)

    Jesús Antonio Luque-Urrutia

    2017-12-01

    Full Text Available Density functional theory (DFT calculations have been used to investigate the behavior of different transition metals from Groups 8 (Fe and Ru and 9 (Co and Rh in an already well-known catalytic mechanism, which is based on an Ru(SIMes(PPh3Cl2=CH(Ph complex. As expected, Ru has proven to perform better than their Fe, Co, and Rh counterparts. Even though the topographic steric maps analysis shows no difference in sterical hindrance for any of the metal centers, geometrically, the Fe-based species show a high rigidity with shorter and stronger bonds confirmed by Mayer Bond Orders. The systems bearing Co as a metallic center might present a reactivity that is, surprisingly, too high according to conceptual DFT, which would consequently be a drawback for the formation of the fundamental species of the reaction pathway: the metallacycle intermediate.

  6. Synergy between Two Metal Catalysts: A Highly Active Silica Supported Bimetallic W/Zr Catalyst for Metathesis of n-Decane

    KAUST Repository

    Samantaray, Manoja; Dey, Raju; Kavitake, Santosh Giridhar; Abou-Hamad, Edy; Bendjeriou-Sedjerari, Anissa; Hamieh, Ali Imad Ali; Basset, Jean-Marie

    2016-01-01

    A well-defined, silica supported, bimetallic precatalyst [≡Si-O-W(Me)5 ≡Si-O-Zr(Np)3](4) has been synthesized for the first time via successively grafting two organometallic complexes [W(CH3)6 (1) followed by ZrNp4 (2)] on a single silica support

  7. The Effect of Nitrogen Surface Ligands on Propane Metathesis: Design and Characterizations of N-modified SBA15-Supported Schrock-type Tungsten Alkylidyne

    KAUST Repository

    Eid, Ahmed A.

    2014-01-01

    Catalysis, which is primarily a molecular phenomenon, is an important field of chemistry because it requires the chemical conversion of molecules into other molecules. It also has an effect on many fields, including, but not limited to, industry

  8. Divergent Pathways and Competitive Mechanisms of Metathesis Reactions between 3-Arylprop-2-ynyl Esters and Aldehydes: An Experimental and Theoretical Study

    Czech Academy of Sciences Publication Activity Database

    Trujillo, Cristina; Sanchez-Sanz, Goar; Karpavičiene, I.; Jahn, Ullrich; Čikotiene, I.; Rulíšek, Lubomír

    2014-01-01

    Roč. 20, č. 33 (2014), s. 10360-10370 ISSN 0947-6539 R&D Projects: GA ČR(CZ) GA14-31419S Grant - others:European Social Fund(XE) VP1-3.1-SMM-07 K-01-002 Institutional support: RVO:61388963 Keywords : 3-arylprop-2-ynyl esters * density functional calculations * isotopic labeling * ketones * Morita-Baylis-Hillman adducts Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.731, year: 2014

  9. MORPHOPHONOLOGICAL PROCESSES OF THE C'LELA NOUN

    African Journals Online (AJOL)

    M A ALIERO

    The indeterminacy/attestation model of metathesis. Language 80.2. Hume, Elizabeth, 2007. The interaction of internal and external factors in metathesis and deletion. Conference on Precedence Relations, CUNY Phonology Forum 9. Hume, Elizabeth and Jeff Mielke, 2001. Consequences of word recognition for metathesis.

  10. Synergism of X irradiation and radiographic contrast medium

    Energy Technology Data Exchange (ETDEWEB)

    Carr, D; Walker, A; Tannahill, A J; White, R G [Glasgow Western Infirmary (UK)

    1981-10-01

    The results indicate that rabbits which had received abdominal x irradiation (750 rad) two hours before RCM (/sup 125/I-labelled meglumine ioglycamate) administration retained a significantly larger amount of RCM in the kidney, liver, spleen and plasma compared with animals which had received RCM with no prior x irradiation. There was no significant difference between the group receiving RCM alone and the group receiving RCM 24 h post-irradiation. With two insignificant exceptions, endotoxin assays were negative.

  11. Discussion of the evolution of the chloride migration coefficient of Portland cement concrete tested by the rapid chloride migration (RCM) test at long-term curing periods up to 5 years

    NARCIS (Netherlands)

    Yu, Z.; Ye, G.; Hunger, M.; Noort, R.

    2013-01-01

    Chloride-induced corrosion of reinforced concrete is one of the main deterioration mechanisms leading to shortening of the service life of concrete structures. Therefore, assessment of the resistance of concrete to chloride ingress plays an important role in predicting the service life of such

  12. First FAO/IAEA research co-ordination meeting (RCM) of the co-ordinated research project on 'Irradiation to ensure the safety and quality of prepared meals'. Working material

    International Nuclear Information System (INIS)

    2002-01-01

    The current trends in global food production, processing and distribution present new challenges to food safety and quality. Food produced in one area can be transported quickly to another area or regions of the world in a matter of hours or days. Changes in eating habits including a preference for fresh, minimally processed and convenience foods and the increasing interval between processing and consumption of foods could contribute to the increase in incidences of food-borne illness because of contamination by pathogenic microorganisms. In many countries, there is a dynamic growth of market for prepared meals to meet the busy life style of populations. Such meals which offer convenience and less time for preparation are marketed in most countries either under chilled with limited shelf-life or frozen for long term sale in supermarkets. In developing countries in particular, many types of ethnic dishes are often freshly prepared and marketed at ambient conditions essentially on a day to day basis. There are growing trends to market frozen prepared meals intended for micro-waving prior to consumption in many countries. Microbiological contamination including pathogenic bacteria (Salmonella, Escherichia coli 0157:H7; Listeria monocytogenes) frequently occurs during the production and processing of prepared meals which provide important vehicles to food-borne disease outbreaks. To get by microbiological problems, the food industry has to resort to freezing the meals and marketing them under frozen condition which is energy intensive and costly. Some prepared meals which are marketed either under refrigeration or at ambient conditions, have limited shelf-life. Thus, measures to ensure microbiological safety and quality of prepared meals to be marketed either under refrigeration or at ambient without compromising their organoleptic properties should be welcomed by the food industry and consumers. Irradiation offers a potential to improve the microbiological safety and shelflife of a number of chilled prepared meals. A number of prepared meals currently marketed under frozen condition could possibly be replaced through irradiation and chilled storage to ensure not only microbiological safety but sufficient shelf-life to meet market requirements, resulting in saving in energy and cost. As for ethnic dishes in developing countries, irradiation either alone or together with chilling could improve not only microbiological quality but could extend shelf-life of the products. However, little data are available to demonstrate the effectiveness of irradiation to improve the microbiological safety and quality of many types of prepared meals currently being marketed either under ambient, chilled or frozen conditions. The overall objective of this CRP is to evaluate the effectiveness of irradiation as a method to ensure microbiological safety and extend shelf-life of prepared meals, stored either under ambient, chilled or frozen and to evaluate the sensory quality of the treated products. The specific objective of this CRP is to use validated methods for microbiological determination of food and validated procedures for irradiation, process control, sensory evaluation and to determine microbiological safety and quality of irradiated prepared meals or ethnic dishes

  13. First FAO/IAEA research co-ordination meeting (RCM) of the co-ordinated research project on 'Irradiation to ensure the safety and quality of prepared meals'. Working material

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2002-07-01

    The current trends in global food production, processing and distribution present new challenges to food safety and quality. Food produced in one area can be transported quickly to another area or regions of the world in a matter of hours or days. Changes in eating habits including a preference for fresh, minimally processed and convenience foods and the increasing interval between processing and consumption of foods could contribute to the increase in incidences of food-borne illness because of contamination by pathogenic microorganisms. In many countries, there is a dynamic growth of market for prepared meals to meet the busy life style of populations. Such meals which offer convenience and less time for preparation are marketed in most countries either under chilled with limited shelf-life or frozen for long term sale in supermarkets. In developing countries in particular, many types of ethnic dishes are often freshly prepared and marketed at ambient conditions essentially on a day to day basis. There are growing trends to market frozen prepared meals intended for micro-waving prior to consumption in many countries. Microbiological contamination including pathogenic bacteria (Salmonella, Escherichia coli 0157:H7; Listeria monocytogenes) frequently occurs during the production and processing of prepared meals which provide important vehicles to food-borne disease outbreaks. To get by microbiological problems, the food industry has to resort to freezing the meals and marketing them under frozen condition which is energy intensive and costly. Some prepared meals which are marketed either under refrigeration or at ambient conditions, have limited shelf-life. Thus, measures to ensure microbiological safety and quality of prepared meals to be marketed either under refrigeration or at ambient without compromising their organoleptic properties should be welcomed by the food industry and consumers. Irradiation offers a potential to improve the microbiological safety and shelflife of a number of chilled prepared meals. A number of prepared meals currently marketed under frozen condition could possibly be replaced through irradiation and chilled storage to ensure not only microbiological safety but sufficient shelf-life to meet market requirements, resulting in saving in energy and cost. As for ethnic dishes in developing countries, irradiation either alone or together with chilling could improve not only microbiological quality but could extend shelf-life of the products. However, little data are available to demonstrate the effectiveness of irradiation to improve the microbiological safety and quality of many types of prepared meals currently being marketed either under ambient, chilled or frozen conditions. The overall objective of this CRP is to evaluate the effectiveness of irradiation as a method to ensure microbiological safety and extend shelf-life of prepared meals, stored either under ambient, chilled or frozen and to evaluate the sensory quality of the treated products. The specific objective of this CRP is to use validated methods for microbiological determination of food and validated procedures for irradiation, process control, sensory evaluation and to determine microbiological safety and quality of irradiated prepared meals or ethnic dishes.

  14. First (Kick-Off) Research Coordination Meeting (RCM) of the IAEA Coordinated Research Project (CRP) on Sodium Properties and Safe Operation of Experimental Facilities in Support of the Development and Deployment of Sodium-Cooled Fast Reactors. Working Material

    International Nuclear Information System (INIS)

    2013-01-01

    General information on recent IAEA activities in the field of fast reactors, including on-going and planned FR-related CRPs, as well as a review of the NAPRO CRP content, objectives, participants, planning and expected outcomes/deliverables, was provided. It was reminded that the NAPRO CRP is being organized in 3 main Work Packages (WP): • WP 1: collection, expert assessment and dissemination of consistent Na property data such as: surface tension, saturation vapor pressure and emissivity, thermo-dynamic behavior of ternary oxides in Na, and solubility - diffusivity of metallic impurities, etc. • WP 2: development of guidelines and best practices for Na facility design and operation, including fill and drain, purification, out-gassing prior to filling, Na storage, component handling, drying of Na piping after repair, etc. • WP 3: development of guidelines and best practices for Na facility safety, including prevention and mitigation of Na leaks, prevention and detection of Na fires, assessment of Na impact in the environment after accidental release, hydrogen hazards in cleaning facilities, etc

  15. The coordinated research project on use of irradiation to ensure the safety and quality of prepared meals. Proceedings of the 3rd FAO/IAEA research coordination meeting (RCM). Working material

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2006-07-01

    Although extensive research has been carried out on the microbiological and sensorial effects of irradiating individual uncooked food items, little work has been reported on the irradiation of complex food systems such as prepared meals. In this Coordinated Research Project (CRP), the potential of using the irradiation technology for convenience foods has been investigated with regard to safety, shelf-life and overall quality, particularly in terms of sensory acceptance. A wide range of ethnic meals as well as meal components were investigated with the objective of meeting continual changes in consumer demands worldwide. Other aspects of the CRP included the adoption of a Hazard Analysis Critical Control Point (HACCP) system for prepared meals and research into consumer willingness to purchase irradiated food at a premium price. The scope of the CRP was therefore wide-ranging. The overall objective of this CRP was to evaluate the effectiveness of irradiation as a method to ensure the microbiological safety and extend the shelf-life of prepared meals, stored under ambient, chilled or frozen conditions, and to evaluate the sensory quality of the treated products. The specific objective of the CRP was to use validated procedures for irradiation treatment and process control, and to use validated methods for assessing microbiological safety and quality as well as the sensory quality of prepared meals mainly of ethnic origin.

  16. 2nd RCM of the CRP on Analytical and Experimental Benchmark Analyses of Accelerator Driven Systems (ADS) and Technical Meeting on Low Enriched Uranium (LEU) Fuel Utilization in Accelerator Driven Sub-critical Systems. Working Material

    International Nuclear Information System (INIS)

    2010-01-01

    The overall objective of the CRP is contributing to the generic R&D efforts in various fields common to innovative fast neutron system development, i.e., heavy liquid metal thermal hydraulics, dedicated transmutation fuels and associated core designs, theoretical nuclear reaction models, measurement and evaluation of nuclear data for transmutation, and development and validation of calculational methods and codes. Ultimately, the CRP’s overall objective is to make contributions towards the realization of a transmutation demonstration facility

  17. The coordinated research project on use of irradiation to ensure the safety and quality of prepared meals. Proceedings of the 3rd FAO/IAEA research coordination meeting (RCM). Working material

    International Nuclear Information System (INIS)

    2006-01-01

    Although extensive research has been carried out on the microbiological and sensorial effects of irradiating individual uncooked food items, little work has been reported on the irradiation of complex food systems such as prepared meals. In this Coordinated Research Project (CRP), the potential of using the irradiation technology for convenience foods has been investigated with regard to safety, shelf-life and overall quality, particularly in terms of sensory acceptance. A wide range of ethnic meals as well as meal components were investigated with the objective of meeting continual changes in consumer demands worldwide. Other aspects of the CRP included the adoption of a Hazard Analysis Critical Control Point (HACCP) system for prepared meals and research into consumer willingness to purchase irradiated food at a premium price. The scope of the CRP was therefore wide-ranging. The overall objective of this CRP was to evaluate the effectiveness of irradiation as a method to ensure the microbiological safety and extend the shelf-life of prepared meals, stored under ambient, chilled or frozen conditions, and to evaluate the sensory quality of the treated products. The specific objective of the CRP was to use validated procedures for irradiation treatment and process control, and to use validated methods for assessing microbiological safety and quality as well as the sensory quality of prepared meals mainly of ethnic origin

  18. Progress report of Sandia National Laboratories (SNL) contribu- tion to IAEA CRP F11016 on ?Utilization of ion accelerators for studying and modeling of radiation induced defects in semicon- ductors and insulators? 3rd RCM.

    Energy Technology Data Exchange (ETDEWEB)

    Vizkelethy, Gyorgy [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2014-10-01

    This report presents the results of Sandia National Laboratories’ (SNL) contribution to IAEA CRP F11016 as mostly raw data. The goal of this CRP is to study the effects of radiation on semiconductors and insulators with the emphasis on the effect of displacement damage due to MeV energy ions on the performance of semiconductor detectors and microelectronic devices. SNL is tasked with performing electrical characterization, irradiation, and IBIC, DLTS, C-­V measurements on devices used in the CRP, as well as calculating damage and ionization profiles for modeling.

  19. Vegetation classification scheme of land surface process in GCM & RCM%全球及区域模式中陆面过程的地表植被覆盖分类方法

    Institute of Scientific and Technical Information of China (English)

    姚凤梅; 张佳华

    2006-01-01

    全球和区域尺度上陆面生态系统与气候密切相关.全球和区域模式的发展对于我们认识气候与陆地生态的变化起到重要作用.在这些模型中,植被覆盖是影响大气-植被间热量、水分和CO2等交换的重要陆面参数.在分析了陆地植被覆盖分类原理基础上,介绍了目前全球不同植被覆盖分类方案,包括基于地基观测的植被分布、基于生物气候特征的分类方案(如:Holdridge的方案);特别近年来陆面过程试验表明,各种遥感数据源(如:NOAA-AVHRR,EOS-MODIS,Landsat-TM)等为我们提供了有利的工具来监测全球植被动态,完善植被分类,并且采用高时空分辨率的全球土地覆盖状况特征,在不同时空尺度揭示植被-大气相互作用.本文分析了代表性的3种基于卫星遥感技术的陆面植被分类方案,分别是BATS(18类)、SIB(9类)、SIB2(12类)和BIOME-BGC(31类)陆地模式的植被覆盖分类方案.最后分析了目前可用于全球植被覆盖分类的新的遥感数据库.

  20. Preparation of “Constrained Geometry” Titanium Complexes of [1,2]Azasilinane Framework for Ethylene/1-Octene Copolymerization

    Directory of Open Access Journals (Sweden)

    Seul Lee

    2017-02-01

    Full Text Available The Me2Si-bridged ansa-Cp/amido half-metallocene, [Me2Si(η5-Me4C5(NtBu]TiCl2, termed a “constrained-geometry catalyst (CGC”, is a representative homogeneous Ziegler catalyst. CGC derivatives with the [1,2]azasilinane framework, in which the amide alkyl substituent is joined by the Si-bridge, were prepared, and the catalytic performances of these species was studied. Me4C5HSi(Me(CH2CH=CH2-NH(C(R(R’CH=CH2 (R, R’ = H or methyl; Me4C5H = tetramethylcyclopentadienyl was susceptible to ring closure metathesis (RCM when treated with Schrock’s Mo-catalyst to afford -Si(Me4C5H(MeCH2CH=CHC(R(R’NH- containing a six-membered ring framework. Using the precursors and the products of RCM, various CGC derivatives, i.e., [-Si(η5-Me4C5(MeCH2CH=CHC(R(HN-]TiMe2 (13, R = H; 15, R = Me, [-Si(η5-Me4C5(MeCH2CH2CH2CH2N]TiMe2 (14, [(η5-Me4C5Si(Me(CH2CH=CH2NCH2CH=CH2]TiMe2 (16, [(η5-Me4C5Si (Me(CH=CH2NCH2CH=CH2]TiMe2 (17, and [(η5-Me4C5Si(Me(CH2CH3NCH2CH2CH3]TiMe2 (18, were prepared. The catalytic activity of the newly prepared complexes was lower than that of CGC when activated with [Ph3C][B(C6F54]/iBu3Al. However, the catalytic activity of these species was improved by using tetrabutylaluminoxane ([iBu2Al]2O instead of iBu3Al and the activity of 14/[Ph3C][B(C6F54]/[iBu2Al]2O was comparable to that of CGC/[Ph3C][B(C6F54]/iBu3Al (4.7 and 5.0 × 106 g/mol-Ti, respectively. Advantageously, the newly prepared complexes produced higher molecular weight poly(ethylene-co-1-octenes than CGC.

  1. Preparation and Reaction Chemistry of Novel Silicon-Substituted 1,3-Dienes

    Directory of Open Access Journals (Sweden)

    Partha P. Choudhury

    2015-09-01

    Full Text Available 2-Silicon-substituted 1,3-dienes containing non transferrable groups known to promote transmetallation were prepared by Grignard chemistry and enyne metathesis. These dienes participated in one pot metathesis/Diels-Alder reactions in regio- and diastereoselective fashions. Electron-rich alkenes showed the fastest rates in metathesis reactions, and ethylene, a commonly used metathesis promoter slowed enyne metathesis. 2-Pyridyldimethylsilyl and 2-thienyldimethylsilyl substituted Diels-Alder cycloadducts participated in cross-coupling chemistry and the 2-thienyldimethylsilyl substituted cycloadducts underwent cross-coupling under very mild reaction conditions.

  2. Large-scale demonstration of reliability centered maintenance at two nuclear generating stations

    International Nuclear Information System (INIS)

    Gaertner, J.P.; Edgar, C.; Rodin, M.E.

    1989-01-01

    This paper reports that after successful single-system pilot applications of Reliability Centered Maintenance (RCM) at various utilities, EPRI with Rochester Gas and Electric and Southern California Edison is undertaking multiple-system applications of RCM at their respective nuclear plants. The objective is to demonstrate the feasibility and cost-effectiveness of large-scale RCM application. In addition, each utility has plant-specific objectives to improve maintenance and plant availability. Each project has selected a prioritized list of some 15-20 systems on which to perform RCM. Each project is employing somewhat different RCM analysis methods, both of which conform to a global RCM definition applicable to all EPRI RCM work to date. Each project has developed important insights for improving cost and value of future analyses. Both projects will have applied the RCM process, including implementation, on several plant systems by April 1989

  3. Reliability Centered Maintenance - Methodologies

    Science.gov (United States)

    Kammerer, Catherine C.

    2009-01-01

    Journal article about Reliability Centered Maintenance (RCM) methodologies used by United Space Alliance, LLC (USA) in support of the Space Shuttle Program at Kennedy Space Center. The USA Reliability Centered Maintenance program differs from traditional RCM programs because various methodologies are utilized to take advantage of their respective strengths for each application. Based on operational experience, USA has customized the traditional RCM methodology into a streamlined lean logic path and has implemented the use of statistical tools to drive the process. USA RCM has integrated many of the L6S tools into both RCM methodologies. The tools utilized in the Measure, Analyze, and Improve phases of a Lean Six Sigma project lend themselves to application in the RCM process. All USA RCM methodologies meet the requirements defined in SAE JA 1011, Evaluation Criteria for Reliability-Centered Maintenance (RCM) Processes. The proposed article explores these methodologies.

  4. A four-phase strategy for the implementation of reflectance confocal microscopy in dermatology

    NARCIS (Netherlands)

    Hoogedoorn, L.; Gerritsen, M.J.P.; Wolberink, E.A.W.; Peppelman, M.; Kerkhof, P.C.M. van de; Erp, P.E.J. van

    2016-01-01

    BACKGROUND: Reflectance confocal microscopy (RCM) is gradually implemented in dermatology. Strategies for further implementation and practical 'hands on' guidelines are lacking. OBJECTIVE: The primary outcome was to conduct a general strategy for further implementation of RCM. The secondary outcome

  5. A framework for intelligent reliability centered maintenance analysis

    International Nuclear Information System (INIS)

    Cheng Zhonghua; Jia Xisheng; Gao Ping; Wu Su; Wang Jianzhao

    2008-01-01

    To improve the efficiency of reliability-centered maintenance (RCM) analysis, case-based reasoning (CBR), as a kind of artificial intelligence (AI) technology, was successfully introduced into RCM analysis process, and a framework for intelligent RCM analysis (IRCMA) was studied. The idea for IRCMA is based on the fact that the historical records of RCM analysis on similar items can be referenced and used for the current RCM analysis of a new item. Because many common or similar items may exist in the analyzed equipment, the repeated tasks of RCM analysis can be considerably simplified or avoided by revising the similar cases in conducting RCM analysis. Based on the previous theory studies, an intelligent RCM analysis system (IRCMAS) prototype was developed. This research has focused on the description of the definition, basic principles as well as a framework of IRCMA, and discussion of critical techniques in the IRCMA. Finally, IRCMAS prototype is presented based on a case study

  6. Development and Implementation of a Condition Based Maintenance Program for Geothermal Power Plants; FINAL

    International Nuclear Information System (INIS)

    Steve Miller; Jim Eddy; Murray Grande; Shawn Bratt; Manuchehr Shirmohamadi

    2002-01-01

    This report describes the development of the RCM team, identifying plant assets and developing an asset hierarchy, the development of sample Failure Mode Effects Analysis (FMEAs), identifying and prioritizing plant systems and components for RCM analysis, and identifying RCM/CBM software/hardware vendors. It also includes the Failure Mode Effects Analysis (FMEA) for all Class I Systems, Maintenance Task Assignments, use of Conditioned Based Maintenance (CBM) Tools and Displays of the RCM software System Development to date

  7. In vivo Diagnosis of Basal Cell Carcinoma Subtype by Reflectance Confocal Microscopy

    NARCIS (Netherlands)

    Peppelman, M.; Wolberink, E.A.W.; Blokx, W.A.M.; Kerkhof, P.C.M. van de; Erp, P.E.J. van; Gerritsen, M.J.P.

    2013-01-01

    Background: Reflectance confocal microscopy (RCM) is a noninvasive imaging technique. Currently, RCM is mainly used for the diagnosis of melanoma and nonmelanoma skin cancer including basal cell carcinoma (BCC). Until now, it has not been possible to distinguish between subtypes of BCC using RCM.

  8. Reflectance confocal microscopy: non-invasive distinction between actinic keratosis and squamous cell carcinoma

    NARCIS (Netherlands)

    Peppelman, M.; Nguyen, K.P.; Hoogedoorn, L.; Erp, P.E.J. van; Gerritsen, M.J.P.

    2015-01-01

    BACKGROUND: Early recognition of squamous cell carcinoma (SCC) is difficult. Non-invasive reflectance confocal microscopic (RCM) imaging of the skin is a promising diagnostic technique. Although several RCM features for SCC and AK have been described, it is not determined whether RCM has the ability

  9. Ring-opening metathesis polymerization based pore-size-selective functionalization of glycidyl methacrylate based monolithic media: access to size-stable nanoparticles for ligand-free metal catalysis.

    Science.gov (United States)

    Bandari, Rajendar; Höche, Thomas; Prager, Andrea; Dirnberger, Klaus; Buchmeiser, Michael R

    2010-04-19

    Monolithic polymeric supports have been prepared by electron-beam-triggered free-radical polymerization using a mixture of glycidyl methacrylate and trimethylolpropane triacrylate in 2-propanol, 1-dodecanol, and toluene. Under appropriate conditions, phase separation occurred, which resulted in the formation of a porous monolithic matrix that was characterized by large (convective) pores in the 30 μm range as well as pores of 7 nm were hydrolyzed by using poly(styrenesulfonic acid) (Mw = 69,400 g mol(-1), PDI=2.4). The remaining epoxy groups inside pores of nanoparticles 2 nm in diameter were formed. The palladium-nanoparticle-loaded monoliths were used in both Heck- and Suzuki-type coupling reactions achieving turnover numbers of up to 167,000 and 63,000, respectively. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Synthesis and Side Chain Liquid Crystal Polymers by Living Ring Opening Metathesis Polymerization. 5. Influence of Mesogenic Group and Interconnecting Group on the Thermotropic Behavior of the Resulting Polymers

    Science.gov (United States)

    1992-07-22

    Scheme I. The first nucleophilic displacement of halide of an n-haloalkan-l-ol with 4-cyano-4’-hydroxybiphenyl employed potassium carbonate in...21 𔃼 polysiloxanes, 23.24 and polyacrylates . 2- All these polymers exhibit an odd-even effect. If one considers the total number of atoms between the...0.019 mol) and 4’-methoxy-4-hydroxybiphenyl (4.0g, 0.020 tool) were heated at 100°C in 40 mL of dimethylformamide in the presence of potassium carbonate

  11. Synthesis of Side Chain Liquid Crystal Polymers by Living Ring Opening Metathesis Polymerization. 3. Influence of Molecular Weight, Interconnecting Unit and Substituent on the Mesomorphic behavior of Polymers with Laterally Attached Mesogens

    Science.gov (United States)

    1992-04-08

    polymethylsiloxanes, 6 -7 polyacrylates ,2,4,5 polymethacrylates, 1 ,3 and polychloroacrylates, 5 exhibit only nematic mesophases regardless of the...corresponding carboxyl chloride. Potassium bicyclo[2.2.1]hept-2-ene-5- carboxylate was prepared by titrating a methanolic solution of the carboxylic acid...Esterification of the Corresponding Benzyl Bromides. Monomers 1I-n were prepared in 47-88% yield using the following procedure. A mixture of potassium bicyclo

  12. and 8-Membered Oxygen-containing Benzo-fused Rings using ...

    African Journals Online (AJOL)

    NJD

    A number of benzo-fused oxygen-containing heterocycles were synthesized from allyl-3-isopropoxy-4-methoxybenzaldehyde using metathesis or an alkene isomerization-metathesis sequence as key synthetic steps. Benzo-fused compounds thus formed included a 3,6-dihydro-1H-2-benzoxocine, ...

  13. Demonstration of reliability centered maintenance

    International Nuclear Information System (INIS)

    Schwan, C.A.; Morgan, T.A.

    1991-04-01

    Reliability centered maintenance (RCM) is an approach to preventive maintenance planning and evaluation that has been used successfully by other industries, most notably the airlines and military. Now EPRI is demonstrating RCM in the commercial nuclear power industry. Just completed are large-scale, two-year demonstrations at Rochester Gas ampersand Electric (Ginna Nuclear Power Station) and Southern California Edison (San Onofre Nuclear Generating Station). Both demonstrations were begun in the spring of 1988. At each plant, RCM was performed on 12 to 21 major systems. Both demonstrations determined that RCM is an appropriate means to optimize a PM program and improve nuclear plant preventive maintenance on a large scale. Such favorable results had been suggested by three earlier EPRI pilot studies at Florida Power ampersand Light, Duke Power, and Southern California Edison. EPRI selected the Ginna and San Onofre sites because, together, they represent a broad range of utility and plant size, plant organization, plant age, and histories of availability and reliability. Significant steps in each demonstration included: selecting and prioritizing plant systems for RCM evaluation; performing the RCM evaluation steps on selected systems; evaluating the RCM recommendations by a multi-disciplinary task force; implementing the RCM recommendations; establishing a system to track and verify the RCM benefits; and establishing procedures to update the RCM bases and recommendations with time (a living program). 7 refs., 1 tab

  14. Report of the second research co-ordination meeting (RCM) for the co-ordinated research project (CRP E2 40 06) on characterization and evaluation of high-dose dosimetry techniques for quality assurance in radiation processing. IAEA, Vienna, 6-10 October 1997

    International Nuclear Information System (INIS)

    Mehta, K.

    1998-01-01

    In many Member States the use of large Cobalt-60 gamma ray facilities and electron beam accelerators with beam energies from about 0.1 to 10 MeV for industrial processing continues to grow. For these processes, quality assurance relies on the application of well-established dosimetry systems and procedures. This is especially the case for health-regulated processes, such as the radiation sterilization of health care products, and the irradiation of food to eliminate pathogenic organisms or to control insect pests. For radiation sterilization, the publication of the international standard ISO 11137 Sterilization of health care products - Requirements for validation and routine control - Radiation sterilization and the European Standard EN 552 - Sterilization of medical devices - Validation and routine control of sterilization by irradiation has resulted in the standardization of requirements to ensure global harmonization. Standardized dosimetry is also valuable in the radiation processing of many widely used commodities, such as polymers, automotive and airborne components, battery parts, computers, audio and video hardware, coatings, lubricants, adhesives, and composites. The major goal of this CRP is to investigate the factors that influence the response of dosimeters and establish procedures to improve dosimetry for quality assurance of the different types of radiation processes. This will help to unify the radiation measurements performed by different radiation processing facilities and other high-dose dosimetry users in Member States and encourage efforts to obtain traceability to primary and secondary standards laboratories. It will also aim to strengthen and expand the present International Dose Assurance Service (IDAS) provided by the Agency

  15. Development of a quality assurance programme for radiation therapy dosimetry in development countries. Report of the second research co-ordination meeting - RCM-650.2 on the CRP E2 40 07, 4-8 December 2000, IAEA DMRP Section, Vienna

    International Nuclear Information System (INIS)

    2001-01-01

    The aim of the Co-ordinated Research Programme ''Development of a Quality Assurance Programme for Radiation Therapy Dosimetry in Developing Countries'' (E2-40-07) is to establish national Quality Assurance (QA) networks for external quality audits for radiotherapy hospitals in developing countries. This is done by setting-up national External Audit Groups (EAG) with laboratory backup for operating TLD audits for radiotherapy dosimetry. The CRP offers a standardized methodology, the same for all participating countries, provides guidelines and gives technical support to the national EAG activities. In 1995-1998, the national EAGs were established in Algeria, Argentina, China, Czech Republic, India, Israel and Malaysia. At present five countries have joined the project: Colombia, Cuba, Philippines, Poland and Viet Nam. The current status of the development of methodology and procedures for QA audits in the participating countries was presented and discussed at length. Each participant has submitted the status report regarding the TLD system, measuring procedures, structure of the national EAG and relations with other relevant national organizations or bodies. The new participants are in the process of adapting the procedures developed by the IAEA and revised by the previous group in this CRP. The participants have received information on state of the art of the quality audit networks in Europe presented by Prof. Dutreix. Further discussions followed the presentations of the results of testing of the EAG measuring systems and operational procedures for audits. Special emphasis was given to issues related to legislation and national regulations in the different countries and confidentiality in reporting the audit results. Procedural problems related to endorsement of the EAGs by the relevant national bodies were noted. The composition of the national EAGs was discussed and optimal structures for the individual countries recommended. The contents of the QA manuals for the EACs, in preparation by the participants, were also discussed. The recommendations were given for organisation of the audits and follow-up procedures whenever large discrepancies in calibrations of clinical beams were detected. A document entitled ''Guidelines for the preparation of a Quality Manual for External Audit Groups on Dosimetry in Radiotherapy'' (IAEA internal report DMRP-9806) has been reviewed and specific recommendations given to the participants. The document is being used as a guide for preparation the quality manual for national EAGs. The ''Guidelines...'' include the quality policy, quality systems and quality structures including process control as it is stated in recommendations of ISO 9000 series and ISO/IEC guide No. 25. The standard operation procedures of the Agency's Dosimetry Laboratory for the TLD audits, including maintenance of the TL reference dosimetry system for radiotherapy and operation of the TLD audits (IAEA internal reports DMRP9809 and DMRP9810) were presented as a reference material for the CRP participants. The working schedules for the five countries were co-ordinated and goals to be achieved outlined with regard to the subsequent implementation steps of the national QA programmes. As the closure of the CRP is planned in 2001, the plans for publications of the results achieved by different countries were discussed

  16. Co-ordinated research project on assessment of levels and health-effects of airborne particulate matter in mining, metal refining and metal working industries using nuclear and related analytical techniques. Report on the first research co-ordination meeting (RCM)

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-12-31

    The objectives of the CRP are to: (1) improve competence for research on workplace monitoring in terms of proper sampling and analytical procedures, (2) obtain relevant and reliable data on sources and levels of workplace pollution in various countries, (3) promote a better understanding of methods for the interpretation of such data including occupational heath studies, and (4) encourage closer collaboration between analytical scientists and researchers in the field of occupational health in the countries concerned. The CRP focuses on the use of nuclear and related analytical techniques for the following kinds of studies: (1) strategies and techniques for sampling of workplace airborne particulate matter and of human tissues and body fluids (hair, blood, etc.) sampling of exposed and non-exposed persons; (2) development of suitable analytical procedures for analysis of such types of samples; (3) workplace and personal monitoring of airborne particulate matter in the mining, refining and metal working industries, and the health effects of such exposure; and (4) tissue analysis of the workers exposed for biological monitoring and the health effects studies. This report includes the core and supplementary programme of the CRP; technical aspects of sampling, analysis, data processing, and quality assurance; and organizational aspects. The report includes also 10 papers contributed by the participants. Each individual contribution was indexed and provided with an abstract. Refs, figs, tabs

  17. Report of the first research coordination meeting (RCM) for the co-ordinated research project (CRP E2 40 07) on development of a quality assurance programme for radiation therapy dosimetry in developing countries. IAEA, Vienna, 6-10 October 1997

    International Nuclear Information System (INIS)

    Izewska, J.

    1998-01-01

    In 1994, a group of consultants was asked to advice the Agency on the expansion of the IAEA/WHO TLD postal dose check service for radiotherapy hospitals by transfer of know-how to national level. The consultants advised the Agency to initiate the Co-ordinated Research Programme (CRP) to transfer the IAEA well established TLD methodology to the countries where existing resources enable set up of the External Audit Groups - nationally recognised groups in charge of operating external quality audits for radiotherapy dosimetry. The External Audit Groups (EAG) include the SSDL, a Measuring Centre (MC) and a Medical Physics Group (MPG), and these groups work in close co-operation during all steps of the TLD audits

  18. Co-ordinated research project on assessment of levels and health-effects of airborne particulate matter in mining, metal refining and metal working industries using nuclear and related analytical techniques. Report on the first research co-ordination meeting (RCM)

    International Nuclear Information System (INIS)

    1998-01-01

    The objectives of the CRP are to: (1) improve competence for research on workplace monitoring in terms of proper sampling and analytical procedures, (2) obtain relevant and reliable data on sources and levels of workplace pollution in various countries, (3) promote a better understanding of methods for the interpretation of such data including occupational heath studies, and (4) encourage closer collaboration between analytical scientists and researchers in the field of occupational health in the countries concerned. The CRP focuses on the use of nuclear and related analytical techniques for the following kinds of studies: (1) strategies and techniques for sampling of workplace airborne particulate matter and of human tissues and body fluids (hair, blood, etc.) sampling of exposed and non-exposed persons; (2) development of suitable analytical procedures for analysis of such types of samples; (3) workplace and personal monitoring of airborne particulate matter in the mining, refining and metal working industries, and the health effects of such exposure; and (4) tissue analysis of the workers exposed for biological monitoring and the health effects studies. This report includes the core and supplementary programme of the CRP; technical aspects of sampling, analysis, data processing, and quality assurance; and organizational aspects. The report includes also 10 papers contributed by the participants. Each individual contribution was indexed and provided with an abstract

  19. Toward an Agile Approach to Managing the Effect of Requirements on Software Architecture during Global Software Development

    OpenAIRE

    Alsahli, Abdulaziz; Khan, Hameed; Alyahya, Sultan

    2016-01-01

    Requirement change management (RCM) is a critical activity during software development because poor RCM results in occurrence of defects, thereby resulting in software failure. To achieve RCM, efficient impact analysis is mandatory. A common repository is a good approach to maintain changed requirements, reusing and reducing effort. Thus, a better approach is needed to tailor knowledge for better change management of requirements and architecture during global software development (GSD).The o...

  20. The challenge of diagnosing seborrheic keratosis by reflectance confocal microscopy.

    Science.gov (United States)

    Guo, A; Chen, J; Yang, C; Ding, Y; Zeng, Q; Tan, L

    2018-05-24

    Seborrheic keratosis (SK) is one of the most common skin tumors seen by dermatologists. It should be differentiated with many diseases, especially skin tumors. Reflectance confocal microscopy (RCM) has been applied for evaluation of SK. There are a few studies that describe the RCM of SK. The aim of the study was to find the challenge of diagnosing seborrheic keratosis by reflectance confocal microscopy. A total of 390 patients with a clinical suspicious diagnosis of seborrheic keratosis were enrolled in this study, and lesions from each patient were imaged with RCM. Thirty-seven of these patients performed a biopsy in order to be given a histological diagnosis. We retrospectively analyzed the outcomes of RCM diagnosis and histological diagnosis, and then found the RCM characteristics of biopsy-proven lesions. According to RCM images, 258 of 390 (66.2%) patients were diagnosed with SK, 97 of 390 (24.9%) patients could not be diagnosed by the dermatologist according to RCM. Of all 37 biopsied lesions, 23 were SK, 6 were actinic keratosis, 2 were basal cell carcinoma, and 2 were squamous cell carcinoma. It is challenge to diagnose seborrheic keratosis by reflectance confocal microscopy. It may due to the variable clinical and RCM appearances of SK, and limited depth of RCM. © 2018 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  1. DOE Research and Development Accomplishments Site Index (A-Z)

    Science.gov (United States)

    Fermi Wigner atomic hydrogen maser atomic nucleus ATP B Bardeen, John Batteries lithium-ion radioisotope - 1959) Calvin, Melvin carbon Calvin Dresselhaus carbon cycle carbon 14 carbon dating carbocation , John C. medicine metathesis method Methanococus jannaschii methanol economy Microwave Background

  2. Ni(II

    African Journals Online (AJOL)

    Preferred Customer

    analytical chemistry, catalysis, electrochemistry, ring-opening metathesis ... Ethanol was dried over anhydrous copper(II) sulfate and distilled over metallic sodium. ... All bacteria were inoculated into Nutrient Broth (Difco) and incubated for 24 h ...

  3. (2E,2′E-3-(4-{[4-(4-Hydroxy-3-methoxyphenylbut-2-en-1-yl]oxy}phenyl-1-(2-hydroxy-4-methoxyphenylprop-2-en-1-one

    Directory of Open Access Journals (Sweden)

    Muhamad S. Fareza

    2016-12-01

    Full Text Available A hybrid of eugenol and a chalcone has been synthesized in good yield via cross olefin metathesis. The title compound (3 was characterized by spectroscopic data including NMR, infrared, and ESI-MS.

  4. Silica-supported tungsten carbynes (≡SiO)xW(≡CH)(Me)y (x = 1, y = 2; X = 2, y = 1): New efficient catalysts for alkyne cyclotrimerization

    KAUST Repository

    Riache, Nassima; Dé ry, Alexandre; Callens, Emmanuel; Poater, Albert; Samantaray, Manoja; Dey, Raju; Hong, Jinhua; Li, Kun; Cavallo, Luigi; Basset, Jean-Marie

    2015-01-01

    demonstrate that this catalyst species is active for alkyne cyclotrimerization without the formation of significant alkyne metathesis products. Additional DFT calculations highlight the importance of the W coordination sphere in supporting this experimental

  5. Presidential Green Chemistry Challenge: 2012 Small Business Award

    Science.gov (United States)

    Presidential Green Chemistry Challenge 2012 award winner, Elevance Renewable Sciences, used Nobel-prize-winning metathesis catalysis to produce high-value difunctional chemicals from renewable feedstocks including natural oils.

  6. Methods of refining natural oils, and methods of producing fuel compositions

    Science.gov (United States)

    Firth, Bruce E.; Kirk, Sharon E.

    2015-10-27

    A method of refining a natural oil includes: (a) providing a feedstock that includes a natural oil; (b) reacting the feedstock in the presence of a metathesis catalyst to form a metathesized product that includes olefins and esters; (c) passivating residual metathesis catalyst with an agent that comprises nitric acid; (d) separating the olefins in the metathesized product from the esters in the metathesized product; and (e) transesterifying the esters in the presence of an alcohol to form a transesterified product and/or hydrogenating the olefins to form a fully or partially saturated hydrogenated product. Methods for suppressing isomerization of olefin metathesis products produced in a metathesis reaction, and methods of producing fuel compositions are described.

  7. Adjustment of regional climate model output for modeling the climatic mass balance of all glaciers on Svalbard.

    NARCIS (Netherlands)

    Möller, M.; Obleitner, F.; Reijmer, C.H.; Pohjola, V.A.; Glowacki, P.; Kohler, J.

    2016-01-01

    Large-scale modeling of glacier mass balance relies often on the output from regional climate models (RCMs). However, the limited accuracy and spatial resolution of RCM output pose limitations on mass balance simulations at subregional or local scales. Moreover, RCM output is still rarely available

  8. Detection of UV-induced pigmentary and epidermal changes over time using in vivo reflectance confocal microscopy

    NARCIS (Netherlands)

    Middelkamp-Hup, Maritza A.; Park, H.-Y.; Lee, Jin; Gilchrest, Barbara A.; Gonzalez, Salvador

    2006-01-01

    In vivo reflectance confocal microscopy (RCM) provides high-resolution optical sections of the skin in its native state, without needing to fix or section the tissue. Melanin provides an excellent contrast for RCM, giving a bright signal in the confocal images. The pigmented guinea-pig is a common

  9. A New Approach to Special Education Finance: The Resource Cost Model.

    Science.gov (United States)

    Geske, Terry G.; Johnston, Mary Jo

    1985-01-01

    Describes current practices in Illinois where a personnel reimbursement formula is used to finance special education. Summarizes the basic components of the Resource Cost Model (RCM), a complex school finance formula, and compares and contrasts RCM with Illinois' current method of financing special education. (MLF)

  10. Confocal histopathology of irritant contact dermatitis in vivo and the impact of skin color (black vs white)

    NARCIS (Netherlands)

    Hicks, Shari P.; Swindells, Kirsty J.; Middelkamp-Hup, Maritza A.; Sifakis, Martine A.; González, Ernesto; González, Salvador

    2003-01-01

    BACKGROUND: The pathogenesis of irritant contact dermatitis and its modulation according to skin color is not well understood. Reflectance confocal microscopy (RCM) enables high-resolution, real-time, in-vivo imaging of human skin. OBJECTIVE: The goal of our study was to use RCM to determine whether

  11. Experimental and Modeling Investigation of the Effect of H2S Addition to Methane on the Ignition and Oxidation at High Pressures

    NARCIS (Netherlands)

    Gersen, Sander; van Essen, Martijn; Darmeveil, Harry; Hashemi, Hamid; Rasmussen, Christian Tihic; Christensen, Jakob Munkholdt; Glarborg, Peter; Levinsky, Howard

    The autoignition and oxidation behavior of CH4/H2S mixtures has been studied experimentally in a rapid compression machine (RCM) and a high-pressure flow reactor. The RCM measurements show that the addition of 1% H2S to methane reduces the autoignition delay time by a factor of 2 at pressures

  12. Determination of the chloride diffusion coefficient in blended cement mortars

    NARCIS (Netherlands)

    Elfmarkova, V.; Spiesz, P.R.; Brouwers, H.J.H.; Bilek, V.; Kersner, Z.

    2014-01-01

    Literature shows that the RCM test development and experience concerns only Ordinary Portland cement. Therefore, a validation of this test method is needed for other types of binders. This study analyzes the application of RCM test for mortars prepared with different binders: Ordinary Portland

  13. Hydrological processes in regional climate model simulations of the central United States flood of June-July 1993

    DEFF Research Database (Denmark)

    Anderson, Christopher J.; Arritt, Raymond W.; Takle, Eugene S.

    2003-01-01

    Thirteen regional climate model (RCM) simulations of June-July 1993 were compared with each other and observations. Water vapor conservation and precipitation characteristics in each RCM were examined for a 10° X 10° subregion of the upper Mississippi River basin, containing the region of maximum...

  14. Nevomelanocytic atypia detection by in vivo reflectance confocal microscopy

    Directory of Open Access Journals (Sweden)

    Ingrida Vaišnorienė

    2014-01-01

    Conclusions: Nevus with histopathologically confirmed nevomelanocytic atypia (dysplastic nevus could not be distinguished from nevus without atypia using analyzed in vivo RCM features of melanocytic atypia. More accurate diagnostics by means of in vivo RCM needs further investigation on reflectance of single and nested cutaneous melanocytes in benign and malignant skin lesions.

  15. Determination of the chloride diffusion coefficient in blended cement mortars

    NARCIS (Netherlands)

    Elfmarkova, V.; Spiesz, P.R.; Brouwers, H.J.H.

    2015-01-01

    The rapid chloride migration test (RCM) is a commonly used accelerated test for the determination of the chloride diffusion coefficient in concrete. Nevertheless, the initial development and further experience with the RCM test concern mainly the ordinary Portland cement system. Therefore, the

  16. The value of in vivo reflectance confocal microscopy in the diagnosis and monitoring of inflammatory and infectious skin diseases: a systematic review

    NARCIS (Netherlands)

    Hoogedoorn, L.; Peppelman, M.; Kerkhof, P.C.M. van de; Erp, P.E.J. van; Gerritsen, M.J.P.

    2015-01-01

    In vivo examination of the skin by reflectance confocal microscopy (RCM) has been performed for about 20 years, leading to a broad spectrum of imaged infectious and inflammatory skin diseases (ISD) with many described RCM features. We systematically reviewed all available literature concerning ISD

  17. Diagnostic accuracy of confocal microscopy imaging vs. punch biopsy for diagnosing and subtyping basal cell carcinoma

    NARCIS (Netherlands)

    Kadouch, D. J.; Leeflang, M. M.; Elshot, Y. S.; Longo, C.; Ulrich, M.; van der Wal, A. C.; Wolkerstorfer, A.; Bekkenk, M. W.; de Rie, M. A.

    2017-01-01

    BackgroundIn vivo reflectance confocal microscopy (RCM) is a promising non-invasive skin imaging technique that could facilitate early diagnosis of basal cell carcinoma (BCC) instead of routine punch biopsies. However, the clinical value and utility of RCM vs. a punch biopsy in diagnosing and

  18. Inter-rater and intra-rater agreement of confocal microscopy imaging in diagnosing and subtyping basal cell carcinoma

    NARCIS (Netherlands)

    Kadouch, D. J.; van Haersma de With, A.; Elshot, Y. S.; Peppelman, M.; Bekkenk, M. W.; Wolkerstorfer, A.; Eekhout, I.; Prinsen, C. A. C.; de Rie, M. A.

    2017-01-01

    Reflectance confocal microscopy (RCM) imaging can be used to diagnose and subtype basal cell carcinoma (BCC) but relies on individual morphologic pattern recognition that might vary among users. We assessed the inter-rater and intra-rater agreement of RCM in correctly diagnosing and subtyping BCC.

  19. Reflectance confocal microscopy: an effective tool for monitoring ultraviolet B phototherapy in psoriasis.

    NARCIS (Netherlands)

    Wolberink, E.A.W.; Erp, P.E.J. van; Boer-van Huizen, R.T. de; Kerkhof, P.C.M. van de; Gerritsen, M.J.P.

    2012-01-01

    Background In vivo reflectance confocal microscopy (RCM) is a novel, noninvasive imaging technique which enables imaging of skin at a cellular resolution comparable to conventional microscopy. Objectives We performed a pilot study to evaluate RCM as a noninvasive tool for monitoring ultraviolet (UV)

  20. Cellular features of psoriatic skin: imaging and quantification using in vivo reflectance confocal microscopy

    NARCIS (Netherlands)

    Wolberink, E.A.W.; Erp, P.E.J. van; Teussink, M.M.; Kerkhof, P.C.M. van de; Gerritsen, M.J.P.

    2011-01-01

    BACKGROUND: In vivo reflectance confocal microscopy (RCM) is a novel, exciting imaging technique. It provides images of cell-and tissue structures and dynamics in situ, in real time, without the need for ex vivo tissue samples. RCM visualizes the superficial part of human skin up to a depth of 250

  1. Effects of ebselen on radiocontrast media-induced hepatotoxicity in rats.

    Science.gov (United States)

    Basarslan, Fatmagul; Yilmaz, Nigar; Davarci, Isil; Akin, Mustafa; Ozgur, Mustafa; Yilmaz, Cahide; Ulutas, Kemal Turker

    2013-09-01

    Oxidative stress is accepted as a potential responsible mechanism in the pathogenesis of radiocontrast media (RCM)-induced hepatotoxicity. Therefore, we aimed to investigate the protective effects of ebselen against RCM-induced hepatotoxicity by measuring tissue oxidant/antioxidant parameters and histological changes in rats. Wistar albino rats were randomly separated into four groups consisting of eight rats per group. Normal saline was given to the rats in control group (group 1). RCM was given to the rats in group 2, and both RCM and ebselen were given to the rats in group 3. Only ebselen was given to the rats in group 4. Liver sections of the killed animals were analyzed to measure the levels of malondialdehyde (MDA) and activities of superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GSH-Px), as well as histopathological changes. In RCM group, SOD and CAT levels were found increased. In RCM-ebselen group, MDA, SOD and CAT levels were found decreased. In RCM-ebselen group, however, GSH-Px activities of liver tissue increased. All these results indicated that ebselen produced a protective mechanism against RCM-induced hepatotoxicity and took part in oxidative stress.

  2. Functionalized linear and cyclic polyolefins

    Energy Technology Data Exchange (ETDEWEB)

    Tuba, Robert; Grubbs, Robert H.

    2018-02-13

    This invention relates to methods and compositions for preparing linear and cyclic polyolefins. More particularly, the invention relates to methods and compositions for preparing functionalized linear and cyclic polyolefins via olefin metathesis reactions. Polymer products produced via the olefin metathesis reactions of the invention may be utilized for a wide range of materials applications. The invention has utility in the fields of polymer and materials chemistry and manufacture.

  3. Process for compound transformation

    KAUST Repository

    Basset, Jean-Marie

    2016-12-29

    Embodiments of the present disclosure provide for methods of using a catalytic system to chemically transform a compound (e.g., a hydrocarbon). In an embodiment, the method does not employ grafting the catalyst prior to catalysis. In particular, embodiments of the present disclosure provide for a process of hydrocarbon (e.g., C1 to C20 hydrocarbon) metathesis (e.g., alkane, olefin, or alkyne metathesis) transformation, where the process can be conducted without employing grafting prior to catalysis.

  4. Synthesis of porphyryl boronates with (un)saturated side-chains

    OpenAIRE

    SENGE, MATHIAS; SERGEEVA, NATALIA

    2008-01-01

    PUBLISHED Porphyrins with (un)saturated side?chains containing boron residues were developed as synthons for porphyrin functionalization. Porphyrins with mono and bis-substituted unsaturated boronyl residues were prepared in good yields (52?66 %) using a cross?metathesis approach in the presence of Grubbs I-generation catalysts. In all cases complete E?stereoselectivity (100 %) was observed. Furthermore, formal cross?metathesis products with ?,??unsaturated chains smoothly underwent additi...

  5. Improved direct production of 2,3-dimethylbutenes and 3,3-dimethylbutene from 2-methylpropene on tungsten hydride based catalysts

    KAUST Repository

    Garron, Anthony; Stoffelbach, Franç ois; Merle, Nicolas; Szeto, Kaï Chung; Thivolle-Cazat, Jean; Basset, Jean-Marie; Norsic, Sé bastien; Taoufik, Mostafa

    2012-01-01

    2-Methylpropene in the presence of W-H/Ni 1%-Al 2O 3-(500) is transformed in high selectivity into a mixture of 2,3-dimethylbutenes (2,3-DMBs = DMB-1 and DMB-2) and neohexene. 2,3-DMBs arise from the unfavoured 2-methylpropene self-metathesis reaction whereas the neohexene originates from a cascade reaction: 2-methylpropene dimerisation followed by cross metathesis. © 2012 The Royal Society of Chemistry.

  6. Selection of maintenance tasks

    Energy Technology Data Exchange (ETDEWEB)

    Dean, B; Rombos, P [Wardrop (W.L.) and Associates Ltd., Winnipeg, MB (Canada)

    1995-10-01

    Two methodologies for maintenance task selection, Reliability Centre Maintenance (RCM) and Degradation Mode Analysis (DMA), are compared with regard to application in the nuclear industry and potential for application at CANDU nuclear power plants. RCM is the favoured one of the two methodologies. It is more thorough than DMA, is well supported within the US nuclear industry, and - with experience in application - is gaining cost effectiveness. There is interest in the use of RCM in other nations, including France and Japan, and it is already being implemented at Bruce A NGS and Bruce B NGS in Canada. DMA lags behind RCM in development and currently there is little experience to support claims of major benefits at reduced cost. Significant advantages over RCM need to be demonstrated if DMA is to gain acceptance in the nuclear industry. (author). 41 refs., 7 tabs., 8 figs.

  7. Responsibility-centered management: a 10-year nursing assessment.

    Science.gov (United States)

    McBride, A B; Neiman, S; Johnson, J

    2000-01-01

    In 1988-89, Indiana University became the first public university to implement responsibility-centered management (RCM) comprehensively. This article describes and assesses the implementation of RCM on the core campus of Indiana University School of Nursing in Indianapolis. It describes how RCM encouraged an information-rich environment, particularly with the advent of economic modeling; decision making linked to strategic goals/objectives; and a performance-based reward structure (e.g., merit pay increases and incentive plans). It ends with a discussion about the worth of RCM and the changes that frame-work produced, particularly in reconceptualizing the roles of the business officer and dean. The most profound consequence of RCM may be the effect it has in encouraging rethinking of what it means to be a school of nursing at this point in time.

  8. Selection of maintenance tasks

    International Nuclear Information System (INIS)

    Dean, B.; Rombos, P.

    1995-10-01

    Two methodologies for maintenance task selection, Reliability Centre Maintenance (RCM) and Degradation Mode Analysis (DMA), are compared with regard to application in the nuclear industry and potential for application at CANDU nuclear power plants. RCM is the favoured one of the two methodologies. It is more thorough than DMA, is well supported within the US nuclear industry, and - with experience in application - is gaining cost effectiveness. There is interest in the use of RCM in other nations, including France and Japan, and it is already being implemented at Bruce A NGS and Bruce B NGS in Canada. DMA lags behind RCM in development and currently there is little experience to support claims of major benefits at reduced cost. Significant advantages over RCM need to be demonstrated if DMA is to gain acceptance in the nuclear industry. (author). 41 refs., 7 tabs., 8 figs

  9. A survey of research projects in maintenance optimization for Electricite de France power plants

    International Nuclear Information System (INIS)

    Jacquot, J.P.

    1996-01-01

    Six years ago, Electricite de France launched a Reliability Centered Maintenance (RCM) pilot project to optimize preventive maintenance for its nuclear power plants. After a feasibility study, a Reliability Centered Maintenance (RCM) method was standardized. It is now applied on a large scale to the 50 EDF nuclear units. A RCM workstation based on this standardized method has been developed and is now used in each plant. In the next step, the author will consider whether a risk based approach can be included in this RCM process in order to analyze critical passive components such as pipes and supports. Considering the potential advantages of these optimization techniques, a dedicated process has been also developed for maintenance of future plants, gas turbines, or nuclear units. For these future plants, a Logistic Support Analysis (LSA) will be added to the RCM process to globally evaluate availability, safety and maintenance costs. This paper will present a survey of these different developments of methods and tools

  10. Imaging rat esophagus using combination of reflectance confocal and multiphoton microscopy

    International Nuclear Information System (INIS)

    Zhuo, S M; Chen, J X; Jiang, X S; Lu, K C; Xie, S S

    2008-01-01

    We combine reflectance confocal microscopy (RCM) with multiphoton microscopy (MPM) to image rat esophagus. The two imaging modalities allow detection of layered–resolved complementary information from esophagus. In the keratinizing layer, the keratinocytes boundaries can be characterized by RCM, while the keratinocytes cytoplasm (keratin) can be further imaged by multiphoton autofluorescence signal. In the epithelium, the epithelial cellular boundaries and nucleus can be detected by RCM, and MPM can be used for imaging epithelial cell cytoplasm and monitoring metabolic state of epithelium. In the stroma, multiphoton autofluorescence signal is used to image elastin and second harmonic generation signal is utilized to detect collagen, while RCM is used to determine the optical property of stroma. Overall, these results suggest that the combination of RCM and MPM has potential to provide more important and comprehensive information for early diagnosis of esophageal cancer

  11. SYNTHESIS AND CHARACTERIZATION OF (MU-5-C5ME5)2TI(R)CL (R = ME, ET, NORMAL-PR, CH=CH2, PH, O-NORMAL-PR) AND THEIR SALT METATHESIS REACTIONS - THERMAL-DECOMPOSITION PATHWAYS OF (MU-5-C5ME5)2TI(ME)R' (R' = ET, CH=CH2, PH, CH2PH)

    NARCIS (Netherlands)

    LUINSTRA, GA; TEUBEN, JH

    Complexes Cp*2Ti(R)Cl (Cp* = eta-5-C5Me5; R = Me (1), Et (2), n-Pr (3), CH=CH2 (4), Ph (5), O-n-Pr (6)) have been prepared by oxidation Of CP*2TiR with lead dichloride. Not every compound Cp*2Ti(R)Cl was accessible and for R = CH2CMe3 and CH2Ph reduction to Cp*2TiCl and R. was observed. Homolysis of

  12. Synthesis and Characterization of (η5-C5Me5)2Ti(R)Cl (R = Me, Et, n-Pr, CH=CH2, Ph, O-n-Pr) and Their Salt Metathesis Reactions. Thermal Decomposition Pathways of (η5-C5Me5)2Ti(Me)R' (R' = Et, CH=CH2, Ph, CH2Ph)

    NARCIS (Netherlands)

    Luinstra, Gerrit A.; Teuben, Jan H.

    1992-01-01

    Complexes Cp*2Ti(R)Cl (Cp* = η5-C5Me5; R = Me (1), Et (2), n-Pr (3), CH=CH2 (41, Ph (5), O-n-Pr (6)) have been prepared by oxidation of Cp*2TiR with lead dichloride. Not every compound Cp*2Ti(R)Cl was accessible and for R = CH2CMe3 and CH2Ph reduction to Cp*2TiCl and R· was observed. Homolysis of

  13. A new dynamical downscaling approach with GCM bias corrections and spectral nudging

    Science.gov (United States)

    Xu, Zhongfeng; Yang, Zong-Liang

    2015-04-01

    To improve confidence in regional projections of future climate, a new dynamical downscaling (NDD) approach with both general circulation model (GCM) bias corrections and spectral nudging is developed and assessed over North America. GCM biases are corrected by adjusting GCM climatological means and variances based on reanalysis data before the GCM output is used to drive a regional climate model (RCM). Spectral nudging is also applied to constrain RCM-based biases. Three sets of RCM experiments are integrated over a 31 year period. In the first set of experiments, the model configurations are identical except that the initial and lateral boundary conditions are derived from either the original GCM output, the bias-corrected GCM output, or the reanalysis data. The second set of experiments is the same as the first set except spectral nudging is applied. The third set of experiments includes two sensitivity runs with both GCM bias corrections and nudging where the nudging strength is progressively reduced. All RCM simulations are assessed against North American Regional Reanalysis. The results show that NDD significantly improves the downscaled mean climate and climate variability relative to other GCM-driven RCM downscaling approach in terms of climatological mean air temperature, geopotential height, wind vectors, and surface air temperature variability. In the NDD approach, spectral nudging introduces the effects of GCM bias corrections throughout the RCM domain rather than just limiting them to the initial and lateral boundary conditions, thereby minimizing climate drifts resulting from both the GCM and RCM biases.

  14. A four-phase strategy for the implementation of reflectance confocal microscopy in dermatology.

    Science.gov (United States)

    Hoogedoorn, L; Gerritsen, M J P; Wolberink, E A W; Peppelman, M; van de Kerkhof, P C M; van Erp, P E J

    2016-08-01

    Reflectance confocal microscopy (RCM) is gradually implemented in dermatology. Strategies for further implementation and practical 'hands on' guidelines are lacking. The primary outcome was to conduct a general strategy for further implementation of RCM. The secondary outcome was the diagnosis of psoriasis and differentiation of stable from unstable psoriatic plaques by means of the 'hands on' protocol, derived from the strategy. We used a four-phased model; an exploring phase, a systematic literature search, a clinical approach and, finally, an integration phase to develop a clinical guideline for RCM in psoriasis. Receiver operating characteristic curve statistics was applied to define the accuracy for the diagnosis of unstable psoriasis. A general strategy for further implementation of RCM and practical approach was developed to examine psoriasis by RCM and to distinguish stable from unstable psoriasis. Unstable psoriasis was diagnosed by epidermal inflammatory cell counts with a sensitivity and specificity of 91.7% and 98.3%, respectively, and with an accuracy of 0.92 (area under the curve). In addition, a monitoring model was proposed. This is the first study that shows a method for implementation of RCM in dermatology. The strategy and hands on protocol for psoriasis may serve as a model for other dermatological entities and additionally may lead to specialized ready-to-use RCM protocols for clinical dermatological practice. © 2016 European Academy of Dermatology and Venereology.

  15. The current role of in vivo reflectance confocal microscopy within the continuum of actinic keratosis and squamous cell carcinoma: a systematic review.

    Science.gov (United States)

    Nguyen, Kim P; Peppelman, Malou; Hoogedoorn, Lisa; Van Erp, Piet E J; Gerritsen, Marie-Jeanne P

    2016-12-01

    Clinical differentiation between actinic keratosis (AK), squamous cell carcinoma (SCC) in situ, and invasive SCC and its variants may be difficult. Reflectance confocal microscopy (RCM) is a non-invasive technique for in vivo skin imaging. To explicate the diagnostic and monitoring use of RCM within the spectrum of AK and SCC, and evaluate the accuracy of RCM for these diagnoses relative to histopathology. A systematic literature search was performed in PubMed, EMBASE, the Cochrane Library, and Web of Science databases. The quality was assessed using the STrengthening the Reporting of OBservational studies in Epidemiology (STROBE) checklist. Twenty-five eligible studies were included. Different diagnostic RCM features have been described for AK, actinic cheilitis (AC), erythroplasia of Queyrat, Bowen disease, invasive SCC, and keratoacanthoma (KA). The overall range of sensitivity and specificity of RCM for the diagnosis of SCC, AK, SCC in situ, and KA was 79-100% and 78-100%, respectively. The current literature describes the use of RCM for diagnosing AK, AC, erythroplasia of Queyrat, Bowen disease, invasive SCC, and KA, as well as for monitoring treatments of AK, with good accuracy. Unfortunately, studies with high methodological quality are lacking. Pre-treatment of hyperkeratotic lesions and uniform definitions of RCM features are required to simplify the differentiation between AKs, SCC in situ, and SCC and its variants in clinical practice.

  16. [In vivo reflectance confocal microscopy in dermatology: a proposal concerning French terminology].

    Science.gov (United States)

    Kanitakis, J; Bahadoran, P; Braun, R; Debarbieux, S; Labeille, B; Perrot, J-L; Vabres, P

    2013-11-01

    Reflectance confocal microscopy (RCM) is a recently introduced non-invasive imaging technique allowing real-time examination of the skin in vivo. Whereas a substantial literature concerning RCM exists in English, so far there is no official terminology in French, despite the fact that an ever-growing number of French-speaking dermatologists now use this new imaging technique. The aim of the present study is to propose a French terminology for RCM in order to allow French-speaking dermatologists to communicate in a precise and homogeneous language on this topic. A group of French-speaking dermatologists with solid experience of RCM, members of the Non-invasive Cutaneous Imaging group of the French Society of Dermatology, endeavored to suggest terms in French concerning RCM. Each group member dealt with a specific paragraph. The members exchanged comments via email and the terminology was finalized during a meeting of the group members in Paris in June 2012. Descriptive terms referring to the RCM aspects of normal and diseased skin were proposed. Some of these already existed, being used in routine dermatopathology, while other specific terms were created or adapted from the English terminology. This terminology will allow French-speaking dermatologists using RCM to communicate their findings in a homogeneous language. It may be enriched in the future by the introduction of additional terms describing new aspects of both normal and, especially, diseased skin. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

  17. High-resolution imaging of basal cell carcinoma: a comparison between multiphoton microscopy with fluorescence lifetime imaging and reflectance confocal microscopy.

    Science.gov (United States)

    Manfredini, Marco; Arginelli, Federica; Dunsby, Christopher; French, Paul; Talbot, Clifford; König, Karsten; Pellacani, Giovanni; Ponti, Giovanni; Seidenari, Stefania

    2013-02-01

    The aim of this study was to compare morphological aspects of basal cell carcinoma (BCC) as assessed by two different imaging methods: in vivo reflectance confocal microscopy (RCM) and multiphoton tomography with fluorescence lifetime imaging implementation (MPT-FLIM). The study comprised 16 BCCs for which a complete set of RCM and MPT-FLIM images were available. The presence of seven MPT-FLIM descriptors was evaluated. The presence of seven RCM equivalent parameters was scored in accordance to their extension. Chi-squared test with Fisher's exact test and Spearman's rank correlation coefficient were determined between MPT-FLIM scores and adjusted-RCM scores. MPT-FLIM and RCM descriptors of BCC were coupled to match the descriptors that define the same pathological structures. The comparison included: Streaming and Aligned elongated cells, Streaming with multiple directions and Double alignment, Palisading (RCM) and Palisading (MPT-FLIM), Typical tumor islands, and Cell islands surrounded by fibers, Dark silhouettes and Phantom islands, Plump bright cells and Melanophages, Vessels (RCM), and Vessels (MPT-FLIM). The parameters that were significantly correlated were Melanophages/Plump Bright Cells, Aligned elongated cells/Streaming, Double alignment/Streaming with multiple directions, and Palisading (MPT-FLIM)/Palisading (RCM). According to our data, both methods are suitable to image BCC's features. The concordance between MPT-FLIM and RCM is high, with some limitations due to the technical differences between the two devices. The hardest difficulty when comparing the images generated by the two imaging modalities is represented by their different field of view. © 2012 John Wiley & Sons A/S.

  18. Identification of tasks of maintenance centered in the reliability

    International Nuclear Information System (INIS)

    Torres V, A.; Rivero O, J.J.

    2004-01-01

    The methodology of Reliability Centered Maintenance (RCM) it has become, after the discovery of their advantages, an objective of many industrial facilities to optimize their maintenance. However, diverse subjective factors affect the determination of the parameters (technical of predictive to apply and times among interventions) that characterize the tasks of RCM. A method to determine the monitoring tasks at condition and the times more recommended for to apply the monitoring by time and the search of faults, with focus in system. This methodology has been computerized inside the code MOSEG Win Ver 1.0. The same has been applied with success to the determination of tasks of RCM in industrial objectives. (Author)

  19. Reliability Centered Maintenance for Savannah River Site`s interim waste management facilities. Revision 1

    Energy Technology Data Exchange (ETDEWEB)

    Hauer, K.A. [Westinghouse Savannah River Co., Aiken, SC (United States); Wilson, J.F. [PRC, Inc. (US)

    1992-06-01

    The application of Reliability Centered Maintenance (RCM) has been shown to be an effective means to optimize maintenance programs or to establish new programs. The key to success of any RCM program is to customize the methodology to meet the specific needs of the implementing organization. This paper discusses how RCM is being used to establish the preventive maintenance program and how the resulting system data is being used to support the Technical Baseline reconstitution effort for the interim Waste Management Division of Westinghouse Savannah River Company (WSRC).

  20. Reliability Centered Maintenance for Savannah River Site's interim waste management facilities

    Energy Technology Data Exchange (ETDEWEB)

    Hauer, K.A. (Westinghouse Savannah River Co., Aiken, SC (United States)); Wilson, J.F. (PRC, Inc. (US))

    1992-01-01

    The application of Reliability Centered Maintenance (RCM) has been shown to be an effective means to optimize maintenance programs or to establish new programs. The key to success of any RCM program is to customize the methodology to meet the specific needs of the implementing organization. This paper discusses how RCM is being used to establish the preventive maintenance program and how the resulting system data is being used to support the Technical Baseline reconstitution effort for the interim Waste Management Division of Westinghouse Savannah River Company (WSRC).

  1. Atomic data for heavy element impurities in fusion reactors. Summary report of the final research coordination meeting

    International Nuclear Information System (INIS)

    Clark, R.E.H.

    2009-04-01

    Eleven experts on the properties of heavy elements of relevance to fusion energy research attended the final Research Coordination Meeting (RCM) on Data for Heavy Element Impurities in Fusion Reactors, held at IAEA Headquarters on 4-6 March 2009. Participants summarized their accomplishments with respect to the revised work plan formulated at the second RCM. The overall work plan for the CRP was assessed and reviewed in detail, and achievements were noted. Discussions, conclusions and recommendations of the RCM are briefly described in this report. (author)

  2. Reliability Centered Maintenance for Savannah River Site's interim waste management facilities

    International Nuclear Information System (INIS)

    Hauer, K.A.; Wilson, J.F.

    1992-01-01

    The application of Reliability Centered Maintenance (RCM) has been shown to be an effective means to optimize maintenance programs or to establish new programs. The key to success of any RCM program is to customize the methodology to meet the specific needs of the implementing organization. This paper discusses how RCM is being used to establish the preventive maintenance program and how the resulting system data is being used to support the Technical Baseline reconstitution effort for the interim Waste Management Division of Westinghouse Savannah River Company (WSRC)

  3. Experimental and Modeling Investigation of the Effectof H2S Addition to Methane on the Ignition and Oxidation at High Pressures

    DEFF Research Database (Denmark)

    Gersen, Sander; van Essen, Martijn; Darmeveil, Harry

    2017-01-01

    The autoignition and oxidation behavior of CH4/H2S mixtures has been studied experimentally in a rapid compression machine (RCM) and a high-pressure flow reactor. The RCM measurements show that the addition of 1% H2S to methane reduces the autoignition delay time by a factor of 2 at pressures....... A comparison of the flow reactordata to modeling predictions shows satisfactory agreement under stoichiometric conditions, while at very reducing conditions, the model underestimates the consumption of both H2S and CH4. Similar to the RCM experiments, the presence of H2S is predicted to promote oxidation...

  4. Climate change impact assessment of extreme precipitation on urban flash floods – case study, Aarhus, Denmark

    DEFF Research Database (Denmark)

    Madsen, Henrik; Sunyer Pinya, Maria Antonia; Rosbjerg, Dan

    projections for estimation of changes in extreme rainfall characteristics. Climate model projections from 20 regional climate models (RCM) from the ENSEMBLES data archive were used in the analysis. Two different estimation methods were applied, using, respectively, a direct estimation of the changes...... in the extreme value statistics of the RCM data, and application of a stochastic weather generator fitted to the changes in rainfall characteristics from the RCM data. The results show a large variability in the projected changes in extreme precipitation between the different RCMs and the two estimation methods...

  5. Identification of tasks of maintenance centered in the reliability; Identificacion de tareas de mantenimiento centrado en la confiabilidad

    Energy Technology Data Exchange (ETDEWEB)

    Torres V, A.; Rivero O, J.J. [Dpto. Ingenieria Nuclear, Instituto Superior de Tecnologias y Ciencias Aplicadas, Ave. Salvador Allende y Luaces, Quinta de los Molinos, Plaza, Ciudad Habana (Cuba)]. e-mail: atorres@fctn.isctn.edu.cu

    2004-07-01

    The methodology of Reliability Centered Maintenance (RCM) it has become, after the discovery of their advantages, an objective of many industrial facilities to optimize their maintenance. However, diverse subjective factors affect the determination of the parameters (technical of predictive to apply and times among interventions) that characterize the tasks of RCM. A method to determine the monitoring tasks at condition and the times more recommended for to apply the monitoring by time and the search of faults, with focus in system. This methodology has been computerized inside the code MOSEG Win Ver 1.0. The same has been applied with success to the determination of tasks of RCM in industrial objectives. (Author)

  6. An evaluation of the Browns Ferry Nuclear Plant preventive maintenance program based on reliability centered maintenance analysis

    International Nuclear Information System (INIS)

    McCullough, C.L.; McCullough, C.A.

    1989-01-01

    Reliability centered maintenance (RCM) techniques were used to support a preventative maintenance (PM) upgrade program (PMUP) performed at TVA Browns Ferry Nuclear Plant (BFNP). The purpose of the RCM analysis was to identify critical equipment based on risk and economic importance and to evaluate the PM activities applicable to that equipment. The analysis may be conveniently divided into three steps, which will be outlined in the Approach section of this paper. The net benefit of the RCM approach was a prioritization of the focus of the PM upgrade program so that plant components receive attention proportional to their importance, and assurance that PM activities properly address the most likely component failure causes

  7. Characteristics and application study of AP1000 NPPs equipment reliability classification method

    International Nuclear Information System (INIS)

    Guan Gao

    2013-01-01

    AP1000 nuclear power plant applies an integrated approach to establish equipment reliability classification, which includes probabilistic risk assessment technique, maintenance rule administrative, power production reliability classification and functional equipment group bounding method, and eventually classify equipment reliability into 4 levels. This classification process and result are very different from classical RCM and streamlined RCM. It studied the characteristic of AP1000 equipment reliability classification approach, considered that equipment reliability classification should effectively support maintenance strategy development and work process control, recommended to use a combined RCM method to establish the future equipment reliability program of AP1000 nuclear power plants. (authors)

  8. Metátese na linguagem infantil: “porfessora” é bom, “professora” é melhor

    Directory of Open Access Journals (Sweden)

    Rosa M. Lima

    2013-12-01

    Full Text Available A leitura e a escrita são ensinadas a crianças cuja linguagem oral contém ainda, muitas vezes, desvios subtis. A metátese é um desses desvios, consistindo na troca da ordem de fonemas na palavra, tal como acontece em “corcodilo”. Analisámos a presença da metátese na linguagem infantil. Num primeiro estudo, investigámos a aquisição da linguagem oral dos 3 aos 7 anos de idade. A metátese mostrou um peso crescente ao longo da idade. Num segundo estudo, analisámos o desempenho de crianças do 4º ano na deteção auditiva e visual da metátese, e na escrita de palavras passíveis de induzir a metátese. A deteção visual da metátese foi inferior ao nível do acaso. Na escrita de palavras, a metátese deu conta de 69% a 75% dos erros observados. Os resultados sugerem que a metátese constitui um processo indicador de domínio da linguagem oral, revelando formas de gestão de estruturas silábicas complexas. Contudo, essas formas de gestão podem cristalizar-se durante o primeiro ciclo, afetando negativamente a aquisição da linguagem escrita. Children often learn to read and write when their oral language is still marked by subtle errors. Metathesis is one such error. It is a phonological process whereby the order of phonemes is interchanged in the word, such as “corcodilo” instead of “crocodilo”. We investigated metathesis in child language. In a first study, we investigated spoken language acquisition from 3 to7 and half years of age. Metathesis increased with age. In a second study, we analysed the performance of children attending the 4th grade, in auditory and visual detection of metathesis, as well as in spelling words prone to metathesis. Performance in the visual detection of metathesis was significantly below chance. In word spelling tasks, metathesis accounted for 69% to 75% of errors. Results suggest that metathesis indexes some mastery of spoken language, and that it reveals the ability to deal with complex

  9. Assessing future climatic changes of rainfall extremes at small spatio-temporal scales

    DEFF Research Database (Denmark)

    Gregersen, Ida Bülow; Sørup, Hjalte Jomo Danielsen; Madsen, Henrik

    2013-01-01

    Climate change is expected to influence the occurrence and magnitude of rainfall extremes and hence the flood risks in cities. Major impacts of an increased pluvial flood risk are expected to occur at hourly and sub-hourly resolutions. This makes convective storms the dominant rainfall type...... in relation to urban flooding. The present study focuses on high-resolution regional climate model (RCM) skill in simulating sub-daily rainfall extremes. Temporal and spatial characteristics of output from three different RCM simulations with 25 km resolution are compared to point rainfall extremes estimated...... from observed data. The applied RCM data sets represent two different models and two different types of forcing. Temporal changes in observed extreme point rainfall are partly reproduced by the RCM RACMO when forced by ERA40 re-analysis data. Two ECHAM forced simulations show similar increases...

  10. Differentiation of Constriction and Restriction: Complex Cardiovascular Hemodynamics.

    Science.gov (United States)

    Geske, Jeffrey B; Anavekar, Nandan S; Nishimura, Rick A; Oh, Jae K; Gersh, Bernard J

    2016-11-29

    Differentiation of constrictive pericarditis (CP) from restrictive cardiomyopathy (RCM) is a complex and often challenging process. Because CP is a potentially curable cause of heart failure and therapeutic options for RCM are limited, distinction of these 2 conditions is critical. Although different in regard to etiology, prognosis, and treatment, CP and RCM share a common clinical presentation of predominantly right-sided heart failure, in the absence of significant left ventricular systolic dysfunction or valve disease, due to impaired ventricular diastolic filling. Fundamental to the diagnosis of either condition is a clear understanding of the underlying hemodynamic principles and pathophysiology. We present a contemporary review of the pathophysiology, hemodynamics, diagnostic assessment, and therapeutic approach to patients presenting with CP and RCM. Copyright © 2016 American College of Cardiology Foundation. Published by Elsevier Inc. All rights reserved.

  11. Hardware-oriented reliability centered maintenance for the diesel generators of Wolsong unit 1

    International Nuclear Information System (INIS)

    Bae, Sang Min; Park, Jin Hee; Kim, Tae Woon; Lee, Yoon Kee; Song, Jin Bae

    1997-01-01

    The DGs (Diesel Generators) in NPP (Nuclear Power Plant) has been used for the emergency electric power source to shut down the nuclear reactor safely in case of station blackout. The RCM (Reliability Centered Maintenance) has been applied to DGs for increasing the safety of NPP. The structured defects of DG were not remedied by the improvement of maintenance method. As the first stage of RCM, to find the structured defects, its failure modes were searched and analyzed through the ten year maintenance information. The structured defects such as the air compressor, the lubricating oil pressure, and the insufficient load were the root causes of main failures. The air reservoir reinstallation, the lubricating oil tube modification, the load bank installation, and the qualitative instrumentation were the solutions for the hardware oriented RCM of DGs. There remains the software oriented RCM such as the rejection of useless maintenance, the preventive maintenance, the database of maintenance information, and the predictive maintenance

  12. Maintenance strategy for tilting table of rolling mill based on reliability considerations

    International Nuclear Information System (INIS)

    Deshpande, V.S.; Modak, J.P.

    2003-01-01

    Reliability centred maintenance (RCM) is a new strategic framework for ensuring that any asset continues to perform, as its users want it to perform. RCM is a process used to determine the maintenance requirement of any physical asset in its operating context. RCM process entails asking seven questions about each of the selected assets. It makes use of two documents namely, RCM information worksheet and RCM decision worksheet. RCM decision diagram integrates all the decision processes into a single strategic framework. RCM concept developed by US commercial airlines industry has been successfully implemented by Military, Navy, Nuclear power plants, electric power generation and distribution undertakings and several other sectors. These projects have been carried out in the United Kingdom, The Republic of Ireland, the United States, Hong Kong, Australia, Spain and Singapore. The fact that people has enthusiastically received RCM at all levels and has enabled users to achieve some remarkable successes in all of these countries, suggests that it can be universally employed. Literature review indicates that RCM approach is not conventionally applied in process industries in India. Presently, predictive maintenance (PDM) approach along with conventional preventive maintenance is used in continuous/process industries. This approach if implemented in totality will increase the production cost to a large degree and make the production uneconomical. Similarly breakdown maintenance (BDM) approach cannot be applied in such industries as each breakdown involves huge costs. RCM approach is a compromise between PDM and BDM approach for optimising the cost and ensuring the availability of machine. The RCM approach has been applied to the tilting table system of rolling mill for the research work reported in this paper. In the present study, preventive maintenance tasks suggested for power transmission subsystem, guiding and transportation subsystem and hydraulic subsystem in

  13. Restoring the Promise of the Right to Speedy Trial to Service Members in Pretrial Arrest and Confinement

    National Research Council Canada - National Science Library

    Shaver, Daniel P

    1994-01-01

    ...). This new version of R.C.M. 707 envisaged the simplification of some 40 years of confusion over what the right to a speedy trial means to persons who are subject to the Uniform Code of Military Justice (UCMJ...

  14. Implementing a Reliability Centered Maintenance Program at NASA's Kennedy Space Center

    National Research Council Canada - National Science Library

    Tuttle, Raymond

    1998-01-01

    .... A reliability centered maintenance (RCM) program seeks to offer equal or greater reliability at decreased cost by insuring only applicable, effective maintenance is performed and by in large part replacing time based maintenance...

  15. Net accumulation of the Greenland ice sheet

    DEFF Research Database (Denmark)

    Kiilsholm, Sissi; Christensen, Jens Hesselbjerg; Dethloff, Klaus

    2003-01-01

    High-resolution (50 km) climate change simulations for an area covering the entire Arctic have been conducted with the regional climate model (RCM) HIRHAM. The experiments were forced at the lateral boundary by large-scale atmospheric conditions from transient climate change scenario simulations...... with HIRHAM for periods representing present-day (1961-1990) and the future (2071-2100) in the two scenarios. We find that due to a much better representation of the surface topography in the RCM, the geographical distribution of present-day accumulation rates simulated by the RCM represents a substantial...... improvement compared to the driving OAGCM. Estimates of the regional net balance are also better represented by the RCM. In the future climate the net balance for the Greenland Ice Sheet is reduced in all the simulation, but discrepancies between the amounts when based on ECHAM4/OPYC3 and HIRHAM are found...

  16. Spatiotemporal closure of fractional laser-ablated channels imaged by optical coherence tomography and reflectance confocal microscopy

    DEFF Research Database (Denmark)

    Banzhaf, Christina A.; Wind, Bas S.; Mogensen, Mette

    2016-01-01

    Background and Objective Optical coherence tomography (OCT) and reflectance confocal microscopy (RCM) offer high-resolution optical imaging of the skin, which may provide benefit in the context of laser-assisted drug delivery. We aimed to characterize postoperative healing of ablative fractional...... laser (AFXL)-induced channels and dynamics in their spatiotemporal closure using in vivo OCT and RCM techniques. Study design/Materials and Methods The inner forearm of healthy subjects (n = 6) was exposed to 10,600 nm fractional CO2 laser using 5 and 25% densities, 120 μm beam diameter, 5, 15, and 25 m......J/microbeam. Treatment sites were scanned with OCT to evaluate closure of AFXL-channels and RCM to evaluate subsequent re-epithelialization. Results OCT and RCM identified laser channels in epidermis and upper dermis as black, ablated tissue defects surrounded by characteristic hyper-and hyporeflective zones. OCT imaged...

  17. Reliability centered maintenance as an optimization tool for electrical power plants

    International Nuclear Information System (INIS)

    Jacquot, J.P.; Bryla, P.; Martin-Mattei, C.; Meuwisse, C.

    1997-08-01

    Seven years ago, Electricite de France launched a Reliability Centered Maintenance (RCM) pilot project to optimize preventive maintenance for its nuclear power plants. After a feasibility study, a RCM method was standardized. It is now applied on a large scale to the 50 EDF nuclear units. A RCM workstation based on this standardized method has been developed and is now used in each plant. In the next step, it is considered whether a Risk based Approach can be included in this RCM process in order to analyze critical passive components such as pipes and supports. Considering the potential advantages of these optimization techniques, a dedicated process has been also developed for maintenance of future plants, gas turbines, or nuclear units. A survey of these different developments of methods and tools is presented. (author)

  18. Enantioselective synthesis of polyhydroxyindolizidinone and quinolizidinone derivatives from a common precursor.

    Science.gov (United States)

    Saha, Nemai; Chattopadhyay, Shital K

    2014-01-01

    A concise asymmetric synthetic route to two new tetrahydroxyindolizidinone and quinolizidinone derivatives has been developed from a common intermediate which featured a highly selective dihydroxylation reaction and a RCM reaction as key steps.

  19. NOAA/EcoFOCI Chukchi Sea mooring time-series data, stations C1, C2, and C3, 2010-08-29 to 2012-08-21, including currents, temperature, salinity, oxygen, chlorophyll a, and nitrate data (NCEI Accession 0157701)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — These EcoFOCI mooring time-series datasets consist of RCM-9 current data, Ecofluorometer, Seacat and nitrate data from moored instruments at 3 stations in the...

  20. Direct Synthesis of Medium-Bridged Twisted Amides via a Transannular Cyclization Strategy

    Science.gov (United States)

    Szostak, Michal; Aubé, Jeffrey

    2009-01-01

    The sequential RCM to construct a challenging medium-sized ring followed by a transannular cyclization across a medium-sized ring delivers previously unattainable twisted amides from simple acyclic precursors. PMID:19708701