WorldWideScience

Sample records for deletion coalescence metathesis

  1. Reduction in syllable onsets in the acquisition of Polish: deletion, coalescence, metathesis and gemination.

    Science.gov (United States)

    łukaszewicz, Beata

    2007-02-01

    This paper focuses on four strategies of onset reduction employed by a single child (4;0-4;4) acquiring Polish: deletion, coalescence, metathesis, and gemination. Deletion and coalescence occur in word-initial onsets while metathesis and gemination are restricted to word-medial position. The data, which constitute an intriguing 'conspiracy' case (Kisseberth, 1970), are analysed within OPTIMALITY THEORY (henceforth, OT; Prince & Smolensky, 1993/2004; McCarthy & Prince, 1995) in which all surface-true 'processes' are motivated through the interaction of ranked and violable constraints. The OT account makes it possible to envisage the four strategies as different surface responses to the undominated *COMPLEXOnset which militates against onset clusters. The choice of a particular strategy as well as its restriction to a particular word position is not random but follows from the interplay between *COMPLEXOnset, sonority-based syllable structure constraints (Margin Hierarchy, CONTACT LAW), context-sensitive markedness constraints (CODA CONDITION, *Nasal-Fricative) and faithfulness constraints. The present study confirms previous sonority-based findings, supplies further evidence for universal sonority mechanisms from word-medial clusters, and points to the coexistence of child-specific and abstract adult-based phonological strategies in the child's system.

  2. 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.

  3. Bubble coalescence

    NARCIS (Netherlands)

    Orvalho, Sandra; Ruzicka, Marek C.; Olivieri, Giuseppe; Marzocchella, Antonio

    2015-01-01

    The goal of this study is to present new experimental data on the effect of the bubble approach velocity and liquid viscosity on pairwise bubble coalescence. Measurements were performed to investigate the dynamics of bubble coalescence under well-defined laboratory conditions. Air and pure

  4. Olefin Metathesis for Chemical Biology

    Science.gov (United States)

    Binder, Joseph B; Raines, Ronald T

    2009-01-01

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

  5. Olefin metathesis in air.

    Science.gov (United States)

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

    2015-01-01

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

  6. Mechanistic studies of olefin metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Grubbs, R.H.

    1979-03-01

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

  7. Photolithographic olefin metathesis polymerization.

    Science.gov (United States)

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

    2013-11-13

    Patterning functional materials is a central challenge across many fields of science. The ability to lithographically fabricate micro- and nanostructures has been one of the most impactful technological breakthroughs of the last century. In part due to the complexity of the chemical processes in photoresists, there is a limited variety of materials that can currently be patterned by photolithography. We report a negative tone photoresist using a photoactivated olefin metathesis catalyst, which can be quickly prepared in a one-pot synthesis from commercially available starting materials. The resist is based on a ruthenium vinyl ether complex, widely regarded as inactive toward olefin metathesis. The combination of this photoactivated catalyst with the fidelity and functional group tolerance of ruthenium-mediated olefin metathesis enables a host of new possibilities for photopatterned materials.

  8. Olefin metathesis in air

    Science.gov (United States)

    Piola, Lorenzo; Nahra, Fady

    2015-01-01

    Summary Since the discovery and now widespread use of olefin metathesis, the evolution of metathesis catalysts towards air stability has become an area of significant interest. In this fascinating area of study, beginning with early systems making use of high oxidation state early transition metal centers that required strict exclusion of water and air, advances have been made to render catalysts more stable and yet more functional group tolerant. This review summarizes the major developments concerning catalytic systems directed towards water and air tolerance. PMID:26664625

  9. 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.

  10. Teaching metathesis "simple" stereochemistry.

    Science.gov (United States)

    Fürstner, Alois

    2013-09-20

    Applications of metal-catalyzed olefin metathesis reactions manifested dramatic growth during the late 20th and early 21st centuries, culminating in the 2005 Nobel Prize awarded to three of the pioneers. The standard catalysts developed during that time frame and their descendants have profoundly changed the mindset of the synthetic community, even though they do not provide a handle to control selectivity issues as fundamental as the E/Z geometry of the newly formed double bond. With yet another generation of catalysts in the making that are far superior in this regard, a new wave seems to be building up that is expected to have enormous impact, too. The current state of the art is critically assessed, as are possible alternatives such as the metathesis of triple bonds followed by stereoselective semi-reduction.

  11. Mechanochemical ruthenium-catalyzed olefin metathesis.

    Science.gov (United States)

    Do, Jean-Louis; Mottillo, Cristina; Tan, Davin; Štrukil, Vjekoslav; Friščić, Tomislav

    2015-02-25

    We describe the development of a mechanochemical approach for Ru-catalyzed olefin metathesis, including cross-metathesis and ring-closing metathesis. The method uses commercially available catalysts to achieve high-yielding, rapid, room-temperature metathesis of solid or liquid olefins on a multigram scale using either no or only a catalytic amount of a liquid.

  12. Metathesis depolymerizable surfactants

    Science.gov (United States)

    Jamison, Gregory M.; Wheeler, David R.; Loy, Douglas A.; Simmons, Blake A.; Long, Timothy M.; McElhanon, James R.; Rahimian, Kamyar; Staiger, Chad L.

    2008-04-15

    A class of surfactant molecules whose structure includes regularly spaced unsaturation in the tail group and thus, can be readily decomposed by ring-closing metathesis, and particularly by the action of a transition metal catalyst, to form small molecule products. These small molecules are designed to have increased volatility and/or enhanced solubility as compared to the original surfactant molecule and are thus easily removed by solvent extraction or vacuum extraction at low temperature. By producing easily removable decomposition products, the surfactant molecules become particularly desirable as template structures for preparing meso- and microstructural materials with tailored properties.

  13. Light-induced olefin metathesis

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    Yuval Vidavsky

    2010-11-01

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

  14. Light-induced olefin metathesis

    Science.gov (United States)

    Vidavsky, Yuval

    2010-01-01

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

  15. Metathesis catalysts and methods thereof

    Energy Technology Data Exchange (ETDEWEB)

    Schrock, Richard Royce; Yuan, Jian

    2016-04-19

    The present application provides, among other things, novel compounds for metathesis reactions, and methods for preparing and using provided compounds. In some embodiments, the present invention provides compounds having the structure of formula I or II. In some embodiments, the present invention provides methods for preparing a compound of formula I or II. In some embodiments, the present invention provides methods for using a provided compound. In some embodiments, a provided compound is useful for stereoselective ring-opening metathesis polymerization. In some embodiments, a provided metathesis method provides cis and/or isotactic polymers.

  16. Counting coalescent histories.

    Science.gov (United States)

    Rosenberg, Noah A

    2007-04-01

    Given a species tree and a gene tree, a valid coalescent history is a list of the branches of the species tree on which coalescences in the gene tree take place. I develop a recursion for the number of valid coalescent histories that exist for an arbitrary gene tree/species tree pair, when one gene lineage is studied per species. The result is obtained by defining a concept of m-extended coalescent histories, enumerating and counting these histories, and taking the special case of m = 1. As a sum over valid coalescent histories appears in a formula for the probability that a random gene tree evolving along the branches of a fixed species tree has a specified labeled topology, the enumeration of valid coalescent histories can considerably reduce the effort required for evaluating this formula.

  17. Synthesis of Tetrasubstituted Alkenes via Metathesis

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    Seung-Mann Paek

    2012-03-01

    Full Text Available Fully substituted olefin generation via metathesis is presented. Catalyst development, optimization of reaction conditions and substrate screening are included. In addition, asymmetric alkene metathesis, the cross metathesis reaction for this transformation and its application in natural products will be discussed.

  18. Industrial processes of olefin metathesis. Pt. 1

    Energy Technology Data Exchange (ETDEWEB)

    Warwel, S.

    1987-05-01

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

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

    Science.gov (United States)

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

    2015-07-29

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

  20. Hydrodynamic effects on coalescence.

    Energy Technology Data Exchange (ETDEWEB)

    Dimiduk, Thomas G.; Bourdon, Christopher Jay; Grillet, Anne Mary; Baer, Thomas A.; de Boer, Maarten Pieter; Loewenberg, Michael (Yale University, New Haven, CT); Gorby, Allen D.; Brooks, Carlton, F.

    2006-10-01

    The goal of this project was to design, build and test novel diagnostics to probe the effect of hydrodynamic forces on coalescence dynamics. Our investigation focused on how a drop coalesces onto a flat surface which is analogous to two drops coalescing, but more amenable to precise experimental measurements. We designed and built a flow cell to create an axisymmetric compression flow which brings a drop onto a flat surface. A computer-controlled system manipulates the flow to steer the drop and maintain a symmetric flow. Particle image velocimetry was performed to confirm that the control system was delivering a well conditioned flow. To examine the dynamics of the coalescence, we implemented an interferometry capability to measure the drainage of the thin film between the drop and the surface during the coalescence process. A semi-automated analysis routine was developed which converts the dynamic interferogram series into drop shape evolution data.

  1. 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.

  2. Olefin metathesis in nano-sized systems

    Science.gov (United States)

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

    2011-01-01

    Summary 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. PMID:21286399

  3. The allylic chalcogen effect in olefin metathesis

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    Yuya A. Lin

    2010-12-01

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

  4. The allylic chalcogen effect in olefin metathesis

    Science.gov (United States)

    Lin, Yuya A

    2010-01-01

    Summary Olefin metathesis has emerged as a powerful tool in organic synthesis. The activating effect of an allylic hydroxy group in metathesis has been known for more than 10 years, and many organic chemists have taken advantage of this positive influence for efficient synthesis of natural products. Recently, the discovery of the rate enhancement by allyl sulfides in aqueous cross-metathesis has allowed the first examples of such a reaction on proteins. This led to a new benchmark in substrate complexity for cross-metathesis and expanded the potential of olefin metathesis for other applications in chemical biology. The enhanced reactivity of allyl sulfide, along with earlier reports of a similar effect by allylic hydroxy groups, suggests that allyl chalcogens generally play an important role in modulating the rate of olefin metathesis. In this review, we discuss the effect of allylic chalcogens in olefin metathesis and highlight its most recent applications in synthetic chemistry and protein modifications. PMID:21283554

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

    Directory of Open Access Journals (Sweden)

    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.

  6. Catalysis: The mechanics of metathesis

    Science.gov (United States)

    Love, Jennifer A.

    2010-07-01

    Olefin metathesis is a flexible and efficient method for making carbon-carbon bonds and has found widespread application in academia and industry. Now, a detailed mechanistic study looking at key catalytic intermediates offers new insight into this reaction, and may prove useful in the development of more active and selective catalysts.

  7. Organometallic chemistry: A new metathesis

    Science.gov (United States)

    Hennessy, Elisabeth T.; Jacobsen, Eric N.

    2016-08-01

    Carbonyls and alkenes, two of the most common functional groups in organic chemistry, generally do not react with one another. Now, a simple Lewis acid has been shown to catalyse metathesis between alkenes and ketones in a new carbonyl olefination reaction.

  8. Methods for suppressing isomerization of olefin metathesis products

    Energy Technology Data Exchange (ETDEWEB)

    Firth, Bruce E.; Kirk, Sharon E.

    2015-10-27

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

  9. Methods for suppressing isomerization of olefin metathesis products

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-09-22

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

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

    Science.gov (United States)

    Morzycki, Jacek W

    2011-01-01

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

  11. Microwave-Assisted Olefin Metathesis

    Science.gov (United States)

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

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

  12. Fast "coalescent" simulation

    Directory of Open Access Journals (Sweden)

    Wall Jeff D

    2006-03-01

    Full Text Available Abstract Background The amount of genome-wide molecular data is increasing rapidly, as is interest in developing methods appropriate for such data. There is a consequent increasing need for methods that are able to efficiently simulate such data. In this paper we implement the sequentially Markovian coalescent algorithm described by McVean and Cardin and present a further modification to that algorithm which slightly improves the closeness of the approximation to the full coalescent model. The algorithm ignores a class of recombination events known to affect the behavior of the genealogy of the sample, but which do not appear to affect the behavior of generated samples to any substantial degree. Results We show that our software is able to simulate large chromosomal regions, such as those appropriate in a consideration of genome-wide data, in a way that is several orders of magnitude faster than existing coalescent algorithms. Conclusion This algorithm provides a useful resource for those needing to simulate large quantities of data for chromosomal-length regions using an approach that is much more efficient than traditional coalescent models.

  13. Halide exchanged Hoveyda-type complexes in olefin metathesis

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    Julia Wappel

    2010-11-01

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

  14. Halide exchanged Hoveyda-type complexes in olefin metathesis

    Science.gov (United States)

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

    2010-01-01

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

  15. Catalytic Alkene Metathesis in Ionic Liquids

    Science.gov (United States)

    Fischmeister, Cédric

    Olefin metathesis has found a tremendous number of application in the past 25 years. Immobilisation of olefin metathesis (pre)catalysts in room temperature ionic liquids (RTILs) offers the opportunity to recover and reuse the catalyst and also to reduce the level of ruthenium (Ru) contaminants in the products.

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

    Science.gov (United States)

    Balcar, Hynek; Čejka, Jiří

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

  17. Candle and candle wax containing metathesis and metathesis-like products

    Science.gov (United States)

    Murphy, Timothy A; Tupy, Michael J; Abraham, Timothy W; Shafer, Andy

    2014-04-01

    A wax comprises a metathesis product and/or a product that resembles, at least in part, a product which may be formed from a metathesis reaction. The wax may be used to form articles, for example, candles (container candles, votive candles, and/or a pillar candles), crayons, fire logs, or tarts. The wax commonly includes other components in addition to the metathesis product.

  18. Application of olefin metathesis in petrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Warwel, S.

    1979-01-01

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

  19. The Olefin Metathesis Reactions in Dendrimers

    Science.gov (United States)

    Astruc, Didier

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

  20. Enantioselective olefin metathesis with cyclometalated ruthenium complexes.

    Science.gov (United States)

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

    2014-09-17

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

  1. Tandem Catalysis Utilizing Olefin Metathesis Reactions.

    Science.gov (United States)

    Zieliński, Grzegorz K; Grela, Karol

    2016-07-01

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

  2. Theoretical investigations of olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

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

    1992-01-01

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

  3. Enantioselective Olefin Metathesis with Cyclometalated Ruthenium Complexes

    Science.gov (United States)

    2015-01-01

    The success of enantioselective olefin metathesis relies on the design of enantioenriched alkylidene complexes capable of transferring stereochemical information from the catalyst structure to the reactants. Cyclometalation of the NHC ligand has proven to be a successful strategy to incorporate stereogenic atoms into the catalyst structure. Enantioenriched complexes incorporating this design element catalyze highly Z- and enantioselective asymmetric ring opening/cross metathesis (AROCM) of norbornenes and cyclobutenes, and the difference in ring strain between these two substrates leads to different propagating species in the catalytic cycle. Asymmetric ring closing metathesis (ARCM) of a challenging class of prochiral trienes has also been achieved. The extent of reversibility and effect of reaction setup was also explored. Finally, promising levels of enantioselectivity in an unprecedented Z-selective asymmetric cross metathesis (ACM) of a prochiral 1,4-diene was demonstrated. PMID:25137310

  4. Coalescence of sessile drops

    CERN Document Server

    Nikolayev, Vadim; Pomeau, Yves; Andrieu, Claire

    2016-01-01

    We present an experimental and theoretical description of the kinetics of coalescence of two water drops on a plane solid surface. The case of partial wetting is considered. The drops are in an atmosphere of nitrogen saturated with water where they grow by condensation and eventually touch each other and coalesce. A new convex composite drop is rapidly formed that then exponentially and slowly relaxes to an equilibrium hemispherical cap. The characteristic relaxation time is proportional to the drop radius R * at final equilibrium. This relaxation time appears to be nearly 10 7 times larger than the bulk capillary relaxation time t b = R * $\\eta$/$\\sigma$, where $\\sigma$ is the gas--liquid surface tension and $\\eta$ is the liquid shear viscosity. In order to explain this extremely large relaxation time, we consider a model that involves an Arrhenius kinetic factor resulting from a liquid--vapour phase change in the vicinity of the contact line. The model results in a large relaxation time of order t b exp(L/R...

  5. Coalescence for Mobile Sensor Networks

    OpenAIRE

    Poduri, Sameera; Sukhatme, Gaurav S.

    2007-01-01

    Coalescence is the problem of isolated mobile robots independently searching for peers with the goal of forming a single connected network. This paper analyzes coalescence time for a worst-case scenario where the robots do not have any knowledge about the environment or positions of other robots and perform independent, memory less search. Using the random direction mobility model, we show that coalescence time has an exponential distribution which is a function of the number of robots, speed...

  6. 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

  7. 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

  8. Allyl sulphides in olefin metathesis: catalyst considerations and traceless promotion of ring-closing metathesis.

    Science.gov (United States)

    Edwards, Grant A; Culp, Phillip A; Chalker, Justin M

    2015-01-11

    Allyl sulphides are reactive substrates in ruthenium-catalysed olefin metathesis reactions, provided each substrate is matched with a suitable catalyst. A profile of catalyst activity is described, along with the first demonstration of allyl sulphides as traceless promoters in relayed ring-closing metathesis reactions.

  9. Bubble coalescence in breathing DNA

    DEFF Research Database (Denmark)

    Novotný, Tomas; Pedersen, Jonas Nyvold; Ambjörnsson, Tobias;

    2007-01-01

    We investigate the coalescence of two DNA bubbles initially located at weak segments and separated by a more stable barrier region in a designed construct of double-stranded DNA. The characteristic time for bubble coalescence and the corresponding distribution are derived, as well as the distribu...

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

    Directory of Open Access Journals (Sweden)

    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.

  11. Alkene Metathesis and Renewable Materials: Selective Transformations of Plant Oils

    Science.gov (United States)

    Malacea, Raluca; Dixneuf, Pierre H.

    The olefin metathesis of natural oils and fats and their derivatives is the basis of clean catalytic reactions relevant to green chemistry processes and the production of generate useful chemicals from renewable raw materials. Three variants of alkene metathesis: self-metathesis, ethenolysis and cross-metathesis applied to plant oil derivatives will show new routes to fine chemicals, bifunctional products, polymer precursours and industry intermediates.

  12. Coalescence of Liquid Drops

    CERN Document Server

    Eggers, J; Stone, H A; Eggers, Jens; Lister, John R.; Stone, Howard A.

    1999-01-01

    When two drops of radius $R$ touch, surface tension drives an initially singular motion which joins them into a bigger drop with smaller surface area. This motion is always viscously dominated at early times. We focus on the early-time behavior of the radius $\\rmn$ of the small bridge between the two drops. The flow is driven by a highly curved meniscus of length $2\\pi \\rmn$ and width $\\Delta\\ll\\rmn$ around the bridge, from which we conclude that the leading-order problem is asymptotically equivalent to its two-dimensional counterpart. An exact two-dimensional solution for the case of inviscid surroundings [Hopper, J. Fluid Mech. ${\\bf 213}$, 349 (1990)] shows that R)]$; and thus the same is true in three dimensions. The case of coalescence with an external viscous fluid is also studied in detail both analytically and numerically. A significantly different structure is found in which the outer fluid forms a toroidal bubble of radius $\\Delta \\propto \\rmn^{3/2}$ at the meniscus and $\\rmn \\sim (t\\gamma/4\\pi\\eta)...

  13. Tandem Ring-Opening-Ring-Closing Metathesis for Functional Metathesis Catalysts.

    Science.gov (United States)

    Nagarkar, Amit A; Yasir, Mohammad; Crochet, Aurelien; Fromm, Katharina M; Kilbinger, Andreas F M

    2016-09-26

    Use of a tandem ring-opening-ring-closing metathesis (RORCM) strategy for the synthesis of functional metathesis catalysts is reported. Ring opening of 7-substituted norbornenes and subsequent ring-closing metathesis forming a thermodynamically stable 6-membered ring lead to a very efficient synthesis of new catalysts from commercially available Grubbs' catalysts. Hydroxy functionalized Grubbs' first- as well as third-generation catalysts have been synthesized. Mechanistic studies have been performed to elucidate the order of attack of the olefinic bonds. This strategy was also used to synthesize the ruthenium methylidene complex.

  14. Recent Applications of Alkene Metathesis in Fine Chemical Synthesis

    Science.gov (United States)

    Bicchielli, Dario; Borguet, Yannick; Delaude, Lionel; Demonceau, Albert; Dragutan, Ileana; Dragutan, Valerian; Jossifov, Christo; Kalinova, Radostina; Nicks, François; Sauvage, Xavier

    During the last decade or so, the emergence of the metathesis reaction in organic synthesis has revolutionised the strategies used for the construction of complex molecular structures. Olefin metathesis is indeed particularly suited for the construction of small open-chain molecules and macrocycles using crossmetathesis and ring-closing metathesis, respectively. These reactions serve, inter alia, as key steps in the synthesis of various agrochemicals and pharmaceuticals such as macrocyclic peptides, cyclic sulfonamides, novel macrolides, or insect pheromones. The present chapter is aiming at illustrating the great synthetic potential of metathesis reactions. Shortcomings, such as the control of olefin geometry and the unpredictable effect of substituents on the reacting olefins, will also be addressed. Examples to be presented include epothilones, amphidinolides, spirofungin A, and archazolid. Synthetic approaches involving silicon-tethered ring-closing metathesis, relay ring-closing metathesis, sequential reactions, domino as well as tandem metathesis reactions will also be illustrated.

  15. Ruthenium-Aryloxide Catalysts for Olefin Metathesis

    Science.gov (United States)

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

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

  16. Methyltrioxorhenium as catalyst for olefin metathesis

    Energy Technology Data Exchange (ETDEWEB)

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

    1991-12-01

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

  17. Thermally Stable, Latent Olefin Metathesis Catalysts

    Science.gov (United States)

    Thomas, Renee M.; Fedorov, Alexey; Keitz, Benjamin K.

    2011-01-01

    Highly thermally stable N-aryl,N-alkyl N-heterocyclic carbene (NHC) ruthenium catalysts were designed and synthesized for latent olefin metathesis. These catalysts showed excellent latent behavior toward metathesis reactions, whereby the complexes were inactive at ambient temperature and initiated at elevated temperatures, a challenging property to achieve with second generation catalysts. A sterically hindered N-tert-butyl substituent on the NHC ligand of the ruthenium complex was found to induce latent behavior toward cross-metathesis reactions, and exchange of the chloride ligands for iodide ligands was necessary to attain latent behavior during ring-opening metathesis polymerization (ROMP). Iodide-based catalysts showed no reactivity toward ROMP of norbornene-derived monomers at 25 °C, and upon heating to 85 °C gave complete conversion of monomer to polymer in less than 2 hours. All of the complexes were very stable to air, moisture, and elevated temperatures up to at least 90 °C, and exhibited a long catalyst lifetime in solution at elevated temperatures. PMID:22282652

  18. Coalescence-induced droplet actuation

    Science.gov (United States)

    Sellier, Mathieu; Verdier, Claude; Nock, Volker

    2011-11-01

    This work investigates a little explored driving mechanism to actuate droplets: the surface tension gradient which arises during the coalescence of two droplets of liquid having different compositions and therefore surface tensions. The resulting surface tension gradient gives rise to a Marangoni flow which, if sufficiently large, can displace the droplet. In order to understand, the flow dynamics arising during the coalescence of droplets of different fluids, a model has been developed in the lubrication framework. The numerical results confirm the existence of a self-propulsion window which depends on two dimensionless groups representing competing effects during the coalescence: the surface tension contrast between the droplets which promotes actuation and species diffusion which tends to make the mixture uniform thereby anihilating Marangoni flow and droplet motion. In parallel, experiments have been conducted to confirm this self-propulsion behaviour. The experiment consists in depositing a droplet of distilled water on a ``hydrophilic highway.'' This stripe was obtained by plasma-treating a piece of PDMS shielded in some parts by glass coverslips. This surface functionalization was found to be the most convenient way to control the coalescence. When a droplet of ethanol is deposited near the ``water slug,'' coalescence occurs and a rapid motion of the resulting mixture is observed. The support of the Dumont d'Urville NZ-France Science & Technology program is gratefully acknowledged.

  19. Alkene metathesis - a tool for the synthesis of conjugated polymers.

    Science.gov (United States)

    Bunz, Uwe H F; Mäker, Dominic; Porz, Michael

    2012-05-29

    Alkene metathesis is a superb methodology. We report the progress using alkene metathesis in the synthesis of polymeric organic semiconductors. Three classes of polymers have been synthesized using acyclic diene metathesis (ADMET) or ring opening metathesis polymerization (ROMP), viz., poly(acetylene)s (PA), poly(arylene-vinylene)s (PAV), and organometallic polymers. For PAs, ROMP of cyclooctatetraenes is best, whereas for PAV, both ADMET and indirect and direct ROMP are viable. Metathesis performs flawlessly with the correct monomers, as molybdenum and particularly the robust Ru carbenes demonstrate. When performing ROMP, one is often rewarded with structurally uniform polymers that can display very low polydispersities. Overall, metathesis is a powerful tool for the preparation of semiconducting polymers.

  20. Partial coalescence of soap bubbles

    Science.gov (United States)

    Harris, Daniel M.; Pucci, Giuseppe; Bush, John W. M.

    2015-11-01

    We present the results of an experimental investigation of the merger of a soap bubble with a planar soap film. When gently deposited onto a horizontal film, a bubble may interact with the underlying film in such a way as to decrease in size, leaving behind a smaller daughter bubble with approximately half the radius of its progenitor. The process repeats up to three times, with each partial coalescence event occurring over a time scale comparable to the inertial-capillary time. Our results are compared to the recent numerical simulations of Martin and Blanchette and to the coalescence cascade of droplets on a fluid bath.

  1. Chelated Ruthenium Catalysts for Z-Selective Olefin Metathesis

    Science.gov (United States)

    Endo, Koji; Grubbs, Robert H.

    2011-01-01

    We report the development of ruthenium-based metathesis catalysts with chelating N-heterocyclic carbene (NHC) ligands which catalyze highly Z-selective olefin metathesis. A very simple and convenient synthetic procedure of such a catalyst has been developed. An intramolecular C-H bond activation of the NHC ligand, which is promoted by anion ligand substitution, forms the appropriate chelate for stereo- controlled olefin metathesis. PMID:21563826

  2. N-Heterocyclic Carbene Complexes in Olefin Metathesis

    Science.gov (United States)

    Luan, Xinjun; Dorta, Reto; Leitgeb, Anita; Slugovc, Christian; Tiede, Sascha; Blechert, Siegfried

    Olefin metathesis is now a synthetic tool found ubiquitously in various fields involving synthesis. Of its many variations, three are prominently used: (1) catalytic ring closing metathesis (RCM) is an extremely powerful method for the construction of carbon-carbon double bonds in organic chemistry; (2) ring opening metathesis polymerisation (ROMP) where polymers are formed by use of the energy released from cyclic strain; and (3) cross metathesis (CM) where non-cyclic partners are coupled through C-C double bond formation. These important transformations and variations on these themes mediated by second generation ruthenium complexes bearing a NHC ligand will be presented in the following sections.

  3. Key processes in ruthenium-catalysed olefin metathesis.

    Science.gov (United States)

    Nelson, David J; Manzini, Simone; Urbina-Blanco, César A; Nolan, Steven P

    2014-09-18

    While the fundamental series of [2+2]cycloadditions and retro[2+2]cycloadditions that make up the pathways of ruthenium-catalysed metathesis reactions is well-established, the exploration of mechanistic aspects of alkene metathesis continues. In this Feature Article, modern mechanistic studies of the alkene metathesis reaction, catalysed by well-defined ruthenium complexes, are discussed. Broadly, these concern the processes of pre-catalyst initiation, propagation and decomposition, which all have a considerable impact on the overall efficiency of metathesis reactions.

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

    Science.gov (United States)

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

    2014-08-01

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

  5. Simulations of coalescing black holes

    CERN Document Server

    Janiuk, Agnieszka

    2016-01-01

    We describe the methods and results of numerical simulations of coalescing black holes. The simulation in dynamical spacetime covers the inspiral, merger, and ringdown phases. We analyze the emission of gravitational waves and properties of a black hole being the merger product. We discuss the results in the context of astrophysical environment of black holes that exist in the Universe.

  6. Ultrasound-induced microbubble coalescence

    NARCIS (Netherlands)

    Postema, Michiel; Marmottant, Philippe; Lancée, Charles T.; Hilgenfeldt, Sascha; Jong, de Nico

    2004-01-01

    We studied the interaction of ultrasound contrast agent bubbles coated with a layer of lipids, driven by 0.5 MHz ultrasound. High-speed photography on the submicrosecond timescale reveals that some bubbles bounce off each other, while others show very fast coalescence during bubble expansion. This f

  7. Coalescence-induced nanodroplet jumping

    Science.gov (United States)

    Cha, Hyeongyun; Xu, Chenyu; Sotelo, Jesus; Chun, Jae Min; Yokoyama, Yukihiro; Enright, Ryan; Miljkovic, Nenad

    2016-10-01

    Water vapor condensation on superhydrophobic surfaces has received much attention in recent years due to the ability of such surfaces to shed microscale water droplets via coalescence-induced droplet jumping, resulting in heat transfer, anti-icing, and self-cleaning performance enhancement. Here we report the coalescence-induced removal of water nanodroplets (R ≈500 nm ) from superhydrophobic carbon nanotube (CNT) surfaces. The two-droplet coalescence time is measured for varying droplet Ohnesorge numbers, confirming that coalescence prior to jumping is governed by capillary-inertial dynamics. By varying the conformal hydrophobic coating thickness on the CNT surface, the minimum jumping droplet radius is shown to increase with increasing solid fraction and decreasing apparent advancing contact angle, allowing us to explore both hydrodynamic limitations stemming from viscous dissipation and surface adhesion limitations. We find that, even for the smallest nanostructure length scale (≤100 nm) and lowest surface adhesions, nonideal surface interactions and the evolved droplet morphology play defining roles in limiting the minimum size for jumping on real surfaces. The outcomes of this work demonstrate the ability to passively shed nanometric water droplets, which has the potential to further increase the efficiency of systems that can harness jumping droplets for a wide range of energy and water applications.

  8. Methods of making organic compounds by metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Abraham, Timothy W.; Kaido, Hiroki; Lee, Choon Woo; Pederson, Richard L.; Schrodi, Yann; Tupy, Michael John

    2015-09-01

    Described are methods of making organic compounds by metathesis chemistry. The methods of the invention are particularly useful for making industrially-important organic compounds beginning with starting compositions derived from renewable feedstocks, such as natural oils. The methods make use of a cross-metathesis step with an olefin compound to produce functionalized alkene intermediates having a pre-determined double bond position. Once isolated, the functionalized alkene intermediate can be self-metathesized or cross-metathesized (e.g., with a second functionalized alkene) to produce the desired organic compound or a precursor thereto. The method may be used to make bifunctional organic compounds, such as diacids, diesters, dicarboxylate salts, acid/esters, acid/amines, acid/alcohols, acid/aldehydes, acid/ketones, acid/halides, acid/nitriles, ester/amines, ester/alcohols, ester/aldehydes, ester/ketones, ester/halides, ester/nitriles, and the like.

  9. Methods of making organic compounds by metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Abraham, Timothy W.; Kaido, Hiroki; Lee, Choon Woo; Pederson, Richard L.; Schrodi, Yann; Tupy, Michael John

    2015-09-01

    Described are methods of making organic compounds by metathesis chemistry. The methods of the invention are particularly useful for making industrially-important organic compounds beginning with starting compositions derived from renewable feedstocks, such as natural oils. The methods make use of a cross-metathesis step with an olefin compound to produce functionalized alkene intermediates having a pre-determined double bond position. Once isolated, the functionalized alkene intermediate can be self-metathesized or cross-metathesized (e.g., with a second functionalized alkene) to produce the desired organic compound or a precursor thereto. The method may be used to make bifunctional organic compounds, such as diacids, diesters, dicarboxylate salts, acid/esters, acid/amines, acid/alcohols, acid/aldehydes, acid/ketones, acid/halides, acid/nitriles, ester/amines, ester/alcohols, ester/aldehydes, ester/ketones, ester/halides, ester/nitriles, and the like.

  10. Organic synthesis with olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

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

    1995-12-31

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

  11. Olefin metathesis : tapping into breakthrough chemical technology

    Energy Technology Data Exchange (ETDEWEB)

    Granson, E.

    2010-06-15

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

  12. 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...

  13. Profluorescent substrates for the screening of olefin metathesis catalysts.

    Science.gov (United States)

    Reuter, Raphael; Ward, Thomas R

    2015-01-01

    Herein we report on a 96-well plate assay based on the fluorescence resulting from the ring-closing metathesis of two profluorophoric substrates. To demonstrate the validity of the approach, four commercially available ruthenium-metathesis catalysts were evaluated in six different solvents. The results from the fluorescent assay agree well with HPLC conversions, validating the usefulness of the approach.

  14. NHC Backbone Configuration in Ruthenium-Catalyzed Olefin Metathesis

    Directory of Open Access Journals (Sweden)

    Veronica Paradiso

    2016-01-01

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

  15. Profluorescent substrates for the screening of olefin metathesis catalysts

    Directory of Open Access Journals (Sweden)

    Raphael Reuter

    2015-10-01

    Full Text Available Herein we report on a 96-well plate assay based on the fluorescence resulting from the ring-closing metathesis of two profluorophoric substrates. To demonstrate the validity of the approach, four commercially available ruthenium-metathesis catalysts were evaluated in six different solvents. The results from the fluorescent assay agree well with HPLC conversions, validating the usefulness of the approach.

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

    Science.gov (United States)

    Paradiso, Veronica; Costabile, Chiara; Grisi, Fabia

    2016-01-20

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

  17. Profluorescent substrates for the screening of olefin metathesis catalysts

    Science.gov (United States)

    Reuter, Raphael

    2015-01-01

    Summary Herein we report on a 96-well plate assay based on the fluorescence resulting from the ring-closing metathesis of two profluorophoric substrates. To demonstrate the validity of the approach, four commercially available ruthenium-metathesis catalysts were evaluated in six different solvents. The results from the fluorescent assay agree well with HPLC conversions, validating the usefulness of the approach. PMID:26664607

  18. Ruthenium-based four-coordinate olefin metathesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

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

    2000-10-02

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

  19. DROPLET COLLISION AND COALESCENCE MODEL

    Institute of Scientific and Technical Information of China (English)

    LI Qiang; CAI Ti-min; HE Guo-qiang; HU Chun-bo

    2006-01-01

    A new droplet collision and coalescence model was presented, a quick-sort method for locating collision partners was also devised and based on theoretical and experimental results, further advancement was made to the droplet collision outcome.The advantages of the two implementations of smoothed particle hydrodynamics (SPH)method were used to limit the collision of droplets to a given number of nearest droplets and define the probability of coalescence, numerical simulations were carried out for model validation. Results show that the model presented is mesh-independent and less time consuming, it can not only maintains the system momentum conservation perfectly, but not susceptible to initial droplet size distribution as well.

  20. Coalescence in coupled Duffing oscillators

    Institute of Scientific and Technical Information of China (English)

    YANG Jun-Zhong

    2009-01-01

    The forced Duffing oscillator has a pair of symmetrical attractors in a proper parameter regime. When a lot of Duffing oscillators are coupled linearly, the system tends to form clusters in which the neighboring oscillators fall onto the same attractor. When the coupling strength is strong, all of the oscillators fall onto one attractor. In this work, we investigate coalescence in the coupled forced Duffing oscillators. Some phenomena are found and explanations are presented.

  1. Improved Ruthenium Catalysts for Z-Selective Olefin Metathesis

    Science.gov (United States)

    Keitz, Benjamin K.; Endo, Koji; Patel, Paresma R.; Herbert, Myles B.; Grubbs, Robert H.

    2011-01-01

    Several new C-H activated ruthenium catalysts for Z-selective olefin metathesis have been synthesized. Both the carboxylate ligand and the aryl group of the N-heterocyclic carbene have been altered and the resulting catalysts were evaluated using a range of metathesis reactions. Substitution of bidentate with monodentate X-type ligands led to a severe attenuation of metathesis activity and selectivity, while minor differences were observed between bidentate ligands within the same family (e.g. carboxylates). The use of nitrato-type ligands, in place of carboxylates, afforded a significant improvement in metathesis activity and selectivity. With these catalysts, turnover numbers approaching 1000 were possible for a variety of cross-metathesis reactions, including the synthesis of industrially-relevant products. PMID:22097946

  2. Olefin metathesis over UV-irradiated silica

    Science.gov (United States)

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

    1997-11-01

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

  3. Cavity coalescence in superplastic deformation

    Energy Technology Data Exchange (ETDEWEB)

    Stowell, M.J.; Livesey, D.W.; Ridley, N.

    1984-01-01

    An analysis of the probability distribution function of particles randomly dispersed in a solid has been applied to cavitation during superplastic deformation and a method of predicting cavity coalescence developed. Cavity size distribution data were obtained from two microduplex nickel-silver alloys deformed superplastically to various extents at elevated temperature, and compared to theoretical predictions. Excellent agreement occurred for small void sizes but the model underestimated the number of voids in the largest size groups. It is argued that the discrepancy results from a combination of effects due to non-random cavity distributions and to enhanced growth rates and incomplete spheroidization of the largest cavities.

  4. 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.

  5. Metathesis access to monocyclic iminocyclitol-based therapeutic agents

    Directory of Open Access Journals (Sweden)

    Albert Demonceau

    2011-05-01

    Full Text Available By focusing on recent developments on natural and non-natural azasugars (iminocyclitols, this review bolsters the case for the role of olefin metathesis reactions (RCM, CM as key transformations in the multistep syntheses of pyrrolidine-, piperidine- and azepane-based iminocyclitols, as important therapeutic agents against a range of common diseases and as tools for studying metabolic disorders. Considerable improvements brought about by introduction of one or more metathesis steps are outlined, with emphasis on the exquisite steric control and atom-economical outcome of the overall process. The comparative performance of several established metathesis catalysts is also highlighted.

  6. Reactivation of a Ruthenium-Based Olefin Metathesis Catalyst

    Science.gov (United States)

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

    2013-01-01

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

  7. Reactivation of a Ruthenium-Based Olefin Metathesis Catalyst.

    Science.gov (United States)

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

    2013-01-14

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

  8. 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.

  9. An alkyne metathesis-based route toortho-dehydrobenzannulenes

    Energy Technology Data Exchange (ETDEWEB)

    Miljanic, Ognjen S.; Vollhardt, Peter C.; Whitener, Glenn D.

    2002-11-07

    An application of alkyne metathesis to 1,2-di(prop-1-ynyl)arenes, producing dehydrobenzannulenes, is described. An efficient method for selective Sonogashira couplings of bromoiodoarenes under conditions of microwave irradiation is also reported.

  10. Advective Coalescence in Chaotic Flows

    Energy Technology Data Exchange (ETDEWEB)

    Nishikawa, Takashi; Toroczkai, Zoltan; Grebogi, Celso

    2001-07-16

    We investigate the reaction kinetics of small spherical particles with inertia, obeying coalescence type of reaction, B+B{yields}B , and being advected by hydrodynamical flows with time-periodic forcing. In contrast to passive tracers, the particle dynamics is governed by the strongly nonlinear Maxey-Riley equations, which typically create chaos in the spatial component of the particle dynamics, appearing as filamental structures in the distribution of the reactants. Defining a stochastic description supported on the natural measure of the attractor, we show that, in the limit of slow reaction, the reaction kinetics assumes a universal behavior exhibiting a t{sup -1} decay in the amount of reagents, which become distributed on a subset of dimension D{sub 2} , where D{sub 2} is the correlation dimension of the chaotic flow.

  11. 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

  12. Nonproductive events in ring-closing metathesis using ruthenium catalysts.

    Science.gov (United States)

    Stewart, Ian C; Keitz, Benjamin K; Kuhn, Kevin M; Thomas, Renee M; Grubbs, Robert H

    2010-06-30

    The relative TONs of productive and nonproductive metathesis reactions of diethyl diallylmalonate are compared for eight different ruthenium-based catalysts. Nonproductive cross metathesis is proposed to involve a chain-carrying ruthenium methylidene. A second more-challenging substrate (dimethyl allylmethylallylmalonate) that forms a trisubstituted olefin product is used to further delineate the effect of catalyst structure on the relative efficiencies of these processes. A steric model is proposed to explain the observed trends.

  13. Mesoporous Molecular Sieves as Supports for Metathesis Catalysts

    Science.gov (United States)

    Balcar, Hynek; Cejka, Jirí

    Mesoporous molecular sieves represent a new family of inorganic oxides with regular nanostructure, large surface areas, large void volumes, and narrow pore size distribution of mesopores. These materials offer new possibilities for designing highly active and selective catalysts for olefin metathesis and metathesis polymerization. Siliceous sieves MCM-41, MCM-48, SBA-15, and organized mesoporous alumina (OMA) were used as supports for preparation of new molybdenum and rhenium oxide catalysts, as well as for heterogenization of well-defined homogeneous catalysts.

  14. Comparing Ru and Fe-catalyzed olefin metathesis.

    Science.gov (United States)

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

    2014-08-01

    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.

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

    Science.gov (United States)

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

    2016-05-01

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

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

    Science.gov (United States)

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

    2016-04-27

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

  17. Multi-body coalescence in Pickering emulsions

    Science.gov (United States)

    Wu, Tong; Wang, Haitao; Jing, Benxin; Liu, Fang; Burns, Peter C.; Na, Chongzheng

    2015-01-01

    Particle-stabilized Pickering emulsions have shown unusual behaviours such as the formation of non-spherical droplets and the sudden halt of coalescence between individual droplets. Here we report another unusual behaviour of Pickering emulsions—the simultaneous coalescence of multiple droplets in a single event. Using latex particles, silica particles and carbon nanotubes as model stabilizers, we show that multi-body coalescence can occur in both water-in-oil and oil-in-water emulsions. The number of droplets involved in the nth coalscence event equals four times the corresponding number of the tetrahedral sequence in close packing. Furthermore, coalescence is promoted by repulsive latex and silica particles but inhibited by attractive carbon nanotubes. The revelation of multi-body coalescence is expected to help better understand Pickering emulsions in natural systems and improve their designs in engineering applications.

  18. Coalescence and Anti-Coalescence Interference of Two-Photon Wavepacket in a Beam Splitter

    Institute of Scientific and Technical Information of China (English)

    WANG Kai-Ge; YANG Guo-Jian

    2004-01-01

    @@ We study theoretically the interference of a two-photon wavepacket in a beam splitter. We find that the spectrum symmetry for the two-photon wavepacket dominates the perfect coalescence and anti-coalescence interference.The coalescence interference is unrelated to photon entanglement. Only the anti-coalescence interference has evidence of photon entanglement. We prove that the two-photon wavepacket with an anti-symmetric spectrum is transparent to pass the 50/50 beam splitter, showing perfect anti-coalescence interference.

  19. Metathesis depolymerization for removable surfactant templates.

    Energy Technology Data Exchange (ETDEWEB)

    Zifer, Thomas (Sandia National Laboratories, Livermore, CA); Wheeler, David Roger; Rahimian, Kamayar; McElhanon, James Ross (Sandia National Laboratories, Livermore, CA); Long, Timothy Michael; Jamison, Gregory Marks; Loy, Douglas Anson (Los Alamos National Laboratories, Los Alamos, NM); Kline, Steven R. (National Institute of Standards and Technology, Gaithersburg, MD); Simmons, Blake Alexander (Sandia National Laboratories, Livermore, CA)

    2005-03-01

    Current methodologies for the production of meso- and nanoporous materials include the use of a surfactant to produce a self-assembled template around which the material is formed. However, post-production surfactant removal often requires centrifugation, calcination, and/or solvent washing which can damage the initially formed material architecture(s). Surfactants that can be disassembled into easily removable fragments following material preparation would minimize processing damage to the material structure, facilitating formation of templated hybrid architectures. Herein, we describe the design and synthesis of novel cationic and anionic surfactants with regularly spaced unsaturation in their hydrophobic hydrocarbon tails and the first application of ring closing metathesis depolymerization to surfactant degradation resulting in the mild, facile decomposition of these new compounds to produce relatively volatile nonsurface active remnants.

  20. Metathesis Cascade Strategies (ROM-RCM-CM): A DOS approach to Skeletally Diverse Sultams

    OpenAIRE

    Jeon, Kyu Ok; Rayabarapu, Dinesh; Rolfe, Alan; Volp, Kelly; Omar, Iman; Hanson, Paul R.

    2009-01-01

    The development of a ring-opening metathesis/ring-closing metathesis/cross metathesis (ROM-RCM-CM) cascade strategy to the synthesis of a diverse collection of bi- and tricyclic sultams is reported. In this study, functionalized sultam scaffolds derived from intramolecular Diels-Alder (IMDA) reactions undergo metathesis cascades to yield a collection tricyclic sultams. Additional appendage based diversity was achieved by utilizing a variety of CM partners.

  1. Chelating ruthenium phenolate complexes: synthesis, general catalytic activity, and applications in olefin metathesis polymerization.

    Science.gov (United States)

    Kozłowska, Anna; Dranka, Maciej; Zachara, Janusz; Pump, Eva; Slugovc, Christian; Skowerski, Krzysztof; Grela, Karol

    2014-10-20

    Cyclic Ru-phenolates were synthesized, and these compounds were used as olefin metathesis catalysts. Investigation of their catalytic activity pointed out that, after activation with chemical agents, these catalysts promote ring-closing metathesis (RCM), enyne and cross-metathesis (CM) reactions, including butenolysis, with good results. Importantly, these latent catalysts are soluble in neat dicyclopentadiene (DCPD) and show good applicability in ring-opening metathesis polymeriyation (ROMP) of this monomer.

  2. Coalescent histories for caterpillar-like families.

    Science.gov (United States)

    Rosenberg, Noah A

    2013-01-01

    A coalescent history is an assignment of branches of a gene tree to branches of a species tree on which coalescences in the gene tree occur. The number of coalescent histories for a pair consisting of a labeled gene tree topology and a labeled species tree topology is important in gene tree probability computations, and more generally, in studying evolutionary possibilities for gene trees on species trees. Defining the Tr-caterpillar-like family as a sequence of n-taxon trees constructed by replacing the r-taxon subtree of n-taxon caterpillars by a specific r-taxon labeled topology Tr, we examine the number of coalescent histories for caterpillar-like families with matching gene tree and species tree labeled topologies. For each Tr with size r≤8, we compute the number of coalescent histories for n-taxon trees in the Tr-caterpillar-like family. Next, as n→∞, we find that the limiting ratio of the numbers of coalescent histories for the Tr family and caterpillars themselves is correlated with the number of labeled histories for Tr. The results support a view that large numbers of coalescent histories occur when a tree has both a relatively balanced subtree and a high tree depth, contributing to deeper understanding of the combinatorics of gene trees and species trees.

  3. Assisted Tandem Catalysis : Metathesis Followed by Asymmetric Hydrogenation from a Single Ruthenium Source

    NARCIS (Netherlands)

    Renom-Carrasco, Marc; Gajewski, Piotr; Pignataro, Luca; de Vries, Johannes G.; Piarulli, Umberto; Gennari, Cesare; Lefort, Laurent

    2015-01-01

    Here we report the first example of a tandem metathesis-asymmetric hydrogenation protocol where the prochiral olefin generated by metathesis is hydrogenated with high enantioselectivity by an in situ formed chiral ruthenium catalyst. We show that either the ruthenium metathesis catalysts or the ruth

  4. Non-coalescence of oppositely charged drops

    CERN Document Server

    Ristenpart, W D; Belmonte, A; Dollar, F; Stone, H A

    2009-01-01

    Oppositely charged drops have long been assumed to experience an attractive force that favors their coalescence. In this fluid dynamics video we demonstrate the existence of a critical field strength above which oppositely charged drops do not coalesce. We observe that appropriately positioned and oppositely charged drops migrate towards one another in an applied electric field; but whereas the drops coalesce as expected at low field strengths, they are repelled from one another after contact at higher field strengths. Qualitatively, the drops appear to `bounce' off one another. We directly image the transient formation of a meniscus bridge between the bouncing drops.

  5. Low Catalyst Loadings in Olefin Metathesis: Synthesis of Nitrogen Heterocycles by Ring Closing Metathesis

    Science.gov (United States)

    Kuhn, Kevin M.; Champagne, Timothy M.; Hong, Soon Hyeok; Wei, Wen-Hao; Nickel, Andrew; Lee, Choon Woo; Virgil, Scott C.; Grubbs, Robert H.; Pederson, Richard L.

    2010-01-01

    (eq 1) A series of ruthenium catalysts have been screened under ring closing metathesis (RCM) conditions to produce five-, six-, and seven-membered carbamate-protected cyclic amines. Many of these catalysts demonstrated excellent RCM activity and yields with as low as 500 ppm catalyst loadings. RCM of the five-membered carbamate-series could be run neat, the six-membered carbamate-series could be run at 1.0 M concentrations and the seven-membered carbamate-series worked best at 0.2 M to 0.05 M concentrations. PMID:20141172

  6. Low catalyst loadings in olefin metathesis: synthesis of nitrogen heterocycles by ring-closing metathesis.

    Science.gov (United States)

    Kuhn, Kevin M; Champagne, Timothy M; Hong, Soon Hyeok; Wei, Wen-Hao; Nickel, Andrew; Lee, Choon Woo; Virgil, Scott C; Grubbs, Robert H; Pederson, Richard L

    2010-03-01

    A series of ruthenium catalysts have been screened under ring-closing metathesis (RCM) conditions to produce five-, six-, and seven-membered carbamate-protected cyclic amines. Many of these catalysts demonstrated excellent RCM activity and yields with as low as 500 ppm catalyst loadings. RCM of the five-membered carbamate series could be run neat, the six-membered carbamate series could be run at 1.0 M, and the seven-membered carbamate series worked best at 0.2-0.05 M.

  7. Homobimetallic Ruthenium-N-Heterocyclic Carbene Complexes For Olefin Metathesis

    Science.gov (United States)

    Sauvage, Xavier; Demonceau, Albert; Delaude, Lionel

    In this chapter, the synthesis and catalytic activity towards olefin metathesis of homobimetallic ruthenium (Ru)-alkylidene, -cyclodiene or -arene complexes bearing phosphine or N-heterocyclic carbene (NHC) ligands are reviewed. Emphasis is placed on the last category of bimetallic compounds. Three representatives of this new type of molecular scaffold were investigated. Thus, [(p-cymene)Ru(m-Cl)3RuCl (h2-C2H4)(L)] complexes with L = PCy3 (15a), IMes (16a), or IMesCl2 (16b) were prepared. They served as catalyst precursors for cross-metathesis (CM) of various styrene derivatives. These experiments revealed the outstanding aptitude of complex 16a (and to a lesser extent of 16b) to catalyze olefin metathesis reactions. Contrary to monometallic Ru-arene complexes of the [RuCl2(p-cymene)(L)] type, the new homobimetallic species did not require the addition of a diazo compound nor visible light illumination to initiate the ring-opening metathesis of norbornene or cyclooctene. When diethyl 2,2-diallylmalonate and N,N-diallyltosylamide were exposed to 16a,b, a mixture of cycloisomerization and ring-closing metathesis (RCM) products was obtained in a nonselective way. Addition of phenylacetylene enhanced the metathetical activity while completely repressing the cycloisomerization process.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1990-03-14

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

  9. Coalescence between two convex liquid surfaces

    Science.gov (United States)

    Yang, Fan; Jian, Zhen; Li, Erqiang; Thoroddsen, S. T.

    2015-11-01

    We study the coalescence of two convex surfaces of the same liquid. One of the convex free surfaces is formed at a circular opening of a closed tank by imposing a negative pressure difference. The other surface is a droplet of larger curvature, which is pendant from a concentric nozzle. The coalescence starts from near-zero velocity, so the configuration can be characterized by two dimensionless numbers: the Ohnesorge number Oh = μ /√{ ργL } and the radius ratio between the two surfaces α =rd /rs . We use high-speed video, PIV and numerical simulations, using the Gerris program, to study the dynamics of the coalescence. Our focus is on the interface shapes, the growth-rate of the neck connecting the two surfaces and the formation of a vortex ring. The growth-rate is compared to earlier models for the coalescence of drops or bubbles.

  10. Coalescence preference in dense packing of bubbles

    Science.gov (United States)

    Kim, Yeseul; Gim, Bopil; Gim, Bopil; Weon, Byung Mook

    2015-11-01

    Coalescence preference is the tendency that a merged bubble from the contact of two original bubbles (parent) tends to be near to the bigger parent. Here, we show that the coalescence preference can be blocked by densely packing of neighbor bubbles. We use high-speed high-resolution X-ray microscopy to clearly visualize individual coalescence phenomenon which occurs in micro scale seconds and inside dense packing of microbubbles with a local packing fraction of ~40%. Previous theory and experimental evidence predict a power of -5 between the relative coalescence position and the parent size. However, our new observation for coalescence preference in densely packed microbubbles shows a different power of -2. We believe that this result may be important to understand coalescence dynamics in dense packing of soft matter. This work (NRF-2013R1A22A04008115) was supported by Mid-career Researcher Program through NRF grant funded by the MEST and also was supported by Ministry of Science, ICT and Future Planning (2009-0082580) and by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry and Education, Science and Technology (NRF-2012R1A6A3A04039257).

  11. Analysis of coalescence behavior for compressed droplets

    Science.gov (United States)

    Choi, Sung Woong; Lee, Dong Eon; Lee, Woo Il; Kim, Han Sang

    2017-03-01

    Coalescence of droplets is a significant phenomenon, and it has been adapted to many applications such as raindrop formation, emulsion polymerization, ink-jet printing, coating, and multiphase flows. In this study, the morphological characteristics of two compressed adjacent droplets between two parallel plates were investigated to study the phenomenon of coalescence of droplets. By controlling the distance of the dispensed droplets, various results for coalescence of droplets were evaluated, especially, from the view of the minor axis, major axis, and meniscus liquid bridge of the coalesced droplet. Experimental results show that the length of the meniscus liquid bridge rapidly increases and then the rate of increase slows with time. The increase rate of the major and minor axes is largely influenced by the meniscus liquid bridge, which is mainly due to the curvature between the droplets. The numerical modeling of the coalescence of the two compressed droplets between two parallel plates was presented and simulation was conducted to realize the coalescence behavior. Comparison with numerical simulation showed that there was a good agreement with the experimental results.

  12. Recent Progress on Enyne Metathesis: Its Application to Syntheses of Natural Products and Related Compounds

    Directory of Open Access Journals (Sweden)

    Miwako Mori

    2010-03-01

    Full Text Available Olefin metathesis using ruthenium carbene complexes is a useful method in synthetic organic chemistry. Enyne metathesis is also catalyzed by these complexes and various carbo- and heterocycles could be synthesized from the corresponding enynes. Dienyne metathesis, cross enyne metathesis and ring-opening enyne metathesis have been further developed. Various complicated compounds, such as the natural products and the related biologically active substances, could be synthesized using these metatheses reactions. Skeletal reorganization using the transition metals and metallotropic rearrangement are also discussed.

  13. Target Specific Tactics in Olefin Metathesis: Synthetic Approach to cis-syn-cis-Triquinanes and -Propellanes.

    Science.gov (United States)

    Kotha, Sambasivarao; Aswar, Vikas R

    2016-04-15

    A concise and simple synthetic approach to cis-syn-cis-triquinanes and -propellanes has been demonstrated via olefin metathesis starting with exo-nadic anhydride. This approach involves a ring-opening and ring-closing metathesis sequence of norbornene derivatives using Grubb's catalyst. Early-stage diallylation of norbornene derivatives is demonstrated followed by ring-closing metathesis that delivers propellanes exclusively. Surprisingly, ring-opening metathesis, late-stage diallylation, followed by ring-closing metathesis delivers triquinane as well as propellane derivatives.

  14. Ruthenium Olefin Metathesis Catalysts Bearing Carbohydrate-Based N-Heterocyclic Carbenes

    Science.gov (United States)

    Keitz, Benjamin K.; Grubbs, Robert H.

    2010-01-01

    Ru-based olefin metathesis catalysts containing carbohydrate-derived NHCs from glucose and galactose were synthesized and characterized by NMR spectroscopy. 2D-NMR spectroscopy revealed the presence of Ru-C (benzylidene) rotamers at RT and the rate of rotation was measured using magnetization transfer and VT-NMR spectroscopy. The catalysts were found to be effective at ring-opening metathesis polymerization (ROMP), ring closing metathesis (RCM), cross metathesis (CM), and asymmetric ring opening cross metathesis (AROCM) and showed surprising selectivity in both CM and AROCM. PMID:21603126

  15. A bis-calixarene from olefin metathesis

    Directory of Open Access Journals (Sweden)

    Shimelis T. Hailu

    2012-06-01

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

  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. Comparing Ru and Fe-catalyzed olefin metathesis

    KAUST Repository

    Poater, Albert

    2014-01-01

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

  18. Building Indenylidene-Ruthenium Catalysts for Metathesis Transformations

    Science.gov (United States)

    Clavier, Hervé; Nolan, Steven P.

    Ruthenium-mediated olefin metathesis has emerged as an indispensable tool in organic synthesis for the formation carbon-carbon double bonds, attested by the large number of applications for natural product synthesis. Among the numerous catalysts developed to mediate olefin metathesis transformations, ruthenium-indenylidene complexes are robust and powerful pre-catalysts. The discovery of this catalyst category was slightly muddled due to a first mis-assignment of the compound structure. This report provides an overview of the synthetic routes for the construction of the indenylidene pattern in ruthenium complexes. The parameters relating to the indenylidene moiety construction will be discussed as well as the mechanism of this formation

  19. A bis-calixarene from olefin metathesis

    Science.gov (United States)

    Hailu, Shimelis T.; Butcher, Ray J.; Hudrlik, Paul F.; Hudrlik, Anne M.

    2012-01-01

    A ring-closing olefin metathesis reaction of tetra­kis­(all­yl­oxy)calix[4]arene gave the bis­ calixarene, (15E,40E,60E)-65,74-bis­(prop-2-en-1-yl­oxy)-13,18,38,43,58,63-hexa­oxado­deca­cyclo­[28.26.8.720,36.111,45.151,55.05,57.07,12.019,24.026,64.032,37.044,49.168,72]tetra­hepta­conta-1,3,5(57),7,9,11,15,19(24),20,22,26,28,30(64),32,34,36,40,44(49),45,47,51,53,55(65),60,68,70,72(74)-hepta­cosa­ene, C74H68O8. It is a cage formed from two calix[4]arene units joined by butenyl groups at three of the O atoms on the narrow rim. The fourth O atom on each calixarene unit is joined with an allyl group. Each of the calix[4]arene units has a flattened cone conformation in which the all­yloxy-substituted aryl group and the opposite aryl group are close together and almost parallel [dihedral angle between planes = 1.09 (11)°], and the other two aryl groups are splayed outward [dihedral angle between planes = 79.53 (11)°]. No guest mol­ecule (e.g. solvent) was observed within the cage. The alkene C atoms of one of the links between the calixarene moieties are disordered over two orientations with occupancies of 0.533 (9) and 0.467 (9). PMID:22719604

  20. A bis-calixarene from olefin metathesis.

    Science.gov (United States)

    Hailu, Shimelis T; Butcher, Ray J; Hudrlik, Paul F; Hudrlik, Anne M

    2012-06-01

    A ring-closing olefin metathesis reaction of tetra-kis-(all-yl-oxy)calix[4]arene gave the bis- calixarene, (15E,40E,60E)-65,74-bis-(prop-2-en-1-yl-oxy)-13,18,38,43,58,63-hexa-oxado-deca-cyclo-[28.26.8.7(20,36).1(11,45).1(51,55).0(5,57).0(7,12).0(19,24).0(26,64).0(32,37).0(44,49).1(68,72)]tetra-hepta-conta-1,3,5(57),7,9,11,15,19(24),20,22,26,28,30(64),32,34,36,40,44(49),45,47,51,53,55(65),60,68,70,72(74)-hepta-cosa-ene, C(74)H(68)O(8). It is a cage formed from two calix[4]arene units joined by butenyl groups at three of the O atoms on the narrow rim. The fourth O atom on each calixarene unit is joined with an allyl group. Each of the calix[4]arene units has a flattened cone conformation in which the all-yloxy-substituted aryl group and the opposite aryl group are close together and almost parallel [dihedral angle between planes = 1.09 (11)°], and the other two aryl groups are splayed outward [dihedral angle between planes = 79.53 (11)°]. No guest mol-ecule (e.g. solvent) was observed within the cage. The alkene C atoms of one of the links between the calixarene moieties are disordered over two orientations with occupancies of 0.533 (9) and 0.467 (9).

  1. Fast olefin metathesis at low catalyst loading.

    Science.gov (United States)

    Peeck, Lars H; Savka, Roman D; Plenio, Herbert

    2012-10-01

    Reactions of the Grubbs 3rd generation complexes [RuCl(2)(NHC)(Ind)(Py)] (N-heterocyclic carbene (NHC)=1,3-bis(2,4,6-trimethylphenylimidazolin)-2-ylidene (SIMes), 1,3-bis(2,6-diisopropylphenylimidazolin)-2-ylidene (SIPr), or 1,3-bis(2,6-diisopropylphenylimidazol)-2-ylidene (IPr); Ind=3-phenylindenylid-1-ene, Py=pyridine) with 2-ethenyl-N-alkylaniline (alkyl=Me, Et) result in the formation of the new N-Grubbs-Hoveyda-type complexes 5 (NHC=SIMes, alkyl=Me), 6 (SIMes, Et), 7 (IPr, Me), 8 (SIPr, Me), and 9 (SIPr, Et) with N-chelating benzylidene ligands in yields of 50-75 %. Compared to their respective, conventional, O-Grubbs-Hoveyda complexes, the new complexes are characterized by fast catalyst activation, which translates into fast and efficient ring-closing metathesis (RCM) reactivity. Catalyst loadings of 15-150 ppm (0.0015-0.015 mol %) are sufficient for the conversion of a wide range of diolefinic substrates into the respective RCM products after 15 min at 50 °C in toluene; compounds 8 and 9 are the most catalytically active complexes. The use of complex 8 in RCM reactions enables the formation of N-protected 2,5-dihydropyrroles with turnover numbers (TONs) of up to 58,000 and turnover frequencies (TOFs) of up to 232,000 h(-1); the use of the N-protected 1,2,3,6-tetrahydropyridines proceeds with TONs of up to 37,000 and TOFs of up to 147,000 h(-1); and the use of the N-protected 2,3,6,7-tetrahydroazepines proceeds with TONs of up to 19,000 and TOFs of up to 76,000 h(-1), with yields for these reactions ranging from 83-92 %.

  2. A study of oil droplet coalescence.

    Science.gov (United States)

    Boyson, T K; Pashley, R M

    2007-12-01

    Oil droplets dispersed in water can be readily studied when they are coated with surfactants, which lower their interfacial tension and enhance their stability. Pure oil droplets are more difficult to study because of their high interfacial tension, which facilitates coalescence and the adsorption of contaminants. In this study, we have characterised the surface charging properties of a water insoluble oil, bromododecane, which has a density close to water. The small density difference allows us to study relatively large drops of this oil and to analyse its coalescence behaviour. The results obtained with this simple, surfactant-free, system suggest that an additional attractive force, such as the long range hydrophobic interaction, might be required to explain oil droplet coalescence behaviour.

  3. Factors influencing ring closure through olefin metathesis - A perspective

    Indian Academy of Sciences (India)

    Subrata Ghosh; Sarita Ghosh; Niladri Sarkar

    2006-05-01

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

  4. 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.

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

    Science.gov (United States)

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

    2016-01-14

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

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

    Science.gov (United States)

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

    2015-11-16

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

  7. 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.

  8. Distribution of coalescent histories under the coalescent model with gene flow.

    Science.gov (United States)

    Tian, Yuan; Kubatko, Laura S

    2016-12-01

    We propose a coalescent model for three species that allows gene flow between both pairs of sister populations. The model is designed for multilocus genomic sequence alignments, with one sequence sampled from each of the three species, and is formulated using a Markov chain representation that allows use of matrix exponentiation to compute analytical expressions for the probability density of coalescent histories. The coalescent history distribution as well as the gene tree topology distribution under this coalescent model with gene flow are then calculated via numerical integration. We analyze the model to compare the distributions of gene tree topologies and coalescent histories for species trees with differing effective population sizes and gene flow rates. Our results suggest conditions under which the species tree and associated parameters are not identifiable from the gene tree topology distribution when gene flow is present, but indicate that the coalescent history distribution may identify the species tree and associated parameters. Thus, the coalescent history distribution can be used to infer parameters such as the ancestral effective population sizes and the rates of gene flow in a maximum likelihood (ML) framework. We conduct computer simulations to evaluate the performance of our method in estimating these parameters, and we apply our method to an Afrotropical mosquito data set (Fontaine et al., 2015). Copyright © 2016 Elsevier Inc. All rights reserved.

  9. Genetic Variability Under the Seedbank Coalescent.

    Science.gov (United States)

    Blath, Jochen; González Casanova, Adrián; Eldon, Bjarki; Kurt, Noemi; Wilke-Berenguer, Maite

    2015-07-01

    We analyze patterns of genetic variability of populations in the presence of a large seedbank with the help of a new coalescent structure called the seedbank coalescent. This ancestral process appears naturally as a scaling limit of the genealogy of large populations that sustain seedbanks, if the seedbank size and individual dormancy times are of the same order as those of the active population. Mutations appear as Poisson processes on the active lineages and potentially at reduced rate also on the dormant lineages. The presence of "dormant" lineages leads to qualitatively altered times to the most recent common ancestor and nonclassical patterns of genetic diversity. To illustrate this we provide a Wright-Fisher model with a seedbank component and mutation, motivated from recent models of microbial dormancy, whose genealogy can be described by the seedbank coalescent. Based on our coalescent model, we derive recursions for the expectation and variance of the time to most recent common ancestor, number of segregating sites, pairwise differences, and singletons. Estimates (obtained by simulations) of the distributions of commonly employed distance statistics, in the presence and absence of a seedbank, are compared. The effect of a seedbank on the expected site-frequency spectrum is also investigated using simulations. Our results indicate that the presence of a large seedbank considerably alters the distribution of some distance statistics, as well as the site-frequency spectrum. Thus, one should be able to detect from genetic data the presence of a large seedbank in natural populations.

  10. Free surface flows: coalescence, spreading and dewetting

    NARCIS (Netherlands)

    Hernandez Sanchez, Jose Federico

    2015-01-01

    Capillary and wetting phenomena are an essential part of nature. Its presence is noticed in many circumstances where solid and liquid surfaces come into contact. In this thesis different types of capillary free surface flows are studied. The topics discussed are mainly the coalescence of viscous ses

  11. Mo-catalyzed asymmetric olefin metathesis in target-oriented synthesis: Enantioselective synthesis of (+)-africanol

    Science.gov (United States)

    Weatherhead, Gabriel S.; Cortez, G. A.; Schrock, Richard R.; Hoveyda, Amir H.

    2004-01-01

    Catalytic asymmetric ring-opening metathesis (AROM) provides an efficient method for the synthesis of a variety of optically enriched small organic molecules that cannot be easily prepared by alternative methods. The development of Mo-catalyzed AROM transformations that occur in tandem with ring-closing metathesis are described. The utility of the Mo-catalyzed AROM/ring-closing metathesis is demonstrated through an enantioselective approach to the synthesis of (+)-africanol. PMID:15056762

  12. Ruthenium-Catalyzed Olefin Metathesis after Tetra-n-butylammonium Fluoride-Mediated Desilylation

    Science.gov (United States)

    Osman, Sami

    2012-01-01

    One-pot procedures expedite organic synthesis but pose challenges in that many reagents must be compatible with each other. We discovered that the presence of nBu4NF hindered rutheniumcatalyzed olefin metathesis when nBu4NF-mediated desilylation and olefin metathesis were performed in one pot. This problem could be solved by the addition of (TMS)2O to remove fluoride anions in order to facilitate the ruthenium-catalyzed olefin metathesis. PMID:23269856

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

    KAUST Repository

    Leitgeb, Anita

    2012-01-01

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

  14. Impact of 50% Alcohol to Jet Blends on Aviation Turbine Fuel Coalescence - Navy Coalescence Test

    Science.gov (United States)

    2014-10-17

    Aviation Turbine Fuels5 are not feasible. The total water concentration of three samples from the influent and effluent of the filter-separator...International. ASTM D3240-11: Standard Test Method for Undissolved Water in Aviation Turbine Fuel, March 2011 6. MIL-DTL-5624V, Detail Specification...Impact of 50% Alcohol to Jet Blends on Aviation Turbine Fuel Coalescence - Navy Coalescence Test NF&LCFT REPORT 441/15-001 17 October 2014

  15. Coalescence of Pickering emulsion droplets induced by electric-field

    Science.gov (United States)

    Chen, Guo; Tan, Peng; Chen, Shuyu; Huang, Jiping; Wen, Weijia; Xu, Lei

    2013-03-01

    Combining high-speed photography with electric current measurement, we investigate the coalescence of Pickering emulsion droplets. Under high enough electric field, the originally-stable droplets coalesce via two distinct approaches: normal coalescence and abnormal coalescence. In the normal coalescence, a liquid bridge grows continuously and merges two droplets together, similar to the classical picture. In the abnormal coalescence, however, the bridge fails to grow indefinitely; instead it breaks up spontaneously due to the geometric constraint from particle shells. Such connecting-then-breaking cycles repeat multiple times, until a stable connection is established. In depth analysis indicates that the defect size in particle shells determines the exact merging behaviors: when the defects are larger than a critical size, normal coalescence will show up; while abnormal coalescence will appear for smaller defects. This project is supported by the Hong Kong GRF Grant (Project No. CUHK404211).

  16. Computational study of productive and non-productive cycles in fluoroalkene metathesis

    Directory of Open Access Journals (Sweden)

    Markéta Rybáčková

    2015-11-01

    Full Text Available A detailed DFT study of the mechanism of metathesis of fluoroethene, 1-fluoroethene, 1,1-difluoroethene, cis- and trans-1,2-difluoroethene, tetrafluoroethene and chlorotrifluoroethene catalysed with the Hoveyda–Grubbs 2nd generation catalyst was performed. It revealed that a successful metathesis of hydrofluoroethenes is hampered by a high preference for a non-productive catalytic cycle proceeding through a ruthenacyclobutane intermediate bearing fluorines in positions 2 and 4. Moreover, the calculations showed that the cross-metathesis of perfluoro- or perhaloalkenes should be a feasible process and that the metathesis is not very sensitive to stereochemical issues.

  17. FeCl3 -Catalyzed Ring-Closing Carbonyl-Olefin Metathesis.

    Science.gov (United States)

    Ma, Lina; Li, Wenjuan; Xi, Hui; Bai, Xiaohui; Ma, Enlu; Yan, Xiaoyu; Li, Zhiping

    2016-08-22

    Exploiting catalytic carbonyl-olefin metathesis is an ongoing challenge in organic synthesis. Reported herein is an FeCl3 -catalyzed ring-closing carbonyl-olefin metathesis. The protocol allows access to a range of carbo-/heterocyclic alkenes with good efficiency and excellent trans diastereoselectivity. The methodology presents one of the rare examples of catalytic ring-closing carbonyl-olefin metathesis. This process is proposed to take place by FeCl3 -catalyzed oxetane formation followed by retro-ring-opening to deliver metathesis products.

  18. Beyond catalyst deactivation: cross-metathesis involving olefins containing N-heteroaromatics

    Science.gov (United States)

    Lafaye, Kevin; Bosset, Cyril; Nicolas, Lionel

    2015-01-01

    Summary Alkenes containing N-heteroaromatics are known to be poor partners in cross-metathesis reactions, probably due to catalyst deactivation caused by the presence of a nitrogen atom. However, some examples of ring-closing and cross-metathesis involving alkenes that incorporate N-heteroaromatics can be found in the literature. In addition, recent mechanistic studies have focused on the rationalization of nitrogen-induced catalysts deactivation. The purpose of this mini-review is to give a brief overview of successful metathesis reactions involving olefins containing N-heteroaromatics in order to delineate some guidelines for the use of these challenging substrates in metathesis reactions. PMID:26664645

  19. Beyond catalyst deactivation: cross-metathesis involving olefins containing N-heteroaromatics.

    Science.gov (United States)

    Lafaye, Kevin; Bosset, Cyril; Nicolas, Lionel; Guérinot, Amandine; Cossy, Janine

    2015-01-01

    Alkenes containing N-heteroaromatics are known to be poor partners in cross-metathesis reactions, probably due to catalyst deactivation caused by the presence of a nitrogen atom. However, some examples of ring-closing and cross-metathesis involving alkenes that incorporate N-heteroaromatics can be found in the literature. In addition, recent mechanistic studies have focused on the rationalization of nitrogen-induced catalysts deactivation. The purpose of this mini-review is to give a brief overview of successful metathesis reactions involving olefins containing N-heteroaromatics in order to delineate some guidelines for the use of these challenging substrates in metathesis reactions.

  20. Cross metathesis of unsaturated epoxides for the synthesis of polyfunctional building blocks

    Directory of Open Access Journals (Sweden)

    Meriem K. Abderrezak

    2015-10-01

    Full Text Available The cross metathesis of 1,2-epoxy-5-hexene (1 with methyl acrylate and acrylonitrile was investigated as an entry to the synthesis of polyfunctional compounds. The resulting cross metathesis products were hydrogenated in a tandem fashion employing the residual ruthenium from the metathesis step as the hydrogenation catalyst. Interestingly, the epoxide ring remained unreactive toward this hydrogenation method. The saturated compound resulting from the cross metathesis of 1 with methyl acrylate was transformed by means of nucleophilic ring-opening of the epoxide to furnish a diol, an alkoxy alcohol and an amino alcohol in high yields.

  1. Beyond catalyst deactivation: cross-metathesis involving olefins containing N-heteroaromatics

    Directory of Open Access Journals (Sweden)

    Kevin Lafaye

    2015-11-01

    Full Text Available Alkenes containing N-heteroaromatics are known to be poor partners in cross-metathesis reactions, probably due to catalyst deactivation caused by the presence of a nitrogen atom. However, some examples of ring-closing and cross-metathesis involving alkenes that incorporate N-heteroaromatics can be found in the literature. In addition, recent mechanistic studies have focused on the rationalization of nitrogen-induced catalysts deactivation. The purpose of this mini-review is to give a brief overview of successful metathesis reactions involving olefins containing N-heteroaromatics in order to delineate some guidelines for the use of these challenging substrates in metathesis reactions.

  2. Partial coalescence from bubbles to drops

    KAUST Repository

    Zhang, F. H.

    2015-10-07

    The coalescence of drops is a fundamental process in the coarsening of emulsions. However, counter-intuitively, this coalescence process can produce a satellite, approximately half the size of the original drop, which is detrimental to the overall coarsening. This also occurs during the coalescence of bubbles, while the resulting satellite is much smaller, approximately 10 %. To understand this difference, we have conducted a set of coalescence experiments using xenon bubbles inside a pressure chamber, where we can continuously raise the pressure from 1 up to 85 atm and thereby vary the density ratio between the inner and outer fluid, from 0.005 up to unity. Using high-speed video imaging, we observe a continuous increase in satellite size as the inner density is varied from the bubble to emulsion-droplet conditions, with the most rapid changes occurring as the bubble density grows up to 15 % of that of the surrounding liquid. We propose a model that successfully relates the satellite size to the capillary wave mode responsible for its pinch-off and the overall deformations from the drainage. The wavelength of the primary wave changes during its travel to the apex, with the instantaneous speed adjusting to the local wavelength. By estimating the travel time of this wave mode on the bubble surface, we also show that the model is consistent with the experiments. This wavenumber is determined by both the global drainage as well as the interface shapes during the rapid coalescence in the neck connecting the two drops or bubbles. The rate of drainage is shown to scale with the density of the inner fluid. Empirically, we find that the pinch-off occurs when 60 % of the bubble fluid has drained from it. Numerical simulations using the volume-of-fluid method with dynamic adaptive grid refinement can reproduce these dynamics, as well as show the associated vortical structure and stirring of the coalescing fluid masses. Enhanced stirring is observed for cases with second

  3. Diversity oriented approach to polycyclics via cross-enyne metathesis and Diels-Alder reaction as key steps

    Indian Academy of Sciences (India)

    Sambasivarao Kotha; Vittal Seema; Shaibal Banerjee; Mrityunjay Kumar Dipak

    2015-01-01

    Polycyclics containing biaryls have been prepared via application of cross-enyne metathesis and the Diels−Alder reaction. Here, ethylene and 1,5-hexadiene were used as a cross-metathesis partners to generate key diene intermediates.

  4. 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.

  5. Molybdenum chloride catalysts for Z-selective olefin metathesis reactions

    Science.gov (United States)

    Koh, Ming Joo; Nguyen, Thach T.; Lam, Jonathan K.; Torker, Sebastian; Hyvl, Jakub; Schrock, Richard R.; Hoveyda, Amir H.

    2017-01-01

    The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.

  6. Kinetically controlled E-selective catalytic olefin metathesis.

    Science.gov (United States)

    Nguyen, Thach T; Koh, Ming Joo; Shen, Xiao; Romiti, Filippo; Schrock, Richard R; Hoveyda, Amir H

    2016-04-29

    A major shortcoming in olefin metathesis, a chemical process that is central to research in several branches of chemistry, is the lack of efficient methods that kinetically favor E isomers in the product distribution. Here we show that kinetically E-selective cross-metathesis reactions may be designed to generate thermodynamically disfavored alkenyl chlorides and fluorides in high yield and with exceptional stereoselectivity. With 1.0 to 5.0 mole % of a molybdenum-based catalyst, which may be delivered in the form of air- and moisture-stable paraffin pellets, reactions typically proceed to completion within 4 hours at ambient temperature. Many isomerically pure E-alkenyl chlorides, applicable to catalytic cross-coupling transformations and found in biologically active entities, thus become easily and directly accessible. Similarly, E-alkenyl fluorides can be synthesized from simpler compounds or more complex molecules.

  7. Ruthenium Carbene Mediated Metathesis of Oleate-Type Fatty Compounds

    Directory of Open Access Journals (Sweden)

    Manie H. C. Vosloo

    2008-04-01

    Full Text Available The complexes RuCl2(PCy32(=CHPh, 1, and RuCl2(PCy3(H2IMes(=CHPh, 2, proved to be active catalysts for the self-metathesis of oleate-type fatty compounds containing the ester, hydroxyl, epoxy and carboxylic acid functional groups. At elevated reaction temperatures 2 showed a higher activity, stability and lower selectivity for primary metathesis products compared to 1. A profound influence of organic functional groups on catalyst activity and selectivity was found and from relative activities and selectivities 2 has proved to be more resistant to deactivation by polar functional groups and more inclined to promote double bond isomerisation than 1. The observed catalyst deactivation by oxygen-containing functional groups could be attributed to a phosphine displacement side reaction.

  8. Regioselective chromatic orthogonality with light-activated metathesis catalysts.

    Science.gov (United States)

    Levin, Efrat; Mavila, Sudheendran; Eivgi, Or; Tzur, Eyal; Lemcoff, N Gabriel

    2015-10-12

    The ability to selectively guide consecutive chemical processes towards a preferred pathway by using light of different frequencies is an appealing concept. Herein we describe the coupling of two photochemical reactions, one the photoisomerization and consequent activation of a sulfur-chelated latent olefin-metathesis catalyst at 350 nm, and the other the photocleavage of a silyl protecting group at 254 nm. Depending on the steric stress exerted by a photoremovable neighboring chemical substituent, we demonstrate the selective formation of either five- or six-membered-ring frameworks by light-triggered ring-closing metathesis. The orthogonality of these light-induced reactions allows the initiation of these processes independently and in interchangeable order, according to the wavelength of light used to promote them.

  9. Asymptotic sampling formulae for Lambda-coalescents

    CERN Document Server

    Berestycki, Julien; Limic, Vlada

    2012-01-01

    We present a robust method which translates information on the speed of coming down from infinity of a genealogical tree into sampling formulae for the underlying population. We apply these results to population dynamics where the genealogy is given by a Lambda-coalescent. This allows us to derive an exact formula for the asymptotic behavior of the site and allele frequency spectrum and the number of segregating sites, as the sample size tends to infinity. Some of our results hold in the case of a general Lambda-coalescent that comes down from infinity, but we obtain more precise information under a regular variation assumption. In this case, we obtain results of independent interest for the time at which a mutation uniformly chosen at random was generated. This exhibits a phase transition at \\alpha=3/2, where \\alpha \\in(1,2) is the exponent of regular variation.

  10. Coalescence and Collisions of Gold Nanoparticles

    Directory of Open Access Journals (Sweden)

    Eduardo Pérez-Tijerina

    2011-01-01

    Full Text Available We study the assembling of small gold clusters subject to collisions and close contact coalescence by using molecular dynamics simulations to simulate events that occur typically in the sputtering process of synthesis. Our results support the notion that the kinetics of coalescence processes strongly determine the geometry and structure of the final particle. While impact velocities, relative orientations, and the initial shape of the interacting particles are unlikely to strictly determine the structural details of the newly formed particle, we found that high initial temperatures and/or impact velocities increase the probability of appearance of icosahedral-like structures, Wulff polyhedra are likely to be formed as a product of the interactions between nanospheres, while the appearance of fcc particles of approximately cuboctahedral shape is mainly due to the interaction between icosahedra.

  11. Hadronization via coalescence at RHIC and LHC

    Directory of Open Access Journals (Sweden)

    Minissale V.

    2016-01-01

    Full Text Available An hadronization model that includes coalescence and fragmentation is used in this work to obtain predictions at both RHIC and LHC energy for light and strange hadrons transverse momentum spectra (π, p, k, Λ and baryon to meson ratios (p/π, Λ/k in a wide range of pT. This is accomplished without changing coalescence parameters. The ratios p/π and Λ/K shows the right behaviour except for some lack of baryon yield in a limited pT range around 6 GeV. This would indicate that the AKK fragmentation functions is too flat at pT < 8 GeV.

  12. Detecting compact binary coalescences with seedless clustering

    Science.gov (United States)

    Coughlin, M.; Thrane, E.; Christensen, N.

    2014-10-01

    Compact binary coalescences are a promising source of gravitational waves for second-generation interferometric gravitational-wave detectors. Although matched filtering is the optimal search method for well-modeled systems, alternative detection strategies can be used to guard against theoretical errors (e.g., involving new physics and/or assumptions about spin or eccentricity) while providing a measure of redundancy. In a previous paper, we showed how "seedless clustering" can be used to detect long-lived gravitational-wave transients in both targeted and all-sky searches. In this paper, we apply seedless clustering to the problem of low-mass (Mtotal≤10M⊙) compact binary coalescences for both spinning and eccentric systems. We show that seedless clustering provides a robust and computationally efficient method for detecting low-mass compact binaries.

  13. Rapid Compact Binary Coalescence Parameter Estimation

    Science.gov (United States)

    Pankow, Chris; Brady, Patrick; O'Shaughnessy, Richard; Ochsner, Evan; Qi, Hong

    2016-03-01

    The first observation run with second generation gravitational-wave observatories will conclude at the beginning of 2016. Given their unprecedented and growing sensitivity, the benefit of prompt and accurate estimation of the orientation and physical parameters of binary coalescences is obvious in its coupling to electromagnetic astrophysics and observations. Popular Bayesian schemes to measure properties of compact object binaries use Markovian sampling to compute the posterior. While very successful, in some cases, convergence is delayed until well after the electromagnetic fluence has subsided thus diminishing the potential science return. With this in mind, we have developed a scheme which is also Bayesian and simply parallelizable across all available computing resources, drastically decreasing convergence time to a few tens of minutes. In this talk, I will emphasize the complementary use of results from low latency gravitational-wave searches to improve computational efficiency and demonstrate the capabilities of our parameter estimation framework with a simulated set of binary compact object coalescences.

  14. A cross-metathesis approach to novel pantothenamide derivatives

    Science.gov (United States)

    Guan, Jinming; Hachey, Matthew; Puri, Lekha; Howieson, Vanessa; Saliba, Kevin J

    2016-01-01

    Summary Pantothenamides are known for their in vitro antimicrobial activity. Our group has previously reported a new stereoselective route to access derivatives modified at the geminal dimethyl moiety. This route however fails in the addition of large substituents. Here we report a new synthetic route that exploits the known allyl derivative, allowing for the installation of larger groups via cross-metathesis. The method was applied in the synthesis of a new pantothenamide with improved stability in human blood. PMID:27340487

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

    Energy Technology Data Exchange (ETDEWEB)

    Heveling, J.

    1984-07-01

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

  16. Scaling laws and dynamics of bubble coalescence

    Science.gov (United States)

    Anthony, Christopher R.; Kamat, Pritish M.; Thete, Sumeet S.; Munro, James P.; Lister, John R.; Harris, Michael T.; Basaran, Osman A.

    2017-08-01

    The coalescence of bubbles and drops plays a central role in nature and industry. During coalescence, two bubbles or drops touch and merge into one as the neck connecting them grows from microscopic to macroscopic scales. The hydrodynamic singularity that arises when two bubbles or drops have just touched and the flows that ensue have been studied thoroughly when two drops coalesce in a dynamically passive outer fluid. In this paper, the coalescence of two identical and initially spherical bubbles, which are idealized as voids that are surrounded by an incompressible Newtonian liquid, is analyzed by numerical simulation. This problem has recently been studied (a) experimentally using high-speed imaging and (b) by asymptotic analysis in which the dynamics is analyzed by determining the growth of a hole in the thin liquid sheet separating the two bubbles. In the latter, advantage is taken of the fact that the flow in the thin sheet of nonconstant thickness is governed by a set of one-dimensional, radial extensional flow equations. While these studies agree on the power law scaling of the variation of the minimum neck radius with time, they disagree with respect to the numerical value of the prefactors in the scaling laws. In order to reconcile these differences and also provide insights into the dynamics that are difficult to probe by either of the aforementioned approaches, simulations are used to access both earlier times than has been possible in the experiments and also later times when asymptotic analysis is no longer applicable. Early times and extremely small length scales are attained in the new simulations through the use of a truncated domain approach. Furthermore, it is shown by direct numerical simulations in which the flow within the bubbles is also determined along with the flow exterior to them that idealizing the bubbles as passive voids has virtually no effect on the scaling laws relating minimum neck radius and time.

  17. Aggregation kinetics of coalescing polymer colloids.

    Science.gov (United States)

    Gauer, Cornelius; Jia, Zichen; Wu, Hua; Morbidelli, Massimo

    2009-09-01

    The aggregation behavior of a soft, rubbery colloidal system with a relatively low glass transition temperature, T(g) approximately -20 degrees C, has been investigated. It is found that the average gyration and hydrodynamic radii, R(g) and R(h), measured by light scattering techniques, evolve in time in parallel, without exhibiting the crossover typical of rigid particle aggregation. Cryogenic scanning electron microscopy (cryo-SEM) images reveal sphere-like clusters, indicating that complete coalescence between particles occurs during aggregation. Since coalescence leads to a reduction in the total colloidal surface area, the surfactant adsorption equilibrium, and thus the colloidal stability, change in the course of aggregation. It is found that to simulate the observed kinetic behavior based on the population balance equations, it is necessary to assume that all the clusters are spherical and to account for variations in the colloidal stability of each aggregating particle pair with time. This indicates that, for the given system, the coalescence is very fast, i.e., its time scale is much smaller than that of the aggregation.

  18. Cosmology with coalescing massive black holes

    Energy Technology Data Exchange (ETDEWEB)

    Hughes, Scott A; Holz, Daniel E [Kavli Institute for Theoretical Physics, University of California, Santa Barbara, CA 93106 (United States)

    2003-05-21

    The gravitational waves generated in the coalescence of massive binary black holes will be measurable by LISA to enormous distances. Redshifts z {approx} 10 or larger (depending somewhat on the mass of the binary) can potentially be probed by such measurements, suggesting that binary coalescences can be made into cosmological tools. We discuss two particularly interesting types of probe. First, by combining gravitational-wave measurements with information about the cosmography of the universe, we can study the evolution of black-hole masses and merger rates as a function of redshift, providing information about the growth of structures at high redshift and possibly constraining hierarchical merger scenarios. Second, if it is possible to associate an 'electromagnetic' counterpart with a coalescence, it may be possible to measure both redshift and luminosity distance to an event with less than {approx}1% error. Such a measurement would constitute an amazingly precise cosmological standard candle. Unfortunately, gravitational lensing uncertainties will reduce the quality of this candle significantly. Though not as amazing as might have been hoped, such a candle would nonetheless very usefully complement other distance-redshift probes, in particular providing a valuable check on systematic effects in such measurements.

  19. Coalescence of a Drop inside another Drop

    Science.gov (United States)

    Mugundhan, Vivek; Jian, Zhen; Yang, Fan; Li, Erqiang; Thoroddsen, Sigurdur

    2016-11-01

    Coalescence dynamics of a pendent drop sitting inside another drop, has been studied experimentally and in numerical simulations. Using an in-house fabricated composite micro-nozzle, a smaller salt-water drop is introduced inside a larger oil drop which is pendent in a tank containing the same liquid as the inner drop. On touching the surface of outer drop, the inner drop coalesces with the surrounding liquid forming a vortex ring, which grows in time to form a mushroom-like structure. The initial dynamics at the first bridge opening up is quantified using Particle Image Velocimetry (PIV), while matching the refractive index of the two liquids. The phenomenon is also numerically simulated using the open-source code Gerris. The problem is fully governed by two non-dimensional parameters: the Ohnesorge number and the diameter ratios of the two drops. The validated numerical model is used to better understand the dynamics of the phenomenon. In some cases a coalescence cascade is observed with liquid draining intermittently and the inner drop reducing in size.

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

    Energy Technology Data Exchange (ETDEWEB)

    Burdett, Kenneth A. (Midland, MI); Mokhtarzadeh, Morteza (Charleston, WV); Timmers, Francis J. (Midland, MI)

    2010-10-12

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

  1. In tandem or alone: a remarkably selective transfer hydrogenation of alkenes catalyzed by ruthenium olefin metathesis catalysts.

    Science.gov (United States)

    Zieliński, Grzegorz Krzysztof; Samojłowicz, Cezary; Wdowik, Tomasz; Grela, Karol

    2015-03-01

    A system for transfer hydrogenation of alkenes, composed of a ruthenium metathesis catalyst and HCOOH, is presented. This operationally simple system can be formed directly after a metathesis reaction to effect hydrogenation of the metathesis product in a single-pot. These hydrogenation conditions are applicable to a wide range of alkenes and offer remarkable selectivity.

  2. Bubble Coalescence Heat Transfer During Subcooled Nucleate Pool Boiling

    Institute of Scientific and Technical Information of China (English)

    Abdoulaye Coulibaly; LIN Xipeng; Bi Jingliang; David M Christopher

    2012-01-01

    Bubble coalescence during subcooled nucleate pool boiling was investigated experimentally using constant wall temperature boundary conditions while the wall heat flux was measured at a various locations to understand the effects of coalescence on the heat transfer. The observations showed that the coalesced bubble moved and oscillated on the heater surface with significant heat transfer variations prior to departure. Some observations also showed coalescence with no increase in the heat transfer rate. The heat flux for boiling with coalescence fluctuated much more than for single bubble boiling due to the vaporization of the liquid layer trapped between the bubbles.

  3. Coalescence of Immiscible Liquid Metal Drop on Graphene

    Science.gov (United States)

    Li, Tao; Li, Jie; Wang, Long; Duan, Yunrui; Li, Hui

    2016-01-01

    Molecular dynamics simulations were performed to investigate the wetting and coalescence of liquid Al and Pb drops on four carbon-based substrates. We highlight the importance of the microstructure and surface topography of substrates in the coalescence process. Our results show that the effect of substrate on coalescence is achieved by changing the wettability of the Pb metal. Additionally, we determine the critical distance between nonadjacent Al and Pb films required for coalescence. These findings improve our understanding of the coalescence of immiscible liquid metals at the atomistic level. PMID:27667589

  4. Coalescence of Pickering Emulsion Droplets Induced by an Electric Field

    Science.gov (United States)

    Chen, Guo; Tan, Peng; Chen, Shuyu; Huang, Jiping; Wen, Weijia; Xu, Lei

    2013-02-01

    Combining high-speed photography with electric current measurement, we investigate the electrocoalescence of Pickering emulsion droplets. Under a high enough electric field, the originally stable droplets coalesce via two distinct approaches: normal coalescence and abnormal coalescence. In the normal coalescence, a liquid bridge grows continuously and merges two droplets together, similar to the classical picture. In the abnormal coalescence, however, the bridge fails to grow indefinitely; instead, it breaks up spontaneously due to the geometric constraint from particle shells. Such connecting-then-breaking cycles repeat multiple times, until a stable connection is established. In depth analysis indicates that the defect size in particle shells determines the exact merging behaviors: when the defect size is larger than a critical size around the particle diameter, normal coalescence will show up, while abnormal coalescence will appear for coatings with smaller defects.

  5. Synthesis of Long Chain Unsaturated-alpha,omega-Dicarboxylic Acids from Renewable Materials via Olefin Metathesis

    Science.gov (United States)

    The self-metathesis reaction of soy, rapeseed, tall, and linseed oil fatty acids was investigated for the synthesis of symmetrical long-chain unsaturated-alpha,omega-dicarboxylic acids. The metathesis reactions were carried out in the presence of a Grubbs catalyst under solvent-free conditions at a...

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

    Science.gov (United States)

    Saá, Carlos

    2016-09-01

    Recent developments in catalytic carbonyl-olefin metathesis are summarized in this Highlight. Schindler and co-workers have reported that the environmentally benign FeCl3 catalyst promotes ring-closing carbonyl-olefin metathesis (RCCOM) in high yield under very mild conditions.

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

    Science.gov (United States)

    Szadkowska, Anna; Grela, Karol

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

  8. New pseudohalide ligands in Ru-catalyzed olefin metathesis : a robust, air-activated iminopyrrolato catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Drouin, S.D.; Foucault, H.M.; Yap, G.P.A.; Fogg, D.E. [Ottawa Univ., ON (Canada). Dept. of Chemistry, Center for Catalysis Research and Innovation

    2005-07-01

    This study demonstrated the feasibility of using iminopyrrolatos as a new pseudohalide ligand in Ru-catalyzed olefin metathesis, particularly in terms of stereo control and anchoring. Ring-closing metathesis (RCM) and cross-metathesis reactions hold promise for pharmaceutical synthesis, as well as green chemistry initiatives to transform seed oils into olefin feedstocks. The advent of robust, functional-group tolerant ruthenium (Ru) catalysts has expanded the deployment of olefin metathesis methodologies by the organic community. Despite recent advances in metathesis activity, major issues remain to be addressed, particularly the problem of short catalyst lifetimes which increase catalyst loading requirements, as well as heavy metal contamination of the organic products. This study revealed that chelation does not prevent isomerization of aryloxide ligands that form larger, seven-membered chelate rings. Complex 5 proved to be a robust olefin metathesis catalyst, effecting RCM of the benchmark substrate diethyl diallylmalonate at 70 degrees C in air, in nondistilled and nondegassed solvent. The reaction revealed complete selectivity for RCM over intermolecular acyclic diene metathesis processes, even in the absence of a solvent. It was shown that RuCl(NN')(Pcy{sub 3})(CHPh) (5) is activated via loss of phosphine. As a result, the catalyst achieves maximum activity in the presence of air, providing a good experimental protocol for metathesis chemistry.

  9. Application of olefin cross-metathesis to organometallics. Synthesis of unsaturated ferrocenyl alcohols and ketones

    Science.gov (United States)

    Seshadri; Lovely

    2000-02-10

    [reaction: see text] The application of olefin cross-metathesis to terminally unsaturated alpha-hydroxy- and alpha-ketoferrocenes is reported. Both substrates provided the terminally functionalized olefins in moderate to good yield. These examples represent the first cases of cross-metathesis of substrates containing an organometallic functional group.

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

    Energy Technology Data Exchange (ETDEWEB)

    Schrodi, Yann [Agoura Hills, CA

    2011-11-29

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Schrodi, Yann

    2016-02-09

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Schrodi, Yann (Agoura Hills, CA)

    2011-11-29

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

  13. The Olefin Metathesis Reactions Combined with Organo-Iron Arene Activation Towards Dendrimers, and Polymers

    Science.gov (United States)

    Astruc, Didier; Martinez, Victor

    The subjects treated in the two lectures of the North Atlantic Treaty Organization (NATO) summer course are (1) the combination of arene activation and perfunctionalization using organo-iron chemistry with olefin metathesis incuding metathesis of dendritic polyolefin molecules; (2) the synthesis of metallodendritic benzylidene complexes that catalyse ring-opening metathesis polymerization (ROMP) under ambient conditions and the formation of dendritic stars; (3) the use of stoichiometric and catalytic electron-transfer processes with standard reservoirs of electrons (reductants) or electron holes (oxidants) iron complexes to achieve noteworthy metathesis reactions or synthesize compounds that are useful in metathesis. Only the two first topics are treated in this chapter, and interested readers can find references concerning the third aspect called in the introduction and subsequently cited in the reference list.

  14. A diversity-oriented approach to spirocyclic and fused hydantoins via olefin metathesis.

    Science.gov (United States)

    Dhara, Kalyan; Midya, Ganesh Chandra; Dash, Jyotirmayee

    2012-09-21

    An efficient and general method is reported to prepare a diverse series of 5,5-spirocyclic and 1,5-, 4,5-, and 3,4-fused bicyclic imidazolidinone derivatives based on selective alkylation and ring closing metathesis (RCM) by exploiting the four possible points of diversity in the hydantoin ring. Hydantoins containing trienes and tetraenes undergo selective RCM and cross metathesis to afford functionalized spirohydantoins. A tandem metathesis sequence involving ring closing-ring opening-ring closing and cross metathesis (RC-RO-RC-CM) occurred with a hydantoin triene to give a bicyclic hydantoin dimer in high yield. The fused bicylic dimer could participate in cross metathesis to produce a functionalized fused hydantoin derivative. The methodology establishes novel routes to unnatural amino acids, proline homologues, and cyclic vicinal diamines.

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

    Energy Technology Data Exchange (ETDEWEB)

    Schrodi, Yann

    2015-09-22

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Schrodi, Yann

    2013-07-09

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

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

    Science.gov (United States)

    Schrodi, Yann

    2013-07-09

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

  18. The tree length of an evolving coalescent

    CERN Document Server

    Pfaffelhuber, Peter; Weisshaupt, Heinz

    2009-01-01

    A well-established model for the genealogy of a large population in equilibrium is Kingman's coalescent. For the population together with its genealogy evolving in time, this gives rise to a time-stationary tree-valued process. We study the sum of the branch lengths, briefly denoted as tree length, and prove that the (suitably compensated) sequence of tree length processes converges, as the population size tends to infinity, to a limit process with cadlag paths, infinite infinitesimal variance, and a Gumbel distribution as its equilibrium.

  19. Le phénomène de coalescence. Etude bibliographique Coalescence Phenomena. A Review

    Directory of Open Access Journals (Sweden)

    Palermo T.

    2006-11-01

    Full Text Available Nous présentons une revue des différents travaux expérimentaux et théoriques effectués sur le phénomène de coalescence en limitant principalement notre discussion au cas de la coalescence d'une goutte isolée à une interface plane ou déformable. La coalescence se divise en deux phases distinctes : le drainage et la rupture du film interfacial. Ce film est constitué du liquide de la phase continue séparant la goutte de l'interface. La condition de rupture est principalement contrôlée par les forces électrostatiques dues à la double couche et par les forces de Van der Waals. Les résultats expérimentaux mettent en évidence un phénomène de coalescence partielle ainsi que l'existence d'une distribution statistique du temps de coalescence. Ils montrent également l'influence complexe de nombreux paramètres physiques et physico-chimiques sur le temps de coalescence. On rappelle les principaux modèles théoriques décrivant le drainage et la rupture des films liquides. Ces modèles permettent, entre autre, d'aboutir à des expressions mathématiques reliant le temps de coalescence à des paramètres tels que la tension interfaciale, les densités et les viscosités des fluides, la taille des gouttes. The problem linked to the stability of oil-in-water emulsions (e. g. deoiling of water and water-in-oil emulsions (e. g. dehydration of crudes is one of the major problems encountered in the petroleum industry. From the thermodynamic standpoint, an emulsion is always unstable (Fig. I. 1. The kinematic stability characterizing the separation rate of the dispersed phase from the continuous phase can nonetheless be controlled by the coalescence of droplets present in the emulsion (Fig. I. 2. This article reviews various experimental and theoretical works on the phenomenon of coalescence but the discussion is limited mainly to the coalescence of an single drop at a flat or deformable interface. The coalescence of a single drop is governed

  20. Mechanisms of rectangular groove-induced multiple-microdroplet coalescences

    Science.gov (United States)

    Shen, Feng; Li, Yi; Wang, Guiren; Liu, Zhaomiao

    2017-01-01

    The mechanism of microdroplet coalescence is a fundamental issue for droplet-based microfluidics. We developed an asymmetric expansion (a rectangular groove) along one side of a microchannel to achieve multiple-microdroplet trapping, collision, and coalescence. Compared with reported symmetric expansions, this asymmetric groove could easily trap microdroplets and control two or three microdroplet coalescences precisely without a requirement for temporal and spatial synchronization. To reveal the mechanisms of multiple-droplet coalescences in a groove, we observed five different coalescence patterns under different flow conditions. Moreover, we characterized the flow behavior quantitatively by simulating the velocity vector fields in both the microdroplets and continuous phase, finding good agreement with experiments. Finally, a map of coalescence forms with different capillary numbers (0.001droplet-based microfluidic devices.

  1. Coalescent: an open-science framework for importance sampling in coalescent theory.

    Science.gov (United States)

    Tewari, Susanta; Spouge, John L

    2015-01-01

    Background. In coalescent theory, computer programs often use importance sampling to calculate likelihoods and other statistical quantities. An importance sampling scheme can exploit human intuition to improve statistical efficiency of computations, but unfortunately, in the absence of general computer frameworks on importance sampling, researchers often struggle to translate new sampling schemes computationally or benchmark against different schemes, in a manner that is reliable and maintainable. Moreover, most studies use computer programs lacking a convenient user interface or the flexibility to meet the current demands of open science. In particular, current computer frameworks can only evaluate the efficiency of a single importance sampling scheme or compare the efficiencies of different schemes in an ad hoc manner. Results. We have designed a general framework (http://coalescent.sourceforge.net; language: Java; License: GPLv3) for importance sampling that computes likelihoods under the standard neutral coalescent model of a single, well-mixed population of constant size over time following infinite sites model of mutation. The framework models the necessary core concepts, comes integrated with several data sets of varying size, implements the standard competing proposals, and integrates tightly with our previous framework for calculating exact probabilities. For a given dataset, it computes the likelihood and provides the maximum likelihood estimate of the mutation parameter. Well-known benchmarks in the coalescent literature validate the accuracy of the framework. The framework provides an intuitive user interface with minimal clutter. For performance, the framework switches automatically to modern multicore hardware, if available. It runs on three major platforms (Windows, Mac and Linux). Extensive tests and coverage make the framework reliable and maintainable. Conclusions. In coalescent theory, many studies of computational efficiency consider only

  2. On the coalescence of sessile drops with miscible liquids.

    Science.gov (United States)

    Borcia, R; Bestehorn, M

    2011-08-01

    Sessile drops sitting on highly wettable solid substrates fuse in qualitatively different ways after contact, depending on the surface tension gradients between the mixing droplets. In early time evolution the drop coalescence can be fast or delayed (intermittent). In long time evolution a secondary drop formation can occur. We study numerically droplet dynamics during coalescence in two and three spatial dimensions, within a phase field approach. We discuss criteria to distinguish different coalescence regimes. A comparison with recent experiments will be done.

  3. Block copolymer adhesion promoters via ring-opening metathesis polymerization

    Science.gov (United States)

    Kent, M.S.; Saunders, R.

    1997-02-18

    Coupling agents are disclosed based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization. 18 figs.

  4. Highly Active Carbene Ruthenium Catalyst for Metathesis of 1-Hexene

    Institute of Scientific and Technical Information of China (English)

    BAI Chen-Xi; ZHANG Zhi-Qiang; L(U) Xiao-Bing; HE Ren; ZHANG Wen-Zhen; LU Shu-Lai

    2006-01-01

    A new carbene ruthenium complex, 1,3-bis(2,6-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene)(PPh3)Cl2-Ru=CHPh, was synthesized and used as catalyst for the metathesis of 1-hexene. The resulting complex exhibited very high catalytic activity whose TOF is up to 6680 h-1. However, at the same time significant olefin isomerization was observed and could be surpressed by changing reaction conditions, such as temperature, time, alkene/Ru molar ratio and solvent.

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

    Directory of Open Access Journals (Sweden)

    Giuseppe Vasapollo

    2011-08-01

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

  6. Poly(trimethylsilylcyclooctatetraene): A soluble conjugated polyacetylene via olefin metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Ginsburg, E.J.; Gorman, C.B.; Grubbs, R.H.; Marder, S.R. (California Institute of Technology, Pasadena (USA))

    1989-09-13

    highly conjugated polymers, such as polyacetylene, polythiophene, and poly(p-phenylene vinylene), have been the subject of intensive research due to their intriguing optical and electronic properties. These parent systems are highly desirable for experimental and theoretical studies due to their simplicity. Their intractability, however, has made characterization an arduous task, and insolubility has severely limited their applications. Researchers have successfully circumvented these obstacles by synthesizing soluble alkyl- and alkoxy-substituted polythiphenes and poly(p-phenylene vinylenes). Analogous soluble highly conjugated polyacetylene derivatives have proven more elusive. The authors report here the synthesis of such a polymer using ring-opening metathesis polymerization (ROMP).

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

    Science.gov (United States)

    Voigtritter, Karl; Ghorai, Subir

    2011-01-01

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

  8. Viscous Coalescence of Two Drops in a Saturated Vapor Phase

    Science.gov (United States)

    Baroudi, Lina; Nagel, Sidney R.; Morris, Jeffrey F.; Lee, Taehun

    2016-11-01

    When two liquid drops come into contact, a microscopic liquid bridge forms between them and rapidly expands until the two drops merge into a single bigger drop. Numerous studies have been devoted to the investigation of the coalescence singularity in the case where the drops coalesce in a medium of negligible vapor pressure such as vacuum or air. However, coalescence of liquid drops may also take place in a medium of relatively high vapor pressure (condensable vapor phase), where the effect of the surrounding vapor phase should not be neglected, such as the merging of drops in clouds. In this study, we carry out Lattice Boltzmann numerical simulations to investigate the dynamics of viscous coalescence in a saturated vapor phase. Attention is paid to the effect of the vapor phase on the formation and growth dynamics of the liquid bridge in the viscous regime. We observe that the onset of the coalescence occurs earlier and the expansion of the bridge initially proceeds faster when the coalescence takes place in a saturated vapor compared to the coalescence in a non-condensable gas. The initially faster evolution of the coalescence process in the saturated vapor is caused by the vapor transport through condensation during the early stages of the coalescence.

  9. Droplets coalescence at microchannel intersection chambers with different shapes

    Science.gov (United States)

    Liu, Zhaomiao; Wang, Xiang; Cao, Rentuo; Pang, Yan

    2016-11-01

    The influence of microchannel intersection chamber shape on droplets coalescence process is investigated in this study. Three kinds of chamber shapes (half-round, triangle and camber) are designed to realize head-on droplets coalescence. The coalescence processes are visualized with high-speed camera system and the internal flow patterns are resolved with micro-PIV system. Experimental analyses on droplets coalescence position, coalescence time and the critical conditions are discussed. Both direct coalescence and late coalescence can be observed in the camber junction while only the late coalescence is present for the half-round and the triangle junction. The critical capillary number Ca* varies for different working systems or intersection shapes. Ca* in the camber junction is larger than that in the other two junctions for each working system and it decreases with the increase of the viscosity ratios for each intersection shape. Moreover, the characteristics of the velocity fields for different coalescence cases are analyzed for in-depth understanding of the process. The authors do appreciate the financial support of No.11572013 of National Nature Scicence Funding of China.

  10. Identification of the most informative regions of the mitochondrial genome for phylogenetic and coalescent analyses.

    Science.gov (United States)

    Non, A L; Kitchen, A; Mulligan, C J

    2007-09-01

    Analysis of complete mitochondrial genome sequences is becoming increasingly common in genetic studies. The availability of full genome datasets enables an analysis of the information content distributed throughout the mitochondrial genome in order to optimize the research design of future evolutionary studies. The goal of our study was to identify informative regions of the human mitochondrial genome using two criteria: (1) accurate reconstruction of a phylogeny and (2) consistent estimates of time to most recent common ancestor (TMRCA). We created two series of datasets by deleting individual genes of varied length and by deleting 10 equal-size fragments throughout the coding region. Phylogenies were statistically compared to the full-coding-region tree, while coalescent methods were used to estimate the TMRCA and associated credible intervals. Individual fragments important for maintaining a phylogeny similar to the full-coding-region tree encompassed bp 577-2122 and 11,399-16,023, including all or part of 12S rRNA, 16S rRNA, ND4, ND5, ND6, and cytb. The control region only tree was the most poorly resolved with the majority of the tree manifest as an unresolved polytomy. Coalescent estimates of TMRCA were less sensitive to removal of any particular fragment(s) than reconstruction of a consistent phylogeny. Overall, we discovered that half the genome, i.e., bp 3669-11,398, could be removed with no significant change in the phylogeny (p(AU)=0.077) while still maintaining overlap of TMRCA 95% credible intervals. Thus, sequencing a contiguous fragment from bp 11,399 through the control region to bp 3668 would create a dataset that optimizes the information necessary for phylogenetic and coalescent analyses and also takes advantage of the wealth of data already available on the control region.

  11. 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.

  12. 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...

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

    Science.gov (United States)

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

    2016-05-25

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

  14. Desymmetrization of 7-azabicycloalkenes by tandem olefin metathesis for the preparation of natural product scaffolds

    Directory of Open Access Journals (Sweden)

    Deppermann Nina

    2007-12-01

    Full Text Available Abstract Background Tandem olefin metathesis sequences are known to be versatile for the generation of natural product scaffolds and have also been used for ring opening of strained carbo- and heterocycles. In this paper we demonstrate the potential of these reactions for the desymmetrization of 7-azabicycloalkenes. Results We have established efficient protocols for the desymmetrization of different 7-azabicycloalkenes by intra- and intermolecular tandem metathesis sequences with ruthenium based catalysts. Conclusion Desymmetrization of 7-azabicycloalkenes by olefin metathesis is an efficient process for the preparation of common natural product scaffolds such as pyrrolidines, indolizidines and isoindoles.

  15. Aromatizing olefin metathesis by ligand isolation inside a metal-organic framework.

    Science.gov (United States)

    Vermeulen, Nicolaas A; Karagiaridi, Olga; Sarjeant, Amy A; Stern, Charlotte L; Hupp, Joseph T; Farha, Omar K; Stoddart, J Fraser

    2013-10-01

    The aromatizing ring-closing metathesis has been shown to take place inside an extended porous framework. Employing a combination of solvent-assisted linker exchange and postsynthesis modification using olefin metathesis, the noninterpenetrated SALEM-14 was formed and converted catalytically into PAH-MOF-1 with polycyclic aromatic hydrocarbon (PAH) pillars. The metal-organic framework in SALEM-14 prevents "intermolecular" olefin metathesis from occurring between the pillars in the presence of the first generation Hoveyda-Grubbs catalyst, while favoring the production of a PAH, which can be released from the framework under acidic conditions in dimethylsulfoxide.

  16. Olefin Metathesis in Homogeneous Aqueous Media Catalyzed by Conventional Ruthenium Catalysts

    Science.gov (United States)

    Binder, Joseph B.; Blank, Jacqueline J.; Raines, Ronald T.

    2008-01-01

    Olefin metathesis in aqueous solvents is sought for applications in green chemistry and with the hydrophilic substrates of chemical biology, such as proteins and polysaccharides. Most demonstrations of metathesis in water, however, utilize exotic complexes. We have examined the performance of conventional catalysts in homogeneous water–organic mixtures, finding that the second-generation Hoveyda–Grubbs catalyst has extraordinary efficiency in aqueous dimethoxyethane and aqueous acetone. High (71–95%) conversions are achieved for ring-closing and cross metathesis of a variety of substrates in these solvent systems. PMID:17949009

  17. Biopolymer-supported ionic-liquid-phase ruthenium catalysts for olefin metathesis.

    Science.gov (United States)

    Clousier, Nathalie; Filippi, Alexandra; Borré, Etienne; Guibal, Eric; Crévisy, Christophe; Caijo, Fréderic; Mauduit, Marc; Dez, Isabelle; Gaumont, Annie-Claude

    2014-04-01

    Original ruthenium supported ionic liquid phase (SILP) catalysts based on alginates as supports were developed for olefin metathesis reactions. The marine biopolymer, which fulfills most of the requisite properties for a support such as widespread abundance, insolubility in the majority of organic solvents, a high affinity for ionic liquids, high chemical stability, biodegradability, low cost, and easy processing, was impregnated by [bmim][PF6 ] containing an ionically tagged ruthenium catalyst. These biosourced catalysts show promising performances in ring-closing metathesis (RCM) and cross-metathesis (CM) reactions, with a high level of recyclability and reusability combined with a good reactivity.

  18. Desymmetrization of 7-azabicycloalkenes by tandem olefin metathesis for the preparation of natural product scaffolds

    Science.gov (United States)

    Maison, Wolfgang; Büchert, Marina; Deppermann, Nina

    2007-01-01

    Background Tandem olefin metathesis sequences are known to be versatile for the generation of natural product scaffolds and have also been used for ring opening of strained carbo- and heterocycles. In this paper we demonstrate the potential of these reactions for the desymmetrization of 7-azabicycloalkenes. Results We have established efficient protocols for the desymmetrization of different 7-azabicycloalkenes by intra- and intermolecular tandem metathesis sequences with ruthenium based catalysts. Conclusion Desymmetrization of 7-azabicycloalkenes by olefin metathesis is an efficient process for the preparation of common natural product scaffolds such as pyrrolidines, indolizidines and isoindoles. PMID:18088413

  19. Poly(aryleneethynylene)s: Properties, Applications and Synthesis Through Alkyne Metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Ortiz, Michael; Yu, Chao; Jin, Yinghua; Zhang, Wei

    2017-06-26

    Functional polymeric materials have seen their way into every facet of materials chemistry and engineering. In this review article, we focus on a promising class of polymers, poly(aryleneethynylene)s, by covering several of the numerous applications found thus far for these materials. Additionally, we survey the current synthetic strategies used to create these polymers, with a focus on the emerging technique of alkyne metathesis. An overview is presented of the most recent catalytic systems that support alkyne metathesis as well as the more useful alkyne metathesis reaction capable of synthesizing poly(aryleneethynylene)s.

  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. Discoal: flexible coalescent simulations with selection.

    Science.gov (United States)

    Kern, Andrew D; Schrider, Daniel R

    2016-12-15

    Here we describe discoal, a coalescent simulator able to generate population samples that include selective sweeps in a feature-rich, flexible manner. discoal can perform simulations conditioning on the fixation of an allele due to drift or either hard or soft sweeps-even those occurring a large genetic distance away from the simulated locus. discoal can simulate sweeps with recurrent mutation to the adaptive allele, recombination, and gene conversion, under non-equilibrium demographic histories and without specifying an allele frequency trajectory in advance. discoal is implemented in the C programming language. Source code is freely available on GitHub (https://github.com/kern-lab/discoal) under a GNU General Public License. kern@dls.rutgers.edu or dan.schrider@rutgers.eduSupplementary information: Supplementary data are available at Bioinformatics online. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

  2. Gravitational Waves from Coalescing Binary Sources

    CERN Document Server

    Maia, M D

    2010-01-01

    Coalescing binary systems (eg pulsars, neutron stars and black holes) are the most likely sources of gravitational radiation, yet to be detected on or near Earth, where the local gravitational field is negligible and the Poincar\\'e symmetry rules. On the other hand, the general theory of gravitational waves emitted by axially symmetric rotating sources predicts the existence of a non-vanishing news function. The existence of such function implies that, for a distant observer, the asymptotic group of isometries, the BMS group, has a translational symmetry that depends on the orbit periodicity of the source, thus breaking the isotropy o the Poincar\\'e translations. These results suggest the application of the asymptotic BMS-covariant wave equation to obtain a proper theoretical basis for the gravitational waves observations.

  3. Relaxation of liquid bridge after droplets coalescence

    Directory of Open Access Journals (Sweden)

    Jiangen Zheng

    2016-11-01

    Full Text Available We investigate the relaxation of liquid bridge after the coalescence of two sessile droplets resting on an organic glass substrate both experimentally and theoretically. The liquid bridge is found to relax to its equilibrium shape via two distinct approaches: damped oscillation relaxation and underdamped relaxation. When the viscosity is low, damped oscillation shows up, in this approach, the liquid bridge undergoes a damped oscillation process until it reaches its stable shape. However, if the viscous effects become significant, underdamped relaxation occurs. In this case, the liquid bridge relaxes to its equilibrium state in a non-periodic decay mode. In depth analysis indicates that the damping rate and oscillation period of damped oscillation are related to an inertial-capillary time scale τc. These experimental results are also testified by our numerical simulations with COMSOL Multiphysics.

  4. Relativistic calculations of coalescing binary neutron stars

    Indian Academy of Sciences (India)

    Joshua Faber; Phillippe Grandclément; Frederic Rasio

    2004-10-01

    We have designed and tested a new relativistic Lagrangian hydrodynamics code, which treats gravity in the conformally flat approximation to general relativity. We have tested the resulting code extensively, finding that it performs well for calculations of equilibrium single-star models, collapsing relativistic dust clouds, and quasi-circular orbits of equilibrium solutions. By adding a radiation reaction treatment, we compute the full evolution of a coalescing binary neutron star system. We find that the amount of mass ejected from the system, much less than a per cent, is greatly reduced by the inclusion of relativistic gravitation. The gravity wave energy spectrum shows a clear divergence away from the Newtonian point-mass form, consistent with the form derived from relativistic quasi-equilibrium fluid sequences.

  5. Void coalescence within periodic clusters of particles

    Science.gov (United States)

    Thomson, C. I. A.; Worswick, M. J.; Pilkey, A. K.; Lloyd, D. J.

    2003-01-01

    The effect of particle clustering on void damage rates in a ductile material under triaxial loading conditions is examined using three-dimensional finite element analysis. An infinite material containing a regular distribution of clustered particles is modelled using a unit cell approach. Three discrete particles are introduced into each unit cell while a secondary population of small particles within the surrounding matrix is represented using the Gurson-Tvergaard-Needleman (GTN) constitutive equations. Deformation strain states characteristic of sheet metal forming are considered; that is, deep drawing, plane strain and biaxial stretching. Uniaxial tensile stress states with varying levels of superimposed hydrostatic tension are also examined. The orientation of a particle cluster with respect to the direction of major principal loading is shown to significantly influence failure strains. Coalescence of voids within a first-order particle cluster (consisting of three particles) is a stable event while collapse of inter-cluster ligaments leads to imminent material collapse through void-sheeting.

  6. Coalescent genealogy samplers: windows into population history.

    Science.gov (United States)

    Kuhner, Mary K

    2009-02-01

    Coalescent genealogy samplers attempt to estimate past qualities of a population, such as its size, growth rate, patterns of gene flow or time of divergence from another population, based on samples of molecular data. Genealogy samplers are increasingly popular because of their potential to disentangle complex population histories. In the last decade they have been widely applied to systems ranging from humans to viruses. Findings include detection of unexpected reproductive inequality in fish, new estimates of historical whale abundance, exoneration of humans for the prehistoric decline of bison and inference of a selective sweep on the human Y chromosome. This review summarizes available genealogy-sampler software, including data requirements and limitations on the use of each program.

  7. Phenomenological gravitational waveforms from spinning coalescing binaries

    CERN Document Server

    Sturani, R; Cadonati, L; Guidi, G M; Healy, J; Shoemaker, D; Vicere', A

    2010-01-01

    An accurate knowledge of the coalescing binary gravitational waveform is crucial for match filtering techniques, which are currently used in the observational searches performed by the LIGO-Virgo collaboration. Following an earlier paper by the same authors we expose the construction of analytical phenomenological waveforms describing the signal sourced by generically spinning binary systems. The gap between the initial inspiral part of the waveform, described by spin-Taylor approximants, and its final ring-down part, described by damped exponentials, is bridged by a phenomenological phase calibrated by comparison with the dominant spherical harmonic mode of a set of waveforms including both numerical and phenomenological waveforms of a different type. All waveforms considered describe equal mass systems with dimension-less spin magnitudes equal to 0.6. The noise-weighted overlap integral between numerical and phenomenological waveforms ranges between 0.93 and 0.98 for a wide span of mass values.

  8. Primary products and mechanistic considerations in alkane metathesis.

    Science.gov (United States)

    Basset, Jean Marie; Copéret, Christophe; Lefort, Laurent; Maunders, Barry M; Maury, Olivier; Le Roux, Erwan; Saggio, Guillaume; Soignier, Sophie; Soulivong, Daravong; Sunley, Glenn J; Taoufik, Mostafa; Thivolle-Cazat, Jean

    2005-06-22

    Alkane metathesis, a reaction catalyzed by the silica-supported tantalum hydride [(SiO)2Ta-H], 1, which transforms acyclic alkanes into their higher and lower homologues, was reported in 1997. New studies conducted in a continuous flow reactor in the case of propane indicate that, by varying the contact time, hydrogen and olefins are primary products. This crucial observation, as well as the known properties of tantalum alkyls to perform alpha-H or beta-H eliminations, supports the proposition of a new mechanism involving metallacyclobutane intermediates just like in olefin metathesis. The observed selectivities for linear and branched Cn+1 and Cn+2 products as well as the linear/branched ratio can be well-explained on the basis of the minimization of steric interactions between 1,2- or 1,3-substituents in the various tantallacyclobutane intermediates or during their formation. Hydrogen plays a specific role in the cleavage of metal alkyls to complete the catalytic cycle.

  9. Partial coalescence in oil-in-water emulsions

    NARCIS (Netherlands)

    Boode, K.

    1992-01-01

    The influence of crystals on the stability against partial coalescence at rest and during Couette flow was examined in emulsions of saturated triglycerides in SDS- or caseinate solutions and in natural cream. Partial coalescence was characterized by determining changes in globule size distribution

  10. Parameter estimation of gravitational wave compact binary coalescences

    Science.gov (United States)

    Haster, Carl-Johan; LIGO Scientific Collaboration Collaboration

    2017-01-01

    The first detections of gravitational waves from coalescing binary black holes have allowed unprecedented inference on the astrophysical parameters of such binaries. Given recent updates in detector capabilities, gravitational wave model templates and data analysis techniques, in this talk I will describe the prospects of parameter estimation of compact binary coalescences during the second observation run of the LIGO-Virgo collaboration.

  11. Dynamics of the evolving Bolthausen-Sznitman coalescent

    CERN Document Server

    Schweinsberg, Jason

    2011-01-01

    Consider a population of fixed size that evolves over time. At each time, the genealogical structure of the population can be described by a coalescent tree whose branches are traced back to the most recent common ancestor of the population. As time goes forward, the genealogy of the population evolves, leading to what is known as an evolving coalescent. We will study the evolving coalescent for populations whose genealogy can be described by the Bolthausen-Sznitman coalescent. We obtain the limiting behavior of the evolution of the time back to the most recent common ancestor and the total length of the branches in the tree. By similar methods, we also obtain a new result concerning the number of blocks in the Bolthausen-Sznitman coalescent.

  12. Satellite Formation during Coalescence of Unequal Size Drops

    KAUST Repository

    Zhang, F. H.

    2009-03-12

    The coalescence of a drop with a flat liquid surface pinches off a satellite from its top, in the well-known coalescence cascade, whereas the coalescence of two equally sized drops does not appear to leave such a satellite. Herein we perform experiments to identify the critical diameter ratio of two drops, above which a satellite is produced during their coalescence. We find that the critical parent ratio is as small as 1.55, but grows monotonically with the Ohnesorge number. The daughter size is typically about 50% of the mother drop. However, we have identified novel pinch-off dynamics close to the critical size ratio, where the satellite does not fully separate, but rather goes directly into a second stage of the coalescence cascade, thus generating a much smaller satellite droplet.

  13. Surfactant effect on drop coalescence and film drainage hydrodynamics

    Science.gov (United States)

    Weheliye, Weheliye; Chinaud, Maxime; Voulgaropoulos, Victor; Angeli, Panagiota

    2015-11-01

    Coalescence of a drop on an aqueous-organic interface is studied in two test geometries A rectangular acrylic vessel and a Hele-Shaw cell (two parallel plates placed 2mm apart) are investigated for the experiments. Time resolved Particle Image Velocimetry (PIV) measurements provide information on the hydrodynamics during the bouncing stage of the droplet and on the vortices generated at the bulk fluid after the droplet has coalesced. The velocity field inside the droplet during its coalescence is presented. By localizing the rupture point of the coalescence in the quasi two dimensional cell, the film drainage dynamics are discussed by acquiring its flow velocity by PIV measurements with a straddling camera. The effect of surface tension forces in the coalescence of the droplet is investigated by introducing surface active agents at various concentrations extending on both sides of the critical micelle concentration.

  14. Critical parameters for the partial coalescence of a droplet

    CERN Document Server

    Gilet, T; Lecomte, J P; Mulleners, K; Vandewalle, N

    2006-01-01

    The partial coalescence of a droplet onto a planar liquid/liquid interface is investigated theoretically by using a dimensional analysis. It mainly depends on the Bond number (gravity vs. surface tension), the Ohnesorge numbers (viscosity in both fluids in contact vs. surface tension) and the density relative difference. An experimental work on 2000 coalescence events is made in order to study the impact of viscosities and gravity on the coalescence process. Global quantities such as the available surface energy of the droplet has been measured during the coalescence. The surface energy is converted into kinetic energy at a constant rate that is independent of the coalescence outcome. The ratio between the daughter droplet size and the mother droplet size is investigated as a function of the dimensionless numbers. Theoretical models are proposed to fit experimental data. The asymmetrical behavior when liquids are inverted indicates that the viscous dissipation is different in both fluids. In the surrounding f...

  15. Synthesis of a tricyclic lactam via Beckmann rearrangement and ring-rearrangement metathesis as key steps.

    Science.gov (United States)

    Kotha, Sambasivarao; Ravikumar, Ongolu; Majhi, Jadab

    2015-01-01

    A tricyclic lactam is reported in a four step synthesis sequence via Beckmann rearrangement and ring-rearrangement metathesis as key steps. Here, we used a simple starting material such as dicyclopentadiene.

  16. Side-chain modification and "grafting onto" via olefin cross-metathesis.

    Science.gov (United States)

    de Espinosa, Lucas Montero; Kempe, Kristian; Schubert, Ulrich S; Hoogenboom, Richard; Meier, Michael A R

    2012-12-13

    Olefin cross-metathesis is introduced as a versatile polymer side-chain modification technique. The reaction of a poly(2-oxazoline) featuring terminal double bonds in the side chains with a variety of functional acrylates has been successfully performed in the presence of Hoveyda-Grubbs second-generation catalyst. Self-metathesis, which would lead to polymer-polymer coupling, can be avoided by using an excess of the cross-metathesis partner and a catalyst loading of 5 mol%. The results suggest that bulky acrylates reduce chain-chain coupling due to self-metathesis. Moreover, different functional groups such as alkyl chains, hydroxyl, and allyl acetate groups, as well as an oligomeric poly(ethylene glycol) and a perfluorinated alkyl chain have been grafted with quantitative conversions.

  17. The preparation of trisubstituted alkenyl nucleoside phosphonates under ultrasound-assisted olefin cross-metathesis.

    Science.gov (United States)

    Sari, Ozkan; Hamada, Manabu; Roy, Vincent; Nolan, Steven P; Agrofoglio, Luigi A

    2013-09-01

    Intermolecular ultrasound-assisted olefin cross-metathesis is reported. This approach allows an easy access to challenging trisubstituted alkenyl nucleoside phosphonates. Regioselective chemoenzymatic deacetylation and Mitsunobu coupling are also described.

  18. Efficient Removal of Ruthenium Byproducts from Olefin Metathesis Products by Simple Aqueous Extraction

    Science.gov (United States)

    Hong, Soon Hyeok; Grubbs, Robert H.

    2008-01-01

    Simple aqueous extraction removed ruthenium byproducts efficiently from ring-closing metathesis (RCM) reactions catalyzed by a PEG-supported N-heterocyclic carbene-based ruthenium complex. PMID:17428062

  19. Olefin metathesis for effective polymer healing via dynamic exchange of strong carbon-carbon bonds

    Energy Technology Data Exchange (ETDEWEB)

    Guan, Zhibin; Lu, Yixuan

    2015-09-15

    A method of preparing a malleable and/or self-healing polymeric or composite material is provided. The method includes providing a polymeric or composite material comprising at least one alkene-containing polymer, combining the polymer with at least one homogeneous or heterogeneous transition metal olefin metathesis catalyst to form a polymeric or composite material, and performing an olefin metathesis reaction on the polymer so as to form reversible carbon-carbon double bonds in the polymer. Also provided is a method of healing a fractured surface of a polymeric material. The method includes bringing a fractured surface of a first polymeric material into contact with a second polymeric material, and performing an olefin metathesis reaction in the presence of a transition metal olefin metathesis catalyst such that the first polymeric material forms reversible carbon-carbon double bonds with the second polymeric material. Compositions comprising malleable and/or self-healing polymeric or composite material are also provided.

  20. Design and synthesis of ruthenium indenylidene-based catalysts for olefin metathesis

    OpenAIRE

    Urbina-Blanco, César A

    2013-01-01

    As part of a European wide effort to develop metathesis catalysts for use in fine chemical and pharmaceutical compound synthesis, this study focuses on the design and synthesis of ruthenium based catalysts for olefin metathesis. The aim, of this work was simple: to develop new, more active, more stable, easy to synthesise and commercially viable Ruthenium based catalysts, as well trying to rationalize the effect of structural changes on reactivity. Two different approaches w...

  1. Concise Syntheses of Insect Pheromones Using Z-Selective Cross Metathesis**

    Science.gov (United States)

    Herbert, Myles B.; Marx, Vanessa M.; Pederson, Richard L.; Grubbs, Robert H.

    2013-01-01

    The shortest synthetic routes to nine cis-pheromones containing a variety of functionality, including an unconjugated (E,Z) diene, are reported. These lepidopteran pheromones are used extensively for pest control, and were easily prepared using ruthenium-based Z-selective cross metathesis, highlighting the advantages of this method over less efficient ways to form Z-olefins. Important insight into the mechanism of Z-selective metathesis was uncovered during experimentation and subsequently explored. PMID:23055437

  2. Macrocyclic olefin metathesis at high concentrations by using a phase-separation strategy.

    Science.gov (United States)

    Raymond, Michaël; Holtz-Mulholland, Michael; Collins, Shawn K

    2014-09-26

    Macrocyclic olefin metathesis has seen advances in the areas of stereochemistry, chemoselectivity, and catalyst stability, but strategies aimed at controlling dilution effects in macrocyclizations are rare. Herein, a protocol to promote macrocyclic olefin metathesis, one of the most common synthetic tools used to prepare macrocycles, at relatively high concentrations (up to 60 mM) is described by exploitation of a phase-separation strategy. A variety of macrocyclic skeletons could be prepared having either different alkyl, aryl, or amino acids spacers.

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

    Science.gov (United States)

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

    2016-02-19

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

  4. Towards New Generations of Metathesis Metal-Carbene Pre-catalysts

    Science.gov (United States)

    Allaert, Bart; Dieltiens, Nicolai; Stevens, Chris; Drozdzak, Renata; Dragutan, Ileana; Dragutan, Valerian; Verpoort, Francis

    : A short general introduction combined with some historical milestones in the field of olefin metathesis is presented followed by an overview of recent representatives of metal carbene initiators. This paper attempts to relief the many superb contributions and overwhelming work invested in intelligent design and innovative synthesis in this area. Despites of recent advances there is still a great interest in the generation of new, better performing, and more environment friendly metathesis.

  5. Synthesis of alkenyl boronates from allyl-substituted aromatics using an olefin cross-metathesis protocol.

    Science.gov (United States)

    Hemelaere, Rémy; Carreaux, François; Carboni, Bertrand

    2013-07-01

    An efficient synthesis of 3-aryl-1-propenyl boronates from pinacol vinyl boronic ester and allyl-substituted aromatics by cross metathesis is reported. Although the allylbenzene derivatives are prone to isomerization reaction under metathesis conditions, we found that some ruthenium catalysts are effective for this methodology. This strategy thus provides an interesting alternative approach to alkyne hydroboration, leading to the preparation of unknown compounds. Moreover, the boron substituent can be replaced by various functional groups in good yields.

  6. Olefin Metathesis Reaction in Water and in Air Improved by Supramolecular Additives.

    Science.gov (United States)

    Tomasek, Jasmine; Seßler, Miriam; Gröger, Harald; Schatz, Jürgen

    2015-10-21

    A range of water-immiscible commercially available Grubbs-type precatalysts can be used in ring-closing olefin metathesis reaction in high yields. The synthetic transformation is possible in pure water under ambient conditions. Sulfocalixarenes can help to boost the reactivity of the metathesis reaction by catalyst activation, improved mass transfer, and solubility of reactants in the aqueous reaction media. Additionally, the use of supramolecular additives allows lower catalyst loadings, but still high activity in pure water under aerobic conditions.

  7. Protonolysis of a Ruthenium-Carbene Bond and Applications in Olefin Metathesis

    Science.gov (United States)

    Keitz, Benjamin K.; Bouffard, Jean; Bertrand, Guy; Grubbs, Robert H.

    2011-01-01

    The synthesis of a ruthenium complex containing an N-heterocylic carbene (NHC) and a mesoionic carbene (MIC) is described wherein addition of a Brønsted acid results in protonolysis of the Ru-MIC bond to generate an extremely active metathesis catalyst. Mechanistic studies implicate a rate-determining protonation step to generate the metathesis active species. The NHC/MIC catalyst was found to have activity exceeding current commercial ruthenium catalysts. PMID:21574621

  8. Supported ruthenium-carbene catalyst on ionic magnetic nanoparticles for olefin metathesis.

    Science.gov (United States)

    Chen, Shu-Wei; Zhang, Zhi-Cheng; Ma, Miaofeng; Zhong, Chong-Min; Lee, Sang-gi

    2014-10-01

    The Grubbs-Hoveyda ruthenium-carbene complex has been covalently immobilized on ionic magnetic nanoparticles utilizing an imidazolium salt linker. The supported catalyst exhibited excellent catalytic activity for ring-closing metathesis (RCM) and cross-metathesis (CM) in the presence of less than 1 mol % of ruthenium. The catalysts can easily be recovered magnetically and reused up to seven times with minimal leaching of ruthenium species.

  9. Alkene Chemoselectivity in Ruthenium-Catalyzed Z-Selective Olefin Metathesis

    Science.gov (United States)

    Cannon, Jeffrey S.

    2013-01-01

    Chelated ruthenium catalysts have achieved highly chemoselective olefin metathesis reactions. Terminal and internal Z olefins were selectively reacted in the presence of internal E olefins. Products were produced in good yield and high stereoselectivity for formation of a new Z olefin. No products of metathesis with the internal E olefin were observed. Chemoselectivity for terminal olefins was also observed over both sterically hindered and electronically deactivated alkenes. PMID:23832646

  10. Species tree inference by minimizing deep coalescences.

    Directory of Open Access Journals (Sweden)

    Cuong Than

    2009-09-01

    Full Text Available In a 1997 seminal paper, W. Maddison proposed minimizing deep coalescences, or MDC, as an optimization criterion for inferring the species tree from a set of incongruent gene trees, assuming the incongruence is exclusively due to lineage sorting. In a subsequent paper, Maddison and Knowles provided and implemented a search heuristic for optimizing the MDC criterion, given a set of gene trees. However, the heuristic is not guaranteed to compute optimal solutions, and its hill-climbing search makes it slow in practice. In this paper, we provide two exact solutions to the problem of inferring the species tree from a set of gene trees under the MDC criterion. In other words, our solutions are guaranteed to find the tree that minimizes the total number of deep coalescences from a set of gene trees. One solution is based on a novel integer linear programming (ILP formulation, and another is based on a simple dynamic programming (DP approach. Powerful ILP solvers, such as CPLEX, make the first solution appealing, particularly for very large-scale instances of the problem, whereas the DP-based solution eliminates dependence on proprietary tools, and its simplicity makes it easy to integrate with other genomic events that may cause gene tree incongruence. Using the exact solutions, we analyze a data set of 106 loci from eight yeast species, a data set of 268 loci from eight Apicomplexan species, and several simulated data sets. We show that the MDC criterion provides very accurate estimates of the species tree topologies, and that our solutions are very fast, thus allowing for the accurate analysis of genome-scale data sets. Further, the efficiency of the solutions allow for quick exploration of sub-optimal solutions, which is important for a parsimony-based criterion such as MDC, as we show. We show that searching for the species tree in the compatibility graph of the clusters induced by the gene trees may be sufficient in practice, a finding that helps

  11. Z-Selective olefin metathesis on peptides: investigation of side-chain influence, preorganization, and guidelines in substrate selection.

    Science.gov (United States)

    Mangold, Shane L; O'Leary, Daniel J; Grubbs, Robert H

    2014-09-01

    Olefin metathesis has emerged as a promising strategy for modulating the stability and activity of biologically relevant compounds; however, the ability to control olefin geometry in the product remains a challenge. Recent advances in the design of cyclometalated ruthenium catalysts has led to new strategies for achieving such control with high fidelity and Z selectivity, but the scope and limitations of these catalysts on substrates bearing multiple functionalities, including peptides, remained unexplored. Herein, we report an assessment of various factors that contribute to both productive and nonproductive Z-selective metathesis on peptides. The influence of sterics, side-chain identity, and preorganization through peptide secondary structure are explored by homodimerization, cross metathesis, and ring-closing metathesis. Our results indicate that the amino acid side chain and identity of the olefin profoundly influence the activity of cyclometalated ruthenium catalysts in Z-selective metathesis. The criteria set forth for achieving high conversion and Z selectivity are highlighted by cross metathesis and ring-closing metathesis on diverse peptide substrates. The principles outlined in this report are important not only for expanding the scope of Z-selective olefin metathesis to peptides but also for applying stereoselective olefin metathesis in general synthetic endeavors.

  12. Z-Selective Olefin Metathesis on Peptides: Investigation of Side-Chain Influence, Preorganization, and Guidelines in Substrate Selection

    Science.gov (United States)

    2015-01-01

    Olefin metathesis has emerged as a promising strategy for modulating the stability and activity of biologically relevant compounds; however, the ability to control olefin geometry in the product remains a challenge. Recent advances in the design of cyclometalated ruthenium catalysts has led to new strategies for achieving such control with high fidelity and Z selectivity, but the scope and limitations of these catalysts on substrates bearing multiple functionalities, including peptides, remained unexplored. Herein, we report an assessment of various factors that contribute to both productive and nonproductive Z-selective metathesis on peptides. The influence of sterics, side-chain identity, and preorganization through peptide secondary structure are explored by homodimerization, cross metathesis, and ring-closing metathesis. Our results indicate that the amino acid side chain and identity of the olefin profoundly influence the activity of cyclometalated ruthenium catalysts in Z-selective metathesis. The criteria set forth for achieving high conversion and Z selectivity are highlighted by cross metathesis and ring-closing metathesis on diverse peptide substrates. The principles outlined in this report are important not only for expanding the scope of Z-selective olefin metathesis to peptides but also for applying stereoselective olefin metathesis in general synthetic endeavors. PMID:25102124

  13. Synthesis of skeletally diverse alkaloid-like molecules: exploitation of metathesis substrates assembled from triplets of building blocks

    Directory of Open Access Journals (Sweden)

    Sushil K. Maurya

    2013-04-01

    Full Text Available A range of metathesis substrates was assembled from triplets of unsaturated building blocks. The approach involved the iterative attachment of a propagating and a terminating building block to a fluorous-tagged initiating building block. Metathesis cascade chemistry was used to “reprogram” the molecular scaffolds. Remarkably, in one case, a cyclopropanation reaction competed with the expected metathesis cascade process. Finally, it was demonstrated that the metathesis products could be derivatised to yield the final products. At each stage, purification was facilitated by the presence of a fluorous-tagged protecting group.

  14. Sarcomeric Pattern Formation by Actin Cluster Coalescence

    Science.gov (United States)

    Friedrich, Benjamin M.; Fischer-Friedrich, Elisabeth; Gov, Nir S.; Safran, Samuel A.

    2012-01-01

    Contractile function of striated muscle cells depends crucially on the almost crystalline order of actin and myosin filaments in myofibrils, but the physical mechanisms that lead to myofibril assembly remains ill-defined. Passive diffusive sorting of actin filaments into sarcomeric order is kinetically impossible, suggesting a pivotal role of active processes in sarcomeric pattern formation. Using a one-dimensional computational model of an initially unstriated actin bundle, we show that actin filament treadmilling in the presence of processive plus-end crosslinking provides a simple and robust mechanism for the polarity sorting of actin filaments as well as for the correct localization of myosin filaments. We propose that the coalescence of crosslinked actin clusters could be key for sarcomeric pattern formation. In our simulations, sarcomere spacing is set by filament length prompting tight length control already at early stages of pattern formation. The proposed mechanism could be generic and apply both to premyofibrils and nascent myofibrils in developing muscle cells as well as possibly to striated stress-fibers in non-muscle cells. PMID:22685394

  15. Sarcomeric pattern formation by actin cluster coalescence.

    Directory of Open Access Journals (Sweden)

    Benjamin M Friedrich

    Full Text Available Contractile function of striated muscle cells depends crucially on the almost crystalline order of actin and myosin filaments in myofibrils, but the physical mechanisms that lead to myofibril assembly remains ill-defined. Passive diffusive sorting of actin filaments into sarcomeric order is kinetically impossible, suggesting a pivotal role of active processes in sarcomeric pattern formation. Using a one-dimensional computational model of an initially unstriated actin bundle, we show that actin filament treadmilling in the presence of processive plus-end crosslinking provides a simple and robust mechanism for the polarity sorting of actin filaments as well as for the correct localization of myosin filaments. We propose that the coalescence of crosslinked actin clusters could be key for sarcomeric pattern formation. In our simulations, sarcomere spacing is set by filament length prompting tight length control already at early stages of pattern formation. The proposed mechanism could be generic and apply both to premyofibrils and nascent myofibrils in developing muscle cells as well as possibly to striated stress-fibers in non-muscle cells.

  16. High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis.

    Science.gov (United States)

    Röttger, Max; Domenech, Trystan; van der Weegen, Rob; Breuillac, Antoine; Nicolaÿ, Renaud; Leibler, Ludwik

    2017-04-07

    Windmills, cars, and dental restoration demand polymer materials and composites that are easy to process, assemble, and recycle while exhibiting outstanding mechanical, thermal, and chemical resistance. Vitrimers, which are polymer networks able to shuffle chemical bonds through exchange reactions, could address these demands if they were prepared from existing plastics and processed with fast production rates and current equipment. We report the metathesis of dioxaborolanes, which is rapid and thermally robust, and use it to prepare vitrimers from polymers as different as poly(methyl methacrylate), polystyrene, and high-density polyethylene that, although permanently cross-linked, can be processed multiple times by means of extrusion or injection molding. They show superior chemical resistance and dimensional stability and can be efficiently assembled. The strategy is applicable to polymers with backbones made of carbon-carbon single bonds.

  17. Nanoporous poly(lactide) by olefin metathesis degradation.

    Science.gov (United States)

    Bertrand, Arthur; Hillmyer, Marc A

    2013-07-31

    We describe an approach to ordered nanoporous poly(lactide) that relies on self-assembly of poly(butadiene)-poly(lactide) (PB-PLA) diblock copolymers followed by selective degradation of PB using olefin metathesis. The block copolymers were obtained by a combination of anionic and ring-opening transesterification polymerizations. The molar mass of each block was tailored to target materials with either a lamellar or cylindrical microphase-separated morphology. Orientation of these nanoscale domains was induced in thin films and monolithic samples through solvent annealing and mechanical deformation, respectively. Selective degradation of PB was achieved by immersing the samples in a solution of Grubbs first-generation catalyst in cyclohexane, a nonsolvent for PLA. Successful elimination of PB was confirmed by size-exclusion chromatography and (1)H NMR spectroscopy. Direct imaging of the resulting nanoporous PLA was obtained by scanning electron microscopy.

  18. Phosphine-Free EWG-Activated Ruthenium Olefin Metathesis Catalysts

    Science.gov (United States)

    Grela, Karol; Szadkowska, Anna; Michrowska, Anna; Bieniek, Michal; Sashuk, Volodymyr

    Hoveyda-Grubbs catalyst has been successfully fine-tuned by us in order to increase its activity and applicability by the introduction of electron-withdrawing groups (EWGs) to diminish donor properties of the oxygen atom. As a result, the stable and easily accessible nitro-substituted Hoveyda-Grubbs catalyst has found a number of successful applications in various research and industrial laboratories. Some other EWG-activated Hoveyda-type catalysts are commercially available. The results described herewith demonstrate that the activity of ruthenium (Ru) metathesis catalysts can be enhanced by introduction of EWGs without detriment to catalysts stability. Equally noteworthy is the observation that different Ru catalysts turned out to be optimal for different applications. This shows that no single catalyst outperforms all others in all possible applications.

  19. High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis

    Science.gov (United States)

    Röttger, Max; Domenech, Trystan; van der Weegen, Rob; Breuillac, Antoine; Nicolaÿ, Renaud; Leibler, Ludwik

    2017-04-01

    Windmills, cars, and dental restoration demand polymer materials and composites that are easy to process, assemble, and recycle while exhibiting outstanding mechanical, thermal, and chemical resistance. Vitrimers, which are polymer networks able to shuffle chemical bonds through exchange reactions, could address these demands if they were prepared from existing plastics and processed with fast production rates and current equipment. We report the metathesis of dioxaborolanes, which is rapid and thermally robust, and use it to prepare vitrimers from polymers as different as poly(methyl methacrylate), polystyrene, and high-density polyethylene that, although permanently cross-linked, can be processed multiple times by means of extrusion or injection molding. They show superior chemical resistance and dimensional stability and can be efficiently assembled. The strategy is applicable to polymers with backbones made of carbon-carbon single bonds.

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

    Directory of Open Access Journals (Sweden)

    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.

  1. 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.

  2. 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.

  3. Directed evolution of artificial metalloenzymes for in vivo metathesis

    Science.gov (United States)

    Jeschek, Markus; Reuter, Raphael; Heinisch, Tillmann; Trindler, Christian; Klehr, Juliane; Panke, Sven; Ward, Thomas R.

    2016-09-01

    The field of biocatalysis has advanced from harnessing natural enzymes to using directed evolution to obtain new biocatalysts with tailor-made functions. Several tools have recently been developed to expand the natural enzymatic repertoire with abiotic reactions. For example, artificial metalloenzymes, which combine the versatile reaction scope of transition metals with the beneficial catalytic features of enzymes, offer an attractive means to engineer new reactions. Three complementary strategies exist: repurposing natural metalloenzymes for abiotic transformations; in silico metalloenzyme (re-)design; and incorporation of abiotic cofactors into proteins. The third strategy offers the opportunity to design a wide variety of artificial metalloenzymes for non-natural reactions. However, many metal cofactors are inhibited by cellular components and therefore require purification of the scaffold protein. This limits the throughput of genetic optimization schemes applied to artificial metalloenzymes and their applicability in vivo to expand natural metabolism. Here we report the compartmentalization and in vivo evolution of an artificial metalloenzyme for olefin metathesis, which represents an archetypal organometallic reaction without equivalent in nature. Building on previous work on an artificial metallohydrolase, we exploit the periplasm of Escherichia coli as a reaction compartment for the ‘metathase’ because it offers an auspicious environment for artificial metalloenzymes, mainly owing to low concentrations of inhibitors such as glutathione, which has recently been identified as a major inhibitor. This strategy facilitated the assembly of a functional metathase in vivo and its directed evolution with substantially increased throughput compared to conventional approaches that rely on purified protein variants. The evolved metathase compares favourably with commercial catalysts, shows activity for different metathesis substrates and can be further evolved in

  4. Dropwise condensation: the deposition growth and coalescence of fluid droplets

    Science.gov (United States)

    Meakin, P.

    1992-01-01

    The dropwise condensation of liquid droplets can frequently be described in terms of a four-stage scenario: (1) Nucleation and growth. (2) Growth and coalescence. (3) Growth and coalescence with renucleation in exposed regions. (4) Growth, coalescence and renucleation with removal of larger droplets. All four stages have been simulated using simple computer models and the results of these models can be described in terms of simple scaling theories. These models and scaling theories can be applied to the condensation of D dimensional droplet on d dimensional substrates where D and d can take on essentially any values with D >= d including non-integer (fractal) values.

  5. Symmetric and Asymmetric Coalescence of Drops on a Substrate

    CERN Document Server

    Hernandez-Sanchez, J F; Eddi, A; Snoeijer, J H

    2012-01-01

    The coalescence of viscous drops on a substrate is studied experimentally and theoretically. We consider cases where the drops can have different contact angles, leading to a very asymmetric coalescence process. Side view experiments reveal that the "bridge" connecting the drops evolves with self-similar dynamics, providing a new perspective on the coalescence of sessile drops. We show that the universal shape of the bridge is accurately described by similarity solutions of the one-dimensional lubrication equation. Our theory predicts a bridge that grows linearly in time and stresses the strong dependence on the contact angles. Without any adjustable parameters, we find quantitative agreement with all experimental observations.

  6. Coalescent: an open-source and scalable framework for exact calculations in coalescent theory

    Directory of Open Access Journals (Sweden)

    Tewari Susanta

    2012-10-01

    Full Text Available Abstract Background Currently, there is no open-source, cross-platform and scalable framework for coalescent analysis in population genetics. There is no scalable GUI based user application either. Such a framework and application would not only drive the creation of more complex and realistic models but also make them truly accessible. Results As a first attempt, we built a framework and user application for the domain of exact calculations in coalescent analysis. The framework provides an API with the concepts of model, data, statistic, phylogeny, gene tree and recursion. Infinite-alleles and infinite-sites models are considered. It defines pluggable computations such as counting and listing all the ancestral configurations and genealogies and computing the exact probability of data. It can visualize a gene tree, trace and visualize the internals of the recursion algorithm for further improvement and attach dynamically a number of output processors. The user application defines jobs in a plug-in like manner so that they can be activated, deactivated, installed or uninstalled on demand. Multiple jobs can be run and their inputs edited. Job inputs are persisted across restarts and running jobs can be cancelled where applicable. Conclusions Coalescent theory plays an increasingly important role in analysing molecular population genetic data. Models involved are mathematically difficult and computationally challenging. An open-source, scalable framework that lets users immediately take advantage of the progress made by others will enable exploration of yet more difficult and realistic models. As models become more complex and mathematically less tractable, the need for an integrated computational approach is obvious. Object oriented designs, though has upfront costs, are practical now and can provide such an integrated approach.

  7. Diversity-oriented approach to macrocyclic cyclophane derivatives by Suzuki-Miyaura cross-coupling and olefin metathesis as key steps.

    Science.gov (United States)

    Kotha, Sambasivarao; Chavan, Arjun S; Shaikh, Mobin

    2012-01-01

    Palladium-catalyzed Suzuki-Miyaura (SM) cross-coupling reaction with allylboronic acid pinacol ester and titanium assisted cross-metathesis (CM)/ring-closing metathesis (RCM) cascade has been used to synthesize macrocyclic cyclophane derivatives.

  8. Partial deletion 11q

    DEFF Research Database (Denmark)

    Hertz, Jens Michael; Tommerup, N; Sørensen, F B;

    1995-01-01

    We describe the cytogenetic findings and the dysmorphic features in a stillborn girl with a large de novo terminal deletion of the long arm of chromosome 11. The karyotype was 46,XX,del(11)(q21qter). By reviewing previous reports of deletion 11q, we found that cleft lip and palate are most...

  9. Schizophrenia and chromosomal deletions

    Energy Technology Data Exchange (ETDEWEB)

    Lindsay, E.A.; Baldini, A. [Baylor College of Medicine, Houston, TX (United States); Morris, M. A. [Univ. of Geneva School of Medicine, NY (United States)] [and others

    1995-06-01

    Recent genetic linkage analysis studies have suggested the presence of a schizophrenia locus on the chromosomal region 22q11-q13. Schizophrenia has also been frequently observed in patients affected with velo-cardio-facial syndrome (VCFS), a disorder frequently associated with deletions within 22q11.1. It has been hypothesized that psychosis in VCFS may be due to deletion of the catechol-o-methyl transferase gene. Prompted by these observations, we screened for 22q11 deletions in a population of 100 schizophrenics selected from the Maryland Epidemiological Sample. Our results show that there are schizophrenic patients carrying a deletion of 22q11.1 and a mild VCFS phenotype that might remain unrecognized. These findings should encourage a search for a schizophrenia-susceptibility gene within the deleted region and alert those in clinical practice to the possible presence of a mild VCFS phenotype associated with schizophrenia. 9 refs.

  10. Quantum deletion is possible

    CERN Document Server

    Elizalde, E

    2000-01-01

    A deleting operation is introduced which differs from the commonly used {\\it controlled-not} (C-not) conditional logical operation $-$to flip the (classical or quantum) state of the last copy in a chain in a deletion process. It is completely reversible, in the classical case, possessing a most natural cloning operation counterpart. We call this deleting procedure R-deletion since, in a way, it can be viewed as a `randomization' of the standard C-not operator. It is a nonlinear operation and has the remarkable property of avoiding in a simple manner the `impossibility of deletion of a quantum state' principle, put forward by Pati and Braunstein recently \\cite{pbn1}.

  11. Genealogies of regular exchangeable coalescents with applications to sampling

    CERN Document Server

    Limic, Vlada

    2010-01-01

    This article considers a model of genealogy corresponding to a regular exchangeable coalescent (also known as Xi-coalescent) started from a large finite configuration, and undergoing neutral mutations. Asymptotic expressions for the number of active lineages were obtained by the author in a previous work. Analogous results for the number of active mutation-free lineages and the combined lineage lengths are derived using the same martingale-based technique. They are given in terms of convergence in probability, while extensions to convergence in moments and convergence almost surely are discussed. The above mentioned results have direct consequences on the sampling theory in the Xi-coalescent setting. In particular, the regular Xi-coalescents that come down from infinity (i.e., with locally finite genealogies), have an asymptotically equal number of families under the corresponding infinite alleles and infinite sites models. In special cases, quantitative asymptotic formulae for the number of families that con...

  12. Coalescence of bubbles and drops in an outer fluid

    CERN Document Server

    Paulsen, Joseph D; Kannan, Anerudh; Burton, Justin C; Nagel, Sidney R

    2014-01-01

    When two liquid drops touch, a microscopic connecting liquid bridge forms and rapidly grows as the two drops merge into one. Whereas coalescence has been thoroughly studied when drops coalesce in vacuum or air, many important situations involve coalescence in a dense surrounding fluid, such as oil coalescence in brine. Here we study the merging of gas bubbles and liquid drops in an external fluid. Our data indicate that the flows occur over much larger length scales in the outer fluid than inside the drops themselves. Thus we find that the asymptotic early regime is always dominated by the viscosity of the drops, independent of the external fluid. A phase diagram showing the crossovers into the different possible late-time dynamics identifies a dimensionless number that signifies when the external viscosity can be important.

  13. Analysis of Void Growth and Coalescence in Porous Polymer Materials. Coalescence in Polymer Materials

    Directory of Open Access Journals (Sweden)

    S. A. Reffas

    2013-06-01

    Full Text Available The use of polymeric materials in engineering applications is growing more and more all over the world. This issue requests new methodologies of analysis in order to assess the material’s capability to withstand complex loads. The use of polyacetal in engineering applications has increased rapidly in the last decade. In order to evaluate the behavior, the damage and coalescence of this type of polymer, a numerical method based on damage which occurs following several stages (nucleation of cavities, their growth and coalescence in more advanced stages of deformation is proposed in this work. A particular attention is given on the stress-strain and the volumetric strain evolution under different triaxiality and for three initial void shapes. Its application to polyacetal allows approving this approach for technical polymers. Finally, this method allow us to compare the obtained results of basic calculations at different triaxiality and to discuss their possible influence on the initial size and the geometrical shape of the porosity on the material failure.

  14. Amphiphilic Cellulose Ethers Designed for Amorphous Solid Dispersion via Olefin Cross-Metathesis.

    Science.gov (United States)

    Dong, Yifan; Mosquera-Giraldo, Laura I; Taylor, Lynne S; Edgar, Kevin J

    2016-02-01

    The design of cellulose ether-based amphiphiles has been difficult and limited because of the harsh conditions typically required for appending ether moieties to cellulose. Olefin cross-metathesis recently has been shown to be a valuable approach for appending a variety of functional groups to cellulose ethers and esters, provided that an olefin handle for metathesis can be attached. This synthetic pathway gives access to these functional derivatives under very mild conditions and at high efficiency. Modification of ethyl cellulose by metathesis to prepare useful derivatives, for example, for solubility and bioavailability enhancement of drugs by amorphous solid dispersion (ASD), has been limited by the low DS(OH) of commercial ethyl cellulose derivatives. This is problematic because ethyl cellulose is otherwise a very attractive substrate for synthesis of amphiphilic derivatives by olefin metathesis. Herein we explore two methods for opening up this design space for ether-based amphiphiles, for example, permitting synthesis of more hydrophilic derivatives. One approach is to start with the more hydrophilic commercial methyl cellulose, which contains much higher DS(OH) and therefore is better suited for introduction of high DS of olefin metathesis "handles". In another approach, we explored a homogeneous one-pot synthesis methodology from cellulose, where controlled DS of ethyl groups was introduced at the same time as the ω-unsaturated alkyl groups, thereby permitting complete control of DS(OH), DS(Et), and ultimately DS of the functional group added by metathesis. We describe the functionalized derivatives available by these successful approaches. In addition, we explore new methods for reduction of the unsaturation in initial metathesis products to provide robust methods for enhancing product stability against further radical-catalyzed reactions. We demonstrate initial evidence that the products show strong promise as amphiphilic matrix polymers for amorphous

  15. Nobel Chemistry in the Laboratory: Synthesis of a Ruthenium Catalyst for Ring-Closing Olefin Metathesis--An Experiment for the Advanced Inorganic or Organic Laboratory

    Science.gov (United States)

    Greco, George E.

    2007-01-01

    An experiment for the upper-level undergraduate laboratory is described in which students synthesize a ruthenium olefin metathesis catalyst, then use the catalyst to carry out the ring-closing metathesis of diethyl diallylmalonate. The olefin metathesis reaction was the subject of the 2005 Nobel Prize in chemistry. The catalyst chosen for this…

  16. Study towards diversity oriented synthesis of optically active substituted cyclopentane fused carbocyclic and oxacyclic medium-sized rings: Competition between Grubbs-II catalyzed ring closing olefin metathesis and ring closing carbonyl-olefin metathesis

    Indian Academy of Sciences (India)

    P CHAKRABORTY; S C ROY

    2016-12-01

    A study towards diversity-oriented synthesis of optically active cyclopentane fused bicyclic frameworks has been accomplished. The common intermediate was prepared from commercially available starting material (S)-carvone. The observations on competition between Grubbs-II catalyzed ring closing metathesis (RCM) and ring closing carbonyl-olefin metathesis (RCCOM) were the key features of the study.

  17. NFKBIA Deletion in Glioblastomas

    Science.gov (United States)

    Bredel, Markus; Scholtens, Denise M.; Yadav, Ajay K.; Alvarez, Angel A.; Renfrow, Jaclyn J.; Chandler, James P.; Yu, Irene L.Y.; Carro, Maria S.; Dai, Fangping; Tagge, Michael J.; Ferrarese, Roberto; Bredel, Claudia; Phillips, Heidi S.; Lukac, Paul J.; Robe, Pierre A.; Weyerbrock, Astrid; Vogel, Hannes; Dubner, Steven; Mobley, Bret; He, Xiaolin; Scheck, Adrienne C.; Sikic, Branimir I.; Aldape, Kenneth D.; Chakravarti, Arnab; Harsh, Griffith R.

    2013-01-01

    BACKGROUND Amplification and activating mutations of the epidermal growth factor receptor (EGFR) oncogene are molecular hallmarks of glioblastomas. We hypothesized that deletion of NFKBIA (encoding nuclear factor of κ-light polypeptide gene enhancer in B-cells inhibitor-α), an inhibitor of the EGFR-signaling pathway, promotes tumorigenesis in glioblastomas that do not have alterations of EGFR. METHODS We analyzed 790 human glioblastomas for deletions, mutations, or expression of NFKBIA and EGFR. We studied the tumor-suppressor activity of NFKBIA in tumor-cell culture. We compared the molecular results with the outcome of glioblastoma in 570 affected persons. RESULTS NFKBIA is often deleted but not mutated in glioblastomas; most deletions occur in nonclassical subtypes of the disease. Deletion of NFKBIA and amplification of EGFR show a pattern of mutual exclusivity. Restoration of the expression of NFKBIA attenuated the malignant phenotype and increased the vulnerability to chemotherapy of cells cultured from tumors with NFKBIA deletion; it also reduced the viability of cells with EGFR amplification but not of cells with normal gene dosages of both NFKBIA and EGFR. Deletion and low expression of NFKBIA were associated with unfavorable outcomes. Patients who had tumors with NFKBIA deletion had outcomes that were similar to those in patients with tumors harboring EGFR amplification. These outcomes were poor as compared with the outcomes in patients with tumors that had normal gene dosages of NFKBIA and EGFR. A two-gene model that was based on expression of NFKBIA and O6-methylguanine DNA methyltransferase was strongly associated with the clinical course of the disease. CONCLUSIONS Deletion of NFKBIA has an effect that is similar to the effect of EGFR amplification in the pathogenesis of glioblastoma and is associated with comparatively short survival. PMID:21175304

  18. Asymmetric allylic alkylation in combination with ring-closing metathesis for the preparation of chiral N-heterocycles

    NARCIS (Netherlands)

    Teichert, Johannes F.; Zhang, Suyan; Zijl, Anthoni W. van; Slaa, Jan Willem; Minnaard, Adriaan J.; Feringa, Bernard

    2010-01-01

    Asymmetric copper-catalyzed allylic substitution with methylmagnesium bromide is employed in combination with ring-closing olefin metathesis or ene-yne metathesis to achieve the synthesis of chiral, unsaturated nitrogen heterocycles. The resulting six- to eight-membered chiral heterocycles are acces

  19. Straightforward synthesis of alpha,beta-unsaturated thioesters via ruthenium-catalyzed olefin cross-metathesis with thioacrylate

    NARCIS (Netherlands)

    van Zijl, Anthoni W.; Minnaard, Adriaan J.; Feringa, Ben L.

    2008-01-01

    The cross-metathesis reaction of S-ethyl thioacrylate with a variety of olefins is effectively catalyzed by using a ruthenium benzylidene olefin metathesis catalyst. This reaction provides a convenient and versatile route to substituted alpha,beta-unsaturated thioesters, key building blocks in organ

  20. Organometallic Catalysis in Diene and Cyclo-olefin Polymerisation Processes. II. The Metathesis Reaction in Polymer Chemistry

    Science.gov (United States)

    Dolgoplosk, B. A.; Korshak, Yu V.

    1984-01-01

    The development of ideas concerning the mechanism of the metathesis reaction and its employment in polymer chemistry are examined. The possible applications of the metathesis reaction in the synthesis of polymers by the polymerisation of cycloolefins and cyclodienes with ring opening and via the degradation of high-molecular-weight rubbers and their modification are discussed. The bibliography includes 160 references.

  1. New library of aminosulfonyl-tagged Hoveyda–Grubbs type complexes: Synthesis, kinetic studies and activity in olefin metathesis transformations

    Directory of Open Access Journals (Sweden)

    Etienne Borré

    2010-12-01

    Full Text Available Seven novel Hoveyda–Grubbs precatalysts bearing an aminosulfonyl function are reported. Kinetic studies indicate an activity enhancement compared to Hoveyda’s precatalyst. A selection of these catalysts was investigated with various substrates in ring-closing metathesis of dienes or enynes and cross metathesis. The results demonstrate that these catalysts show a good tolerance to various chemical functions.

  2. New library of aminosulfonyl-tagged Hoveyda–Grubbs type complexes: Synthesis, kinetic studies and activity in olefin metathesis transformations

    Science.gov (United States)

    Borré, Etienne; Caijo, Frederic

    2010-01-01

    Summary Seven novel Hoveyda–Grubbs precatalysts bearing an aminosulfonyl function are reported. Kinetic studies indicate an activity enhancement compared to Hoveyda’s precatalyst. A selection of these catalysts was investigated with various substrates in ring-closing metathesis of dienes or enynes and cross metathesis. The results demonstrate that these catalysts show a good tolerance to various chemical functions. PMID:21165173

  3. Kinetically E-selective macrocyclic ring-closing metathesis

    Science.gov (United States)

    Shen, Xiao; Nguyen, Thach T.; Koh, Ming Joo; Xu, Dongmin; Speed, Alexander W. H.; Schrock, Richard R.; Hoveyda, Amir H.

    2017-01-01

    Macrocyclic compounds are central to the development of new drugs, but preparing them can be challenging because of the energy barrier that must be surmounted in order to bring together and fuse the two ends of an acyclic precursor such as an alkene (also known as an olefin). To this end, the catalytic process known as ring-closing metathesis (RCM) has allowed access to countless biologically active macrocyclic organic molecules, even for large-scale production. Stereoselectivity is often critical in such cases: the potency of a macrocyclic compound can depend on the stereochemistry of its alkene; alternatively, one isomer of the compound can be subjected to stereoselective modification (such as dihydroxylation). Kinetically controlled Z-selective RCM reactions have been reported, but the only available metathesis approach for accessing macrocyclic E-olefins entails selective removal of the Z-component of a stereoisomeric mixture by ethenolysis, sacrificing substantial quantities of material if E/Z ratios are near unity. Use of ethylene can also cause adventitious olefin isomerization—a particularly serious problem when the E-alkene is energetically less favoured. Here, we show that dienes containing an E-alkenyl–B(pinacolato) group, widely used in catalytic cross-coupling, possess the requisite electronic and steric attributes to allow them to be converted stereoselectively to E-macrocyclic alkenes. The reaction is promoted by a molybdenum monoaryloxide pyrrolide complex and affords products at a yield of up to 73 per cent and an E/Z ratio greater than 98/2. We highlight the utility of the approach by preparing recifeiolide (a 12-membered-ring antibiotic) and pacritinib (an 18-membered-ring enzyme inhibitor), the Z-isomer of which is less potent than the E-isomer. Notably, the 18-membered-ring moiety of pacritinib—a potent anti-cancer agent that is in advanced clinical trials for treating lymphoma and myelofibrosis—was prepared by RCM carried out at a

  4. Coalescence and noncoalescence of sessile drops: impact of surface forces.

    Science.gov (United States)

    Karpitschka, Stefan; Hanske, Christoph; Fery, Andreas; Riegler, Hans

    2014-06-17

    Due to capillarity, sessile droplets of identical liquids will instantaneously fuse when they come in contact at their three-phase lines. However, with drops of different, completely miscible liquids, instantaneous coalescence can be suppressed. Instead, the drops remain in a state of noncoalescence for some time, with the two drop bodies connected only by a thin neck. The reason for this noncoalescence is the surface tension difference, Δγ, between the liquids. If Δγ is sufficiently large, then it induces a sufficiently strong Marangoni flow, which keeps the main drop bodies temporarily separated. Studies with spreading drops have revealed that the boundary between instantaneous coalescence and noncoalescence is sharp (Karpitschka, S.; Riegler, H. J. Fluid. Mech. 2014, 743, R1). The boundary is a function of two parameters only: Δγ and Θ(a), the arithmetic mean of the contact angles in the moment of drop-drop contact. It appears plausible that surface forces (the disjoining pressure) could also influence the coalescence behavior. However, in experiments with spreading drops, surface forces always promote coalescence and their influence might be obscured. Therefore, we present here coalescence experiments with partially wetting liquids and compare the results to the spreading case. We adjust different equilibrium contact angles (i.e., different surface forces) with different substrate surface coatings. As for spreading drops, we observe a sharp boundary between regimes of coalescence and noncoalescence. The boundary follows the same power law relation for both partially and completely wetting cases. Therefore, we conclude that surface forces have no significant, explicit influence on the coalescence behavior of sessile drops from different miscible liquids.

  5. Shear driven droplet shedding and coalescence on a superhydrophobic surface

    Science.gov (United States)

    Moghtadernejad, S.; Tembely, M.; Jadidi, M.; Esmail, N.; Dolatabadi, A.

    2015-03-01

    The interest on shedding and coalescence of sessile droplets arises from the importance of these phenomena in various scientific problems and industrial applications such as ice formation on wind turbine blades, power lines, nacelles, and aircraft wings. It is shown recently that one of the ways to reduce the probability of ice accretion on industrial components is using superhydrophobic coatings due to their low adhesion to water droplets. In this study, a combined experimental and numerical approach is used to investigate droplet shedding and coalescence phenomena under the influence of air shear flow on a superhydrophobic surface. Droplets with a size of 2 mm are subjected to various air speeds ranging from 5 to 90 m/s. A numerical simulation based on the Volume of Fluid method coupled with the Large Eddy Simulation turbulent model is carried out in conjunction with the validating experiments to shed more light on the coalescence of droplets and detachment phenomena through a detailed analysis of the aerodynamics forces and velocity vectors on the droplet and the streamlines around it. The results indicate a contrast in the mechanism of two-droplet coalescence and subsequent detachment with those related to the case of a single droplet shedding. At lower speeds, the two droplets coalesce by attracting each other with successive rebounds of the merged droplet on the substrate, while at higher speeds, the detachment occurs almost instantly after coalescence, with a detachment time decreasing exponentially with the air speed. It is shown that coalescence phenomenon assists droplet detachment from the superhydrophobic substrate at lower air speeds.

  6. Factors governing partial coalescence in oil-in-water emulsions.

    Science.gov (United States)

    Fredrick, Eveline; Walstra, Pieter; Dewettinck, Koen

    2010-01-15

    The consequences of the instability mechanism partial coalescence in oil-in-water food emulsions show a discrepancy. On the one hand, it needs to be avoided in order to achieve an extended shelf life in food products like sauces, creams and several milk products. On the other hand, during the manufacturing of products like ice cream, butter and whipped toppings partial coalescence is required to achieve the desired product properties. It contributes to the structure formation, the physicochemical properties (stability, firmness,...) and the sensory perception, like fattiness and creaminess of the final food products. This review critically summarises the findings of partial coalescence in oil-in-water emulsions in order to provide insight in how to enhance and retard it. Next to the pioneering work, a large set of experimental results of more recent work is discussed. First, the general mechanism of partial coalescence is considered and a distinction is made between partial and 'true' coalescence. The main differences are: the required solid particles in the dispersed oil phase, the formation of irregular clusters and the increased aggregation rate. Second, the kinetics of partial coalescence is discussed. In more detail, potential parameters affecting the rate of partial coalescence are considered by means of the encounter frequency and capture efficiency of the fat globules. The flow conditions, the fat volume fraction and the physicochemical properties of continuous aqueous phase affect both the encounter frequency and capture efficiency while the actual temperature, temperature history and the composition and formulation of the emulsion mainly affect the capture efficiency.

  7. Review of the Dynamics of Coalescence and Demulsification by High-Voltage Pulsed Electric Fields

    OpenAIRE

    Ye Peng; Tao Liu; Haifeng Gong; Xianming Zhang

    2016-01-01

    The coalescence of droplets in oil can be implemented rapidly by high-voltage pulse electric field, which is an effective demulsification dehydration technological method. At present, it is widely believed that the main reason of pulse electric field promoting droplets coalescence is the dipole coalescence and oscillation coalescence in pulse electric field, and the optimal coalescence pulse electric field parameters exist. Around the above content, the dynamics of high-voltage pulse electric...

  8. Z-Selective ethenolysis with a ruthenium metathesis catalyst: experiment and theory.

    Science.gov (United States)

    Miyazaki, Hiroshi; Herbert, Myles B; Liu, Peng; Dong, Xiaofei; Xu, Xiufang; Keitz, Benjamin K; Ung, Thay; Mkrtumyan, Garik; Houk, K N; Grubbs, Robert H

    2013-04-17

    The Z-selective ethenolysis activity of chelated ruthenium metathesis catalysts was investigated with experiment and theory. A five-membered chelated catalyst that was successfully employed in Z-selective cross metathesis reactions has now been found to be highly active for Z-selective ethenolysis at low ethylene pressures, while tolerating a wide variety of functional groups. This phenomenon also affects its activity in cross metathesis reactions and prohibits crossover reactions of internal olefins via trisubstituted ruthenacyclobutane intermediates. In contrast, a related catalyst containing a six-membered chelated architecture is not active for ethenolysis and seems to react through different pathways more reminiscent of previous generations of ruthenium catalysts. Computational investigations of the effects of substitution on relevant transition states and ruthenacyclobutane intermediates revealed that the differences of activities are attributed to the steric repulsions of the anionic ligand with the chelating groups.

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

    Science.gov (United States)

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

    2015-01-01

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

  10. Divergent dendrimer synthesis via the Passerini three-component reaction and olefin cross-metathesis.

    Science.gov (United States)

    Kreye, Oliver; Kugele, Dennis; Faust, Lorenz; Meier, Michael A R

    2014-02-01

    The combination of the Passerini reaction and olefin cross-metathesis is shown to be a very useful approach for the divergent synthesis of dendrimers. Castor oil-derived platform chemicals, such as 10-undecenoic acid and 10-undecenal, are reacted in a Passerini reaction with an unsaturated isocyanide to obtain a core unit having three terminal double bonds. Subsequent olefin cross-metathesis with tert-butyl acrylate, followed by hydrogenation of the double bonds and hydrolysis of the tert-butyl ester, leads to an active core unit bearing three carboxylic acid groups as reactive sites. Iterative steps of the Passerini reaction with 10-undecenal and 10-isocyanodec-1-ene for branching, and olefin cross-metathesis with tert-butyl acrylate, followed by hydrogenation and hydrolysis allow the synthesis of a third-generation dendrimer. All steps of the synthesis are carefully characterized by NMR, GPC, MS, and IR.

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

    Science.gov (United States)

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

    2015-01-01

    Summary Hoveyda–Grubbs type catalysts with cationic tags on NHC ligands were linker-free immobilized on the surface of lamellar zeolitic supports (MCM-22, MCM-56, MCM-36) and on mesoporous molecular sieves SBA-15. The activity of prepared hybrid catalysts was tested in olefin metathesis reactions: the activity in ring-closing metathesis of citronellene and N,N-diallyltrifluoroacetamide decreased in the order of support MCM-22 ≈ MCM-56 > SBA-15 > MCM-36; the hybrid catalyst based on SBA-15 was found the most active in self-metathesis of methyl oleate. All catalysts were reusable and exhibited low Ru leaching (<1% of Ru content). XPS analysis revealed that during immobilization ion exchange between Hoveyda–Grubbs type catalyst and zeolitic support occurred in the case of Cl− counter anion; in contrast, PF6 − counter anion underwent partial decomposition. PMID:26664629

  12. Kinetic Selectivity of Olefin Metathesis Catalysts Bearing Cyclic (Alkyl)(Amino)Carbenes

    Science.gov (United States)

    Anderson, Donde R.; Ung, Thay; Mkrtumyan, Garik; Bertrand, Guy; Grubbs, Robert H.; Schrodi, Yann

    2008-01-01

    The evaluation of ruthenium olefin metathesis catalysts 4–6 bearing cyclic (alkyl)(amino)carbenes (CAACs) in the cross-metathesis of cis-1,4-diacetoxy-2-butene (7) with allylbenzene (8) and the ethenolysis of methyl oleate (11) is reported. Relative to most NHC-substituted complexes, CAAC-substituted catalysts exhibit lower E/Z ratios (3:1 at 70% conversion) in the cross-metathesis of 7 and 8. Additionally, complexes 4–6 demonstrate good selectivity for the formation of terminal olefins versus internal olefins in the ethenolysis of 11. Indeed, complex 6 achieved 35 000 TONs, the highest recorded to date. CAAC-substituted complexes exhibit markedly different kinetic selectivity than most NHC-substituted complexes. PMID:18584055

  13. The Effects of NHC-Backbone Substitution on Efficiency in Ruthenium-based Olefin Metathesis

    Science.gov (United States)

    Kuhn, Kevin M.; Bourg, Jean-Baptiste; Chung, Cheol K.; Virgil, Scott C.; Grubbs, Robert H.

    2009-01-01

    A series of ruthenium olefin metathesis catalysts bearing N-heterocyclic carbene (NHC) ligands with varying degrees of backbone and N-aryl substitution have been prepared. These complexes show greater resistance to decomposition through C–H activation of the N-aryl group, resulting in increased catalyst lifetimes. This work has utilized robotic technology to examine the activity and stability of each catalyst in metathesis, providing insights into the relationship between ligand architecture and enhanced efficiency. The development of this robotic methodology has also shown that, under optimized conditions, catalyst loadings as low as 25 ppm can lead to 100% conversion in the ring-closing metathesis of diethyl diallylmalonate. PMID:19351207

  14. Linker-free, silica-bound olefin-metathesis catalysts: applications in heterogeneous catalysis.

    Science.gov (United States)

    Cabrera, José; Padilla, Robin; Bru, Miriam; Lindner, Ronald; Kageyama, Takeharu; Wilckens, Kristina; Balof, Shawna L; Schanz, Hans-Jörg; Dehn, Richard; Teles, J Henrique; Deuerlein, Stephan; Müller, Kevin; Rominger, Frank; Limbach, Michael

    2012-11-12

    A set of heterogenized olefin-metathesis catalysts, which consisted of Ru complexes with the H(2)ITap ligand (1,3-bis(2',6'-dimethyl-4'dimethyl aminophenyl)-4,5-dihydroimidazol-2-ylidene) that had been adsorbed onto a silica support, has been prepared. These complexes showed strong binding to the solid support without the need for tethering groups on the complex or functionalized silica. The catalysts were tested in the ring-opening-ring-closing-metathesis (RO-RCM) of cyclooctene (COE) and the self-metathesis of methyl oleate under continuous-flow conditions. The best complexes showed a TON>4000, which surpasses the previously reported materials that were either based on the Grubbs-Hoveyda II complex on silica or on the classical heterogeneous Re(2)O(7)/B(2)O(3) catalyst.

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

    Science.gov (United States)

    Hamzaoui, Bilel; Pelletier, Jérémie D A; Abou-Hamad, Edy; Basset, Jean-Marie

    2016-03-28

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

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

    Directory of Open Access Journals (Sweden)

    Hynek Balcar

    2015-11-01

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

  17. 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.

  18. Z-Selective Catalytic Olefin Cross-Metathesis

    Science.gov (United States)

    Meek, Simon J.; O’Brien, Robert V.; Llaveria, Josep; Schrock, Richard R.; Hoveyda, Amir H.

    2011-01-01

    Alkenes are found in a great number of biologically active molecules and are employed in numerous transformations in organic chemistry. Many olefins exist as E or higher energy Z isomers. Catalytic procedures for stereoselective formation of alkenes are therefore valuable; nonetheless, methods for synthesis of 1,2-disubstituted Z olefins are scarce. Here we report catalytic Z-selective cross-metathesis reactions of terminal enol ethers, which have not been reported previously, and allylic amides, employed thus far only in E-selective processes; the corresponding disubstituted alkenes are formed in up to >98% Z selectivity and 97% yield. Transformations, promoted by catalysts that contain the highly abundant and inexpensive molybdenum, are amenable to gram scale operations. Use of reduced pressure is introduced as a simple and effective strategy for achieving high stereoselectivity. Utility is demonstrated by syntheses of anti-oxidant C18 (plasm)-16:0 (PC), found in electrically active tissues and implicated in Alzheimer’s disease, and the potent immunostimulant KRN7000. PMID:21430774

  19. Organic and composite aerogels through ring opening metathesis polymerization (ROMP)

    Science.gov (United States)

    Mohite, Dhairyashil P.

    Aerogels are open-cell nanoporous materials, unique in terms of low density, low thermal conductivity, low dielectric constants and high acoustic attenuation. Those exceptional properties stem from their complex hierarchical solid framework (agglomerates of porous, fractal secondary nanoparticles), but they also come at a cost: low mechanical strength. This issue has been resolved by crosslinking silica aerogels with organic polymers. The crosslinking polymer has been assumed to form a conformal coating on the surface of the skeletal framework by covalent bridging elementary building blocks. However, "assuming" is not enough: for correlating nanostructure with bulk material properties, it is important to know the exact location of the polymer on the aerogel backbone. For that investigation, we synthesized a new norbornene derivative of triethoxysilane (Si-NAD) that can be attached to skeletal silica nanoparticles. Those norbornene-modified silica aerogels were crosslinked with polynorbornene by ring opening metathesis polymerization (ROMP). The detailed correlation between nanostructure and mechanical strength was probed with a wide array of characterization methods ranging from molecular to bulk through nano. Subsequently, it was reasoned that since the polymer dominates the exceptional mechanical properties of polymer crosslinked aerogels, purely organic aerogels with the same nanostructure and interparticle connectivity should behave similarly. That was explored and confirmed by: (a) synthesis of a difunctional nadimide monomer (bis-NAD), and preparation of robust polyimide aerogels by ROMP of its norbornene end-caps; and, (b) synthesis of dimensionally stable ROMP-derived polydicyclopentadiene aerogels by grafting the nanostructure with polymethylmethacrylate (PMMA) via free radical chemistry.

  20. Enhanced solid-state metathesis routes to carbon nanotubes.

    Science.gov (United States)

    Mack, Julia J; Tari, Susanne; Kaner, Richard B

    2006-05-15

    Ignition of three solids creates multiwalled carbon nanotubes in seconds. A solid-state metathesis (exchange) reaction between hexachloroethane (C2Cl6) and lithium acetylide (Li2C2) with 5% cobalt dichloride (CoCl2) added as an initiator produces up to 7% carbon nanotubes, as observed via transmission electron microscopy. Using the concept that sulfur can promote nanotube growth, the reaction yield can be increased to 15% by switching to CoS as the initiator. The more readily available, inexpensive calcium carbide (CaC2) can be substituted for lithium acetylide while maintaining comparable yields. Switching initiators to FeS can be used to further enhance the yield. A systematic study of the C2Cl6/CaC2 reaction system indicates that a yield up to 25% can be realized by using 6% FeS as the initiator. Reaction temperatures for the C(2)Cl6/CaC2 system of up to 3550 degrees C are calculated using thermodynamic data assuming quantitative yield and adiabatic conditions.

  1. Reduction of surface charges during coalescence of elastomer particles.

    Science.gov (United States)

    Gauer, Cornelius; Wu, Hua; Morbidelli, Massimo

    2010-07-15

    Reaction-limited aggregation of soft elastomer particles has been studied with specific attention to the fate of surface charges during coalescence. The employed system is an aqueous dispersion of fluoroelastomer particles, which are known to coalesce completely at 70 degrees C. In contrast to diffusion-limited conditions, under reaction-limited conditions the stability of the system is expected to change during aggregation because of surface reduction and charge accumulation resulting from coalescence. This allows investigating the mechanism of charge relocation during cluster coalescence. For particles stabilized by ionic surfactants, it has been found that the charges are mobile (i.e., they redistribute between aqueous solution and particle surface according to their adsorption equilibrium) (Gauer, C.; Jia, Z.; Wu, H.; Morbidelli, M. Langmuir 2009, 25, 9703). In this work, we consider the case of fixed charges, as those given by charged polymer end groups covalently bound to the particle surface. We demonstrate that a loss of fixed surface charges occurs during the coalescence and strongly affects the time evolution and the shape of the resulting cluster mass distribution.

  2. Liquid Marble Coalescence and Triggered Microreaction Driven by Acoustic Levitation.

    Science.gov (United States)

    Chen, Zhen; Zang, Duyang; Zhao, Liang; Qu, Mengfei; Li, Xu; Li, Xiaoguang; Li, Lixin; Geng, Xingguo

    2017-06-27

    Liquid marbles show promising potential for application in the microreactor field. Control of the coalescence between two or among multiple liquid marbles is critical; however, the successful merging of two isolated marbles is difficult because of their mechanically robust particle shells. In this work, the coalescence of multiple liquid marbles was achieved via acoustic levitation. The dynamic behaviors of the liquid marbles were monitored by a high-speed camera. Driven by the sound field, the liquid marbles moved toward each other, collided, and eventually coalesced into a larger single marble. The underlying mechanisms of this process were probed via sound field simulation and acoustic radiation pressure calculation. The results indicated that the pressure gradient on the liquid marble surface favors the formation of a liquid bridge between the liquid marbles, resulting in their coalescence. A preliminary indicator reaction was induced by the coalescence of dual liquid marbles, which suggests that expected chemical reactions can be successfully triggered with multiple reagents contained in isolated liquid marbles via acoustic levitation.

  3. A fluid-mechanical model of elastocapillary coalescence

    KAUST Repository

    Singh, Kiran

    2014-03-25

    © 2014 Cambridge University Press. We present a fluid-mechanical model of the coalescence of a number of elastic objects due to surface tension. We consider an array of spring-block elements separated by thin liquid films, whose dynamics are modelled using lubrication theory. With this simplified model of elastocapillary coalescence, we present the results of numerical simulations for a large number of elements, N = O(104). A linear stability analysis shows that pairwise coalescence is always the most unstable mode of deformation. However, the numerical simulations show that the cluster sizes actually produced by coalescence from a small white-noise perturbation have a distribution that depends on the relative strength of surface tension and elasticity, as measured by an elastocapillary number K. Both the maximum cluster size and the mean cluster size scale like K-1/2 for small K. An analytical solution for the response of the system to a localized perturbation shows that such perturbations generate propagating disturbance fronts, which leave behind \\'frozen-in\\' clusters of a predictable size that also depends on K. A good quantitative comparison between the cluster-size statistics from noisy perturbations and this \\'frozen-in\\' cluster size suggests that propagating fronts may play a crucial role in the dynamics of coalescence.

  4. Synchronized reinjection and coalescence of droplets in microfluidics.

    Science.gov (United States)

    Lee, Manhee; Collins, Jesse W; Aubrecht, Donald M; Sperling, Ralph A; Solomon, Laura; Ha, Jong-Wook; Yi, Gi-Ra; Weitz, David A; Manoharan, Vinothan N

    2014-02-07

    Coalescence of two kinds of pre-processed droplets is necessary to perform chemical and biological assays in droplet-based microfluidics. However, a robust technique to accomplish this does not exist. Here we present a microfluidic device to synchronize the reinjection of two different kinds of droplets and coalesce them, using hydrostatic pressure in conjunction with a conventional syringe pump. We use a device consisting of two opposing T-junctions for reinjecting two kinds of droplets and control the flows of the droplets by applying gravity-driven hydrostatic pressure. The hydrostatic-pressure operation facilitates balancing the droplet reinjection rates and allows us to synchronize the reinjection. Furthermore, we present a simple but robust module to coalesce two droplets that sequentially come into the module, regardless of their arrival times. These re-injection and coalescence techniques might be used in lab-on-chip applications requiring droplets with controlled numbers of solid materials, which can be made by coalescing two pre-processed droplets that are formed and sorted in devices.

  5. Coalescence of liquid drops: Different models versus experiment

    KAUST Repository

    Sprittles, J. E.

    2012-01-01

    The process of coalescence of two identical liquid drops is simulated numerically in the framework of two essentially different mathematical models, and the results are compared with experimental data on the very early stages of the coalescence process reported recently. The first model tested is the "conventional" one, where it is assumed that coalescence as the formation of a single body of fluid occurs by an instant appearance of a liquid bridge smoothly connecting the two drops, and the subsequent process is the evolution of this single body of fluid driven by capillary forces. The second model under investigation considers coalescence as a process where a section of the free surface becomes trapped between the bulk phases as the drops are pressed against each other, and it is the gradual disappearance of this "internal interface" that leads to the formation of a single body of fluid and the conventional model taking over. Using the full numerical solution of the problem in the framework of each of the two models, we show that the recently reported electrical measurements probing the very early stages of the process are better described by the interface formation/disappearance model. New theory-guided experiments are suggested that would help to further elucidate the details of the coalescence phenomenon. As a by-product of our research, the range of validity of different "scaling laws" advanced as approximate solutions to the problem formulated using the conventional model is established. © 2012 American Institute of Physics.

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

    Science.gov (United States)

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

    2012-08-22

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

  7. Cross-metathesis reaction of α- and β-vinyl C-glycosides with alkenes

    Directory of Open Access Journals (Sweden)

    Ivan Šnajdr

    2015-08-01

    Full Text Available Cross-metathesis of α- and β-vinyl C-deoxyribosides and α-vinyl C-galactoside with various terminal alkenes under different conditions was studied. The cross-metathesis of the former proceeded with good yields of the corresponding products in ClCH2CH2Cl the latter required the presence of CuI in CH2Cl2 to achieve good yields of the products. A simple method for the preparation of α- and β-vinyl C-deoxyribosides was also developed. In addition, feasibility of deprotection and further transformations were briefly explored.

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

    DEFF Research Database (Denmark)

    Madsen, Robert

    2007-01-01

    , protecting groups and substituents. Subsequent ring-closing metathesis with a ruthenium carbene complex affords highly functionalized carbocycles with ring-sizes ranging from five- to eight-membered rings. The application of these methods for the synthesis of carbocyclic natural products from carbohydrates......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...

  9. The Discovery of Quinoxaline-Based Metathesis Catalysts from Synthesis of Grazoprevir (MK-5172).

    Science.gov (United States)

    Williams, Michael J; Kong, Jongrock; Chung, Cheol K; Brunskill, Andrew; Campeau, Louis-Charles; McLaughlin, Mark

    2016-05-01

    Olefin metathesis (OM) is a reliable and practical synthetic methodology for challenging carbon-carbon bond formations. While existing catalysts can effect many of these transformations, the synthesis and development of new catalysts is essential to increase the application breadth of OM and to achieve improved catalyst activity. The unexpected initial discovery of a novel olefin metathesis catalyst derived from synthetic efforts toward the HCV therapeutic agent grazoprevir (MK-5172) is described. This initial finding has evolved into a class of tunable, shelf-stable ruthenium OM catalysts that are easily prepared and exhibit unique catalytic activity.

  10. A Light-Activated Olefin Metathesis Catalyst Equipped with a Chromatic Orthogonal Self-Destruct Function.

    Science.gov (United States)

    Sutar, Revannath L; Levin, Efrat; Butilkov, Danielle; Goldberg, Israel; Reany, Ofer; Lemcoff, N Gabriel

    2016-01-11

    A sulfur-chelated photolatent ruthenium olefin metathesis catalyst has been equipped with supersilyl protecting groups on the N-heterocyclic carbene ligand. The silyl groups function as an irreversible chromatic kill switch, thus decomposing the catalyst when it is irradiated with 254 nm UV light. Therefore, different types of olefin metathesis reactions may be started by irradiation with 350 nm UV light and prevented by irradiation with shorter wavelengths. The possibility to induce and impede catalysis just by using light of different frequencies opens the pathway for stereolithographic applications and novel light-guided chemical sequences.

  11. Synthesis of Electronically Modified Ru-Based Neutral 16 VE Allenylidene Olefin Metathesis Precatalysts

    Directory of Open Access Journals (Sweden)

    Siegfried Blechert

    2012-05-01

    Full Text Available Electronic modifications within Ru-based olefin metathesis precatalysts have provided a number of new complexes with significant differences in reactivity profiles. So far, this aspect has not been studied for neutral 16 VE allenylidenes. The first synthesis of electronically altered complexes of this type is reported. Following the classical dehydration approach (vide infra modified propargyl alcohols were transformed to the targeted allenylidene systems in the presence of PCy3. The catalytic performance was investigated in RCM reaction (ring closing metathesis of benchmark substrates such as diallyltosylamide (6 and diethyl diallylmalonate (7.

  12. Simple and highly Z-selective ruthenium-based olefin metathesis catalyst.

    Science.gov (United States)

    Occhipinti, Giovanni; Hansen, Fredrik R; Törnroos, Karl W; Jensen, Vidar R

    2013-03-01

    A one-step substitution of a single chloride anion of the Grubbs-Hoveyda second-generation catalyst with a 2,4,6-triphenylbenzenethiolate ligand resulted in an active olefin metathesis catalyst with remarkable Z selectivity, reaching 96% in metathesis homocoupling of terminal olefins. High turnover numbers (up to 2000 for homocoupling of 1-octene) were obtained along with sustained appreciable Z selectivity (>85%). Apart from the Z selectivity, many properties of the new catalyst, such as robustness toward oxygen and water as well as a tendency to isomerize substrates and react with internal olefin products, resemble those of the parent catalyst.

  13. Nobel Prize in Chemistry. Development of the Olefin Metathesis Method in Organic Synthesis

    Science.gov (United States)

    Casey, Charles P.

    2006-02-01

    The 2005 Nobel Prize in Chemistry was awarded to Yves Chauvin of the Institut Français du Pétrole, Robert H. Grubbs of CalTech, and Richard R. Schrock of MIT "for development of the metathesis method in organic synthesis". The discoveries of the laureates provided a chemical reaction now used daily in the chemical industry for the efficient and more environmentally friendly production of important pharmaceuticals, fuels, synthetic fibers, and many other products. This article tells the story of how olefin metathesis became a truly useful synthetic transformation and a triumph for mechanistic chemistry, and illustrates the importance of fundamental research. See JCE Featured Molecules .

  14. A Thermo- and Photo-Switchable Ruthenium Initiator For Olefin Metathesis.

    Science.gov (United States)

    Sashuk, Volodymyr; Danylyuk, Oksana

    2016-05-01

    A ruthenium carbene complex bearing azobenzene functionality is reported. The complex exists in the form of two isomers differing by the size of the chelate ring. Both isomers were isolated by applying kinetic or thermodynamic control during the synthesis and characterized by X-ray diffraction analysis. The isomerization of the complex was studied by UV/Vis spectroscopy. The stable isomer was tested as a catalyst in olefin metathesis. The complex was activated at about 100 °C to promote ring-closing and ring-opening polymerization metathesis reactions. The activation took place also at room temperature under middle ultraviolet radiation.

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

    Energy Technology Data Exchange (ETDEWEB)

    Hsu, J.C.

    1979-01-01

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

  16. Sunflower-based Feedstocks in Nonfood Applications: Perspectives from Olefin Metathesis

    Science.gov (United States)

    Marvey, Bassie B.

    2008-01-01

    Sunflower (Helianthus annuus L.) oil remains under-utilised albeit one of the major seed oils produced world-wide. Moreover, the high oleic sunflower varieties make the oil attractive for applications requiring high temperature processes and those targeting the C=C double bond functionality. Herein an overview of the recent developments in olefin metathesis of sunflower-based feedstocks is presented. The improved performance of olefin metathesis catalysts leading to high turnover numbers, high selectivity and catalyst recyclability, opens new opportunities for tailoring sunflower-based feedstocks into products required for possible new niche market applications. Promising results in biofuel, biopolymers, fragrances and fine chemicals applications have been reported. PMID:19325810

  17. Recent applications of ring-closing metathesis in the synthesis of lactams and macrolactams.

    Science.gov (United States)

    Hassan, Hani Mutlak A

    2010-12-28

    Lactams are an important class of compounds owing to their presence in numerous biologically active molecules of natural and unnatural nature. They are also highly versatile intermediates that can be elaborated into interesting compounds for potential use in organic and medicinal chemistry endeavors. In this feature article, the reader will be given a background to olefin metathesis followed by concise discussions (with selected examples) to report recent applications of ring-closing metathesis to form lactams and macrolactams from acyclic diene precursors, an area which continues to deposit attractive applications in the chemical literature en route or in the final step to the target molecules.

  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. Synthesis and Trapping of Iminoboranes by M=B/C=N Bond Metathesis.

    Science.gov (United States)

    Nutz, Marco; Borthakur, Bitupon; Dewhurst, Rian D; Deißenberger, Andrea; Dellermann, Theresa; Schäfer, Marius; Krummenacher, Ivo; Phukan, Ashwini K; Braunschweig, Holger

    2017-06-26

    Although the metathesis of metal-boron double bonds with elemental chalcogenides is an established process, no similar reactivity has been observed with element-nitrogen bonds. Such a reaction would provide a new route to iminoborane compounds (RB≡NR'), which have recently experienced renewed synthetic interest. Herein, we present the first observation of M=B/C=N metathesis reactions, which led to the isolation of a stable iminoborane in addition to further iminoborane cycloaddition products. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Olefin Metathesis Reaction in Water and in Air Improved by Supramolecular Additives

    Directory of Open Access Journals (Sweden)

    Jasmine Tomasek

    2015-10-01

    Full Text Available A range of water-immiscible commercially available Grubbs-type precatalysts can be used in ring-closing olefin metathesis reaction in high yields. The synthetic transformation is possible in pure water under ambient conditions. Sulfocalixarenes can help to boost the reactivity of the metathesis reaction by catalyst activation, improved mass transfer, and solubility of reactants in the aqueous reaction media. Additionally, the use of supramolecular additives allows lower catalyst loadings, but still high activity in pure water under aerobic conditions.

  1. A new antiproton beam transfer scheme without coalescing

    Energy Technology Data Exchange (ETDEWEB)

    Weiren Chou et al.

    2003-06-04

    An effective way to increase the luminosity in the Fermilab Tevatron collider program Run2 is to improve the overall antiproton transfer efficiency. During antiproton coalescing in the Main Injector (MI), about 10-15% particles get lost. This loss could be avoided in a new antiproton transfer scheme that removes coalescing from the process. Moreover, this scheme would also eliminate emittance dilution due to coalescing. This scheme uses a 2.5 MHz RF system to transfer antiprotons from the Accumulator to the Main Injector. It is then followed by a bunch rotation in the MI to shorten the bunch length so that it can be captured by a 53 MHz RF bucket. Calculations and ESME simulations show that this scheme works. No new hardware is needed to implement this scheme.

  2. Spontaneous Jumping of Coalescing Drops on a Superhydrophobic Surface

    Science.gov (United States)

    Boreyko, Jonathan; Chen, Chuan-Hua

    2009-11-01

    When micrometric drops coalesce in-plane on a superhydrophobic surface, a surprising out-of-plane jumping motion was observed. Such jumping motion triggered by drop coalescence was reproduced on a Leidenfrost surface. High-speed imaging revealed that this jumping motion results from the elastic interaction of the bridged drops with the superhydrophobic/Leidenfrost surface. Experiments on both the superhydrophobic and Leidenfrost surfaces compare favorably to a simple scaling model relating the kinetic energy of the merged drop to the surface energy released upon coalescence. The spontaneous jumping motion on water repellent surfaces enables the autonomous removal of water condensate independently of gravity; this process is highly desirable for sustained dropwise condensation.

  3. Spontaneous Jumping of Coalescing Drops on a Superhydrophobic Surface

    CERN Document Server

    Boreyko, Jonathan

    2009-01-01

    When micrometric drops coalesce in-plane on a superhydrophobic surface, a surprising out-of-plane jumping motion was observed. Such jumping motion triggered by drop coalescence was reproduced on a Leidenfrost surface. High-speed imaging revealed that this jumping motion results from the elastic interaction of the bridged drops with the superhydrophobic/Leidenfrost surface. Experiments on both the superhydrophobic and Leidenfrost surfaces compare favorably to a simple scaling model relating the kinetic energy of the merged drop to the surface energy released upon coalescence. The spontaneous jumping motion on water repellent surfaces enables the autonomous removal of water condensate independently of gravity; this process is highly desirable for sustained dropwise condensation.

  4. Capillary-inertial colloidal catapults upon drop coalescence

    Science.gov (United States)

    Chavez, Roger L.; Liu, Fangjie; Feng, James J.; Chen, Chuan-Hua

    2016-07-01

    Surface energy released upon drop coalescence is known to power the self-propelled jumping of liquid droplets on superhydrophobic solid surfaces, and the jumping droplets can additionally carry colloidal payloads toward self-cleaning. Here, we show that drop coalescence on a spherical particle leads to self-propelled launching of the particle from virtually any solid surface. The main prerequisite is an intermediate wettability of the particle, such that the momentum from the capillary-inertial drop coalescence process can be transferred to the particle. By momentum conservation, the launching velocity of the particle-drop complex is proportional to the capillary-inertial velocity based on the drop radius and to the fraction of the liquid mass in the total mass. The capillary-inertial catapult is not only an alternative mechanism for removing colloidal contaminants, but also a useful model system for studying ballistospore launching.

  5. A unified criterion for the growth and coalescence of microvoids

    Science.gov (United States)

    Morin, Léo; Leblond, Jean-Baptiste; Benzerga, A. Amine; Kondo, Djimédo

    2016-12-01

    A yield criterion is developed which unifies void growth and void coalescence theories. Standard void growth theory assumes that plastic flow is diffuse, if not prevalent everywhere within the matrix of the elementary cell considered. On the other hand, void coalescence theory assumes states of post-localized plasticity whereby plastic flow is restricted to intervoid ligaments. The new theory accommodates both scenarios through some appropriate choice of microscopic velocity fields. An important implication for actual evolution problems is a seamless transition from void growth to void coalescence. This is in contrast with previous hybrid approaches whereby abrupt transitions are associated with the presence of unavoidable corners in the effective yield surface. More generally, the new criterion is applicable to describe yielding in porous metal plasticity for both low and high void volume fractions.

  6. How geometry determines the coalescence of low-viscosity drops

    CERN Document Server

    Eddi, A; Snoeijer, J H

    2013-01-01

    The coalescence of water drops on a substrate is studied experimentally. We focus on the rapid growth of the bridge connecting the two drops, which very quickly after contact ensues from a balance of surface tension and liquid inertia. For drops with contact angles below $90^\\circ$, we find that the bridge grows with a self-similar dynamics that is characterized by a height $h\\sim t^{2/3}$. By contrast, the geometry of coalescence changes dramatically for contact angles at $90^\\circ$, for which we observe $h\\sim t^{1/2}$, just as for freely suspended spherical drops in the inertial regime. We present a geometric model that quantitatively captures the transition from 2/3 to 1/2 exponent, and unifies the inertial coalescence of sessile drops and freely suspended drops.

  7. Metathesis transformations of natural products: cross-metathesis of natural rubber and mandarin oil by Ru-alkylidene catalysts.

    Science.gov (United States)

    Martínez, Araceli; Gutiérrez, Selena; Tlenkopatchev, Mikhail A

    2012-05-18

    This study reports on the degradation of natural rubber (NR) via crossmetathesis with mandarin oil and d-limonene, an abundant compound in essential oils; that were used as chain transfer agents (CTAs) and green solvents. Reactions were performed in the presence of the ruthenium-alkylidene catalysts (PCy₃)₂(Cl)₂Ru=CHPh (I) and (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) (PCy₃)Cl₂Ru=CHPh (II), respectively. Catalyst II bears an N-heterocyclic carbene ligand (NHC) bounded to the ruthenium atom, which has a strong basic character; therefore it is more active toward trisubstituted olefins in comparison with catalyst I. In both cases, isolated monoterpene-terminated isoprene oligomers were obtained as products of the cross-metathesis degradation of NR. In the presence of catalyst II molecular weight values around M(n) × 10² and yields of 80% were obtained; whereas with catalyst I, the molecular weights of products were about M(n) × 10⁴ with yields ranging 70 to 74%. The composition and yield of NR degradation products were determined by GC/MS (EI) analysis and it was found that the oligomers obtained have primarily one vinyl group and one terpene-monocyclic group at the chain end, with isoprene units A(m) = 2, 3 y 4.

  8. Molecular structure of the coalescence of liquid interfaces

    Science.gov (United States)

    Koplik, Joel; Banavar, Jayanth R.

    1992-01-01

    When two bodies of liquid merge, their interfaces must also rupture and rearrange into one. Virtually no information is available concerning the small-scale dynamics of this process. Molecular dynamics simulations of coalescence in systems of about 10,000 Lennard-Jones particles have been performed, arranged so as to mimic laboratory experiments on dense liquids. The coalescence event begins when molecules near the boundary of one liquid body thermally fluctuate into the range of attraction of the other, forming a string of mutually attracting molecules. These molecules gradually thicken into a tendril, which continues to thicken as the bodies smoothly combine in a zipper-like merger.

  9. Dynamics of Coalescence-Induced Jumping Water Droplets

    CERN Document Server

    Miljkovic, Nenad; Enright, Ryan; Wang, Evelyn N

    2013-01-01

    This fluid dynamics video shows the different interaction mechanisms of coalescence-induced droplet jumping during condensation on a nanostructured superhydrophobic surface. High speed imaging was used to show jumping behavior on superhydrophobic copper oxide and carbon nanotube surfaces. Videos demonstrating multi-jumping droplets, jumping droplet return to the surface, and droplet-droplet electrostatic repulsions were analyzed. Experiments using external electric fields in conjunction with high speed imaging in a custom built experimental chamber were used to show that all coalescence-induced jumping droplets on superhydrophobic surfaces become positively charged upon leaving the surface, which is detailed in the video.

  10. Foam drainage wave coalescing and its energy evolution

    Institute of Scientific and Technical Information of China (English)

    SUN QiCheng; HUANG Jin; WANG GuangQian

    2008-01-01

    Liquid foam is a dense packing of gas bubbles in a small amount of surfactant solution. Liquid drains out of foams until equilibrium is reached due to the compromise between gravity and capillarity, which greatly affects the stability of foam. Based on a series of work on foam structure and drainage we conducted previously, this paper reports the results on coalescence of an original forced drainage wave at a low flow rate with subsequent drainage waves with higher flow rates. The evolutions of vis-cous energy and surface energy during the process of coalescence are theoretically analyzed.

  11. The effect of quark coalescence on conical signals

    CERN Document Server

    Greco, Vincenzo; Noronha, Jorge; Gyulassy, Miklos

    2009-01-01

    We explore the effect of hadronization by partonic coalescence on a "conical" signal at the partonic level. We show that, by transferring partons from a lower to a higher $p_T$, coalescence makes the conical signal stronger and hence less susceptible to thermal smearing, provided the signal is integrated over a large momentum bin and effects such as non-collinearity and a finite Wigner function width are taken into account. We explore the role of this effect in baryon/meson scaling and calculate the effect of resonances decays on such a conical signal.

  12. Metathesis of carbon dioxide and phenyl isocyanate catalysed by group(IV) metal alkoxides: An experimental and computational study

    Indian Academy of Sciences (India)

    Akshai Kumar; Ashoka G Samuelson

    2011-01-01

    The insertion reactions of zirconium(IV) -butoxide and titanium(IV) -butoxide with a heterocumulene like carbodiimide, carbon dioxide or phenyl isocyanate are compared. Both give an intermediate which carries out metathesis at elevated temperatures by inserting a second heterocumulene in a head-to-head fashion. The intermediate metallacycle extrudes a new heterocumulene, different from the two that have inserted leading to metathesis. As the reaction is reversible, catalytic metathesis is feasible. In stoichiometric reactions heterocumulene insertion, metathesis and metathesis cum insertion products are observed. However, catalytic amounts of the metal alkoxide primarily led to metathesis products. It is shown that zirconium alkoxides promote catalytic metathesis (isocyanates, carbon dioxide) more efficiently than the corresponding titanium alkoxide. The difference in the metathetic activity of these alkoxides has been explained by a computational study using model complexes Ti(OMe)4 (1bTi) and Zr(OMe)4 (1bZr). The computation was carried out at the B3LYP/LANL2DZ level of theory.

  13. Bond Energies in Models of the Schrock Metathesis Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Vasiliu, Monica; Li, Shenggang; Arduengo, Anthony J.; Dixon, David A.

    2011-06-23

    Heats of formation, adiabatic and diabatic bond dissociation energies (BDEs) of the model Schrock-type metal complexes M(NH)(CRR)(OH)₂ (M = Cr, Mo, W; CRR = CH₂, CHF, CF₂) and MO₂(OH)₂ compounds, and Brønsted acidities and fluoride affinities for the M(NH)(CH₂)(OH) ₂ transition metal complexes are predicted using high level CCSD(T) calculations. The metallacycle intermediates formed by reaction of C₂H4 with M(NH)-(CH₂)(OH)2 and MO₂(OH)₂ are investigated at the same level of theory. Additional corrections were added to the complete basis set limit to obtain near chemical accuracy ((1 kcal/mol). A comparison between adiabatic and diabatic BDEs is made and provides an explanation of trends in the BDEs. Electronegative groups bonded on the carbenic carbon lead to less stable Schrock-type complexes as the adiabatic BDEs ofMdCF₂ andMdCHF bonds are much lower than theMdCH₂ bonds. The Cr compounds have smaller BDEs than theWorMo complexes and should be less stable. Different M(NH)(OH)₂(C₃H₆) and MO(OH)₂(OC₂H4) metallacycle intermediates are investigated, and the lowest-energy metallacycles have a square pyramidal geometry. The results show that consideration of the singlet_triplet splitting in the carbene in the initial catalyst as well as in the metal product formed by the retro [2+2] cycloaddition is a critical component in the design of an effective olefin metathesis catalyst in terms of the parent catalyst and the groups being transferred.

  14. Diphenylamido Precursors to Bisalkoxide Molybdenum Olefin Metathesis Catalysts

    Science.gov (United States)

    Sinha, Amritanshu; Müller, Peter; Hoveyda, Amir H.

    2008-01-01

    We have found that Mo(NAr)(CHR′)(NPh2)2 (R′ = t-Bu or CMe2Ph) and Mo(NAr′)(CHCMe2Ph)(NPh2)2 (Ar = 2,6-i-Pr2C6H3; Ar′ = 2,6-Me2C6H3) can be prepared through addition of two equivalents of LiNPh2 to Mo(NR″)(CHR′)(OTf)2(dme) species (R″ = Ar or Ar′ dme = 1,2-dimethoxyethane), although yields are low. A high yield route consists of addition of LiNPh2 to bishexafluro-t-butoxide species. An X-ray structure of Mo(NAr)(CHCMe2Ph)(NPh2)2 reveals that the two diphenylamido groups are oriented in a manner that allows an 18 electron count to be achieved. The diphenylamido complexes react readily with t-BuOH and (CF3)2MeCOH, but not readily with the sterically demanding biphenol H2[Biphen] (Biphen2- = 3,3′-Di-t-butyl-5,5′,6,6′-tetramethyl-1,1′-Biphenyl-2,2′-diolate). The diphenylamido complexes do react with various 3,3′-disubstituted binaphthols to yield binaphtholate catalysts that can be prepared in situ and employed for a simple asymmetric ring-closing metathesis reaction. In several cases conversions and enantioselectivities were comparable to reactions in which isolated catalysts were employed. PMID:19030118

  15. 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).

  16. Ring-Opening Metathesis Activity of Ruthenium-Based Olefin Metathesis Catalyst Coordinated with 1,3-Bis(2,6-Diisopropylphenyl)-4,5-Dihydroimidazoline

    Science.gov (United States)

    Karabulut, Solmaz; Verpoort, Francis

    A 1,3-bis-(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene substituted ruthenium (Ru)-based complex (4) has been prepared starting from (PCy3)2(Cl)2Ru=CHPh (2). The catalytic performance of catalyst (4) is checked on ring-opening metathesis polymerization (ROMP) of the low strain monomer, cycloocta-1,5-diene (COD), and also compared with catalyst (2) and (3).

  17. The Right Computational Recipe for Olefin Metathesis with Ru-Based Catalysts: The Whole Mechanism of Ring-Closing Olefin Metathesis.

    Science.gov (United States)

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

    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).

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

    KAUST Repository

    Poater, Albert

    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.

  19. Modelling for three dimensional coalescence of two bubbles

    Science.gov (United States)

    Han, R.; Li, S.; Zhang, A. M.; Wang, Q. X.

    2016-06-01

    This paper is concerned with the three dimensional (3D) interaction and coalescence of two bubbles subject to buoyancy and the dynamics of the subsequent joined bubble using the boundary integral method (BIM). An improved density potential method is implemented to control the mesh quality. It helps to avoid the numerical instabilities, which occur after coalescence. Numerical convergence tests are conducted in terms of mesh sizes and time steps. The 3D numerical model agrees well with an axisymmetric BIM model for axisymmetric cases as well as experimental results captured by high-speed camera. The bubble jetting, interaction, and coalescence of the two bubbles depend on the maximum bubble radii, the centre distance between two bubbles at inception, and the angle β between the centre line and the direction of buoyancy. We investigate coalescence of two bubbles for β = 0, π/4, and π/2, respectively, and at various centre distances at inception. Numerical results presented include the bubble and jet shapes, the velocity, and pressure fields surrounding the bubbles, as well as the time histories of bubble volumes, jet velocities, and positions of centroid of the bubble system.

  20. Coalescence of Liquid Drops: Different Models Versus Experiment

    CERN Document Server

    Sprittles, James

    2012-01-01

    The process of coalescence of two identical liquid drops is simulated numerically in the framework of two essentially different mathematical models, and the results are compared with experimental data on the very early stages of the coalescence process reported recently. The first model tested is the `conventional' one, where it is assumed that coalescence as the formation of a single body of fluid occurs by an instant appearance of a liquid bridge smoothly connecting the two drops, and the subsequent process is the evolution of this single body of fluid driven by capillary forces. The second model under investigation considers coalescence as a process where a section of the free surface becomes trapped between the bulk phases as the drops are pressed against each other, and it is the gradual disappearance of this `internal interface' that leads to the formation of a single body of fluid and the conventional model taking over. Using the full numerical solution of the problem in the framework of each of the tw...

  1. Expected Bounds on Compact Binary Coalescence Rates from LIGO Observations

    Science.gov (United States)

    Sampson, Laura; LIGO Scientific Collaboration Collaboration

    2016-03-01

    The Advanced LIGO detectors have recently completed their first observing run, with a sensitive spacetime volume over 27 times larger than the initial LIGO configuration. In this talk we will examine the expected bounds on compact binary coalescence rates from O1 observations, and discuss the corresponding impact on astrophysical models.

  2. Void Coalescence Processes Quantified Through Atomistic and Multiscale Simulation

    Energy Technology Data Exchange (ETDEWEB)

    Rudd, R E; Seppala, E T; Dupuy, L M; Belak, J

    2007-01-12

    Simulation of ductile fracture at the atomic scale reveals many aspects of the fracture process including specific mechanisms associated with void nucleation and growth as a precursor to fracture and the plastic deformation of the material surrounding the voids and cracks. Recently we have studied void coalescence in ductile metals using large-scale atomistic and continuum simulations. Here we review that work and present some related investigations. The atomistic simulations involve three-dimensional strain-controlled multi-million atom molecular dynamics simulations of copper. The correlated growth of two voids during the coalescence process leading to fracture is investigated, both in terms of its onset and the ensuing dynamical interactions. Void interactions are quantified through the rate of reduction of the distance between the voids, through the correlated directional growth of the voids, and through correlated shape evolution of the voids. The critical inter-void ligament distance marking the onset of coalescence is shown to be approximately one void radius based on the quantification measurements used, independent of the initial separation distance between the voids and the strain-rate of the expansion of the system. No pronounced shear flow is found in the coalescence process. We also discuss a technique for optimizing the calculation of fine-scale information on the fly for use in a coarse-scale simulation, and discuss the specific case of a fine-scale model that calculates void growth explicitly feeding into a coarse-scale mechanics model to study damage localization.

  3. Void Coalescence Processes Quantified through Atomistic and Multiscale Simulation

    Energy Technology Data Exchange (ETDEWEB)

    Rudd, R E; Seppala, E T; Dupuy, L M; Belak, J

    2005-12-31

    Simulation of ductile fracture at the atomic scale reveals many aspects of the fracture process including specific mechanisms associated with void nucleation and growth as a precursor to fracture and the plastic deformation of the material surrounding the voids and cracks. Recently we have studied void coalescence in ductile metals using large-scale atomistic and continuum simulations. Here we review that work and present some related investigations. The atomistic simulations involve three-dimensional strain-controlled multi-million atom molecular dynamics simulations of copper. The correlated growth of two voids during the coalescence process leading to fracture is investigated, both in terms of its onset and the ensuing dynamical interactions. Void interactions are quantified through the rate of reduction of the distance between the voids, through the correlated directional growth of the voids, and through correlated shape evolution of the voids. The critical inter-void ligament distance marking the onset of coalescence is shown to be approximately one void radius based on the quantification measurements used, independent of the initial separation distance between the voids and the strain-rate of the expansion of the system. No pronounced shear flow is found in the coalescence process.

  4. Coalescent processes arising in a study of diffusive clustering

    CERN Document Server

    Greven, Andreas; Winter, Anita

    2007-01-01

    This paper studies spatial coalescents on $\\Z^2$. In our setting, the partition elements are located at the sites of $\\Z^2$ and undergo local delayed coalescence and migration. The system starts in either locally finite configurations or in configurations containing countably many partition elements per site. Our goal is to determine the longtime behavior with an initial population of countably many individuals per site restricted to a box $[-t^{\\alpha/2}, t^{\\alpha/2}]^2 \\cap \\Z^2$ and observed at time $t^\\beta$ with $1 \\geq \\beta \\geq \\alpha\\ge 0$. We study both asymptotics, as $t\\to\\infty$, for a fixed value of $\\alpha$ as the parameter $\\beta\\in[\\alpha,1]$ varies, and for a fixed $\\beta=1$, as the parameter $\\alpha\\in [0,1]$ varies. A new random object, the so-called {\\em coalescent with rebirth}, is constructed and shown to arise in the limit. In view of future applications we introduce the spatial coalescent with rebirth and study its longtime asymptotics as well. The present paper is the basis for fort...

  5. Effects of Coalescence on Shear-Induced Gelation of Colloids.

    Science.gov (United States)

    Jaquet, Baptiste; Lazzari, Stefano; Colonna, Luca; Colombo, Gabriele; Soos, Miroslav; Morbidelli, Massimo

    2017-02-07

    Shearing lyophobic colloidal suspensions can lead to aggregation, followed by gelation, if the formed clusters grow to sizes large enough to percolate. If the temperature is set over the glass transition temperature of the suspended material, the particles embedded in the same aggregate start to coalesce with one another. Coalescence occurs to the finite viscosity of the particles' material, which leads to material diffusion from particle to particle. The driving force of this process is the reduction of the particle-dispersant interface and, as a consequence, the decrease the center-to-center separation of the particles. This leads to decreased cluster size, and hence a delayed gelation. Simultaneously, coalescence reinforces the particle-particle bonds formed upon aggregation, leading to clusters that are able to resist higher hydrodynamic forces before breaking up, hence leading to faster gelation. These two competing effects, combined with the natural complexity of colloidal aggregation makes it rather difficult to understand and predict which trend becomes dominant. In the present work, the shear-induced gelation of model polymeric colloidal systems with different glass transition temperatures has been studied. Starting with their interaction potential we investigate the impact of temperature on the gel time in concentrated suspensions (φ = 5%) under steady shear, followed by the effect of temperature on the stress-resistance of fully destabilized clusters under agitation. The results of the present work allow for a systematic view and deepened understanding of the factors governing shear-induced gelation in the presence of coalescence.

  6. Flow Induced Coalescence of Drops in a Viscous Liquid

    Science.gov (United States)

    Leal, L. Gary

    2002-11-01

    The problem of flow-induced coalescence has been the subject of many experimental and theoretical studies. In recent years, this work has been motivated by the role that this process plays in the formation of polymer blends, which is currently the major route to new polymeric materials with desired macroscopic properties. In order to control this process, we need to understand the conditions for coalescence and their dependence on fluid and flow properties, including the effects of surfactants (known as "compatibilizers" in the polymer blend literature). With a few exceptions, experimental studies have been based upon measurements of the mean drop size (or size distribution) in an emulsion or blend following flow in either blending devices or simple rheometry flows. The four-roll mill, on the other hand, provides an opportunity to study the coalescence process at the scale of individual drops. When such experiments are carried out, we find some surprises vis a vis expectations from simple models of the drop collision/film drainage and rupture process that leads to coalescence. In this talk, we review recent experimental work in this field, and discuss the relationship to present theory

  7. Factors governing partial coalescence in oil-in-water emulsions

    NARCIS (Netherlands)

    Fredrick, E.; Walstra, P.; Dewettinck, K.

    2010-01-01

    The consequences of the instability mechanism partial coalescence in oil-in-water food emulsions show a discrepancy. On the one hand, it needs to be avoided in order to achieve an extended shelf life in food products like sauces, creams and several milk products. On the other hand, during the manufa

  8. A fluid-mechanical model of elastocapillary coalescence

    CERN Document Server

    Singh, Kiran; Vella, Dominic

    2013-01-01

    We present a fluid-mechanical model of the coalescence of a number of elastic objects due to surface tension. We consider an array of spring-block elements separated by thin liquid films, whose dynamics are modelled using lubrication theory. With this simplified model of elastocapillary coalescence, we present the results of numerical simulations for a large number of elements, $N=O(10^4)$. A linear stability analysis shows that pairwise coalescence is always the most unstable mode of deformation. However, the numerical simulations show that the cluster sizes actually produced by coalescence from a small white-noise perturbation have a distribution that depends on the relative strength of surface tension and elasticity, as measured by an elastocapillary number $K$. Both the maximum cluster size and the mean cluster size scale like $K^{-1/2}$ for small $K$. An analytical solution for the response of the system to a localized perturbation shows that such perturbations generate propagating disturbance fronts, wh...

  9. Factors governing partial coalescence in oil-in-water emulsions

    NARCIS (Netherlands)

    Fredrick, E.; Walstra, P.; Dewettinck, K.

    2010-01-01

    The consequences of the instability mechanism partial coalescence in oil-in-water food emulsions show a discrepancy. On the one hand, it needs to be avoided in order to achieve an extended shelf life in food products like sauces, creams and several milk products. On the other hand, during the

  10. 2005 Nobel Prize in Chemistry: Development of the Olefin Metathesis Method in Organic Synthesis

    Science.gov (United States)

    Casey, Charles P.

    2006-01-01

    The 2005 Nobel Prize in Chemistry was awarded "for the development of the metathesis method in organic synthesis". The discoveries of the laureates provided a chemical reaction used daily in the chemical industry for the efficient and more environmentally friendly production of important pharmaceuticals, fuels, synthetic fibers, and many other…

  11. 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.

  12. Cationic tungsten-oxo-alkylidene-N-heterocyclic carbene complexes: highly active olefin metathesis catalysts.

    Science.gov (United States)

    Schowner, Roman; Frey, Wolfgang; Buchmeiser, Michael R

    2015-05-20

    The synthesis, structure, and olefin metathesis activity of the first neutral and cationic W-oxo-alkylidene-N-heterocyclic carbene (NHC) catalysts are reported. Neutral W-oxo-alkylidene-NHC catalysts can be prepared in up to 90% isolated yield. Depending on the ligands used, they possess either an octahedral (Oh) or trigonal bipyramidal ligand sphere. They can be activated with excess AlCl3 to form cationic olefin metathesis-active W-complexes; however, these readily convert into neutral chloro-complexes. Well-defined, stable cationic species can be prepared by stoichiometric substitution of one chloro ligand in the parent, neutral W-oxo-alkylidene-NHC complexes with Ag(MeCN)2B(Ar(F))4 or NaB(Ar(F))4; B(Ar(F))4 = B(3,5-(CF3)2-C6H3)4. They are highly active olefin metathesis catalysts, allowing for turnover numbers up to 10,000 in various olefin metathesis reactions including alkenes bearing nitrile, sec-amine, and thioether groups.

  13. 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...

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

    Science.gov (United States)

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

    2014-01-13

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

  15. Olefin Ring Closing Metathesis and Hydrosilylation Reaction in Aqueous Medium by Grubbs Second Generation Ruthenium Catalyst

    Science.gov (United States)

    The Grubbs second generation ruthenium catalyst was shown to catalyze various olefin ring closing metathesis and hydrosilylation reactions in aqueous medium. Reactions proceeded in pure water without any additives or co-solvents, in a short period of time. We found that inhomogen...

  16. Hydrogen bond templated 1:1 macrocyclization through an olefin metathesis/hydrogenation sequence.

    Science.gov (United States)

    Trita, Andrada Stefania; Roisnel, Thierry; Mongin, Florence; Chevallier, Floris

    2013-07-19

    The construction of pyridine-containing macrocyclic architectures using a nonmetallic template is described. 4,6-Dichlororesorcinol was used as an exotemplate to self-organize two aza-heterocyclic units by OH···N hydrogen bonds. Subsequent sequential double olefin metathesis/hydrogenation reactions employing a single ruthenium-alkylidene precatalyst open access to macrocyclic molecules.

  17. Olefin Metathesis Mediated By: - Schiff Base Ru-Alkylidenes -Ru-Alkylidenes Bearing Unsymmetrical NH Ligands

    Science.gov (United States)

    Monsaert, Stijn; Voort, Pascal Van Der; Ledoux, Nele; Allaert, Bart; Drozdzak, Renata; Verpoort, Francis

    The classic Grubbs second-generation complex 2 was modified through 1. The introduction of a bidentate Schiff base ligand 2. Changes in the amino side groups of the NHC ligand Representative olefin metathesis test reactions show the effects induced by the ligand modifications and demonstrate some interesting new properties of the described catalysts. catalysts.

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

    Science.gov (United States)

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

    2014-12-12

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

  19. 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...

  20. Amino acids as chiral anionic ligands for ruthenium based asymmetric olefin metathesis.

    Science.gov (United States)

    Ivry, Elisa; Ben-Asuly, Amos; Goldberg, Israel; Lemcoff, N Gabriel

    2015-03-01

    Several amino acid ligands were introduced into the Hoveyda-Grubbs 2nd generation complex by a facile anionic ligand exchange. The chiral pre-catalysts obtained displayed enantioselectivity in asymmetric ring-closing and ring-opening cross-metathesis reactions. Reduction of the lability of the carboxylate ligands was found to be cardinal for improving the observed enantiomeric product enrichment.

  1. "Click" and Olefin Metathesis Chemistry in Water at Room Temperature Enabled by Biodegradable Micelles.

    Science.gov (United States)

    Lipshutz, Bruce H; Bošković, Zarko; Crowe, Christopher S; Davis, Victoria K; Whittemore, Hannah C; Vosburg, David A; Wenzel, Anna G

    2013-11-12

    The two laboratory reactions focus on teaching several concepts associated with green chemistry. Each uses a commercial, nontoxic, and biodegradable surfactant, TPGS-750-M, to promote organic reactions within the lipophilic cores of nanoscale micelles in water. These experiments are based on work by K. Barry Sharpless (an azide-alkyne "click" reaction) and Robert Grubbs (an olefin cross-metathesis reaction); both are suitable for an undergraduate organic laboratory. The copper-catalyzed azide-alkyne [3+2] cycloaddition of benzyl azide and 4-tolylacetylene is very rapid: the triazole product is readily isolated by filtration and is characterized by thin-layer chromatography and melting point analysis. The ruthenium-catalyzed olefin cross-metathesis reaction of benzyl acrylate with 1-hexene is readily monitored by thin-layer chromatography and gas chromatography. The metathesis experiment comparatively evaluates the efficacy of a TPGS-750-M/water medium relative to a traditional reaction performed in dichloromethane (a common solvent used for olefin metathesis).

  2. Attractive Noncovalent Interactions in the Mechanism of Grubbs Second-Generation Ru Catalysts for Olefin Metathesis.

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Yan; Truhlar, Donald G.

    2007-05-10

    Second-generation ruthenium carbenoid catalysts for olefin metathesis are a hundred to a thousand times more active than first-generation catalysts, despite a slower initiation step. A new density functional capable of treating medium-range correlation energy shows that the relative rates of generation of the catalyst are determined by attractive noncovalent interactions.

  3. Solvent-free cyclization of linear dienes using olefin metathesis and the Thorpe-Ingold effect

    Energy Technology Data Exchange (ETDEWEB)

    Forbees, M.D.E.; Myers, T.L.; Maynard, H.D.; Schulz, G.R. (Univ. of North Carolina, Chapel Hill (United States)); Patton, J.T.; Smith, D.W. Jr.; Wagener, K.B. (Univ. of Florida, Gainesville (United States))

    1992-12-30

    The olefin metathesis reaction is of great synthetic utility in polymer chemistry. The recent development of ring-opening (ROMP) and acyclic diene (ADMET) metathesis polymerization reactions has opened new avenues for the synthesis of novel polymeric materials. Recently the authors used ADMET to synthesize several photochemically active poly(keto olefins) using the catalyst Mo(CHCMe[sub 2]Ph)(NAr)(OCMe(CF[sub 3])[sub 2])[sub 2] (Ar = 2,6-diisopropylphenyl) (1) developed by Schrock and co-workers in 1990. In the course of that work, they discovered that neat samples of highly substituted dienes will cyclize quantitatively via metathesis to give difunctional five- and seven-membered rings instead of the expected linear polymer. Examples of substituted diene cyclizations by metathesis even in the presence of a solvent are rare. Their systematic exploitation in organic synthesis has therefore been limited to two recent studies by Fu and Grubbs, who cyclized several substituted diene ethers, amines, and amides to unsaturated oxygen and nitrogen heterocycles. Cyclization of unsubstituted dienes in various solvents has been reported, but complete conversion occurred in only a few cases. Formation of cyclic alkene oligomers from back-biting during the ROMP reaction is also known. The reactions reported here are unusual in that they are intermolecular between catalyst and substrate, yet can give 100% yield of product solely from the monomer in the absence of solvent. 13 refs.

  4. “Click” and Olefin Metathesis Chemistry in Water at Room Temperature Enabled by Biodegradable Micelles

    Science.gov (United States)

    Lipshutz, Bruce H.; Bošković, Zarko; Crowe, Christopher S.; Davis, Victoria K.; Whittemore, Hannah C.; Vosburg, David A.; Wenzel, Anna G.

    2013-01-01

    The two laboratory reactions focus on teaching several concepts associated with green chemistry. Each uses a commercial, nontoxic, and biodegradable surfactant, TPGS-750-M, to promote organic reactions within the lipophilic cores of nanoscale micelles in water. These experiments are based on work by K. Barry Sharpless (an azide–alkyne “click” reaction) and Robert Grubbs (an olefin cross-metathesis reaction); both are suitable for an undergraduate organic laboratory. The copper-catalyzed azide–alkyne [3+2] cycloaddition of benzyl azide and 4-tolylacetylene is very rapid: the triazole product is readily isolated by filtration and is characterized by thin-layer chromatography and melting point analysis. The ruthenium-catalyzed olefin cross-metathesis reaction of benzyl acrylate with 1-hexene is readily monitored by thin-layer chromatography and gas chromatography. The metathesis experiment comparatively evaluates the efficacy of a TPGS-750-M/water medium relative to a traditional reaction performed in dichloromethane (a common solvent used for olefin metathesis). PMID:24324282

  5. Construction of carbocyclic ring of indoles using ruthenium-catalyzed ring-closing olefin metathesis.

    Science.gov (United States)

    Yoshida, Kazuhiro; Hayashi, Kazushi; Yanagisawa, Akira

    2011-09-16

    The selective synthesis of substituted indoles was achieved by the ring-closing olefin metathesis (RCM)/elimination sequence or the RCM/tautomerization sequence of functionalized pyrrole precursors. The RCM/elimination sequence was also applied to double ring closure to yield a substituted carbazole.

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

    Science.gov (United States)

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

    2011-06-22

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

  7. 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.

  8. Cis-Selective Ring-Opening Metathesis Polymerization with Ruthenium Catalysts

    Science.gov (United States)

    Keitz, Benjamin K.; Fedorov, Alexey; Grubbs, Robert H.

    2012-01-01

    Using a C-H activated, ruthenium-based metathesis catalyst, the cis selective ROMP of several monocyclic alkenes, as well as norbornene and oxanorbornene-type monomers is reported. The cis content of the isolated polymers depended heavily on monomer structure and temperature. By lowering the temperature, cis content as high as 96% could be obtained. PMID:22239675

  9. 2005 Nobel Prize in Chemistry: Development of the Olefin Metathesis Method in Organic Synthesis

    Science.gov (United States)

    Casey, Charles P.

    2006-01-01

    The 2005 Nobel Prize in Chemistry was awarded "for the development of the metathesis method in organic synthesis". The discoveries of the laureates provided a chemical reaction used daily in the chemical industry for the efficient and more environmentally friendly production of important pharmaceuticals, fuels, synthetic fibers, and many other…

  10. 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.

  11. Experimental study on interaction and coalescence of synchronized multiple bubbles

    Science.gov (United States)

    Cui, P.; Wang, Q. X.; Wang, S. P.; Zhang, A. M.

    2016-01-01

    Experiments are carried out on the interaction and coalescence of two, three, and four bubbles with approximately the same sizes, distributed evenly and symmetrically. The bubbles are generated simultaneously by electric discharges, using an in-house designed series circuit, and their interaction is captured using a high-speed camera. Particular attentions are paid to if/when coalescence of bubbles happens and the motion of the joined bubbles. Some new features are observed, which depend mainly on the dimensionless distance γbb = dbb/Rmax, where dbb is the inter-bubble distance and Rmax is the maximum bubble radius. For γbb > 2, a jet forms and penetrates each side bubble, directed to the center of the configuration, resulting in a protrusion. Towards the end of collapse, a large portion of bubble gases is compressed into the protrusion from the main part of the toroidal bubble. For γbb bubbles coalesce during expansion, and the part of the joined bubble's surface distal from the center of the configuration collapses faster than elsewhere. The experiments show that the oscillation period of multi-bubbles does not change appreciably without coalescence but increases significantly with coalescence. For three bubbles initiated at collinear positions with γbb > 2, the jets that form from the side bubbles are towards the middle, and the middle bubble splits into two parts, moving towards the two side bubbles. For γbb bubbles merge with the middle bubble during expansion, forming an ellipsoid bubble; the joined bubble collapses predominantly from two sides, where two inward jets form towards the end of collapse.

  12. Investigation of drop coalescence via transient shape evolution: A sequential event based approach

    CERN Document Server

    Haldar, Krishnayan; Behera, Manas Ranjan; Chakraborty, Sudipto

    2015-01-01

    While a drop of liquid is placed on another liquid surface, two possible coalescence outcomes are observed. The parent drop bounces several times, floats and then disappears within the liquid pool without producing daughter droplets. This is called complete coalescence. Another outcome is the generation of secondary droplets from the primary drop itself. This is called partial coalescence. Repetitions of such phenomenon as a successive self-similar event is also known as coalescence cascade. In a nutshell, complete coalescence is governed strongly by swallowing mechanism whereas partial coalescence is attributed to slippage mechanism and solutal Marangoni flow. Here we use high speed camera and witness that water drop coalesces completely after impacting on pool of liquid whereas drop of non-ionic surfactant (TWEEN 20) coalesces partially. We also observe that number of daughter droplet generation is a strong function of surfactant concentration. Here we utilise the images to elaborately explain both the phen...

  13. Distinguished exchangeable coalescents and generalized Fleming-Viot processes with immigration

    CERN Document Server

    Foucart, Clément

    2010-01-01

    Coalescents with multiple collisions (also called Lambda-coalescents or simple exchangeable coalescents) are used as models of genealogies. We study a new class of Markovian coalescent processes connected to a population model with immigration. Imagine an infinite population with immigration labelled at each generation by N:={1,2,...}. Some ancestral lineages cannot be followed backwards after some time because their ancestor is outside the population. The individuals with an immigrant ancestor constitute a distinguished family and we define exchangeable distinguished coalescent processes as a model for genealogy with immigration, focussing on simple distinguished coalescents, i.e such that when a coagulation occurs all the blocks involved merge as a single block. These processes are characterized by two finite measures on [0,1] denoted by M=(\\Lambda_{0},\\Lambda_{1}). We call them M-coalescents. We show by martingale arguments that the condition of coming down from infinity for the M-coalescent coincides with...

  14. Synthetic studies on taxanes: A domino-enyne metathesis/Diels-Alder approach to the AB-ring

    Indian Academy of Sciences (India)

    Krishna P Kaliappan; Velayutham Ravikumar; Sandip A Pujari

    2008-01-01

    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.

  15. 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...

  16. A Comparison of the Performance of the Semiempirical PM6 Method Versus DFT Methods in Ru-Catalyzed Olefin Metathesis

    Science.gov (United States)

    Correa, Andrea; Poater, Albert; Ragone, Francesco; Cavallo, Luigi

    In this work we compare the performance of the semiempirical PM6 method with a more accurate DFT method when applied to Ru-catalyzed olefin metathesis. We demonstrate that the PM6 method reproduces with interesting accuracy the geometries located with a DFT approach. As for the energetics, the relative DFT stability of the metallacycle with respect to the coordination intermediate is reproduced with reasonable accuracy by the PM6 method, whereas the olefin coordination energy and the energy barrier of the metathesis step are overestimated. Further, for the same system we performed a PM6-based meta-dynamics study of the olefin metathesis reaction, which indicated a reasonable good behavior of the system also under dynamic conditions. In conclusion, the obtained results validate the use of the semiempirical PM6 method for preliminary and computationally fast screening on new ligands/substrates in Ru catalyzed olefin metathesis.

  17. Combinatorial screening of an in situ generated library of tungsten oxyhalide and imido complexes for olefin metathesis.

    Science.gov (United States)

    Romer, Duane R; Sussman, Victor J; Burdett, Ken; Chen, Yu; Miller, Kami J

    2014-10-13

    A series of substituted tungsten(VI) halides with general formula WECl4 (E = O or -NR (imido)) were screened via a high throughput study to identify potential new olefin metathesis catalysts. The tungsten species were treated with a series of aluminum alkyl activators and modifier ligands to generate active catalyst species in situ. Ring-opening metathesis polymerization (ROMP) of cyclooctene was used as a primary screen to identify potential metathesis catalysts and active catalysts were subjected to a secondary screen to evaluate tolerance toward polar functional groups. Several combinations from the high throughput campaign yielded active metathesis catalysts for the ROMP of cyclooctene. However, none of the catalysts examined in this study exhibited any evidence of significant polar functional group tolerance as determined by the results of the secondary cyclooctene/butyl acetate screen.

  18. Catalyst-controlled stereoselective olefin metathesis as a principal strategy in multistep synthesis design: a concise route to (+)-neopeltolide.

    Science.gov (United States)

    Yu, Miao; Schrock, Richard R; Hoveyda, Amir H

    2015-01-01

    Molybdenum-, tungsten-, and ruthenium-based complexes that control the stereochemical outcome of olefin metathesis reactions have been recently introduced. However, the complementary nature of these systems through their combined use in multistep complex molecule synthesis has not been illustrated. A concise diastereo- and enantioselective route that furnishes the anti-proliferative natural product neopeltolide is now disclosed. Catalytic transformations are employed to address every stereochemical issue. Among the featured processes are an enantioselective ring-opening/cross-metathesis promoted by a Mo monoaryloxide pyrrolide (MAP) complex and a macrocyclic ring-closing metathesis that affords a trisubstituted alkene and is catalyzed by a Mo bis(aryloxide) species. Furthermore, Z-selective cross-metathesis reactions, facilitated by Mo and Ru complexes, have been employed in the stereoselective synthesis of the acyclic dienyl moiety of the target molecule.

  19. Efficient ring-closing metathesis of alkenyl bromides: the importance of protecting the catalyst during the olefin approach.

    Science.gov (United States)

    Gatti, Michele; Drinkel, Emma; Wu, Linglin; Pusterla, Ivano; Gaggia, Fiona; Dorta, Reto

    2010-11-01

    We present the first productive ring-closing metathesis reaction that leads to the construction of cyclic alkenyl bromides. Efficient catalysis employing commercially available Grubbs II catalyst is possible through appropriate modification of the starting bromoalkene moiety.

  20. 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.

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

    Directory of Open Access Journals (Sweden)

    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.

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

    Science.gov (United States)

    Tracz, Andrzej; Matczak, Mateusz; Urbaniak, Katarzyna

    2015-01-01

    Summary 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. PMID:26664602

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

    Science.gov (United States)

    Tracz, Andrzej; Matczak, Mateusz; Urbaniak, Katarzyna; Skowerski, Krzysztof

    2015-01-01

    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.

  4. Tube-in-tube reactor as a useful tool for homo- and heterogeneous olefin metathesis under continuous flow mode.

    Science.gov (United States)

    Skowerski, Krzysztof; Czarnocki, Stefan J; Knapkiewicz, Paweł

    2014-02-01

    A tube-in-tube reactor was successfully applied in homo- and heterogeneous olefin metathesis reactions under continuous flow mode. It was shown that the efficient removal of ethylene facilitated by connection of the reactor with a vacuum pump significantly improves the outcome of metathesis reactions. The beneficial aspects of this approach are most apparent in reactions performed at low concentration, such as macrocyclization reactions. The established system allows achievement of both improved yield and selectivity, and is ideal for industrial applications.

  5. Deletion (2)(q37)

    Energy Technology Data Exchange (ETDEWEB)

    Stratton, R.F.; Tolworthy, J.A.; Young, R.S. [South Texas Genetics Center, San Antonio, TX (United States)

    1994-06-01

    We report on a 5-month-old girl with widely spaced nipples, redundant nuchal skin, coarctation of the aorta, anal atresia with distal fistula, postnatal growth retardation, hypotonia, and sparse scalp hair. Initial clinical assessment suggested the diagnosis of Ullrich-Turner syndrome. Chromosome analysis showed a 46,XX,del(2)(q37) karyotype in peripheral lymphocytes. We compare her findings to those of other reported patients with terminal deletions of 2q. 8 refs., 2 figs., 1 tab.

  6. Low-Frequency Gravitational Radiation from Coalescing Massive Black Holes

    CERN Document Server

    Sesana, A; Madau, P; Volonteri, M

    2005-01-01

    We compute the expected low-frequency gravitational wave signal from coalescing massive black hole (MBH) binaries at the center of galaxies. We follow the merging history of halos and associated holes via cosmological Monte Carlo realizations of the merger hierarchy from early times to the present in a LCDM cosmology. MBHs get incorporated through a series of mergers into larger and larger halos, sink to the centre owing to dynamical friction, accrete a fraction of the gas in the merger remnant to become more massive, and form a binary system. Stellar dynamical processes dominates the orbital evolution of the binary at large separations, while gravitational wave emission takes over at small radii, causing the final coalescence of the system. We discuss the observability of inspiraling MBH binaries by a low-frequency gravitational wave experiment such as the planned Laser Interferometer Space Antenna (LISA), discriminating between resolvable sources and unresolved confusion noise. Over a 3-year observing perio...

  7. Twin Binaries: Studies of Stability, Mass Transfer, and Coalescence

    CERN Document Server

    Lombardi, James C; Dooley, Katherine L; Gearity, Kyle; Kalogera, Vassiliki; Rasio, Frederic A

    2010-01-01

    Motivated by suggestions that binaries with almost equal-mass components ("twins") play an important role in the formation of double neutron stars and may be rather abundant among binaries, we study the stability of synchronized close and contact binaries with identical components in circular orbits. In particular, we investigate the dependency of the innermost stable circular orbit on the core mass, and we study the coalescence of the binary that occurs at smaller separations. For twin binaries composed of convective main-sequence stars, subgiants, or giants with low mass cores (M_c ~0.15M), we find that stable contact configurations exist at all separations down to the Roche limit, when mass shedding through the outer Lagrangian points triggers a coalescence of the envelopes and leaves the cores orbiting in a central tight binary. We discuss the implications of our results to the formation of binary neutron stars.

  8. Arrested of coalescence of emulsion droplets of arbitrary size

    Science.gov (United States)

    Mbanga, Badel L.; Burke, Christopher; Blair, Donald W.; Atherton, Timothy J.

    2013-03-01

    With applications ranging from food products to cosmetics via targeted drug delivery systems, structured anisotropic colloids provide an efficient way to control the structure, properties and functions of emulsions. When two fluid emulsion droplets are brought in contact, a reduction of the interfacial tension drives their coalescence into a larger droplet of the same total volume and reduced exposed area. This coalescence can be partially or totally hindered by the presence of nano or micron-size particles that coat the interface as in Pickering emulsions. We investigate numerically the dependance of the mechanical stability of these arrested shapes on the particles size, their shape anisotropy, their polydispersity, their interaction with the solvent, and the particle-particle interactions. We discuss structural shape changes that can be induced by tuning the particles interactions after arrest occurs, and provide design parameters for the relevant experiments.

  9. A variational void coalescence model for ductile metals

    KAUST Repository

    Siddiq, Amir

    2011-08-17

    We present a variational void coalescence model that includes all the essential ingredients of failure in ductile porous metals. The model is an extension of the variational void growth model by Weinberg et al. (Comput Mech 37:142-152, 2006). The extended model contains all the deformation phases in ductile porous materials, i.e. elastic deformation, plastic deformation including deviatoric and volumetric (void growth) plasticity followed by damage initiation and evolution due to void coalescence. Parametric studies have been performed to assess the model\\'s dependence on the different input parameters. The model is then validated against uniaxial loading experiments for different materials. We finally show the model\\'s ability to predict the damage mechanisms and fracture surface profile of a notched round bar under tension as observed in experiments. © Springer-Verlag 2011.

  10. Hydrodynamics of coalescing binary neutron stars ellipsoidal treatment

    CERN Document Server

    Lai, D; Lai, Dong; Shapiro, Stu

    1994-01-01

    We employ an approximate treatment of dissipative hydrodynamics in three dimensions to study the coalescence of binary neutron stars driven by the emission of gravitational waves. The stars are modeled as compressible ellipsoids obeying a polytropic equation of state; all internal fluid velocities are assumed to be linear functions of the coordinates. The hydrodynamic equations then reduce to a set of coupled ordinary differential equations for the evolution of the principal axes of the ellipsoids, the internal velocity parameters and the binary orbital parameters. Gravitational radiation reaction and viscous dissipation are both incorporated. We set up exact initial binary equilibrium configurations and follow the transition from the quasi-static, secular decay of the orbit at large separation to the rapid dynamical evolution of the configurations just prior to contact. A hydrodynamical instability resulting from tidal interactions significantly accelerates the coalescence at small separation, leading to app...

  11. Anti-coalescence of bosons on a lossy beam splitter

    Science.gov (United States)

    Vest, Benjamin; Dheur, Marie-Christine; Devaux, Éloïse; Baron, Alexandre; Rousseau, Emmanuel; Hugonin, Jean-Paul; Greffet, Jean-Jacques; Messin, Gaétan; Marquier, François

    2017-06-01

    Two-boson interference, a fundamentally quantum effect, has been extensively studied with photons through the Hong-Ou-Mandel effect and observed with guided plasmons. Using two freely propagating surface plasmon polaritons (SPPs) interfering on a lossy beam splitter, we show that the presence of loss enables us to modify the reflection and transmission factors of the beam splitter, thus revealing quantum interference paths that do not exist in a lossless configuration. We investigate the two-plasmon interference on beam splitters with different sets of reflection and transmission factors. Through coincidence-detection measurements, we observe either coalescence or anti-coalescence of SPPs. The results show that losses can be viewed as a degree of freedom to control quantum processes.

  12. Bulky N-Phosphino-Functionalized N-Heterocyclic Carbene Ligands: Synthesis, Ruthenium Coordination Chemistry, and Ruthenium Alkylidene Complexes for Olefin Metathesis.

    Science.gov (United States)

    Brown, Christopher C; Rominger, Frank; Limbach, Michael; Hofmann, Peter

    2015-11-01

    Ruthenium chemistry and applications in catalytic olefin metathesis based on N-phosphino-functionalized N-heterocyclic carbene ligands (NHCPs) are presented. Alkyl NHCP Ru coordination chemistry is described, and access to several potential synthetic precursors for ruthenium alkylidene complexes is outlined, incorporating both trimethylsilyl and phenyl alkylidenes. The Ru alkylidene complexes are evaluated as potential olefin metathesis catalysts and were shown to behave in a latent fashion. They displayed catalytic activity at elevated temperatures for both ring closing metathesis and ring opening metathesis polymerization.

  13. Ordered coalescence of nanocrystals: a path to strong macroporous nanoceramics

    Energy Technology Data Exchange (ETDEWEB)

    Shen Zhijian; Xiong Yan [Berzelii Center EXSELENT for Porous Materials and Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University, Stockholm S-106 91 (Sweden); Hoeche, Thomas [Leibniz-Institut fuer Oberflaechenmodifizierung e.V., Permoserstrasse 15, Leipzig D-04318 (Germany); Salamon, David [Membrane Technology Group, University of Twente, PO Box 217, 7500 AE Enschede (Netherlands); Fu Zhengyi [State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China); Belova, Lyubov, E-mail: shen@mmk.su.se [Department of Materials Science and Engineering, Royal Institute of Technology, Stockholm S-100 44 (Sweden)

    2010-05-21

    A versatile approach for integrating two apparently conflicting physical properties, high porosity and high mechanical strength, in polycrystalline bulks is established and demonstrated for the case of alumina ceramics. Macroporous alumina nanoceramics are synthesized by stimulating coalescence-mediated necking, which enables the formation of strong crystallographically coherent necks between adjacent grains. The work places a general emphasis on manipulating crystal growth on the nanoscale and on preparing highly porous polycrystalline bulk ceramics with improved mechanical rigidity.

  14. Gravitational wave emission from the coalescence of white dwarfs

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Berro, E [Departament de Fisica Aplicada, Universitat Politecnica de Catalunya, Escola Politecnica Superior de Castelldefels, Avda del Canal OlImpic s/n, 08860 Castelldefels (Spain); Institut d' Estudis Espacials de Catalunya, Ed. Nexus, c/Gran Capita 2, 08034 Barcelona (Spain); Loren-Aguilar, P [Institut d' Estudis Espacials de Catalunya, Ed. Nexus, c/Gran Capita 2, 08034 Barcelona (Spain); Institut de Ciencies de l' Espai (CSIC), Campus UAB, Facultat de Ciencies, Torre C-5, 08193 Bellaterra (Spain); Isern, J [Institut d' Estudis Espacials de Catalunya, Ed. Nexus, c/Gran Capita 2, 08034 Barcelona (Spain); Institut de Ciencies de l' Espai (CSIC), Campus UAB, Facultat de Ciencies, Torre C-5, 08193 Bellaterra (Spain); Pedemonte, A G [Departament de Fisica Aplicada, Universitat Politecnica de Catalunya, Escola Politecnica Superior de Castelldefels, Avda del Canal OlImpic s/n, 08860 Castelldefels (Spain); Guerrero, J [Institut d' Estudis Espacials de Catalunya, Ed. Nexus, c/Gran Capita 2, 08034 Barcelona (Spain); Institut de Ciencies de l' Espai (CSIC), Campus UAB, Facultat de Ciencies, Torre C-5, 08193 Bellaterra (Spain); Lobo, J A [Institut d' Estudis Espacials de Catalunya, Ed. Nexus, c/Gran Capita 2, 08034 Barcelona (Spain); Departament de Fisica Fonamental, Universitat de Barcelona, c/MartI i Franques 1, 08028 Barcelona (Spain)

    2005-05-21

    We have computed the gravitational wave emission arising from the coalescence of several close white dwarf binary systems. In order to do so, we have followed the evolution of such systems using a smoothed particle hydrodynamics code. Here we present some of the results obtained so far, paying special attention to the detectability of the emitted gravitational waves. Within this context, we show which could be the impact of individual merging episodes for LISA.

  15. Bubble coalescence dynamics and supersaturation in electrolytic gas evolution

    Energy Technology Data Exchange (ETDEWEB)

    Stover, R.L. [Univ. of California, Berkeley, CA (United States). Dept. of Chemical Engineering]|[Lawrence Berkeley National Lab., CA (United States). Energy and Environment Div.

    1996-08-01

    The apparatus and procedures developed in this research permit the observation of electrolytic bubble coalescence, which heretofore has not been possible. The influence of bubble size, electrolyte viscosity, surface tension, gas type, and pH on bubble coalescence was examined. The Navier-Stokes equations with free surface boundary conditions were solved numerically for the full range of experimental variables that were examined. Based on this study, the following mechanism for bubble coalescence emerges: when two gas bubbles coalesce, the surface energy decreases as the curvature and surface area of the resultant bubble decrease, and the energy is imparted into the surrounding liquid. The initial motion is driven by the surface tension and slowed by the inertia and viscosity of the surrounding fluid. The initial velocity of the interface is approximately proportional to the square root of the surface tension and inversely proportional to the square root of the bubble radius. Fluid inertia sustains the oblate/prolate oscillations of the resultant bubble. The period of the oscillations varies with the bubble radius raised to the 3/2 power and inversely with the square root of the surface tension. Viscous resistance dampens the oscillations at a rate proportional to the viscosity and inversely proportional to the square of the bubble radius. The numerical simulations were consistent with most of the experimental results. The differences between the computed and measured saddle point decelerations and periods suggest that the surface tension in the experiments may have changed during each run. By adjusting the surface tension in the simulation, a good fit was obtained for the 150-{micro}m diameter bubbles. The simulations fit the experiments on larger bubbles with very little adjustment of surface tension. A more focused analysis should be done to elucidate the phenomena that occur in the receding liquid film immediately following rupture.

  16. FTEC: a coalescent simulator for modeling faster than exponential growth

    OpenAIRE

    Reppell, Mark; Boehnke, Michael; Zöllner, Sebastian

    2012-01-01

    Summary: Recent genetic studies as well as recorded history point to massive growth in human population sizes during the recent past. To model and understand this growth accurately we introduce FTEC, an easy-to-use coalescent simulation program capable of simulating haplotype samples drawn from a population that has undergone faster than exponential growth. Samples drawn from a population that has undergone faster than exponential growth show an excess of very rare variation and more rapid LD...

  17. Characteristic dynamics near two coalescing eigenvalues incorporating continuum threshold effects

    Science.gov (United States)

    Garmon, Savannah; Ordonez, Gonzalo

    2017-06-01

    It has been reported in the literature that the survival probability P(t) near an exceptional point where two eigenstates coalesce should generally exhibit an evolution P (t ) ˜t2e-Γ t, in which Γ is the decay rate of the coalesced eigenstate; this has been verified in a microwave billiard experiment [B. Dietz et al., Phys. Rev. E 75, 027201 (2007)]. However, the heuristic effective Hamiltonian that is usually employed to obtain this result ignores the possible influence of the continuum threshold on the dynamics. By contrast, in this work we employ an analytical approach starting from the microscopic Hamiltonian representing two simple models in order to show that the continuum threshold has a strong influence on the dynamics near exceptional points in a variety of circumstances. To report our results, we divide the exceptional points in Hermitian open quantum systems into two cases: at an EP2A two virtual bound states coalesce before forming a resonance, anti-resonance pair with complex conjugate eigenvalues, while at an EP2B two resonances coalesce before forming two different resonances. For the EP2B, which is the case studied in the microwave billiard experiment, we verify that the survival probability exhibits the previously reported modified exponential decay on intermediate time scales, but this is replaced with an inverse power law on very long time scales. Meanwhile, for the EP2A the influence from the continuum threshold is so strong that the evolution is non-exponential on all time scales and the heuristic approach fails completely. When the EP2A appears very near the threshold, we obtain the novel evolution P (t ) ˜1 -C1√{t } on intermediate time scales, while further away the parabolic decay (Zeno dynamics) on short time scales is enhanced.

  18. Capillary-Inertial Colloidal Catapult upon Drop Coalescence

    Science.gov (United States)

    Chavez, Roger; Liu, Fangjie; Feng, James; Chen, Chuan-Hua

    2014-11-01

    To discharge micron-sized particles such as colloidal contaminants and biological spores, an enormous power density is needed to compete against the strong adhesive forces between the small particles and the supporting surface as well as the significant air friction exerted on the particles. Here, we demonstrate a colloidal catapult that achieves such a high power density by extracting surface energy released upon drop coalescence within an extremely short time period, which is governed by the capillary-inertial process converting the released surface energy into the bulk inertia of the merged drop. When two drops coalesce on top of a spherical particle, the resulting capillary-inertial oscillation is perturbed by the solid particle, giving rise to a net momentum eventually propelling the particle to launch from the supporting surface. The measured launching velocity follows a scaling law that accounts for the redistribution of the momentum of the merged drop onto the particle-drop complex, and is therefore proportional to the capillary-inertial velocity characterizing the coalescing drops. The interfacial flow process associated with the colloidal catapult is elucidated with both high-speed imaging and phase-field simulations.

  19. Coalescence control of elastomer clusters by fixed surface charges.

    Science.gov (United States)

    Gauer, Cornelius; Wu, Hua; Morbidelli, Massimo

    2010-02-04

    We studied the coalescence behavior of a fluorinated elastomer colloid, stabilized by fixed surface charges, with a glass transition temperature of about -20 degrees C, as a function of temperature under diffusion-limited cluster-cluster aggregation (DLCA) conditions. We first measured the aggregation kinetics by in situ dynamic light scattering and then simulated it through the Smoluchowski approach (i.e., population balance equations) using the only unknown parameter, the fractal dimension D(f) of the clusters, as the fit parameter. It was found that the estimated D(f) value increased as the temperature increased, starting from 1.7 at 25 degrees C and reaching the upper limit of 3.0 for T > or = 55 degrees C. These results indicate that the coalescence extent increases as the temperature increases. Such temperature-dependent coalescence behavior cannot be explained by thermodynamic considerations, and it must be related to a certain kinetic resistance. We explain this effect by considering the resistance of the fixed charges to relocation on the particle surface, which decreases as the temperature increases.

  20. Phylogenomics and coalescent analyses resolve extant seed plant relationships.

    Directory of Open Access Journals (Sweden)

    Zhenxiang Xi

    Full Text Available The extant seed plants include more than 260,000 species that belong to five main lineages: angiosperms, conifers, cycads, Ginkgo, and gnetophytes. Despite tremendous effort using molecular data, phylogenetic relationships among these five lineages remain uncertain. Here, we provide the first broad coalescent-based species tree estimation of seed plants using genome-scale nuclear and plastid data By incorporating 305 nuclear genes and 47 plastid genes from 14 species, we identify that i extant gymnosperms (i.e., conifers, cycads, Ginkgo, and gnetophytes are monophyletic, ii gnetophytes exhibit discordant placements within conifers between their nuclear and plastid genomes, and iii cycads plus Ginkgo form a clade that is sister to all remaining extant gymnosperms. We additionally observe that the placement of Ginkgo inferred from coalescent analyses is congruent across different nucleotide rate partitions. In contrast, the standard concatenation method produces strongly supported, but incongruent placements of Ginkgo between slow- and fast-evolving sites. Specifically, fast-evolving sites yield relationships in conflict with coalescent analyses. We hypothesize that this incongruence may be related to the way in which concatenation methods treat sites with elevated nucleotide substitution rates. More empirical and simulation investigations are needed to understand this potential weakness of concatenation methods.

  1. Phylogenomics and coalescent analyses resolve extant seed plant relationships.

    Science.gov (United States)

    Xi, Zhenxiang; Rest, Joshua S; Davis, Charles C

    2013-01-01

    The extant seed plants include more than 260,000 species that belong to five main lineages: angiosperms, conifers, cycads, Ginkgo, and gnetophytes. Despite tremendous effort using molecular data, phylogenetic relationships among these five lineages remain uncertain. Here, we provide the first broad coalescent-based species tree estimation of seed plants using genome-scale nuclear and plastid data By incorporating 305 nuclear genes and 47 plastid genes from 14 species, we identify that i) extant gymnosperms (i.e., conifers, cycads, Ginkgo, and gnetophytes) are monophyletic, ii) gnetophytes exhibit discordant placements within conifers between their nuclear and plastid genomes, and iii) cycads plus Ginkgo form a clade that is sister to all remaining extant gymnosperms. We additionally observe that the placement of Ginkgo inferred from coalescent analyses is congruent across different nucleotide rate partitions. In contrast, the standard concatenation method produces strongly supported, but incongruent placements of Ginkgo between slow- and fast-evolving sites. Specifically, fast-evolving sites yield relationships in conflict with coalescent analyses. We hypothesize that this incongruence may be related to the way in which concatenation methods treat sites with elevated nucleotide substitution rates. More empirical and simulation investigations are needed to understand this potential weakness of concatenation methods.

  2. Nickel, copper and cobalt coalescence in copper cliff converter slag

    Directory of Open Access Journals (Sweden)

    Wolf A.

    2016-01-01

    Full Text Available The aim of this investigation is to assess the effect of various additives on coalescence of nickel, copper and cobalt from slags generated during nickel extraction. The analyzed fluxes were silica and lime while examined reductants were pig iron, ferrosilicon and copper-silicon compound. Slag was settled at the different holding temperatures for various times in conditions that simulated the industrial environment. The newly formed matte and slag were characterized by their chemical composition and morphology. Silica flux generated higher partition coefficients for nickel and copper than the addition of lime. Additives used as reducing agents had higher valuable metal recovery rates and corresponding partition coefficients than fluxes. Microstructural studies showed that slag formed after adding reductants consisted of primarily fayalite, with some minute traces of magnetite as the secondary phase. Addition of 5 wt% of pig iron, ferrosilicon and copper-silicon alloys favored the formation of a metallized matte which increased Cu, Ni and Co recoveries. Addition of copper-silicon alloys with low silicon content was efficient in copper recovery but coalescence of the other metals was low. Slag treated with the ferrosilicon facilitated the highest cobalt recovery while copper-silicon alloys with silicon content above 10 wt% resulted in high coalescence of nickel and copper, 87 % and 72 % respectively.

  3. Improved quark coalescence for a multi-phase transport model

    Science.gov (United States)

    He, Yuncun; Lin, Zi-Wei

    2017-07-01

    The string melting version of a multi-phase transport model is often applied to high-energy heavy-ion collisions since the dense matter thus formed is expected to be in parton degrees of freedom. In this work we improve its quark coalescence component, which describes the hadronization of the partonic matter to a hadronic matter. We removed the previous constraint that forced the numbers of mesons, baryons, and antibaryons in an event to be separately conserved through the quark coalescence process. A quark now could form either a meson or a baryon depending on the distance to its coalescence partner(s). We then compare results from the improved model with the experimental data on hadron d N /d y ,pT spectra, and v2 in heavy-ion collisions from √{s NN}=62.4 GeV to 5.02 TeV. We show that, besides being able to describe these observables for low-pTpions and kaons, the improved model also better describes the low-p T baryon observables in general, especially the baryon p T spectra and antibaryon-to-baryon ratios for multistrange baryons.

  4. Ion coalescence of neutron encoded TMT 10-plex reporter ions.

    Science.gov (United States)

    Werner, Thilo; Sweetman, Gavain; Savitski, Maria Fälth; Mathieson, Toby; Bantscheff, Marcus; Savitski, Mikhail M

    2014-04-01

    Isobaric mass tag-based quantitative proteomics strategies such as iTRAQ and TMT utilize reporter ions in the low mass range of tandem MS spectra for relative quantification. The recent extension of TMT multiplexing to 10 conditions has been enabled by utilizing neutron encoded tags with reporter ion m/z differences of 6 mDa. The baseline resolution of these closely spaced tags is possible due to the high resolving power of current day mass spectrometers. In this work we evaluated the performance of the TMT10 isobaric mass tags on the Q Exactive Orbitrap mass spectrometers for the first time and demonstrated comparable quantification accuracy and precision to what can be achieved on the Orbitrap Elite mass spectrometers. However, we discovered, upon analysis of complex proteomics samples on the Q Exactive Orbitrap mass spectrometers, that the proximate TMT10 reporter ion pairs become prone to coalescence. The fusion of the different reporter ion signals into a single measurable entity has a detrimental effect on peptide and protein quantification. We established that the main reason for coalescence is the commonly accepted maximum ion target for MS2 spectra of 1e6 on the Q Exactive instruments. The coalescence artifact was completely removed by lowering the maximum ion target for MS2 spectra from 1e6 to 2e5 without any losses in identification depth or quantification quality of proteins.

  5. The coalescence and organization of lahars at Semeru volcano, Indonesia

    Science.gov (United States)

    Doyle, E. E.; Cronin, S. J.; Cole, S. E.; Thouret, J.-C.

    2010-10-01

    We present multi-parameter geophysical measurements of rainfall-induced lahars at Semeru Volcano, East Java, using two observation sites 510 m apart, 11.5 km from the summit. Our study site in the Curah Lengkong channel is composed of a 30-m wide box-valley, with a base of gravel and lava bedrock, representing an ideal geometry for high density measurements of active lahars. Instrumentation included pore-pressure sensors (stage), a broad-band seismograph (arrival times, vibrational energy, and turbulence), video footage, and direct bucket sampling. A total of 8 rainfall-induced lahars were recorded, with durations of 1-3 h, heights 0.5-2 m, and peak velocities 3-6 m/s. Flow types ranged from dilute to dense hyperconcentrated flows. These recorded flows were commonly composed of partly coalesced, discrete and unsteady gravity current packets, represented by multiple peaks within each lahar. These packets most likely originate from multiple lahar sources, and can be traced between instrument sites. Those with the highest concentrations and greatest wetted areas were often located mid-lahar at our measured reach, accelerating towards the flow front. As these lahars travel downstream, the individual packets thus coalesce and the flow develops a more organised structure. Observations of different degrees of coalescence between these discrete flow packets illustrate that a single mature debris flow may have formed from multiple dynamically independent lahars, each with different origins.

  6. An experimental study on the coalescence process of binary droplets in oil under ultrasonic standing waves.

    Science.gov (United States)

    Luo, Xiaoming; Cao, Juhang; He, Limin; Wang, Hongping; Yan, Haipeng; Qin, Yahua

    2017-01-01

    The coalescence process of binary droplets in oil under ultrasonic standing waves was investigated with high-speed photography. Three motion models of binary droplets in coalescence process were illustrated: (1) slight translational oscillation; (2) sinusoidal translational oscillation; (3) migration along with acoustic streaming. To reveal the droplets coalescence mechanisms, the influence of main factors (such as acoustic intensity, droplet size, viscosity and interfacial tension, etc) on the motion and coalescence of binary droplets was studied under ultrasonic standing waves. Results indicate that the shortest coalescence time is achieved when binary droplets show sinusoidal translational oscillation. The corresponding acoustic intensity in this case is the optimum acoustic intensity. Under the optimum acoustic intensity, drop size decrease will bring about coalescence time decrease by enhancing the binary droplets oscillation. Moreover, there is an optimum interfacial tension to achieve the shortest coalescence time.

  7. Sunflower-based Feedstocks in Nonfood Applications: Perspectives from Olefin Metathesis

    Directory of Open Access Journals (Sweden)

    Bassie B. Marvey

    2008-08-01

    Full Text Available Sunflower (Helianthus annuus L. oil remains under-utilised albeit one of the major seed oils produced world-wide. Moreover, the high oleic sunflower varieties make the oil attractive for applications requiring high temperature processes and those targeting the C=C double bond functionality. Herein an overview of the recent developments in olefin metathesis of sunflower-based feedstocks is presented. The improved performance of olefin metathesis catalysts leading to high turnover numbers, high selectivity and catalyst recyclability, opens new opportunities for tailoring sunflower-based feedstocks into products required for possible new niche market applications. Promising results in biofuel, biopolymers, fragrances and fine chemicals applications have been reported.

  8. 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.

  9. Production of propene from 1-butene metathesis reaction on tungsten based heterogeneous catalysts

    Institute of Scientific and Technical Information of China (English)

    Huijuan Liu; Ling Zhang; Xiujie Li; Shengjun Huang; Shenglin Liu; Wenjie Xin; Sujuan Xie; Longya Xu

    2009-01-01

    A new propene production route from 1-butene metathesis has been developed on heterogeneous 10WO_3/Al_2O_3-HY catalysts with different HY contents. It is found that the catalysts play bi-functionally first for the isomerization of 1-butene to 2-butene and then for the cross-metathesis between 1-butene and 2-butene to propene and 2-pentene. The combination of HY zeolite and Al_2O_3 is prerequisite for the production of propene. The propene yield keeps increasing with the HY content in the range of 10-70 wt%,where 10WO_3/Al_2O_3-70HY exhibits the highest propene yield. The MS-H_2-TPR and MS-O_2-TPO characterizations indicate that the increase of HY content in the catalysts weakens the interaction between W species and supports,whereas enhance the probability of coking on the metal species and acid sites.

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

    Science.gov (United States)

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

    2013-05-01

    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.

  11. Olefin metathesis and quadruple hydrogen bonding: A powerful combination in multistep supramolecular synthesis

    Science.gov (United States)

    Scherman, Oren A.; Ligthart, G. B. W. L.; Ohkawa, Haruki; Sijbesma, Rint P.; Meijer, E. W.

    2006-08-01

    We show that combining concepts generally used in covalent organic synthesis such as retrosynthetic analysis and the use of protecting groups, and applying them to the self-assembly of polymeric building blocks in multiple steps, results in a powerful strategy for the self-assembly of dynamic materials with a high level of architectural control. We present a highly efficient synthesis of bifunctional telechelic polymers by ring-opening metathesis polymerization (ROMP) with complementary quadruple hydrogen-bonding motifs. Because the degree of functionality for the polymers is 2.0, the formation of alternating, blocky copolymers was demonstrated in both solution and the bulk leading to stable, microphase-separated copolymer morphologies. ring-opening metathesis polymerization | self-assembly | block copolymer | retrosynthesis

  12. Cascade Metathesis Reactions for the Synthesis of Taxane and Isotaxane Derivatives

    Science.gov (United States)

    Ma, Cong; Letort, Aurélien; Aouzal, Rémi; Wilkes, Antonia; Maiti, Gourhari; Farrugia, Louis J.; Ricard, Louis

    2016-01-01

    Abstract Tricyclic isotaxane and taxane derivatives have been synthesized by a very efficient cascade ring‐closing dienyne metathesis (RCDEYM) reaction, which formed the A and B rings in one operation. When the alkyne is present at C13 (with no neighboring gem‐dimethyl group), the RCEDYM reaction leads to 14,15‐isotaxanes 16 a,b and 18 b with the gem‐dimethyl group on the A ring. If the alkyne is at the C11 position (and thus flanked by a gem‐dimethyl group), RCEDYM reaction only proceeds in the presence of a trisubstituted olefin at C13, which disfavors the competing diene ring‐closing metathesis reaction, to give the tricyclic core of Taxol 44. PMID:27062670

  13. High-Performance Isocyanide Scavengers for Use in Low-Waste Purification of Olefin Metathesis Products.

    Science.gov (United States)

    Szczepaniak, Grzegorz; Urbaniak, Katarzyna; Wierzbicka, Celina; Kosiński, Krzysztof; Skowerski, Krzysztof; Grela, Karol

    2015-12-21

    Three isocyanides containing a tertiary nitrogen atom were investigated for use as small-molecule ruthenium scavenging agents in the workup of olefin metathesis reactions. The proposed compounds are odorless, easy to obtain, and highly effective in removing metal residues, sometimes bringing the metal content below 0.0015 ppm. The most successful of the tested compounds, II, performs very well, even with challenging polar products. The performance of these scavengers is compared and contrasted with other known techniques, such as silica gel filtration and the use of self-scavenging catalysts. As a result, a new hybrid purification method is devised, which gives better results than using either a self-scavenging catalyst or a scavenger alone. Additionally, isocyanide II is shown to be a deactivating (reaction quenching) agent for olefin metathesis and superior to ethyl vinyl ether.

  14. Cascade Metathesis Reactions for the Synthesis of Taxane and Isotaxane Derivatives.

    Science.gov (United States)

    Ma, Cong; Letort, Aurélien; Aouzal, Rémi; Wilkes, Antonia; Maiti, Gourhari; Farrugia, Louis J; Ricard, Louis; Prunet, Joëlle

    2016-05-10

    Tricyclic isotaxane and taxane derivatives have been synthesized by a very efficient cascade ring-closing dienyne metathesis (RCDEYM) reaction, which formed the A and B rings in one operation. When the alkyne is present at C13 (with no neighboring gem-dimethyl group), the RCEDYM reaction leads to 14,15-isotaxanes 16 a,b and 18 b with the gem-dimethyl group on the A ring. If the alkyne is at the C11 position (and thus flanked by a gem-dimethyl group), RCEDYM reaction only proceeds in the presence of a trisubstituted olefin at C13, which disfavors the competing diene ring-closing metathesis reaction, to give the tricyclic core of Taxol 44.

  15. Synthesis and properties of new bolaform and macrocyclic galactose-based surfactants obtained by olefin metathesis.

    Science.gov (United States)

    Satgé, Céline; Granet, Robert; Verneuil, Bernard; Champavier, Yves; Krausz, Pierre

    2004-05-17

    A series of galactose-based surfactants with various structures likely to display new interesting properties were synthesized. Four monocatenary surfactants were elaborated by microwave-assisted galactosylation of undecanol or 10-undecenol. These compounds were slightly soluble in water. Their tensioactive properties were determined at 45 degrees C. Olefin metathesis was used to synthesize the two single-chain bolaforms from undec-10-enyl galactopyranosides; two pseudomacrocyclic bolaforms were prepared by grafting two carbamates at O-4 and O-4' sugar positions of the single-chain bolaforms. These four surfactants are insoluble in water and undergo monolayer compression. Cyclization of these bolaforms by olefin metathesis led to macrocyclic surfactant analogues of archaeobacterial membrane components.

  16. 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.

  17. Concise syntheses of insect pheromones using Z-selective cross metathesis.

    Science.gov (United States)

    Herbert, Myles B; Marx, Vanessa M; Pederson, Richard L; Grubbs, Robert H

    2013-01-02

    Very short synthetic routes to nine cis-olefin-containing pheromones containing a variety of functionality, including an unconjugated (E,Z) diene, are reported. These lepidopteran pheromones are used extensively for pest control, and were easily prepared using ruthenium-based Z-selective cross metathesis, highlighting the advantages of this method over less efficient ways to form Z olefins. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    KAUST Repository

    Zhang, Hefeng

    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.

  19. Ruthenium indenylidene “1st generation” olefin metathesis catalysts containing triisopropyl phosphite

    Directory of Open Access Journals (Sweden)

    Stefano Guidone

    2015-09-01

    Full Text Available The reaction of triisopropyl phosphite with phosphine-based indenylidene pre-catalysts affords “1st generation” cis-complexes. These have been used in olefin metathesis reactions. The cis-Ru species exhibit noticeable differences with the trans-Ru parent complexes in terms of structure, thermal stability and reactivity. Experimental data underline the importance of synergistic effects between phosphites and L-type ligands.

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

    Directory of Open Access Journals (Sweden)

    Luigi Cavallo

    2011-01-01

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

  1. Ruthenium indenylidene "1(st) generation" olefin metathesis catalysts containing triisopropyl phosphite.

    Science.gov (United States)

    Guidone, Stefano; Nahra, Fady; Slawin, Alexandra M Z; Cazin, Catherine S J

    2015-01-01

    The reaction of triisopropyl phosphite with phosphine-based indenylidene pre-catalysts affords "1(st) generation" cis-complexes. These have been used in olefin metathesis reactions. The cis-Ru species exhibit noticeable differences with the trans-Ru parent complexes in terms of structure, thermal stability and reactivity. Experimental data underline the importance of synergistic effects between phosphites and L-type ligands.

  2. Ruthenium-Catalyzed Olefin Cross-Metathesis with Tetrafluoroethylene and Analogous Fluoroolefins.

    Science.gov (United States)

    Takahira, Yusuke; Morizawa, Yoshitomi

    2015-06-10

    This Communication describes a successful olefin cross-metathesis with tetrafluoroethylene and its analogues. A key to the efficient catalytic cycle is interconversion between two thermodynamically stable, generally considered sluggish, Fischer carbenes. This newly demonstrated catalytic transformation enables easy and short-step synthesis of a new class of partially fluorinated olefins bearing plural fluorine atoms, which are particularly important and valuable compounds in organic synthesis and medicinal chemistry as well as the materials and polymer industries.

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

    Science.gov (United States)

    Bahri-Laleh, Naeimeh; Credendino, Raffaele

    2011-01-01

    Summary In this study we have investigated computationally the origin of the cis–trans selectivity in the Ru-catalyzed cross metathesis (CM) of a prototype monosubstituted olefin, i.e., propene. Our calculations suggest that the origin of the preferential formation of trans-olefins is in the product release step, which prevents the initially formed cis-olefin from escaping the metal, and returns it to the reaction pool until the trans-olefin is formed. PMID:21286393

  4. Ruthenium indenylidene “1st generation” olefin metathesis catalysts containing triisopropyl phosphite

    Science.gov (United States)

    Guidone, Stefano; Nahra, Fady; Slawin, Alexandra M Z

    2015-01-01

    Summary The reaction of triisopropyl phosphite with phosphine-based indenylidene pre-catalysts affords “1st generation” cis-complexes. These have been used in olefin metathesis reactions. The cis-Ru species exhibit noticeable differences with the trans-Ru parent complexes in terms of structure, thermal stability and reactivity. Experimental data underline the importance of synergistic effects between phosphites and L-type ligands. PMID:26425210

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

    Science.gov (United States)

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

    2014-02-28

    The synthesis and characterisation of [Ru(H)(η(5)-3-phenylindenyl)((i)Bu-Phoban)2] 4 is reported ((i)Bu-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 [RuCl2(PPh3)2(3-phenylindenylidene)] (M10).

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

    KAUST Repository

    Manzini, Simone

    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.

  7. 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

    Methyl 5-deoxy-5-iodo-pentofuranosides are reductively ring-opened and propargylated in a tandem fashion in the presence of zinc. The 1,7-enynes thus obtained are subjected to ring-closing enyne metathesis with catalyst B to produce functionalized 1-vinyl cyclohexenes. By adding BnNH2 to the tand...... chemistry. These procedures constitute efficient methods for rapid carbocyclization and annulation of carbohydrates to produce a variety of functionalized five- and six-membered ring systems....

  8. Olefin metathesis reaction on GaN (0 0 0 1) surfaces

    Science.gov (United States)

    Makowski, Matthew S.; Zemlyanov, Dmitry Y.; Ivanisevic, Albena

    2011-03-01

    Proof-of-concept reactions were performed on GaN (0 0 0 1) surfaces to demonstrate surface termination with desired chemical groups using an olefin cross-metathesis reaction. To prepare the GaN surfaces for olefin metathesis, the surfaces were hydrogen terminated with hydrogen plasma, chlorine terminated with phosphorous pentachloride, and then terminated with an alkene group via a Grignard reaction. The olefin metathesis reaction then bound 7-bromo-1-heptene. The modified surfaces were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and water contact angle measurements following each step in the reaction scheme. The XPS data was used to qualitatively identify surface chemical species and to quantitatively determine molecular surface coverage. The bromine atom in 7-bromo-1-heptene served as a heteroatom for identification with XPS. The reaction scheme resulted in GaN substrates with a surface coverage of 0.10 monolayers and excellent stability towards oxidation when exposed to oxygen plasma.

  9. Bis-mixed-carbene ruthenium-thiolate-alkylidene complexes: synthesis and olefin metathesis activity.

    Science.gov (United States)

    Dahcheh, Fatme; Stephan, Douglas W

    2015-01-28

    A series of bis-carbene Ru-hydride species, including (IMes)(Im(OMe)2)(PPh3)RuHCl (1) and (SIMes)(Me2Im(OMe)2)(PPh3)RuHCl (2) were prepared and subsequently shown to react with aryl-vinyl-sulfides to give the bis-carbene-alkylidene complexes: Im(OMe)2(SIMes)RuCl(SR)(=CHCH3) (R = p-FC6H4 (3), p-(NO2)C6H4 (4)), Im(OMe)2(IMes)RuCl(=CHCH3)(SPh) (5), Me2Im(OMe)2(SIMes)RuCl(=CHCH3)(SPh) (6), Im(OMe)2(SIMes)(F5C6S)RuCl(=CHR) (R = C4H9 (9), C5H11 (10)). The activity of these species in the standard Grubbs' tests for ring-opening metathesis polymerization, ring-closing and cross-metathesis are reported. Although these thiolate derivatives are shown to exhibit modest metathesis activities, the reactivity is enhanced in the presence of BCl3.

  10. Tandem ring-opening/ring-closing metathesis polymerization: relationship between monomer structure and reactivity.

    Science.gov (United States)

    Park, Hyeon; Lee, Ho-Keun; Choi, Tae-Lim

    2013-07-24

    Monomers containing either cycloalkenes with low ring strain or 1-alkynes are poor monomers for olefin metathesis polymerization. Ironically, keeping two inactive functional groups in proximity within one molecule can make it an excellent monomer for metathesis polymerization. Recently, we demonstrated that monomer 1 having cyclohexene and propargyl moieties underwent rapid tandem ring-opening/ring-closing metathesis (RO/RCM) polymerization via relay-type mechanism. Furthermore, living polymerization was achieved when a third-generation Grubbs catalyst was used. Here, we present a full account on this tandem polymerization by investigating how various structural modifications of the monomers affected the reactivity of the tandem polymerization. We observed that changing the ring size of the cycloalkene moieties, the length of the alkynes, and linker units influenced not only the polymerization rates but also the reactivities of Diels-Alder reaction, which is a post-modification reaction of the resulting polymers. Also, the mechanism of tandem polymerization was studied by conducting end-group analysis using (1)H NMR analysis, thereby concluding that the polymerization occurred by the alkyne-first pathway. With this mechanistic conclusion, factors responsible for the dramatic structure-reactivity relationship were proposed. Lastly, tandem RO/RCM polymerization of monomers containing sterically challenging trisubstituted cycloalkenes was successfully carried out to give polymer repeat units having tetrasubstituted cycloalkenes.

  11. Synthesis and Application of Novel Ruthenium Catalysts for High Temperature Alkene Metathesis

    Directory of Open Access Journals (Sweden)

    Tegene T. Tole

    2017-01-01

    Full Text Available Four pyridinyl alcohols and the corresponding hemilabile pyridinyl alcoholato ruthenium carbene complexes of the Grubbs second generation-type RuCl(H2IMes(O^N(=CHPh, where O^N = 1-(2′-pyridinyl-1,1-diphenyl methanolato, 1-(2′-pyridinyl-1-(2′-chlorophenyl,1-phenyl methanolato, 1-(2′-pyridinyl-1-(4′-chlorophenyl,1-phenyl methanolato and 1-(2′-pyridinyl-1-(2′-methoxyphenyl,1-phenyl methanolato, are synthesized in very good yields. At high temperatures, the precatalysts showed high stability, selectivity and activity in 1-octene metathesis compared to the Grubbs first and second generation precatalysts. The 2-/4-chloro- and 4-methoxy-substituted pyridinyl alcoholato ligand-containing ruthenium precatalysts showed high performance in the 1-octene metathesis reaction in the range 80–110 °C. The hemilabile 4-methoxy-substituted pyridinyl alcoholato ligand improved the catalyst stability, activity and selectivity for 1-octene metathesis significantly at 110 °C.

  12. Studies of the mechanism of the olefin metathesis reaction and the process of active site formation on photoreduced molybdenum-silicate catalysts. 2. Productive and degenerative metathesis of C/sub 2/H/sub 4/-C/sub 2/D/sub 4/ and C/sub 3/H/sub 6/-C/sub 3/D/sub 6/ mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Elev, I.V.; Shelimov, B.N.; Kazanskii, V.B.

    1987-10-01

    The specific catalytic activity of photoreduced Mo/sup 4 +//SiO/sub 2/ samples has been compared for productive and degenerate metathesis reactions of C/sub 3/H/sub 6/-C/sub 3/D/sub 6/ and C/sub 2/H/sub 4/-C/sub 2/D/sub 4/ mixtures. It has been found, that, under comparable conditions, the rate of degenerate metathesis of ethylene is 4-5 times slower than the rate of productive metathesis of propylene, although the rate of degenerate metathesis of propylene is 5 x 10/sup 3/-10/sup 4/ times greater than its rate of productive metathesis. Based on these results, it is concluded that degenerate metathesis of propylene occurs via the involvement of secondary (ethylidene) carbenes.

  13. Breakup and coalescence characteristics of a hollow cone swirling spray

    Science.gov (United States)

    Saha, Abhishek; Lee, Joshua D.; Basu, Saptarshi; Kumar, Ranganathan

    2012-12-01

    This paper deals with an experimental study of the breakup characteristics of water emanating from hollow cone hydraulic injector nozzles induced by pressure-swirling. The experiments were conducted using two nozzles with different orifice diameters 0.3 mm and 0.5 mm and injection pressures (0.3-4 MPa) which correspond to Rep = 7000-26 000. Two types of laser diagnostic techniques were utilized: shadowgraph and phase Doppler particle anemometry for a complete study of the atomization process. Measurements that were made in the spray in both axial and radial directions indicate that both velocity and average droplet diameter profiles are highly dependent on the nozzle characteristics, Weber number and Reynolds number. The spatial variation of diameter and velocity arises principally due to primary breakup of liquid films and subsequent secondary breakup of large droplets due to aerodynamic shear. Downstream of the nozzle, coalescence of droplets due to collision was also found to be significant. Different types of liquid film breakup were considered and found to match well with the theory. Secondary breakup due to shear was also studied theoretically and compared to the experimental data. Coalescence probability at different axial and radial locations was computed to explain the experimental results. The spray is subdivided into three zones: near the nozzle, a zone consisting of film and ligament regime, where primary breakup and some secondary breakup take place; a second zone where the secondary breakup process continues, but weakens, and the centrifugal dispersion becomes dominant; and a third zone away from the spray where coalescence is dominant. Each regime has been analyzed in detail, characterized by timescale and Weber number and validated using experimental data.

  14. Partial coalescence of sessile drops with different liquids

    Science.gov (United States)

    Borcia, Rodica; Bestehorn, Michael

    2014-11-01

    We examine numerically the interaction between two deformable drops consisting of two perfectly miscible liquids sitting on a solid substrate under a given contact angle. Driven by solutal Marangoni forces, several distinct coalescence regimes are achieved after the droplets collision. Phase diagrams for different control parameters are emphasized, which give predictions about drop behavior along the solid substrates, control of various interfacial effects, manipulations of tiny droplets in micro- and nano-fluidic devices without power supply, design of droplets or cleaning surfaces. This work was partially supported by Deutsche Forschungsgemeinschaft (DFG) under the project ``Dynamics of interfaces between drops with miscible liquids''.

  15. Gravitational Radiation of Binaries Coalescence into Intermediate Mass Black Holes

    Institute of Scientific and Technical Information of China (English)

    李瑾; 仲元红; 潘宇

    2012-01-01

    This paper discusses the gravitation waveforms of binaries coalescence into intermediate mass black holes (about 30 times of the solar mass). We focus on the non-spinning intermediate mass black hole located less than 100 Mpc from earth. By comparing two simulation waveforms (effective one body numerical relativity waveform (EOBNR), phenomenological waveform), we discuss the relationship between the effective distance and frequency; and through analyzing large amounts of data in event, we find that the phenomenological waveform is much smoother than EOBNR waveform, and has higher accuracy at the same effective distance.

  16. 3D General Relativistic Simulations of Coalescing Binary Neutron Stars

    CERN Document Server

    Oohara, K I; Nakamura, Takashi; Oohara, Ken-ichi

    1999-01-01

    We develop a 3 dimensional computer code to study a coalescing neutron star binary. The code can currently follow the evolution up to two stars begin to merge from two spherical stars of mass 1 solar mass and radius 8.9km with separation 35.4km. As for coordinate conditions, we use conformal slicing and pseudo-minimal distortion conditions. The evolution equations for the metric is integrated using the CIP method while the van Leer's scheme is used to integrate the equations for the matter. We present a few results of our simulations including gravitational radiation.

  17. Three-electron coalescence points in two and three dimensions

    CERN Document Server

    Loos, Pierre-François; Gill, Peter M W

    2015-01-01

    The form of the wave function at three-electron coalescence points is examined for several spin states using an alternative method to the usual Fock expansion. We find that, in two- and three-dimensional systems, the non-analytical nature of the wave function is characterized by the appearance of logarithmic terms, reminiscent of those that appear as both electrons approach the nucleus of the helium atom. The explicit form of these singularities is given in terms of the interelectronic distances for a doublet and two quartet states of three electrons in a harmonic well.

  18. Growth of Gallium Nitride Nanorods and Their Coalescence Overgrowth

    Science.gov (United States)

    2012-09-07

    NRs on silicon substrate, thermal stress can be released such that wafer cracking can be avoided and the crystal quality of the coalesced overgrown...thick GaN template, which is deposited with MOCVD on c-plane sapphire substrate [1, 14]. On the wafer , a two-dimensional (2-D) triangular pattern of...mask to form a triangular bump [1]. Figure 5(a) shows the cross-sectional TEM image of a few fallen QW NRs. We focus the observation at the circled

  19. Advances in longer-chain aliphatic olefins metathesis%长碳链烯烃歧化研究进展

    Institute of Scientific and Technical Information of China (English)

    郑敏; 陈胜利; 袁桂梅; 王雪莲; 桑磊; 尤菊; 张军辉

    2012-01-01

    The research of C4-olefin to produce propylene was the emphasis of aliphatic olefin metathesis technology,but attentions were also paid to longer-chain aliphatic olefins metathesis reaction.The progress of the metathesis reaction of longer-chain aliphatic olefins over rhenium based catalysis,molybdenum based catalysis and tungsten based catalysis were introduced.The study of longer-chain olefin metathesis over tungsten based catalyst,including the optimal operating condition of 1-hexene self-metathesis,1-heptene self-metathesis and 1-octene self-metathesis.The effect of pretreatment on metathesis performance of tungsten based catalyst is primarily introduced.Moreover,the studies of deactivation of metathesis catalyst by oxygenate poisoning and deactivation of tungsten based catalyst by coke formation are also introduced.%目前,虽然直链烯烃歧化研究的重点仍是碳四烯烃歧化制丙烯技术,但是长碳链烯烃歧化研究已开始引起人们的重视。本文介绍了铼基催化剂、钼基催化剂和钨基催化剂催化长碳链烯烃歧化反应的研究进展。重点介绍了钨基催化剂上长碳链歧化研究状况,分别介绍了钨基催化剂上1-己烯自歧化、1-庚烯自歧化、1-辛烯自歧化的最优工艺条件研究以及预处理条件对钨基催化剂歧化性能的影响。同时分别介绍了含氧化合物对歧化催化剂中毒失活的研究以及钨基催化剂上结焦失活的研究状况。

  20. Review of the Dynamics of Coalescence and Demulsification by High-Voltage Pulsed Electric Fields

    Directory of Open Access Journals (Sweden)

    Ye Peng

    2016-01-01

    Full Text Available The coalescence of droplets in oil can be implemented rapidly by high-voltage pulse electric field, which is an effective demulsification dehydration technological method. At present, it is widely believed that the main reason of pulse electric field promoting droplets coalescence is the dipole coalescence and oscillation coalescence in pulse electric field, and the optimal coalescence pulse electric field parameters exist. Around the above content, the dynamics of high-voltage pulse electric field promoting the coalescence of emulsified droplets is studied by researchers domestically and abroad. By review, the progress of high-voltage pulse electric field demulsification technology can get a better understanding, which has an effect of throwing a sprat to catch a whale on promoting the industrial application.

  1. Resonant oscillations and tidal heating in coalescing binary neutron stars

    CERN Document Server

    Lai, D

    1994-01-01

    Tidal interaction in a coalescing neutron star binary can resonantly excite the g-mode oscillations of the neutron star when the frequency of the tidal driving force equals the intrinsic g-mode frequencies. We study the g-mode oscillations of cold neutron stars using recent microscopic nuclear equations of state, where we determine self-consistently the sound speed and Brunt-V\\"ais\\"al\\"a frequency in the nuclear liquid core. The properties of the g-modes associated with the stable stratification of the core depend sensitively on the pressure-density relation as well as the symmetry energy of the dense nuclear matter. The frequencies of the first ten g-modes lie approximately in the range of 10-100 Hz. Resonant excitations of these g-modes during the last few minutes of the binary coalescence result in energy transfer and angular momentum transfer from the binary orbit to the neutron star. The angular momentum transfer is possible because a dynamical tidal lag develops even in the absence of fluid viscosity. ...

  2. Formation of deuterons by coalescence: Consequences for deuteron number fluctuations

    Science.gov (United States)

    Fecková, Zuzana; Steinheimer, Jan; Tomášik, Boris; Bleicher, Marcus

    2016-05-01

    Two scenarios for cluster production have long been discussed in the literature: (i) direct emission of the clusters from a (grand-canonical) thermal source or (ii) subsequent formation of the clusters by coalescence of single nucleons. While both approaches have been successfully applied in the past it has not yet been clarified which of the two mechanisms dominates the cluster production. We propose to use recently developed event-by-event techniques to study particle multiplicity fluctuations on nuclear clusters and employ this analysis to the deuteron number fluctuations to disentangle the two production mechanisms. We argue that for a grand-canonical cluster formation, the cluster fluctuations will follow Poisson distribution, while for the coalescence scenario, the fluctuations will strongly deviate from the Poisson expectation. We estimate the effect to be 10% for the variance and up to a factor of 5 for the kurtosis of the deuteron number multiplicity distribution. Our prediction can be tested in the beam energy scan program at the BNL Relativistic Heavy Ion Collider as well as experiments at the GSI Facility for Antiproton and Ion Research and the Nuclotron-based Ion Collider Facility.

  3. Antideuteron yield at the AGS and coalescence implications

    CERN Document Server

    Armstrong, T A; Batsouli, S; Bennett, S J; Bertaina, M; Chikanian, A; Coe, S D; Cormier, T M; Davies, R; Dover, C B; Fachini, P; Fadem, B S; Finch, L E; George, N K; Greene, S V; Haridas, P; Hill, J C; Hirsch, A S; Hoversten, R; Huang, H Z; Jaradat, H; Kumar, B S; Lainis, T; Lajoie, J G; Li, Q; Libby, B; Majka, R D; Miller, T E; Munhoz, M G; Nagle, J L; Pless, I A; Pope, J K; Porile, N T; Pruneau, C A; Rabin, M S Z; Reid, J D; Rimai, A; Rose, A; Rotondo, F S; Sandweiss, J; Scharenberg, R P; Slaughter, A J; Smith, G A; Tincknell, M L; Toothacker, W S; Van Buren, G; Wohn, F K; Xu, Z

    2000-01-01

    We present Experiment 864's measurement of invariant antideuteron yields in 11.5A GeV/c Au + Pt collisions. The analysis includes 250 million triggers representing 14 billion 10% central interactions sampled for events with high mass candidates. We find (1/2 pi pt) d^(2)N/dydpt = 3.5 +/- 1.5 (stat.) +0.9,-0.5 (sys.) x 10^(-8) GeV^(-2)c^(2) for 1.8=0.35 GeV/c (y(cm)=1.6) and 3.7 +/- 2.7 (stat.) +1.4,-1.5 (sys.) x 10^(-8) GeV^(-2)c^(2) for 1.4=0.26 GeV/c, and a coalescence parameter B2-bar of 4.1 +/- 2.9 (stat.) +2.3,-2.4 (sys.) x 10^(-3) GeV^(2)c^(-3). Implications for the coalescence model and antimatter annihilation are discussed.

  4. Impact of 50% Synthesized Iso-Paraffins (SIP) on Middle Distillate Fuel Filtration and Coalescence

    Science.gov (United States)

    2014-10-30

    Impact of 50% Synthesized Iso-Paraffins (SIP) on Middle Distillate Fuel Filtration and Coalescence NF&LCFT REPORT 441/15-003 30 October 2014...October 2014 Page 1 Impact of 50% Synthesized Iso-Paraffins (SIP) on Middle Distillate Fuel Filtration and Coalescence 1.0 BACKGROUND In...Paraffins (SIP) on Middle 5a. CONTRACT NUMBER N/A Distillate Fuel F-76 Filtration and Coalescence 5b. GRANT NUMBER N/A 5c. PROGRAM

  5. Short time dynamics of water coalescence on a flat water pool

    CERN Document Server

    Lim, Su Jin; Fezzaa, Kamel; Weon, Byung Mook

    2016-01-01

    Coalescence is an important hydrodynamic event that frequently takes place in nature as well as in industry. Here we provide an experimental study on short time dynamics of water coalescence, particularly when a water droplet comes in contact with a flat water surface, by utilizing high-resolution high-penetration ultrafast X-ray microscopy. Our results demonstrate a possibility that an extreme curvature difference between a drop and a flat surface can significantly modify the hydrodynamics of water coalescence, which is unexpected in the existing theory. We suggest a plausible explanation for why coalescence can be modified by an extreme curvature difference.

  6. On the length of an external branch in the Beta-coalescent

    CERN Document Server

    Dhersin, Jean-Stephane; Siri-Jegousse, Arno; Yuan, Linglong

    2012-01-01

    In this paper, we consider Beta$(2-{\\alpha},{\\alpha})$ (with $1<{\\alpha}<2$) and related ${\\Lambda}$-coalescents. If $T^{(n)}$ denotes the length of an external branch of the $n$-coalescent, we prove the convergence of $n^{{\\alpha}-1}T^{(n)}$ when $n$ tends to $ \\infty $, and give the limit. To this aim, we give asymptotics for the number $\\sigma^{(n)}$ of collisions which occur in the $n$-coalescent until the end of the chosen external branch, and for the block counting process associated with the $n$-coalescent.

  7. 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.

  8. Properties and metathesis activity of monomeric and dimeric Mo centres variously located on γ-alumina A DFT study

    Science.gov (United States)

    Handzlik, Jarosław

    2007-05-01

    Ethene metathesis proceeding on monomeric and dimeric Mo species on the (1 0 0) and (1 1 0) γ-alumina is investigated by density functional theory, applying the cluster approach. The calculated vibrational frequencies of the surface OH groups are assigned to the experimental IR bands. It is shown that both monomeric and dimeric Mo forms can be the active sites of olefin metathesis. Metathesis activity and stability of the Mo-methylidene centres depend on their location on alumina. The differences in the sites reactivity are explained on the basis of their geometrical and electronic structure parameters. For the monomeric centres, isomerisation of the trigonal bipyramidal intermediate to the stable square pyramidal molybdacyclobutane is kinetically favoured over the cycloreversal step. The situation is opposite in the case of the dimeric species.

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

    Science.gov (United States)

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

    2016-03-18

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

  10. New Enantiomerically Pure Alkylimido Mo-Based Complexes. Synthesis, Characterization, and Activity as Chiral Olefin Metathesis Catalysts

    Science.gov (United States)

    Pilyugina, Tatiana S.; Schrock, Richard R.; Müller, Peter; Hoveyda, Amir H.

    2008-01-01

    Molybdenum olefin metathesis catalysts that contain aliphatic 1-phenylcyclohexylimido (NPhCy) and 2-phenyl-2-adamantylimido (NPhAd) groups and (S)-Biphen or (R)-Trip)(THF) ligands (Biphen = 3,3′-di-tert-butyl-5,5′,6,6′-tetramethyl-1,1′-biphenyl-2,2′-diolate; Trip = 3,3′-bis(2,4,6-triisopropylphenyl)-2,2′-binaphtholate) have been prepared. Their catalytic activity and enantioselectivity in desymmetrization reactions such as ring-closing metathesis of amines and lactams and ring-opening/cross-metathesis of substituted norborneols with styrene were compared to the results obtained with the only known alkylimido catalyst Mo(NAd)(CHCMe2Ph)[(S)-Biphen]. The activities and enantioselectivities provided by these new chiral complexes vary significantly, but in virtually all instances explored were not superior to the adamantylimido analogs. PMID:19079732

  11. 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.

  12. 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.

  13. Effective immobilisation of a metathesis catalyst bearing an ammonium-tagged NHC ligand on various solid supports

    Directory of Open Access Journals (Sweden)

    Krzysztof Skowerski

    2016-01-01

    Full Text Available An ammonium-tagged ruthenium complex, 8, was deposited on several widely available commercial solid materials such as silica gel, alumina, cotton, filter paper, iron powder or palladium on carbon. The resulting catalysts were tested in toluene or ethyl acetate, and found to afford metathesis products in high yield and with extremely low ruthenium contamination. Depending on the support used, immobilised catalyst 8 shows also additional traits, such as the possibility of being magnetically separated or the use for metathesis and subsequent reduction of the obtained double bond in one pot.

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

    Science.gov (United States)

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

    2016-01-01

    Summary 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. PMID:26877818

  15. 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.

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

    Directory of Open Access Journals (Sweden)

    Dey Raju

    2016-03-01

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

  17. 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.

  18. Characterization and Dynamics of Substituted Ruthenacyclobutanes Relevant to the Olefin Cross-Metathesis Reaction

    Science.gov (United States)

    Blake, Garrett; VanderVelde, David G.; Grubbs, Robert H.

    2011-01-01

    The reaction of the phosphonium alkylidene [(H2IMes)RuCl2=CHP(Cy)3)]+ BF4– with propene, 1-butene, and 1-hexene at –45 °C affords various substituted, metathesis-active ruthenacycles. These metallacycles were found to equilibrate over extended reaction times in response to decreases in ethylene concentrations, which favored increased populations of α-monosubstituted and α,α’-disubstituted (both cis and trans) ruthenacycles. On an NMR timescale, rapid chemical exchange was found to preferentially occur between the β-hydrogens of the cis and trans stereoisomers prior to olefin exchange. Exchange on an NMR timescale was also observed between the α- and β-methylene groups of the monosubstituted ruthenacycle (H2IMes)Cl2Ru(CHRCH2CH2) (R = CH3, CH2CH3, (CH2)3CH3). EXSY NMR experiments at –87 °C were used to determine the activation energies for both of these exchange processes. In addition, new methods have been developed for the direct preparation of metathesis-active ruthenacyclobutanes via the protonolysis of dichloro(1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)(benzylidene) bis(pyridine)ruthenium(II) and its 3-bromopyridine analog. Using either trifluoroacetic acid or silica-bound toluenesulfonic acid as the proton source, the ethylene-derived ruthenacyclobutane (H2IMes)Cl2Ru(CH2CH2CH2) was observed in up to 98% yield via NMR at –40 °C. On the basis of these studies, mechanisms accounting for the positional and stereochemical exchange within ruthenacyclobutanes are proposed, as well as the implications of these dynamics towards olefin metathesis catalyst and reaction design are described. PMID:21452876

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

    Science.gov (United States)

    Mango, Frank D; Jarvie, Daniel M

    2010-01-20

    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 degrees C. Focus was on two metathetic equilibria: methane, ethane, and propane, reported earlier, Q (K = [(C(1))*(C(3))]/[(C(2))(2)]), and between these hydrocarbons and n-butane, Q* (K = [(C(1))*(n-C(4))]/[(C(2))*(C(3))]), 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 [C(n)] to smaller intermediates (fission) as gas generation creates open catalytic sites ([ ]): [C(n)] + [ ] --> [C(n-m)] + [C(m)]. Fission rates increasing exponentially with olefin molecular weight could contribute to these effects. AMW would fall over time, and selective fission of [C(3)] and [n-C(4)] would draw Q and Q* from equilibrium. The results support metathesis as the source of thermodynamic equilibrium in natural gas.

  20. 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.

  1. Molecular dynamics of coalescence and collisions of silver nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Guevara-Chapa, Enrique, E-mail: enrique_guevara@hotmail.com [Universidad Autónoma de Nuevo León, Facultad de Ciencias Físico Matemáticas (Mexico); Mejía-Rosales, Sergio [Universidad Autónoma de Nuevo León, Center for Innovation, Research and Development in Engineering and Technology (CIIDIT), and CICFIM-Facultad de Ciencias Físico Matemáticas (Mexico)

    2014-12-15

    We study how different relative orientations and impact velocity on the collision of two silver nanoparticles affect the first stages of the formation of a new, larger nanoparticle. In order to do this, we implemented a set of molecular dynamics simulations on the NVE ensemble on pairs of silver icosahedral nanoparticles at several relative orientations, that allowed us to follow the dynamics of the first nanoseconds of the coalescence processes. Using bond angle analysis, we found that the initial relative orientation of the twin planes has a critical role on the final stability of the resulting particle, and on the details of the dynamics itself. When the original particles have their closest twins aligned to each other, the formed nanoparticle will likely stabilize its structure onto a particle with a defined center and a low surface-to-volume ratio, while nanoparticles with misaligned twins will promote the formation of highly defective particles with a high inner energy.

  2. A void coalescence model for combined tension and shear

    Science.gov (United States)

    Butcher, C.; Chen, Z. T.

    2009-03-01

    The influence of shear loading on damage development in Gurson-based models has long been neglected resulting in inadequate fracture strain predictions at low triaxiality where shear effects become significant. The plastic limit-load fracture criterion used in advanced Gurson models neglects the influence of shear loading and overestimates the fracture strain and porosity at low triaxiality. In this paper, we extend the recently proposed shear damage model of Xue [1] to provide a stronger physical foundation by removing the simplifying assumptions. Then we directly modify the plastic limit-load fracture criterion by coupling with the extended shear damage model to account for shear weakening and failure of the intervoid ligament in void coalescence. We apply the modified plastic limit-load criterion to predict the necking of sheet tensile specimens and find very good agreement with the available experimental results.

  3. Coalescence of Black Hole-Neutron Star Binaries

    Directory of Open Access Journals (Sweden)

    Masaru Shibata

    2011-08-01

    Full Text Available We review the current status of general relativistic studies for the coalescence of black hole-neutron star (BH-NS binaries. First, procedures for a solution of BH-NS binaries in quasi-equilibrium circular orbits and the numerical results, such as quasi-equilibrium sequence and mass-shedding limit, of the high-precision computation, are summarized. Then, the current status of numerical-relativity simulations for the merger of BH-NS binaries is described. We summarize our understanding for the merger and/or tidal disruption processes, the criterion for tidal disruption, the properties of the remnant formed after the tidal disruption, gravitational waveform, and gravitational-wave spectrum.

  4. On the coalescence-dispersion modeling of turbulent molecular mixing

    Science.gov (United States)

    Givi, Peyman; Kosaly, George

    1987-01-01

    The general coalescence-dispersion (C/D) closure provides phenomenological modeling of turbulent molecular mixing. The models of Curl and Dopazo and O'Brien appear as two limiting C/D models that bracket the range of results one can obtain by various models. This finding is used to investigate the sensitivtiy of the results to the choice of the model. Inert scalar mixing is found to be less model-sensitive than mixing accompanied by chemical reaction. Infinitely fast chemistry approximation is used to relate the C/D approach to Toor's earlier results. Pure mixing and infinite rate chemistry calculations are compared to study further a recent result of Hsieh and O'Brien who found that higher concentration moments are not sensitive to chemistry.

  5. Double two-photon coalescence in a controlled propagation

    Science.gov (United States)

    Raczyński, Andrzej; Zaremba, Jarosław; Zielińska-Raczyńska, Sylwia

    2017-03-01

    The propagation, storage, and release of two quantized light fields in an optically dressed atomic medium in the tripod configuration are studied. Using the formalism of spinor dark-state polaritons, the probabilities are obtained of finding outgoing photons of two possible localizations and two possible types, i.e., having different frequencies or polarizations. An additional interaction at the storage stage is applied which modifies the atomic coherences due to the stored photons; this results in a modification of the states of the outgoing photons. The conditions are examined for the photons' spatial and type coalescence typical of the Hong-Ou-Mandel effect, i.e., a zero probability of finding the outgoing photons having not only different localizations but also types. These results can possibly be observed in rubidium vapors.

  6. Modeling gravitational radiation from coalescing binary black holes

    CERN Document Server

    Baker, J; Loustó, C O; Takahashi, R

    2002-01-01

    With the goal of bringing theory, particularly numerical relativity, to bear on an astrophysical problem of critical interest to gravitational wave observers we introduce a model for coalescence radiation from binary black hole systems. We build our model using the "Lazarus approach", a technique that bridges far and close limit approaches with full numerical relativity to solve Einstein equations applied in the truly nonlinear dynamical regime. We specifically study the post-orbital radiation from a system of equal-mass non-spinning black holes, deriving waveforms which indicate strongly circularly polarized radiation of roughly 3% of the system's total energy and 12% of its total angular momentum in just a few cycles. Supporting this result we first establish the reliability of the late-time part of our model, including the numerical relativity and close-limit components, with a thorough study of waveforms from a sequence of black hole configurations varying from previously treated head-on collisions to rep...

  7. Coalescence-induced jumping of droplet: Inertia and viscosity effects

    Science.gov (United States)

    Farokhirad, Samaneh; Morris, Jeffrey F.; Lee, Taehun

    2015-10-01

    The problem of coalescence-induced self-propelled jumping of droplet is studied using three-dimensional numerical simulation. The focus is on the effect of inertia and in particular the effect of air density on the behavior of the merged droplet during jumping. A lattice Boltzmann method is used for two identical, static micro-droplets coalescing on a homogeneous substrate with contact angle ranging from 0∘ to 180∘. The results reveal that the effect of air density is significant on detachment of the merged droplet from the substrate at the later stage of the jumping process; the larger the air density, the larger the jumping height of the droplet. Analysis of streamlines and vorticity contours is performed for density ratios ranging from 60 to 800. These show a generation of vortical structures inside and around the droplet. The intensity of these structures gets weaker after droplet departure as the air inertia is decreased. The results are also presented in terms of phase diagrams of the merged droplet jumping for different Ohnesorge numbers (Oh) and surface wettabilities for both small and large density ratios. The critical value of contact angle where the merged droplet jumps away from the substrate is independent of density ratio and has a value around 150∘. However, the critical value of Oh depends on both density ratio and wettability of the surface for contact angles greater than 150∘. In this range of contact angle, the diagrams show two distinct dynamical regimes for different density ratios, namely, inertial and viscous regimes.

  8. Coalescence of silver clusters by immersion in diluted HF solution

    Energy Technology Data Exchange (ETDEWEB)

    Milazzo, R. G.; Mio, A. M.; D’Arrigo, G.; Spinella, C. [CNR-IMM Institute for Microelectronics and Microsystems, I-95121 Catania (Italy); Grimaldi, M. G. [Department of Physics and Astronomy, Università di Catania, I-95123 Catania (Italy); MATIS IMM-CNR, I-95123 Catania (Italy); Rimini, E. [CNR-IMM Institute for Microelectronics and Microsystems, I-95121 Catania (Italy); Department of Physics and Astronomy, Università di Catania, I-95123 Catania (Italy)

    2015-07-14

    The galvanic displacement deposition of silver on H-terminated Si (100) in the time scale of seconds is instantaneous and characterized by a cluster density of 10{sup 11}-10{sup 12} cm{sup −2}. The amount of deposited Ag follows a t{sup 1/2} dependence in agreement with a Cottrell diffusion limited mechanism. At the same time, during the deposition, the cluster density reduces by a factor 5. This behavior is in contrast with the assumption of immobile clusters. We show in the present work that coalescence and aggregation occur also in the samples immersed in the diluted hydrofluoric acid (HF) solution without the presence of Ag{sup +}. Clusters agglomerate according to a process of dynamic coalescence, typical of colloids, followed by atomic redistribution at the contact regions with the generation of multiple internal twins and stacking-faults. The normalized size distributions in terms of r/r{sub mean} follow also the prediction of the Smoluchowski ripening mechanism. No variation of the cluster density occurs for samples immersed in pure H{sub 2}O solution. The different behavior might be associated to the strong attraction of clusters to oxide-terminated Si surface in presence of water. The silver clusters are instead weakly bound to hydrophobic H-terminated Si in presence of HF. HF causes then the detachment of clusters and a random movement on the silicon surface with mobility of about 10{sup −13} cm{sup 2}/s. Attractive interaction (probably van der Waals) among particles promotes coarsening.

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

    Directory of Open Access Journals (Sweden)

    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.

  10. 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.

  11. Synthetic, mechanistic, and computational investigations of nitrile-alkyne cross-metathesis.

    Science.gov (United States)

    Geyer, Andrea M; Wiedner, Eric S; Gary, J Brannon; Gdula, Robyn L; Kuhlmann, Nicola C; Johnson, Marc J A; Dunietz, Barry D; Kampf, Jeff W

    2008-07-16

    The terminal nitride complexes NW(OC(CF 3) 2Me) 3(DME) ( 1-DME), [Li(DME) 2][NW(OC(CF 3) 2Me) 4] ( 2), and [NW(OCMe 2CF 3) 3] 3 ( 3) were prepared in good yield by salt elimination from [NWCl 3] 4. X-ray structures revealed that 1-DME and 2 are monomeric in the solid state. All three complexes catalyze the cross-metathesis of 3-hexyne with assorted nitriles to form propionitrile and the corresponding alkyne. Propylidyne and substituted benzylidyne complexes RCW(OC(CF 3) 2Me) 3 were isolated in good yield upon reaction of 1-DME with 3-hexyne or 1-aryl-1-butyne. The corresponding reactions failed for 3. Instead, EtCW(OC(CF 3)Me 2) 3 ( 6) was prepared via the reaction of W 2(OC(CF 3)Me 2) 6 with 3-hexyne at 95 degrees C. Benzylidyne complexes of the form ArCW(OC(CF 3)Me 2) 3 (Ar = aryl) then were prepared by treatment of 6 with the appropriate symmetrical alkyne ArCCAr. Three coupled cycles for the interconversion of 1-DME with the corresponding propylidyne and benzylidyne complexes via [2 + 2] cycloaddition-cycloreversion were examined for reversibility. Stoichiometric reactions revealed that both nitrile-alkyne cross-metathesis (NACM) cycles as well as the alkyne cross-metathesis (ACM) cycle operated reversibly in this system. With catalyst 3, depending on the aryl group used, at least one step in one of the NACM cycles was irreversible. In general, catalyst 1-DME afforded more rapid reaction than did 3 under comparable conditions. However, 3 displayed a slightly improved tolerance of polar functional groups than did 1-DME. For both 1-DME and 3, ACM is more rapid than NACM under typical conditions. Alkyne polymerization (AP) is a competing reaction with both 1-DME and 3. It can be suppressed but not entirely eliminated via manipulation of the catalyst concentration. As AP selectively removes 3-hexyne from the system, tandem NACM-ACM-AP can be used to prepare symmetrically substituted alkynes with good selectivity, including an arylene-ethynylene macrocycle

  12. Synthesis of all-hydrocarbon stapled α-helical peptides by ring-closing olefin metathesis.

    Science.gov (United States)

    Kim, Young-Woo; Grossmann, Tom N; Verdine, Gregory L

    2011-06-01

    This protocol provides a detailed procedure for the preparation of stapled α-helical peptides, which have proven their potential as useful molecular probes and as next-generation therapeutics. Two crucial features of this protocol are (i) the construction of peptide substrates containing hindered α-methyl, α-alkenyl amino acids and (ii) the ring-closing olefin metathesis (RCM) of the resulting resin-bound peptide substrates. The stapling systems described in this protocol, namely bridging one or two turns of an α-helix, are highly adaptable to most peptide sequences, resulting in favorable RCM kinetics, helix stabilization and promotion of cellular uptake.

  13. Synthesis of Cyclic Porphyrin Trimers through Alkyne Metathesis Cyclooligomerization and Their Host–Guest Binding Study

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Chao; Long, Hai; Jin, Yinghua; Zhang, Wei

    2016-06-17

    Cyclic porphyrin trimers were synthesized through one-step cyclooligomerization via alkyne metathesis from diyne monomers. These macrocycles show interesting host-guest binding interactions with fullerenes, selectively binding C70 (6 x 103 M-1) over C60 and C84 (no binding observed). The fullerene-encapsulated host-guest complex can undergo guest or host exchange in the presence of another guest (2,4,6-tri(4-pyridyl)-1,3,5-triazine) or host (cage COP5) molecule with higher binding affinity.

  14. Olefin Metathesis Polymerization: The Unexpected Role of Carbenoid Species in Formation of Macromolecules

    Science.gov (United States)

    Snyder, Donald M.

    1996-02-01

    Today most undergraduate organic chemistry texts present some material on polymers, but the coverage in these texts is necessarily quite limited. Step-growth and free-radical chain growth systems, along with some mention of coordination polymerization, usually constitute the bulk of introductory material. Very little of the advances in polymer chemistry since the 1960's is reflected in the undergraduate curriculum. One particularly interesting topic still rarely seen outside of the research literature is the subject of metathesis polymerization. This article is intended to present the interested reader with a brief introduction to the mechanism of this unique process, its historical background, and some recent developments in the field.

  15. Template-directed synthesis of flexible porphyrin nanocage and nanorings via one-step olefin metathesis.

    Science.gov (United States)

    Zhu, Bin; Chen, Huanxin; Lin, Wei; Ye, Yang; Wu, Jing; Li, Shijun

    2014-10-29

    We describe the fabrication of a suite of flexible porphyrin cages and nanorings from a simple tetraalkene-derived zinc porphyrin monomer via a highly efficient template-directed strategy. The zinc porphyrin monomers were preorganized together by coordination with N atoms of multidentate ligands. Subsequent one-step olefin metathesis furnished a bisporphyrin cage, a triporphyrin nanoring, and a hexaporphyrin nanoring. In the case of the hexaporphyrin nanoring, 24 terminal olefins from six porphyrin monomers reacted with each other to form 12 new double bonds, delivering the final product. The triporphyrin and hexaporphyrin nanorings were further employed as hosts to encapsulate C60 and C70.

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

    Science.gov (United States)

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

    2015-07-17

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

  17. Olefin Metathesis With Ruthenium-Arene Catalysts Bearing N-Heterocyclic Carbene Ligands

    Science.gov (United States)

    Delaude, Lionel; Demonceau, Albert

    In this chapter, we summarize the main results of our investigations on the ring-opening metathesis polymerization (ROMP) of cyclooctene catalyzed by various ruthenium (Ru)-arene complexes bearing imidazolin-2-ylidene, imidazolidin- 2-ylidene, or triazolin-5-ylidene ligands. Three major findings emerged from this study. First, we underscored the intervention of a photochemical activation step due to visible light illumination. Second, we established that the presence of an endocyclic double bond in the carbene ligand central heterocycle was not crucial to achieve high catalytic efficiencies. Third, we demonstrated that ortho-metallation of the N-heterocyclic carbene (NHC) ligand by the Ru center led to inactive catalysts.

  18. An olefin metathesis-iodoetherification-dehydroiodination strategy for spiroketal subunits of the polyether antibiotics

    Science.gov (United States)

    Tony, Kurissery A.; Dabideen, Darrin; Li, Jialiang; Díaz-Hernández, Maria Dolores; Jiménez-Barbero, Jesús; Mootoo, David R.

    2012-01-01

    The convergent synthesis of two pentacyclic analogs of the polyether monensin A is described. Although different with respect to the configuration of the alcohol at the 3 position of the six membered ring of the spiroketal subunit, the configuration at the acetal center in both structures is unchanged and is consistent with the anomeric effect. The key synthetic steps are the coupling of two complex segments via an olefin metathesis, and the subsequent conversion of a dihydroxyalkene to the spiroketal through an iodoetherification-dehydroiodination sequence. The compatibility of these transformations with a variety of functional groups makes the overall strategy appropriate for highly substituted frameworks. PMID:19813766

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

    KAUST Repository

    Falivene, Laura

    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.

  20. Room Temperature Ionic Liquids as Green Solvent Alternatives in the Metathesis of Oleochemical Feedstocks

    Directory of Open Access Journals (Sweden)

    Priya A. Thomas

    2016-02-01

    Full Text Available One of the most important areas of green chemistry is the application of environmentally friendly solvents in catalysis and synthesis. Conventional organic solvents pose a threat to the environment due to the volatility, highly flammability, toxicity and carcinogenic properties they exhibit. The recently emerged room temperature ionic liquids (RTILs are promising green solvent alternatives to the volatile organic solvents due to their ease of reuse, non-volatility, thermal stability and ability to dissolve a variety of organic and organometallic compounds. This review explores the use of RTILs as green solvent media in olefin metathesis for applications in the oleochemical industry.

  1. C18:1 Methyl ester metathesis in [bmim][X] type ionic liquids.

    Science.gov (United States)

    Thomas, Priya A; Marvey, Bassie B

    2009-11-18

    The efficacy of [bmim][X] ionic liquids (ILs) (X = PF(6) (-), BF(4) (-) and NTf(2) (-)) as reaction media for methyl oleate metathesis was compared with that of conventional organic solvents (PhCl, PhMe, DCM and DCE) using the well-defined first and second generation Grubbs precatalysts, RuCl(2)(PCy(3))(L)(=CHPh) (L = PCy(3) or H(2)IMes). Best catalytic performance, with excellent selectivity (>98%) at moderate reaction temperatures, was achieved in [bmim][X] ILs compared to conventional solvents. The effects of anion, reaction temperature, solvent polarity, solvent viscosity, and ligand-anion interaction on the reaction are also addressed.

  2. Nanoporous A1N particle production from a solid-state metathesis reaction

    Institute of Scientific and Technical Information of China (English)

    Yan Guo-Jun; Chen Guang-De; Wu Ye-Long

    2009-01-01

    This paper reports that nanoporous AlN particles are synthesized from solid-state metathesis reactions using AlCl3and Mg3N2 as reactants. The samples are characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction, high-resolution transmission electron microscopy (HRTEM), ultraviolet-visible (UV-vis) absorption spectroscopy and Raman spectroscopy. The results show that samples with walls 10 nm in thickness and pores between 10 nm and 100 nm in diameter were produced successfully from these reactions, and their band gap and vibration modes agree with those of A1N bulk crystal.

  3. Rapid Solid-State Metathesis Routes to Nanostructured Silicon-Germainum

    Science.gov (United States)

    Kaner, Richard B. (Inventor); Bux, Sabah K. (Inventor); Fleurial, Jean-Pierre (Inventor); Rodriguez, Marc (Inventor)

    2014-01-01

    Methods for producing nanostructured silicon and silicon-germanium via solid state metathesis (SSM). The method of forming nanostructured silicon comprises the steps of combining a stoichiometric mixture of silicon tetraiodide (SiI4) and an alkaline earth metal silicide into a homogeneous powder, and initating the reaction between the silicon tetraiodide (SiI4) with the alkaline earth metal silicide. The method of forming nanostructured silicon-germanium comprises the steps of combining a stoichiometric mixture of silicon tetraiodide (SiI4) and a germanium based precursor into a homogeneous powder, and initiating the reaction between the silicon tetraiodide (SiI4) with the germanium based precursors.

  4. Mitochondrial Myopathy with DNA Deletions

    OpenAIRE

    J Gordon Millichap

    1992-01-01

    Deletions of mitochondrial DNA (mtDNA) are reported in 19 of 56 patients with mitochondrial myopathy examined in the Department of Neurology and Neuromuscular Research Laboratory, Mayo Clinic, Rochester, MN.

  5. Dynamics of coalescence and spreading of liquid polymeric particles during coating formation

    Science.gov (United States)

    Fedyaev, V. L.; Galimov, E. R.; Galimova, N. Ya; Gimranov, I. R.; Siraev, A. R.

    2017-01-01

    Processes of agglutination, coalescence and spreading of polymeric powder particles during coating formation are considered using methods of mathematical modeling. The relationships to evaluate time of particles agglutination, velocity of coalescence and spreading of material on the surface of a treated body are given. Recommendations on intensification of the given technological stages are presented.

  6. Coalescence kinetics of oil-in-water emulsions studied with microfluidics

    NARCIS (Netherlands)

    Krebs, T.; Schroen, C.G.P.H.; Boom, R.M.

    2013-01-01

    We report the results of experiments on the coalescence dynamics in flowing oil-in-water emulsions using an integrated microfluidic device. The microfluidic circuit permits direct observation of shear-induced collisions and coalescence events between emulsion droplets. Three mineral oils with a rang

  7. Application of parametric equations of motion to study the resonance coalescence in H2(+).

    Science.gov (United States)

    Kalita, Dhruba J; Gupta, Ashish K

    2012-12-07

    Recently, occurrence of coalescence point was reported in H(2)(+) undergoing multiphoton dissociation in strong laser field. We have applied parametric equations of motion and smooth exterior scaling method to study the coalescence phenomenon of H(2)(+). The advantage of this method is that one can easily trace the different states that are changing as the field parameters change. It was reported earlier that in the parameter space, only two bound states coalesce [R. Lefebvre, O. Atabek, M. Sindelka, and N. Moiseyev, Phys. Rev. Lett. 103, 123003 (2009)]. However, it is found that increasing the accuracy of the calculation leads to the coalescence between resonance states originating from the bound and the continuum states. We have also reported many other coalescence points.

  8. Coalescence of drops and bubbles rising through a non-Newtonian fluid in a tube.

    Science.gov (United States)

    Al-Matroushi, Eisa; Borhan, Ali

    2009-04-01

    We conducted an experimental study of the interaction and coalescence of two drops (of the same fluid) or bubbles translating under the action of buoyancy in a cylindrical tube. The close approach of two Newtonian fluid particles of different size in a non-Newtonian continuous phase was examined using image analysis, and measurements of the coalescence time are reported for various particle size ratios, Bond numbers, and particle-to-suspending-fluid viscosity ratios. The flow disturbance behind the leading bubble and the viscoelastic nature of the continuous phase seemed to retard bubble coalescence. The time scale for coalescence of liquid drops in highly elastic continuous phase was influenced by the relative motion of the drops and their coalescence behavior.

  9. Organic-Inorganic Hybrid Silica Material Derived from a Monosilylated Grubbs-Hoveyda Ruthenium Carbene as a Recyclable Metathesis Catalyst

    Directory of Open Access Journals (Sweden)

    Michel Wong Chi Man

    2010-08-01

    Full Text Available The synthesis of a monosilylated Grubbs-Hoveyda ruthenium alkylidene complex is described, as well as the preparation and characterization of the corresponding material by sol-gel cogelification with tetraethoxysilane (TEOS and the assay of this recyclable supported catalyst in ring-closing diene and enyne metathesis reactions under thermal and microwave conditions.

  10. Metátese de olefinas no Brasil: "Brazil is romping it!" Olefin metathesis in Brazil: Brazil is romping it!

    Directory of Open Access Journals (Sweden)

    José Milton E. Matos

    2007-04-01

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

  11. Enantioselective synthesis of benzofurans and benzoxazines via an olefin cross-metathesis-intramolecular oxo-Michael reaction.

    Science.gov (United States)

    Zhang, Jun-Wei; Cai, Quan; Gu, Qing; Shi, Xiao-Xin; You, Shu-Li

    2013-09-11

    Chiral phosphoric acid and Hoveyda-Grubbs II were found to catalyze an olefin cross-metathesis-intramolecular oxo-Michael cascade reaction of the ortho-allylphenols and enones to provide a variety of benzofuran and benzoxazine derivatives in moderate to good yields and enantioselectivity.

  12. Liquid-phase synthesis of bridged peptides using olefin metathesis of a protected peptide with a long aliphatic chain anchor.

    Science.gov (United States)

    Aihara, Keisuke; Komiya, Chiaki; Shigenaga, Akira; Inokuma, Tsubasa; Takahashi, Daisuke; Otaka, Akira

    2015-02-01

    Bridged peptides including stapled peptides are attractive tools for regulating protein-protein interactions (PPIs). An effective synthetic methodology in a heterogeneous system for the preparation of these peptides using olefin metathesis and hydrogenation of protected peptides with a long aliphatic chain anchor is reported.

  13. 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

    -closing metathesis to afford the key conduritol B intermediate 7. This can trifurcate to form three different benzyl-protected myo-inositol headgroups 4-6, which after phosphorylation and attachment of the glycerolipid part give phosphatidylinositols 1-3. Preliminary biological testing against human colon...

  14. Poly(dendrimers) with phosphorescent iridium(III) complex-based side chains prepared via ring-opening metathesis polymerization

    NARCIS (Netherlands)

    Lai, W.-Y.; Balfour, M.N.; Levell, J.W.; Bansal, A.K.; Burn, P.L.; Lo, S.-C.; Samuel, I.D.W.

    2012-01-01

    Phosphorescent poly(dendrimers) with a norbornene-derived backbone have been synthesized using ring-opening metathesis polymerization with the Grubbs III catalyst. The dendrimers are comprised of a heteroleptic iridium(III) complex core with two 2-phenylpyridyl ligands and a phenyltriazolyl ligand,

  15. Synthesis of a novel uridine analogue and its use in attempts to form new cyclonucleosides using ring-closing metathesis

    Institute of Scientific and Technical Information of China (English)

    MONDON; Martine; LEN; Christophe

    2010-01-01

    One novel nucleoside analogue having a hex-5-enyl group and an allyl group in the 5’-C and 3-N position was synthesized regioand diastereoselectively from D-glucose in twelve steps.In order to reach a particular conformation of nucleosides the nucleoside formation of restricted cyclonucleoside analogues was studied via Ring-Closing Metathesis.

  16. Ring opening of monocyclic dimethyl cyclopropene via metathesis by tungsten catalyst- A computational study

    Indian Academy of Sciences (India)

    Jay Singh Meena; Pompozhi Protasis Thankachan

    2014-05-01

    Metathesis reaction of 3,3-disubstituted cyclopropene mediated by the model catalyst tungsten alkylidene W(NH)(CH2)(OCH3)2 has been studied at the B3LYP/LANL2DZ level of theory. The stationary points on the potential energy surface for ring opening metathesis were calculated considering all stereochemically distinct approaches of the 3,3-disubstituted cyclopropene to the model tungsten catalyst. The ring opening of cyclopropene moiety proceeds in two steps i.e., cycloaddition and ring opening. Each step involves a twisted trigonal bipyramidal transition structure. The syn orientation of cyclopropene to the NH group of the tungsten alkylidene is more favourable for product formation. Cyclopropene addition to tungsten alkylidene takes place preferentially on the CNO face; which is favoured by 10.89 kcal/mol over the COO face. The energy barriers for the syn cycloaddition and syn ring opening steps are 8.47 and 10.94 kcal/mol, respectively. The ring opening step is the rate determining step for the reaction of cyclopropene with tungsten catalyst, in contrast with the case of the molybdenum catalyst.

  17. 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.

  18. In Situ Generation of Molybdenum-Based Catalyst for Alkyne Metathesis: Further Developments and Mechanistic Insights

    Directory of Open Access Journals (Sweden)

    Geng Lopez Joaquin

    2016-03-01

    Full Text Available Molybdenum-based catalysts are among the best candidates to achieve alkyne metathesis. They can be either well-defined carbynes, previously synthesized before their use, but also prepared in situ upon using stable molybdenum carbonyl complexes, or high oxidation state molybdenum salts that need a previous alkylation, both type of precursors being “activated” by hydroxyl-containing compounds such as phenols and silanols. This paper is presenting studies made on these systems, directed towards the knowledge of the reaction paths leading to the active species, and in particular to define the essential role of hydroxyl-containing co-catalyst in the formation of the active species, still ill-defined. From an analysis of the byproducts formed during the reaction, as well as of the initial products, reaction paths to access catalytic carbyne species is suggested, where the ligand environment consists of phenoxy (or siloxy groups, typically required and identified to lead to alkyne metathesis in the case of well-defined catalysts.

  19. Dynamic Covalent Synthesis of Aryleneethynylene Cages through Alkyne Metathesis: Dimer, Tetramer, or Interlocked Complex?

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Qi; Yu, Chao; Zhang, Chenxi; Long, Hai; Azarnoush, Setareh; Jin, Yinghua; Zhang, Wei

    2016-05-01

    A dynamic covalent approach towards rigid aryleneethynylene covalent organic polyhedrons (COPs) was explored. Our study on the relationship of the COP structures and the geometry of their building blocks reveals that the topology of aryleneethynylene COPs strongly depends on the size of the building blocks. A tetramer (D2h symmetric), dimer, or interlocked complex can be formed from monomers with the same face-to-edge angle but in different sizes. As alkyne metathesis is a self-exchange reaction and non-directional, the cyclooligomerization of multi-alkyne monomers involves both intramolecular cyclization and intermolecular metathesis reaction, resulting in complicated thermodynamic process disturbed by kinetic competition. Although a tetrahedron-shaped tetramer (Td symmetric) has comparable thermodynamic stability to a D2h symmetric tetramer, its formation is kinetically disfavored and was not observed experimentally. Aryleneethynylene COPs consist of purely unsaturated carbon backbones and exhibit large internal cavities, which would have interesting applications in host-guest chemistry and development of porous materials.

  20. Hypercoordinate β-carbon in Grubbs and Schrock olefin metathesis metallacycles.

    Science.gov (United States)

    Remya, Premaja R; Suresh, Cherumuttathu H

    2015-10-28

    Metallacyclobutane (MCB) intermediates of Grubbs and Schrock olefin metathesis catalysts are well-known for their unusually short single bond-like metal to Cβ distance and unusually long CαCβ distances. From the analysis of structural, bond order, electron density and (13)C NMR data of a large variety of MCB systems, we show that the Cβ of the metallacycle possesses pentacoordinate geometry due to the agostic type interaction of the metal with the CαCβ bonds. The pentacoordination of Cβ to the metal center is characterized by a catastrophe ring critical point (RCP) in the quantum theory of atoms-in-molecule (QTAIM) analysis. Fine tuning of the ligand environment changes the catastrophe point to a fifth bond critical point (BCP) which is clearly brought out in the case of two ruthenium olefin metathesis systems. Several Ru and W agostic MCB complexes exhibiting pentacoordinate Cβ as well as their non-agostic isomers have been reported at the BP86/def2-TZVPP level of DFT. The agostic systems showed a significant bond order between metal and Cβ (0.17-0.36), single bond-like electron density values at the catastrophe RCP/BCP and a significantly large difference in (13)C NMR chemical shift values between Cα and Cβ atoms.

  1. Highly Active Chiral Ruthenium Catalysts for Asymmetric Ring-Closing Olefin Metathesis

    Science.gov (United States)

    Funk, Timothy W.; Berlin, Jacob M.

    2008-01-01

    The synthesis of olefin metathesis catalysts containing chiral, monodentate N-heterocyclic carbenes and their application to asymmetric ring-closing metathesis (ARCM) is reported. These catalysts retain the high levels of reactivity found in the related achiral variants (1a and 1b). Using the parent chiral catalysts 2a and 2b and derivatives that contain steric bulk in the meta positions of the N-bound aryl rings (catalysts 3-5), five- through seven-membered rings were formed in up to 92% ee. The addition of sodium iodide to catalysts 2a-4a (to form 2b-4bin situ) caused a dramatic increase in enantioselectivity for many substrates. Catalyst 5a, which gave high enantiomeric excesses for certain substrates without the addition of NaI, could be used in loadings of ≤1 mol %. Mechanistic explanations for the large sodium iodide effect as well as possible mechanistic pathways leading to the observed products are discussed. PMID:16464082

  2. Theory-assisted development of a robust and Z-selective olefin metathesis catalyst.

    Science.gov (United States)

    Occhipinti, Giovanni; Koudriavtsev, Vitali; Törnroos, Karl W; Jensen, Vidar R

    2014-08-01

    DFT calculations have predicted a new, highly Z-selective ruthenium-based olefin metathesis catalyst that is considerably more robust than the recently reported (SIMes)(Cl)(RS)RuCH(o-OiPrC6H4) (3a, SIMes = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene, R = 2,4,6-triphenylbenzene) [J. Am. Chem. Soc., 2013, 135, 3331]. Replacing the chloride of 3a by an isocyanate ligand to give 5a was predicted to increase the stability of the complex considerably, at the same time moderately improving the Z-selectivity. Compound 5a is easily prepared in a two-step synthesis starting from the Hoveyda-Grubbs second-generation catalyst 3. In agreement with the calculations, the isocyanate-substituted 5a appears to be somewhat more Z-selective than the chloride analogue 3a. More importantly, 5a can be used in air, with unpurified and non-degassed substrates and solvents, and in the presence of acids. These are traits that are unprecedented among highly Z-selective olefin metathesis catalysts and also very promising with respect to applications of the new catalyst.

  3. Z-Selective Olefin Metathesis Processes Catalyzed by a Molybdenum Hexaisopropylterphenoxide Monopyrrolide Complex

    Science.gov (United States)

    Flook, Margaret M.; Jiang, Annie J.; Schrock, Richard R.; Müller, Peter; Hoveyda, Amir H.

    2009-01-01

    The molybdenum-based monoaryloxide monopyrrolide (MAP) species, Mo(NAd)(CHCMe2Ph)(C4H4N)(HIPTO) (2a), which contains “small” imido (Ad = 1-adamantyl) and “large” aryloxide (HIPTO = O-2,6(2,4,6-i-Pr3C6H2)C6H3) ligands, catalyzes Z-selective metathesis reactions as a consequence of intermediate metallacyclobutane species not being able to have a (anti) substituent pointing toward the HIPTO group. ROMP of dicarbomethoxynorbornadiene (DCMNBD) with 2% 2a in toluene leads to >99% cis and >99% syndiotactic poly(DCMNBD), while ROMP of cyclooctene and 1,5-cyclooctadiene (300 equiv)with initiator 2a leads to poly(cyclooctene) and poly(cyclooctadiene) that have cis contents of >99%; all are previously unknown microstructures. Z-selectivity is also observed in the metathesis of cis-4-octene and cis-3-hexene by initiator 2a to give cis-3-heptene. PMID:19462947

  4. Stitched α-helical peptides via bis ring-closing metathesis.

    Science.gov (United States)

    Hilinski, Gerard J; Kim, Young-Woo; Hong, Jooyeon; Kutchukian, Peter S; Crenshaw, Charisse M; Berkovitch, Shaunna S; Chang, Andrew; Ham, Sihyun; Verdine, Gregory L

    2014-09-03

    Conformationally stabilized α-helical peptides are capable of inhibiting disease-relevant intracellular or extracellular protein-protein interactions in vivo. We have previously reported that the employment of ring-closing metathesis to introduce a single all-hydrocarbon staple along one face of an α-helical peptide greatly increases α-helical content, binding affinity to a target protein, cell penetration through active transport, and resistance to proteolytic degradation. In an effort to improve upon this technology for stabilizing a peptide in a bioactive α-helical conformation, we report the discovery of an efficient and selective bis ring-closing metathesis reaction leading to peptides bearing multiple contiguous staples connected by a central spiro ring junction. Circular dichroism spectroscopy, NMR, and computational analyses have been used to investigate the conformation of these "stitched" peptides, which are shown to exhibit remarkable thermal stabilities. Likewise, trypsin proteolysis assays confirm the achievement of a structural rigidity unmatched by peptides bearing a single staple. Furthermore, fluorescence-activated cell sorting (FACS) and confocal microscopy assays demonstrate that stitched peptides display superior cell penetrating ability compared to their stapled counterparts, suggesting that this technology may be useful not only in the context of enhancing the drug-like properties of α-helical peptides but also in producing potent agents for the intracellular delivery of proteins and oligonucleotides.

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

    KAUST Repository

    Qureshi, Ziyauddin S.

    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.

  6. Direct synthesis of Z-alkenyl halides through catalytic cross-metathesis

    Science.gov (United States)

    Koh, Ming Joo; Nguyen, Thach T.; Zhang, Hanmo; Schrock, Richard R.; Hoveyda, Amir H.

    2016-03-01

    Olefin metathesis has had a large impact on modern organic chemistry, but important shortcomings remain: for example, the lack of efficient processes that can be used to generate acyclic alkenyl halides. Halo-substituted ruthenium carbene complexes decompose rapidly or deliver low activity and/or minimal stereoselectivity, and our understanding of the corresponding high-oxidation-state systems is limited. Here we show that previously unknown halo-substituted molybdenum alkylidene species are exceptionally reactive and are able to participate in high-yielding olefin metathesis reactions that afford acyclic 1,2-disubstituted Z-alkenyl halides. Transformations are promoted by small amounts of a catalyst that is generated in situ and used with unpurified, commercially available and easy-to-handle liquid 1,2-dihaloethene reagents, and proceed to high conversion at ambient temperature within four hours. We obtain many alkenyl chlorides, bromides and fluorides in up to 91 per cent yield and complete Z selectivity. This method can be used to synthesize biologically active compounds readily and to perform site- and stereoselective fluorination of complex organic molecules.

  7. Ruthenium-based olefin metathesis catalysts bearing pH-responsive ligands: External control of catalyst solubility and activity

    Science.gov (United States)

    Balof, Shawna Lynn

    2011-12-01

    Sixteen novel, Ru-based olefin metathesis catalysts bearing pH responsive ligands were synthesized. The pH-responsive groups employed with these catalysts included dimethylamino (NMe2) modified NHC ligands as well as N-donor dimethylaminopyridine (DMAP) and 3-(o-pyridyl)propylidene ligands. These pH-responsive ligands provided the means by which the solubility and/or activity profiles of the catalysts produced could be controlled via acid addition. The main goal of this dissertation was to design catalyst systems capable of performing ring opening metathesis (ROMP) and ring closing metathesis (RCM) reactions in both organic and aqueous media. In an effort to quickly gain access to new catalyst structures, a template synthesis for functionalized NHC ligand precursors was designed, in addition to other strategies, to obtain ligand precursors with ancillary NMe2 groups. Kinetic studies for the catalysts produced from these precursors showed external control of catalyst solubility was afforded via protonation of the NMe2 groups of their NHC ligands. Additionally, this protonation afforded external control of catalyst propagation rates for several catalysts. This is the first known independent external control for the propagation rates of ROMP catalysts. The incorporation of pH-responsive N-donor ligands into catalyst structures also provided the means for the external control of metathesis activity, as the protonation of these ligands resulted in an increased initiation rate based on their fast and irreversible dissociation from the metal center. The enhanced external control makes these catalysts applicable to a wide range of applications, some of which have been explored by us and/or through collaboration. Three of the catalysts designed showed remarkable metathesis activity in aqueous media. These catalysts displayed comparable RCM activity in aqueous media to a class of water-soluble catalysts reported by Grubbs et al., considered to be the most active catalyst for

  8. The Dynamics of Liquid Drops Coalescing in the Inertial Regime

    CERN Document Server

    Sprittles, James E

    2014-01-01

    We examine the dynamics of two coalescing liquid drops in the `inertial regime', where the effects of viscosity are negligible and the propagation of the bridge front connecting the drops can be considered as `local'. The solution fully computed in the framework of classical fluid-mechanics allows this regime to be identified and the accuracy of the approximating scaling laws proposed to describe the propagation of the bridge to be established. It is shown that the scaling law known for this regime has a very limited region of accuracy and, as a result, in describing experimental data it has frequently been applied outside its limits of applicability. The origin of the scaling law's shortcoming appears to be the fact that it accounts for the capillary pressure due only to the longitudinal curvature of the free surface as the driving force for the process. To address this deficiency, the scaling law is extended to account for both the longitudinal and azimuthal curvatures at the bridge front which, fortuitousl...

  9. Resonant tidal excitation of superfluid neutron stars in coalescing binaries

    CERN Document Server

    Yu, Hang

    2016-01-01

    We study the resonant tidal excitation of g-modes in coalescing superfluid neutron star binaries and investigate how such tidal driving impacts the gravitational-wave signal of the inspiral. Previous studies of this type treated the neutron star core as a normal fluid and thus did not account for its expected superfluidity. The source of buoyancy that supports the g-modes is fundamentally different in the two cases: in a normal fluid core the buoyancy is due to gradients in the proton-to-neutron fraction whereas in a superfluid core it is due to gradients in the muon-to-electron fraction. The latter yields a stronger stratification and a superfluid neutron star therefore has a denser spectrum of g-modes with frequencies above 10 Hz. As a result, many more g-modes undergo resonant tidal excitation as the binary sweeps through the bandwidth of gravitational-wave detectors such as LIGO. We find that roughly 10 times more orbital energy is transferred into g-mode oscillations if the neutron star has a superfluid ...

  10. Inferring the dynamics of diversification: a coalescent approach.

    Directory of Open Access Journals (Sweden)

    Hélène Morlon

    Full Text Available Recent analyses of the fossil record and molecular phylogenies suggest that there are fundamental limits to biodiversity, possibly arising from constraints in the availability of space, resources, or ecological niches. Under this hypothesis, speciation rates decay over time and biodiversity eventually saturates, with new species emerging only when others are driven to extinction. This view of macro-evolution contradicts an alternative hypothesis that biodiversity is unbounded, with species ever accumulating as they find new niches to occupy. These contrasting theories of biodiversity dynamics yield fundamentally different explanations for the disparity in species richness across taxa and regions. Here, we test whether speciation rates have decayed or remained constant over time, and whether biodiversity is saturated or still expanding. We first derive a general likelihood expression for internode distances in a phylogeny, based on the well-known coalescent process from population genetics. This expression accounts for either time-constant or time-variable rates, time-constant or time-variable diversity, and completely or incompletely sampled phylogenies. We then compare the performance of different diversification scenarios in explaining a set of 289 phylogenies representing amphibians, arthropods, birds, mammals, mollusks, and flowering plants. Our results indicate that speciation rates typically decay over time, but that diversity is still expanding at present. The evidence for expanding-diversity models suggests that an upper limit to biodiversity has not yet been reached, or that no such limit exists.

  11. Energetics and phasing of nonprecessing spinning coalescing black hole binaries

    CERN Document Server

    Nagar, Alessandro; Reisswig, Christian; Pollney, Denis

    2015-01-01

    We present an improved numerical relativity (NR) calibration of the new effective-one-body (EOB) model for coalescing non precessing spinning black hole binaries recently introduced by Damour and Nagar [Physical Review D 90, 044018 (2014)]. We do so by comparing the EOB predictions to both the phasing and the energetics provided by two independent sets of NR data covering mass ratios $1\\leq q \\leq 8$ and dimensionless spin range $-0.95\\leq \\chi\\leq +0.98$. One set of data is a subset of the Simulating eXtreme Spacetimes (SXS) catalog of public waveforms; the other set consists of new simulations obtained with the Llama code plus Cauchy Characteristic Evolution. We present the first systematic computation of the gauge-invariant relation between the binding energy and the total angular momentum, $E_{b}(j)$, for a large sample of, spin-aligned, SXS and Llama data. The EOB model presented here has only two calibration parameters, one entering the non spinning sector, as a 5PN effective correction to the interacti...

  12. Fabrication of Janus hydrogels with stiffness gradient using drop coalescence

    Science.gov (United States)

    Lee, Donghee; Golden, Kale; Ryu, Sangjin

    2016-11-01

    The stiffness of the extracellular matrix (ECM) regulates cellular behaviors, and polyacrylamide (PAAM) gels with stiffness gradient have been used to simulate inhomogeneous ECM and to study the effects of the ECM stiffness on cells. Such hydrogel substrates with stiffness gradient can be fabricated with relatively complicated methods using microfluidics and moving masks. In our study, we develop a simpler method for fabricating Janus hydrogel which has a gradient of stiffness. Two prepolymer solutions were prepared for soft and stiff gel compositions, respectively, and one drop of each solution was placed on a hydrophobic patterned glass. Then, these two drops were gently squeezed by another glass being slowly lowered until coalescence, and gel polymerization was initiated after a certain time period for mixing. The motion of the drops was guided by the hydrophobic pattern. AFM nano-indentation showed that the fabricated Janus PAAM gels have a stiffness gradient which could be controlled by increasing mixing time. This study was supported by Bioengineering for Human Health Grant from UNL and UNMC.

  13. The doping effect of fluorinated aromatic hydrocarbon solvents on the performance of common olefin metathesis catalysts: application in the preparation of biologically active compounds.

    Science.gov (United States)

    Samojłowicz, Cezary; Bieniek, Michał; Zarecki, Andrzej; Kadyrov, Renat; Grela, Karol

    2008-12-21

    Aromatic fluorinated hydrocarbons, used as solvents for olefin metathesis reactions, catalysed by standard commercially available Ru precatalysts, allow substantially higher yields to be obtained, especially of challenging substrates, including natural and biologically active compounds.

  14. 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.

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

    Science.gov (United States)

    Hauke, Sylvia

    2014-01-01

    Summary 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. PMID:24991253

  16. Catalyst-Controlled Stereoselective Olefin Metathesis as a Principal Strategy in Multi-Step Synthesis Design. A Concise Route to (+)-Neopeltolide**

    Science.gov (United States)

    Yu, Miao; Schrock, Richard R.

    2014-01-01

    Mo-, W- and Ru-based complexes that control the stereochemical outcome of olefin metathesis reactions have been recently introduced. However, the complementary nature of these systems through their combined use in multistep complex molecule synthesis has not been illustrated. Here, we disclose a concise diastereo- and enantioselective route that furnishes the anti-proliferative natural product neopeltolide. Catalytic transformations are employed to address every stereochemical issue. Among the featured processes are an enantioselective ring-opening/cross-metathesis promoted by a Mo monopyrrolide aryloxide (MAP) complex and a macrocyclic ring-closing metathesis affording a trisubstituted alkene catalyzed by a Mo bis-aryloxide species. Furthermore, Z-selective cross-metathesis reactions, facilitated by Mo and Ru complexes, have been employed in stereoselective synthesis of the acyclic dienyl moiety of the target molecule. PMID:25377347

  17. Sequence diversity under the multispecies coalescent with Yule process and constant population size.

    Science.gov (United States)

    Heled, Joseph

    2012-03-01

    The study of sequence diversity under phylogenetic models is now classic. Theoretical studies of diversity under the Kingman coalescent appeared shortly after the introduction of the coalescent. In this paper we revisit this topic under the multispecies coalescent, an extension of the single population model to multiple populations. We derive exact formulas for the sequence dissimilarity of two sequences drawn at random under a basic multispecies setup. The multispecies model uses three parameters--the species tree birth rate under the pure birth process (Yule), the species effective population size and the mutation rate. We also discuss the effects of relaxing some of the model assumptions.

  18. Synthesis of linear [5]catenanes via olefin metathesis dimerization of pseudorotaxanes composed of a [2]catenane and a secondary ammonium salt.

    Science.gov (United States)

    Iwamoto, Hajime; Tafuku, Shinji; Sato, Yoshihiko; Takizawa, Wataru; Katagiri, Wataru; Tayama, Eiji; Hasegawa, Eietsu; Fukazawa, Yoshimasa; Haino, Takeharu

    2016-01-01

    [5]Catenanes were synthesized by olefin metathesis dimerization. The reaction of pseudorotaxanes, which were derived from a [2]catenane and one equivalent of an ammonium salt bearing two terminal olefins in dichloromethane, with a catalytic amount of Grubbs catalyst afforded linear [5]catenanes in 12% yield. Intermolecular and intramolecular olefin metathesis reactions were controlled by the length of the alkyl chain of the ammonium salts.

  19. An Electronic Rationale for Observed Initiation Rates in Ruthenium-Mediated Olefin Metathesis: Charge Donation in Phosphine And N-Heterocyclic Carbene Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Getty, K.; Delgado-Jaime, M.U.; Kennepohl, P.

    2009-06-01

    Ru K-edge XAS data indicate that second generation ruthenium-based olefin metathesis precatalysts (L = N-heterocyclic carbene) possess a more electron-deficient metal center than in the corresponding first generation species (L = tricyclohexylphosphine). This surprising effect is also observed from DFT calculations and provides a simple rationale for the slow phosphine dissociation kinetics previously noted for second-generation metathesis precatalysts.

  20. Axially chiral macrocyclic E-alkene bearing bisazole component formed by sequential C-H homocoupling and ring-closing metathesis.

    Science.gov (United States)

    Nishio, Shotaro; Somete, Takashi; Sugie, Atsushi; Kobayashi, Tohru; Yaita, Tsuyoshi; Mori, Atsunori

    2012-05-18

    Clipping by ring-closing metathesis freezes rotation of a C-C bond to result in forming axial chirality. Treatment of bisbenzimidazole bearing an N-(3-butenyl) substituent with a Grubbs' catalyst undergoes ring-closing metathesis, in which the stereochemistry of the thus formed olefin was exclusively E-form. Analysis by HPLC with a chiral stationary column confirmed clear baseline separation of each enantiomer.