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

Directory of Open Access Journals (Sweden)

Javier Miró

2015-08-01

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

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

Directory of Open Access Journals (Sweden)

Motoo Tori

2010-06-01

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

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.

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.

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

NARCIS (Netherlands)

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

2003-01-01

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

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.

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

Science.gov (United States)

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

2013-09-20

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

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

Directory of Open Access Journals (Sweden)

Sambasivarao Kotha

2015-07-01

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

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

DEFF Research Database (Denmark)

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

1999-01-01

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

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

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Thibault E. Schmid

2015-09-01

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

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

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Goti Andrea

2007-12-01

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

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...

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

Science.gov (United States)

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

2016-02-05

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

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

DEFF Research Database (Denmark)

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

2011-01-01

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

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

KAUST Repository

Saidi, Aya

2016-11-01

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

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

OpenAIRE

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

2008-01-01

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

Theoretical investigation of the photochemical C2-C6 cyclisation of enyne-heteroallenes.

Science.gov (United States)

Spöler, Carsten; Engels, Bernd

2003-10-06

Herein we discuss computations that explain experimental results regarding a highly efficient triplet analogue of the C(2)-C(6) cyclisation of enyne-heteroallenes recently discovered by Schmittel and co-workers.1 To shed some light on the reasons for the differences found between enyne-carbodiimides, enyne-ketenimines and enyne-allenes, we have computed the reaction profiles of the C(2)-C(6) and of the C(2)-C(7) cyclisations for various model compounds, assuming that the reactions take place on the lowest-lying triplet surfaces. Our results nicely explain the differences and the unexpected high efficiency found for the enyne-carbodiimides. The differences between enyne-carbodiimides and enyne-ketenimines prove to be due to differences in the shapes of the corresponding triplet surfaces. In contrast to the enyne-carbodiimides, for which our calculations predict that a direct cyclisation to the biradical intermediates should occur after the vertical excitation, the enyne-ketenimines relax into a local minimum on the triplet surface. As a consequence, further reaction channels are opened. Our computations indicate that enyne-allene compounds do not react because the necessary excitation energy lies outside the range of the employed triplet photosensitizer. Finally, the close agreement between our results and the experimental findings indicates that the underlying reasons for the differences in the photochemical behaviour of enyne-carbodiimides, enyne-ketenimines and enyne-allenes are related to differences in the electronic structures of the parent systems, while substituent effects are less important.

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.

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

KAUST Repository

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

2016-01-01

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

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.

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

Science.gov (United States)

Kotha, Sambasivarao; Gunta, Rama

2015-01-01

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

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

OpenAIRE

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

2016-01-01

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

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

KAUST Repository

Zhang, Hefeng; Gnanou, Yves; Hadjichristidis, Nikolaos

2014-01-01

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

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).

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

KAUST Repository

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

2014-01-01

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

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

DEFF Research Database (Denmark)

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

2006-01-01

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

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Home; Journals; Journal of Chemical Sciences. Krishna P Kaliappan. Articles written in Journal of Chemical Sciences. Volume 120 Issue 1 January 2008 pp 205-216. Synthetic studies on taxanes: A domino-enyne metathesis/Diels-Alder approach to the AB-ring · Krishna P Kaliappan Velayutham Ravikumar Sandip A Pujari.

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

DEFF Research Database (Denmark)

Madsen, Robert

2007-01-01

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

Preparation and Reaction Chemistry of Novel Silicon-Substituted 1,3-Dienes

Directory of Open Access Journals (Sweden)

Partha P. Choudhury

2015-09-01

Full Text Available 2-Silicon-substituted 1,3-dienes containing non transferrable groups known to promote transmetallation were prepared by Grignard chemistry and enyne metathesis. These dienes participated in one pot metathesis/Diels-Alder reactions in regio- and diastereoselective fashions. Electron-rich alkenes showed the fastest rates in metathesis reactions, and ethylene, a commonly used metathesis promoter slowed enyne metathesis. 2-Pyridyldimethylsilyl and 2-thienyldimethylsilyl substituted Diels-Alder cycloadducts participated in cross-coupling chemistry and the 2-thienyldimethylsilyl substituted cycloadducts underwent cross-coupling under very mild reaction conditions.

Two Novel Thermal Biradical Cyclizations of Enyne-Ketenimines: Theory, Experiment, and Synthetic Potential.

Science.gov (United States)

Schmittel, Michael; Steffen, Jens-Peter; Wencesla Ángel, Miguel Á; Engels, Bernd; Lennartz, Christian; Hanrath, Michael

1998-06-19

Both benzocarbazoles and quinolines can be synthesized from enyne ketenimines 1 generated in situ via biradical intermediates (see reaction below). Which of the heterocyclic ring systems is formed depends on the choice of the substituent R 1 at the alkyne terminus. © 1998 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

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.

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.

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

Czech Academy of Sciences Publication Activity Database

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

2015-01-01

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

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

Science.gov (United States)

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

2018-01-09

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

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

Science.gov (United States)

Kilbinger, Andreas F M

2012-01-01

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

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

Directory of Open Access Journals (Sweden)

Sambasivarao Kotha

2015-07-01

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

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

Science.gov (United States)

Kotha, Sambasivarao; Ravikumar, Ongolu

2015-01-01

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

Convergent synthesis of the HIJKLM ring system of ciguatoxin CTX3C.

Science.gov (United States)

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

2011-09-02

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

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

DEFF Research Database (Denmark)

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

2004-01-01

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

Structural diversification of the aminobicyclo[4.3.0]nonane skeleton using alkynylsilyl-derived allylic trichloroacetimidates.

Science.gov (United States)

Mostafa, Mohamed A B; McMillan, Angus E; Sutherland, Andrew

2017-04-05

The amino substituted bicyclo[4.3.0]nonane is a molecular scaffold found in a wide range of natural products and medicinal agents. Despite this, synthetic methods for the general preparation of this structural motif are sparse. Here we evaluate a diastereoselective approach for the preparation of vinylsilyl derived aminobicyclo[4.3.0]nonanes using a one-pot multi-bond forming process involving a Pd(ii)-catalysed Overman rearrangement, a Ru(ii)-catalysed ring closing enyne metathesis reaction, followed by a hydrogen bonding directed Diels-Alder reaction. We show that a benzyldimethylsilyl-substituted alkene analogue is amenable to further functionalisation and the late stage generation of diverse sp 3 -rich, drug-like aminobicyclo[4.3.0]nonane scaffolds with up to six stereogenic centres.

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

Science.gov (United States)

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

2016-04-01

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

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

KAUST Repository

Merle, Nicolas

2017-09-25

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

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

KAUST Repository

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

2017-01-01

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

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

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.

The metathesis of alkynes

Directory of Open Access Journals (Sweden)

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.

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

KAUST Repository

Rouen, Mathieu

2014-09-11

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

Metathesis reactions for the synthesis of ring-fused carbazoles

CSIR Research Space (South Africa)

Pelly, SC

2005-12-09

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

Synthesis of enyne and aryl vinyl sulfoxides: functionalization via Pummerer rearrangement.

Science.gov (United States)

Souza, Frederico B; Shamim, Anwar; Argomedo, Luiz M Z; Pimenta, Daniel C; Stefani, Hélio A

2015-11-01

An efficient methodology for the synthesis of aryl-substituted vinyl sulfoxides through direct substitution of aryl-substituted alkynyl grignard reagents on menthyl-p-toluenesulfinate followed by Suzuki-Miyaura cross-coupling reaction has been developed. It has also been described that the reaction of alkyl-substituted and cycloalkyl-substituted alkynyl grignard reagents with menthyl-p-toluenesulfinate led to two products, i.e., alkynyl sulfoxide derivatives, as a result of substitution, and enyne sulfoxide derivatives, which resulted from substitution followed by Michael type addition. It was possible to selectively synthesize the enyne sulfoxide derivatives by changing the concentration of the grignard reagent. These alkenyl sulfoxides were transformed into the corresponding [Formula: see text]-thio aldehydes in high yields via additive Pummerer rearrangement.

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

Science.gov (United States)

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

2010-01-01

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

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

Science.gov (United States)

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

2011-02-07

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

Transition metal-catalyzed couplings of alkynes to 1,3-enynes: modern methods and synthetic applications.

Science.gov (United States)

Trost, Barry M; Masters, James T

2016-04-21

The metal-catalyzed coupling of alkynes is a powerful method for the preparation of 1,3-enynes, compounds that are of broad interest in organic synthesis. Numerous strategies have been developed for the homo- and cross coupling of alkynes to enynes via transition metal catalysis. In such reactions, a major issue is the control of regio-, stereo-, and, where applicable, chemoselectivity. Herein, we highlight prominent methods for the selective synthesis of these valuable compounds. Further, we illustrate the utility of these processes through specific examples of their application in carbocycle, heterocycle, and natural product syntheses.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-10-15

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

Alkane Metathesis

KAUST Repository

Basset, Jean-Marie

2015-03-29

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

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.

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

KAUST Repository

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

2016-01-01

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

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

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

Seco-B-Ring Steroidal Dienynes with Aromatic D Ring: Design, Synthesis and Biological Evaluation

Directory of Open Access Journals (Sweden)

Marcin Szybinski

2017-10-01

Full Text Available Continuing our structure-activity studies on the vitamin D analogs with the altered intercyclic seco-B-ring fragment, we designed compounds possessing dienyne system conjugated with the benzene D ring. Analysis of the literature data and the docking experiments seemed to indicate that the target compounds could mimic the ligands with a good affinity to the vitamin D receptor (VDR. Multi-step synthesis of the C/D-ring building block of the tetralone structure was achieved and its enol triflate was coupled with the known A-ring fragments, possessing conjugated enyne moiety, using Sonogashira protocol. The structures of the final products were confirmed by NMR, UV and mass spectroscopy. Their binding affinities for the full-length human VDR were determined and it was established that compound substituted at C-2 with exomethylene group showed significant binding to the receptor. This analog was also able to induce monocytic differentiation of HL-60 cells.

Transition metal-catalyzed carbocyclization of nitrogen and oxygen-tethered 1,n-enynes and diynes: synthesis of five or six-membered heterocyclic compounds.

Science.gov (United States)

Zhang, Di-Han; Zhang, Zhen; Shi, Min

2012-10-25

Cycloisomerization of 1,n-enynes and diynes is a powerful method in organic synthesis to access heterocyclic compounds and has drawn increasing attention from organic chemists. In this paper, we attempted to summarize our recent results on the transition metal-catalyzed cycloisomerization to synthesize five or six-membered heterocyclic compounds using 1,n-enynes and diynes having a propargylic ester moiety. First, we will describe the synthesis of 2,3-disubstituted 3-pyrrolines via gold catalyzed cycloisomerization of 1,6-diynes. In addition, we will also disclose a novel silver catalyzed tandem 1,3-acyloxy migration/Mannich-type addition/elimination of the sulfonyl group of N-sulfonylhydrazone-propargylic esters to 5,6-dihydropyridazin-4-one derivatives. Furthermore, we will introduce three interesting examples of the synthesis of bicyclic compounds via titanium or rhodium catalyzed carbocyclization of enynes. In this context, we have presented that 1,n-enynes and diynes containing propargylic esters are highly reactive and useful starting materials for the cycloisomerization catalyzed by a transition metal catalyst.

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.

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

International Nuclear Information System (INIS)

Kuznetsov, N Yu; Bubnov, Yu N

2015-01-01

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

THE RINGS OF CHARIKLO UNDER CLOSE ENCOUNTERS WITH THE GIANT PLANETS

Energy Technology Data Exchange (ETDEWEB)

Araujo, R. A. N.; Sfair, R.; Winter, O. C., E-mail: ran.araujo@gmail.com, E-mail: rsfair@feg.unesp.br, E-mail: ocwinter@gmail.com [UNESP - Univ. Estadual Paulista, Grupo de Dinâmica Orbital e Planetologia, CEP 12516-410, Guaratingueta, SP (Brazil)

2016-06-20

The Centaur population is composed of minor bodies wandering between the giant planets that frequently perform close gravitational encounters with these planets, leading to a chaotic orbital evolution. Recently, the discovery of two well-defined narrow rings was announced around the Centaur 10199 Chariklo. The rings are assumed to be in the equatorial plane of Chariklo and to have circular orbits. The existence of a well-defined system of rings around a body in such a perturbed orbital region poses an interesting new problem. Are the rings of Chariklo stable when perturbed by close gravitational encounters with the giant planets? Our approach to address this question consisted of forward and backward numerical simulations of 729 clones of Chariklo, with similar initial orbits, for a period of 100 Myr. We found, on average, that each clone experiences during its lifetime more than 150 close encounters with the giant planets within one Hill radius of the planet in question. We identified some extreme close encounters that were able to significantly disrupt or disturb the rings of Chariklo. About 3% of the clones lose their rings and about 4% of the clones have their rings significantly disturbed. Therefore, our results show that in most cases (more than 90%), the close encounters with the giant planets do not affect the stability of the rings in Chariklo-like systems. Thus, if there is an efficient mechanism that creates the rings, then these structures may be common among these kinds of Centaurs.

Diversity-Oriented Approaches to Polycyclics and Bioinspired Molecules via the Diels-Alder Strategy: Green Chemistry, Synthetic Economy, and Beyond.

Science.gov (United States)

Kotha, Sambasivarao; Chavan, Arjun S; Goyal, Deepti

2015-05-11

We describe diverse approaches to various dienes and their utilization in the Diels-Alder reaction to produce a variety of polycycles. The dienes covered here are prepared by simple alkylation reaction or via the Claisen rearrangement or by enyne metathesis of alkyne or enyne building blocks. Here, we have also included the Diels-Alder chemistry of dendralenes, a higher analog of cross-conjugated dienes. The present article is inclusive of o-xylylene derivatives that are generated in situ starting with benzosultine or benzosulfone derivatives. The Diels-Alder reaction of these dienes with various dienophiles gave diverse polycyclic systems and biologically important targets.

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

Directory of Open Access Journals (Sweden)

Despoina Chriti

2015-12-01

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

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.

Zinc Mediated Tandem Fragmentation-Allylation of Methyl 5-Iodopentofuranosides

DEFF Research Database (Denmark)

Hyldtoft, Lene; Madsen, Robert

1999-01-01

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

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.

Alkane Metathesis

KAUST Repository

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

2015-01-01

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

A tandem cross-metathesis/semipinacol rearrangement reaction.

Science.gov (United States)

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

2012-05-18

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

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

KAUST Repository

Riache, Nassima

2014-10-03

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

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

DEFF Research Database (Denmark)

Jensen, Thomas; Mikkelsen, Mette; Lauritsen, Anne

2009-01-01

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

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

Czech Academy of Sciences Publication Activity Database

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

2011-01-01

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

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

Directory of Open Access Journals (Sweden)

Shawna L. Balof

2015-10-01

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

The activation mechanism of Fe-based olefin metathesis catalysts

KAUST Repository

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

2014-01-01

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

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.

Exceptionally Stable and Efficient Solid Supported Hoveyda-Type Catalyst

Czech Academy of Sciences Publication Activity Database

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

2015-01-01

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

Conductance of closed and open long Aharonov-Bohm-Kondo rings

Science.gov (United States)

Shi, Zheng; Komijani, Yashar

2017-02-01

We calculate the finite temperature linear dc conductance of a generic single-impurity Anderson model containing an arbitrary number of Fermi liquid leads, and apply the formalism to closed and open long Aharonov-Bohm-Kondo (ABK) rings. We show that, as with the short ABK ring, there is a contribution to the conductance from the connected four-point Green's function of the conduction electrons. At sufficiently low temperatures this contribution can be eliminated, and the conductance can be expressed as a linear function of the T matrix of the screening channel. For closed rings we show that at temperatures high compared to the Kondo temperature, the conductance behaves differently for temperatures above and below vF/L , where vF is the Fermi velocity and L is the circumference of the ring. For open rings, when the ring arms have both a small transmission and a small reflection, we show from the microscopic model that the ring behaves like a two-path interferometer, and that the Kondo temperature is unaffected by details of the ring. Our findings confirm that ABK rings are potentially useful in the detection of the size of the Kondo screening cloud, the π /2 scattering phase shift from the Kondo singlet, and the suppression of Aharonov-Bohm oscillations due to inelastic scattering.

Intermolecular rhodium-catalyzed [2 + 2 + 2] carbocyclization reactions of 1,6-enynes with symmetrical and unsymmetrical alkynes†

Science.gov (United States)

Andrew Evans, P.; Sawyer, James R.; Lai, Kwong Wah; Huffman, John C.

2006-01-01

The crossed intermolecular rhodium-catalyzed [2 + 2 + 2] carbocyclization of carbon and heteroatom tethered 1,6-enynes can be accomplished with symmetrical and unsymmetrical alkynes, to afford the corresponding bicyclohexadienes in an efficient and highly selective manner. PMID:16075089

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.

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

DEFF Research Database (Denmark)

Skaanderup, Philip Robert; Madsen, Robert

2001-01-01

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

{open_quotes}O{close_quotes} ring sealed process tube, Phase II, test project

Energy Technology Data Exchange (ETDEWEB)

Johnson, R.E.

1951-04-09

The {open_quotes}O{close_quotes} ring seal has been proposed to replace the van stone flange and the bellows thermal expansion assembly currently used on the existing Hanford piles to achieve water and gas seals, respectively. Possible advantages of the {open_quotes}O{close_quotes} ring seal are: (1) simplification of component parts and elimination of van stone corrosion; (2) simplification of maintenance; (3) lower costs of initial erection; (4) increased strength. This test supplements Test Project No. 27 (a preliminary thermal cycling test) in applying the {open_quotes}O{close_quotes} ring seal assembly to actual pile operating conditions.

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

Science.gov (United States)

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

2018-01-15

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

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

Science.gov (United States)

Schrodi, Yann [Agoura Hills, CA

2011-11-29

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

Comparing Ru and Fe-catalyzed olefin metathesis

KAUST Repository

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

2014-01-01

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

Development of neutron shielding material using metathesis-polymer matrix

Energy Technology Data Exchange (ETDEWEB)

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

2004-04-21

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

Ultrasound-assisted self-metathesis reactions of monounsaturated fatty acids

Directory of Open Access Journals (Sweden)

Elmkaddem Mohammed Kamal

2016-09-01

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

Unsaturated Fatty Acid Esters Metathesis Catalyzed by Silica Supported WMe5

KAUST Repository

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

2015-01-01

Metathesis of unsaturated fatty acid esters (FAEs) by silica supported multifunctional W-based catalyst is disclosed. This transformation represents a novel route towards unsaturated di-esters. Especially, the self-metathesis of ethyl undecylenate

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

Directory of Open Access Journals (Sweden)

Patrick Claude

2011-12-01

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

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

KAUST Repository

Samantaray, Manoja

2016-06-01

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

Methods for treating a metathesis feedstock with metal alkoxides

Science.gov (United States)

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

2018-04-17

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

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.

A metal-catalyzed enyne-cyclization step for the synthesis of bi- and tricyclic scaffolds amenable to molecular library production

DEFF Research Database (Denmark)

Wu, Peng; Cohrt, Anders Emil O'Hanlon; Petersen, Rico

2016-01-01

A facile metal-catalyzed diversification step for the synthesis of novel bi- and tricyclic scaffolds from enyne substrates is reported in this study. From a single starting material, topologically diverse scaffolds for library synthesis can be generated and decorated in a few steps. The methodology...

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.

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

KAUST Repository

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

2016-01-01

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

A general enantioselective route to the chamigrene natural product family

KAUST Repository

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

2010-01-01

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

A general enantioselective route to the chamigrene natural product family

KAUST Repository

White, David E.

2010-06-01

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

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

Science.gov (United States)

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

2007-05-24

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

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

Science.gov (United States)

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

2016-06-13

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

by a solid-state metathesis approach

Indian Academy of Sciences (India)

Wintec

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

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

Science.gov (United States)

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

2016-09-21

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

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

KAUST Repository

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

2012-01-01

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

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

Science.gov (United States)

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

2017-01-01

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

Metathesis: A "Change-Your-Partners" Dance

Indian Academy of Sciences (India)

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

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

KAUST Repository

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

2017-01-01

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

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

KAUST Repository

Samantaray, Manoja

2017-02-10

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

South African Journal of Chemistry - Vol 60 (2007)

African Journals Online (AJOL)

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

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

Indian Academy of Sciences (India)

RITABRATA DATTA

2017-11-06

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

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

DEFF Research Database (Denmark)

Ascic, Erhad

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

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

KAUST Repository

Pump, Eva

2015-06-30

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

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

KAUST Repository

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

2015-01-01

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

Borostannylation of Alkynes and Enynes. Scope and Limitations of the Reaction and Utility of the Adducts

Science.gov (United States)

Singidi, Ramakrishna Reddy; RajanBabu, T. V.

2010-01-01

The utility of the bis-metallating reagent 1,3-dimethyl-2-trimethylstannyl-2-bora-1,3-diazacyclopentane (1) has not been fully realized because of the hydrolytic instability of the products derived from catalyzed vicinal syn-additions to alkynes. The isolation of variety of such adducts derived from alkynes (and also from hitherto unreported additions to 1,3-enynes) as stable boron pinacolates is reported. Examples of the applications of resulting products in tandem cross-coupling reactions and as dienes in Diels-Alder reactions are illustrated. PMID:20459076

Model-independent and fast determination of optical functions in storage rings via multiturn and closed-orbit data

Directory of Open Access Journals (Sweden)

Bernard Riemann

2011-06-01

Full Text Available Multiturn (or turn-by-turn data acquisition has proven to be a new source of direct measurements for Twiss parameters in storage rings. On the other hand, closed-orbit measurements are a long-known tool for analyzing closed-orbit perturbations with conventional beam position monitor (BPM systems and are necessarily available at every storage ring. This paper aims at combining the advantages of multiturn measurements and closed-orbit data. We show that only two multiturn BPMs and four correctors in one localized drift space in the storage ring (diagnostic drift are sufficient for model-independent and absolute measuring of β and φ functions at all BPMs, including the conventional ones, instead of requiring all BPMs being equipped with multiturn electronics.

Model-independent and fast determination of optical functions in storage rings via multiturn and closed-orbit data

Science.gov (United States)

Riemann, Bernard; Grete, Patrick; Weis, Thomas

2011-06-01

Multiturn (or turn-by-turn) data acquisition has proven to be a new source of direct measurements for Twiss parameters in storage rings. On the other hand, closed-orbit measurements are a long-known tool for analyzing closed-orbit perturbations with conventional beam position monitor (BPM) systems and are necessarily available at every storage ring. This paper aims at combining the advantages of multiturn measurements and closed-orbit data. We show that only two multiturn BPMs and four correctors in one localized drift space in the storage ring (diagnostic drift) are sufficient for model-independent and absolute measuring of β and φ functions at all BPMs, including the conventional ones, instead of requiring all BPMs being equipped with multiturn electronics.

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

KAUST Repository

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

2013-01-01

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

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.

Revisiting the metathesis of 13C-monolabeled ethane

KAUST Repository

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

2010-01-01

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

Mo-catalyzed cross-metathesis reaction of propynylferrocene

Czech Academy of Sciences Publication Activity Database

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

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

Metathesis synthesis and characterization of complex metal fluoride ...

Indian Academy of Sciences (India)

Administrator

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

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

Science.gov (United States)

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

2017-12-01

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

Thermoset polymers via ring opening metathesis polymerization of functionalized oils

Science.gov (United States)

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

2012-11-27

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

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.

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

KAUST Repository

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

2017-01-01

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

The activation mechanism of Ru-indenylidene complexes in olefin metathesis

KAUST Repository

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

2013-01-01

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

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.

Synthesis of Mono(perfluoroalkyl) Cyclodextrins via Cross Metathesis

Czech Academy of Sciences Publication Activity Database

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

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

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.

Model-Based, Closed-Loop Control of PZT Creep for Cavity Ring-Down Spectroscopy.

Science.gov (United States)

McCartt, A D; Ognibene, T J; Bench, G; Turteltaub, K W

2014-09-01

Cavity ring-down spectrometers typically employ a PZT stack to modulate the cavity transmission spectrum. While PZTs ease instrument complexity and aid measurement sensitivity, PZT hysteresis hinders the implementation of cavity-length-stabilized, data-acquisition routines. Once the cavity length is stabilized, the cavity's free spectral range imparts extreme linearity and precision to the measured spectrum's wavelength axis. Methods such as frequency-stabilized cavity ring-down spectroscopy have successfully mitigated PZT hysteresis, but their complexity limits commercial applications. Described herein is a single-laser, model-based, closed-loop method for cavity length control.

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

KAUST Repository

Saidi, Aya

2017-12-21

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

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

International Nuclear Information System (INIS)

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

2008-01-01

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

Rare-earth-metal nitridophosphates through high-pressure metathesis

International Nuclear Information System (INIS)

Kloss, Simon David; Schnick, Wolfgang

2015-01-01

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

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

National Research Council Canada - National Science Library

Low, Tammy K

2006-01-01

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

Convergent Synthesis of Pancratistatin from Piperonal and Xylose

DEFF Research Database (Denmark)

Dam, Johan Hygum; Madsen, Robert

2009-01-01

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

Posterior pelvic ring fractures: Closed reduction and percutaneous CT-guided sacroiliac screw fixation

International Nuclear Information System (INIS)

Jacob, Augustinus Ludwig; Messmer, Peter; Stock, Klaus-Wilhelm; Suhm, Norbert; Baumann, Bernard; Regazzoni, Pietro; Steinbrich, Wolfgang

1997-01-01

Purpose. To assess the midterm results of closed reduction and percutaneous fixation (CRPF) with computed tomography (CT)-guided sacroiliac screw fixation in longitudinal posterior pelvic ring fractures. Methods. Thirteen patients with 15 fractures were treated. Eleven patients received a unilateral, two a bilateral, screw fixation. Twenty-seven screws were implanted. Continuous on-table traction was used in six cases. Mean radiological follow-up was 13 months. Results. Twenty-five (93%) screws were placed correctly. There was no impingement of screws on neurovascular structures. Union occurred in 12 (80%), delayed union in 2 (13%), and nonunion in 1 of 15 (7%) fractures. There was one screw breakage and two axial dislocations. Conclusion. Sacroiliac CRPF of longitudinal fractures of the posterior pelvic ring is technically simple, minimally invasive, well localized, and stable. It should be done by an interventional/surgical team. CT is an excellent guiding modality. Closed reduction may be a problem and succeeds best when performed as early as possible

Metathesis synthesis and characterization of complex metal fluoride ...

Indian Academy of Sciences (India)

Administrator

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

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

NARCIS (Netherlands)

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

2006-01-01

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

The enantioselective total synthesis of (+)-clusianone.

Science.gov (United States)

Horeischi, Fiene; Guttroff, Claudia; Plietker, Bernd

2015-02-11

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

A simple approach to the construction of the core structure present

Indian Academy of Sciences (India)

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

The asymmetric Schrock olefin metathesis catalysts. A computational study

NARCIS (Netherlands)

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

2005-01-01

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

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.

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

KAUST Repository

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

2015-01-01

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

A facile stereospecific synthesis of (Z)-2-sulfonyl-substituted 1,3-enynes via Sonogashira coupling of (E)-α-iodovinyl sulfones with 1-alkynes

Institute of Scientific and Technical Information of China (English)

无

2007-01-01

(E)-α-Iodovinyl sulfones 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol% of Pd(PPh3)4 and 10 mol% of CuI to stereospecifically afford the corresponding (Z)-2-sulfonyl-substituted 1,3-enynes 3 in high yields.(C) 2007 Ming Zhong Cai. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

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

KAUST Repository

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

2013-01-01

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

Explicitly-correlated ring-coupled-cluster-doubles theory: Including exchange for computations on closed-shell systems

Energy Technology Data Exchange (ETDEWEB)

Hehn, Anna-Sophia; Holzer, Christof; Klopper, Wim, E-mail: klopper@kit.edu

2016-11-10

Highlights: • Ring-coupled-cluster-doubles approach now implemented with exchange terms. • Ring-coupled-cluster-doubles approach now implemented with F12 functions. • Szabo–Ostlund scheme (SO2) implemented for use in SAPT. • Fast convergence to the limit of a complete basis. • Implementation in the TURBOMOLE program system. - Abstract: Random-phase-approximation (RPA) methods have proven to be powerful tools in electronic-structure theory, being non-empirical, computationally efficient and broadly applicable to a variety of molecular systems including small-gap systems, transition-metal compounds and dispersion-dominated complexes. Applications are however hindered due to the slow basis-set convergence of the electron-correlation energy with the one-electron basis. As a remedy, we present approximate explicitly-correlated RPA approaches based on the ring-coupled-cluster-doubles formulation including exchange contributions. Test calculations demonstrate that the basis-set convergence of correlation energies is drastically accelerated through the explicitly-correlated approach, reaching 99% of the basis-set limit with triple-zeta basis sets. When implemented in close analogy to early work by Szabo and Ostlund [36], the new explicitly-correlated ring-coupled-cluster-doubles approach including exchange has the perspective to become a valuable tool in the framework of symmetry-adapted perturbation theory (SAPT) for the computation of dispersion energies of molecular complexes of weakly interacting closed-shell systems.

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

KAUST Repository

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

2014-01-01

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

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

KAUST Repository

Pump, Eva

2014-06-09

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

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.

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

Czech Academy of Sciences Publication Activity Database

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

2017-01-01

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

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...

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

KAUST Repository

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

2016-01-01

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

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.

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

DEFF Research Database (Denmark)

Petersen, Mette Terp; Nielsen, Thomas Eiland

2013-01-01

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

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

Science.gov (United States)

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

2005-06-21

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2008-12-20

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

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

Directory of Open Access Journals (Sweden)

Meriem K. Abderrezak

2017-11-01

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

Digital closed orbit feedback system for the Advanced Photon Source storage ring

International Nuclear Information System (INIS)

Chung, Y.; Barr, D.; Decker, G.; Galayda, J.; Lenkszus, F.; Lumpkin, A.; Votaw, A.J.

1995-01-01

Closed orbit feedback for the Advanced Photon Source (APS) storage ring employs unified global an local feedback systems for stabilization of particle and photon beams based on digital signal processing (DSP). Hardware and software aspects of the system will be described. In particular, we will discuss global and local orbit feedback algorithms, PID (proportional, integral, and derivative) control algorithm. application of digital signal processing to compensate for vacuum chamber eddy current effects, resolution of the interaction between global and local systems through decoupling, self-correction of the local bump closure error, user interface through the APS control system, and system performance in the frequency and time domains. The system hardware, including the DSPS, is distributed in 20 VNE crates around the ring, and the entire feedback system runs synchronously at 4-kHz sampling frequency in order to achieve a correction bandwidth exceeding 100 Hz. The required data sharing between the global and local feedback systems is facilitated via the use of fiber-optically-networked reflective memories

Mesoporous molecular sieves as advanced supports for olefin metathesis catalysts

Czech Academy of Sciences Publication Activity Database

Balcar, Hynek; Čejka, Jiří

2013-01-01

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

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

KAUST Repository

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

2012-01-01

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

Global DC closed orbit correction experiments on the NSLS X-ray ring and SPEAR

International Nuclear Information System (INIS)

Chung, Y.; Decker, G.; Evans, K. Jr.; Safranek, J.; So, I.; Tang, Y.; Corbett, W.J.; Hettel, R.

1993-01-01

The global closed orbit correction experiments conducted on the NSLS X-ray ring and the SPEAR using the technique of singular value decomposition (SVD) are presented. The beam response matrix, defined as beam motion at beam position monitor (BPM) locations per unit kick by corrector magnets, was measured and then analyzed using SVD. The BPMs and correctors are reconfigured into open-quotes transformedclose quotes BPMs (t-BPMs) and open-quotes transformedclose quotes correctors (t-correctors), with each T-BPM coupled to at most one t-corrector and vice versa for orbit correction. The decoupled t-BPMs are used to estimate the limit on orbit correction, while the decoupled t-correctors are used to optimize the corrector strengths. As a result the vertical r.m.s. orbit error at the BPM locations was reduced from 208 μm to 61 μm about an arbitrary reference orbit in the NSLS X-ray ring. In SPEAR, the vertical closed orbit was brought to the BPM centers at the selected BPM locations with an r.m.s. error of 215 μm reduced from the initial 780 μm

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

Czech Academy of Sciences Publication Activity Database

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

2014-01-01

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

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

KAUST Repository

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

2015-01-01

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

and 8-Membered Oxygen-containing Benzo-fused Rings using ...

African Journals Online (AJOL)

NJD

A number of benzo-fused oxygen-containing heterocycles were synthesized from allyl-3-isopropoxy-4-methoxybenzaldehyde using metathesis or an alkene isomerization-metathesis sequence as key synthetic steps. Benzo-fused compounds thus formed included a 3,6-dihydro-1H-2-benzoxocine, ...

Digital closed orbit feedback system for the advanced photon source storage ring

International Nuclear Information System (INIS)

Chung, Y.; Barr, D.; Decker, G.

1995-01-01

The Advanced Photon Source (APS) is a dedicated third-generation synchrotron light source with a nominal energy of 7 GeV and a circumference of 1104 m. The closed orbit feedback system for the APS storage ring employs unified global and local feedback systems for stabilization of particle and photon beams based on digital signal processing (DSP). Hardware and software aspects of the system will be described in this paper. In particular, we will discuss global and local orbit feedback algorithms, PID (proportional, integral, and derivative) control algorithm, application of digital signal processing to compensate for vacuum chamber eddy current effects, resolution of the interaction between global and local systems through decoupling, self-correction of the local bump closure error, user interface through the APS control system, and system performance in the frequency and time domains. The system hardware including the DSPs is distributed in 20 VME crates around the ring, and the entire feedback system runs synchronously at 4-kHz sampling frequency in order to achieve a correction bandwidth exceeding 100 Hz. The required data sharing between the global and local feedback systems is facilitated via the use of fiber-optically-networked reflective memories

Alternative loop rings

CERN Document Server

Goodaire, EG; Polcino Milies, C

1996-01-01

For the past ten years, alternative loop rings have intrigued mathematicians from a wide cross-section of modern algebra. As a consequence, the theory of alternative loop rings has grown tremendously. One of the main developments is the complete characterization of loops which have an alternative but not associative, loop ring. Furthermore, there is a very close relationship between the algebraic structures of loop rings and of group rings over 2-groups. Another major topic of research is the study of the unit loop of the integral loop ring. Here the interaction between loop rings and group ri

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

OpenAIRE

Lüning , Ulrich; Winkelmann , Ole

2009-01-01

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

Novel phosphanucleoside analogs of dideoxynucleosides

Czech Academy of Sciences Publication Activity Database

Páv, Ondřej; Buděšínský, Miloš; Rosenberg, Ivan

2017-01-01

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

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.

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

KAUST Repository

Martínez, Juan Pablo

2016-04-10

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

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

KAUST Repository

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

2016-01-01

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

Studies on the selectivity of the reaction of (CO){sub 5}W=C(aryl)H with enynes: transfer of the carbene ligand to the C=C Bond versus insertion of the C triple bond C into the W=C Bond

Energy Technology Data Exchange (ETDEWEB)

Fischer, H.; Volkland, H.P.; Stumpf, R.

1996-10-01

The strongly electrophilic monophenylcarbene complex [(CO){sub 5}W=C(Ph)H] (2a) reacts with the enynes H-C triple bond C-R(R=-C(Me)=CH{sub 2})(3), -C{sub 6}H{sub 4}-CH=CH{sub 2}-p (5) and subsequently with PMe{sub 3} to form the C{sub a}lpha-PMe{sub 3} adducts of the vinylidene complexes [(CO){sub 5}W-{l_brace}C(PMe{sub 3})=CH-C{sub 3}H{sub 3}(Me)Ph{r_brace}] (4) and [(CO){sub 5}W {l_brace}C(PMe{sub 3})=CH-C{sub 6}H{sub 4}-C{sub 3}H{sub 4}Ph{r_brace}] (6). The reaction very likely proceeds by transfer of the carbene ligand to the C=C bond of the enyne to form a cyclopropyl-substituted alkyne complex which is in equilibrium with its vinylidene isomer.

New ROMP Synthesis of Ferrocenyl Dendronized Polymers.

Science.gov (United States)

Liu, Xiong; Ling, Qiangjun; Zhao, Li; Qiu, Guirong; Wang, Yinghong; Song, Lianxiang; Zhang, Ying; Ruiz, Jaime; Astruc, Didier; Gu, Haibin

2017-10-01

First- and second-generation Percec-type dendronized ferrocenyl norbornene macromonomers containing, respectively, three and nine ferrocenyl termini are synthesized and polymerized by ring-opening metathesis polymerization using Grubbs' third-generation olefin metathesis catalyst with several monomer/catalyst feed ratios between 10 and 50. The rate of polymerization is highly dependent on the generation of the dendronized macromonomers, but all these ring-opening metathesis polymerization reactions are controlled, and near-quantitative monomer conversions are achieved. The numbers of ferrocenyl groups obtained are in agreement with the theoretical ones according to the cyclic voltammetry studies as determined using the Bard-Anson method. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A GLOBAL REGISTRATION ALGORITHM OF THE SINGLE-CLOSED RING MULTI-STATIONS POINT CLOUD

Directory of Open Access Journals (Sweden)

R. Yang

2018-04-01

Full Text Available Aimed at the global registration problem of the single-closed ring multi-stations point cloud, a formula in order to calculate the error of rotation matrix was constructed according to the definition of error. The global registration algorithm of multi-station point cloud was derived to minimize the error of rotation matrix. And fast-computing formulas of transformation matrix with whose implementation steps and simulation experiment scheme was given. Compared three different processing schemes of multi-station point cloud, the experimental results showed that the effectiveness of the new global registration method was verified, and it could effectively complete the global registration of point cloud.

Palladium-catalyzed regio- and stereoselective cross-addition of terminal alkynes to ynol ethers and synthesis of 1,4-enyn-3-ones.

Science.gov (United States)

Babu, Madala Hari; Dwivedi, Vikas; Kant, Ruchir; Reddy, Maddi Sridhar

2015-03-16

Conjugated enynes, enol ethers, and enynones are versatile building blocks that can be elaborated by a wide variety of synthetic transformations. The selective synthesis of such units is a prerequisite for their effective utilization. The synthesis of conjugated 2-phenoxyenynes through a palladium-catalyzed cross-addition of terminal alkynes to phenylethynyl ethers (hydroalkynylation) is now presented. The reaction is highly regio-, stereo-, and chemoselective, and shows excellent tolerance toward functional groups. The addition further features very mild reaction conditions (room temperature) and an inexpensive catalytic system (without a ligand and with a cheaply available Pd catalyst). The thus synthesized enynyl ethers with allylic hydroxy tethers, which survived the reaction, were shown to be ready precursors for valuable 1-en-4-yn-3-ones. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rh-Catalyzed (5+2) Cycloadditions of 3-Acyloxy-1,4-enynes and Alkynes: Computational Study of Mechanism, Reactivity, and Regioselectivity

Science.gov (United States)

Xu, Xiufang; Liu, Peng; Shu, Xing-zhong; Tang, Weiping; Houk, K. N.

2013-01-01

The mechanism of Rh-catalyzed (5+2) cycloadditions of 3-acyloxy-1,4-enyne (ACE) and alkynes is investigated using density functional theory calculations. The catalytic cycle involves 1,2-acyloxy migration, alkyne insertion, and reductive elimination to form the cycloheptatriene product. In contrast to the (5+2) cycloadditions with vinylcyclopropanes (VCP), in which alkyne inserts into a rhodium-allyl bond, alkyne insertion into a Rh–C(sp2) bond is preferred. The 1,2-acyloxy migration is found to be the rate-determining step of the catalytic cycle. The electron-rich p-dimethylaminobenzoate substrate promotes 1,2-acyloxy migration and significantly increases the reactivity. In the regioselectivity-determining alkyne insertion step, the alkyne substituent prefers to be distal to the forming C–C bond and thus distal to the OAc group in the product. PMID:23725341

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

KAUST Repository

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

2016-01-01

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

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

KAUST Repository

Merle, Nicolas

2016-12-05

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

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

DEFF Research Database (Denmark)

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

2009-01-01

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

The olefin metathesis reaction: reorganization and cyclization of organic compounds

International Nuclear Information System (INIS)

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

2005-01-01

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

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

Czech Academy of Sciences Publication Activity Database

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

2017-01-01

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

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

Czech Academy of Sciences Publication Activity Database

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

2014-01-01

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

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.

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

KAUST Repository

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

2015-01-01

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

Total synthesis of ciguatoxin and 51-hydroxyCTX3C.

Science.gov (United States)

Inoue, Masayuki; Miyazaki, Keisuke; Ishihara, Yuuki; Tatami, Atsushi; Ohnuma, Yuyu; Kawada, Yuuya; Komano, Kazuo; Yamashita, Shuji; Lee, Nayoung; Hirama, Masahiro

2006-07-26

Ciguatoxins, the principal causative toxins of ciguatera seafood poisoning, are large ladder-like polycyclic ethers with the 13 ether rings ranging from five- to nine-membered. In this paper, we describe the total synthesis of the two most toxic members of the ciguatoxin family, ciguatoxin 1 and 51-hydroxyCTX3C 2, based on a unified synthetic strategy. The key features in our syntheses were (i) direct construction of the O,S-acetal from the corresponding left and right wing fragments (3, 4, 14); (ii) stereo- and chemoselective radical reaction of the alpha-oxyradical with pentafluorophenyl acrylate to achieve cyclization of the seven-membered G-ring; (iii) ring-closing metathesis reaction to build the nine-membered F-ring; and (iv) an efficient protective group strategy using the oxidatively removable 2-naphthylmethyl groups.

Energy spectra of quantum rings.

Science.gov (United States)

Fuhrer, A; Lüscher, S; Ihn, T; Heinzel, T; Ensslin, K; Wegscheider, W; Bichler, M

2001-10-25

Quantum mechanical experiments in ring geometries have long fascinated physicists. Open rings connected to leads, for example, allow the observation of the Aharonov-Bohm effect, one of the best examples of quantum mechanical phase coherence. The phase coherence of electrons travelling through a quantum dot embedded in one arm of an open ring has also been demonstrated. The energy spectra of closed rings have only recently been studied by optical spectroscopy. The prediction that they allow persistent current has been explored in various experiments. Here we report magnetotransport experiments on closed rings in the Coulomb blockade regime. Our experiments show that a microscopic understanding of energy levels, so far limited to few-electron quantum dots, can be extended to a many-electron system. A semiclassical interpretation of our results indicates that electron motion in the rings is governed by regular rather than chaotic motion, an unexplored regime in many-electron quantum dots. This opens a way to experiments where even more complex structures can be investigated at a quantum mechanical level.

A Short Synthesis of (+)-Cyclophellitol

DEFF Research Database (Denmark)

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

2005-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2012-06-21

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

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

Directory of Open Access Journals (Sweden)

Jubi John

2014-06-01

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

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

Czech Academy of Sciences Publication Activity Database

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

2011-01-01

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

Polarization Insensitivity in Double-Split Ring and Triple-Split Ring Terahertz Resonators

International Nuclear Information System (INIS)

Wu Qian-Nan; Lan Feng; Tang Xiao-Pin; Yang Zi-Qiang

2015-01-01

A modified double-split ring resonator and a modified triple-split ring resonator, which offer polarization-insensitive performance, are investigated, designed and fabricated. By displacing the two gaps of the conventional double-split ring resonator away from the center, the second resonant frequency for the 0° polarized wave and the resonant frequency for the 90° polarized wave become increasingly close to each other until they are finally identical. Theoretical and experimental results show that the modified double-split ring resonator and the modified triple-split ring resonator are insensitive to different polarized waves and show strong resonant frequency dips near 433 and 444 GHz, respectively. The results of this work suggest new opportunities for the investigation and design of polarization-dependent terahertz devices based on split ring resonators. (paper)

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

KAUST Repository

Tretiakov, Mykyta

2018-03-27

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

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.

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

KAUST Repository

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

2013-01-01

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

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

KAUST Repository

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

2013-01-01

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

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

KAUST Repository

Qureshi, Ziyauddin

2017-01-05

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

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

KAUST Repository

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

2017-01-01

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

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

Science.gov (United States)

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

2017-05-05

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

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

Directory of Open Access Journals (Sweden)

Tahmina Haque

2015-03-01

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

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

KAUST Repository

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

2010-01-01

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

Synthesis and Evaluation of a 2,11-Cembranoid-Inspired Library.

Science.gov (United States)

Welford, Amanda J; Caldwell, John J; Liu, Manjuan; Richards, Meirion; Brown, Nathan; Lomas, Cara; Tizzard, Graham J; Pitak, Mateusz B; Coles, Simon J; Eccles, Suzanne A; Raynaud, Florence I; Collins, Ian

2016-04-11

The 2,11-cembranoid family of natural products has been used as inspiration for the synthesis of a structurally simplified, functionally diverse library of octahydroisobenzofuran-based compounds designed to augment a typical medicinal chemistry library screen. Ring-closing metathesis, lactonisation and SmI2 -mediated methods were exemplified and applied to the installation of a third ring to mimic the nine-membered ring of the 2,11-cembranoids. The library was assessed for aqueous solubility and permeability, with a chemical-space analysis performed for comparison to the family of cembranoid natural products and a sample set of a screening library. Preliminary investigations in cancer cells showed that the simpler scaffolds could recapitulate the reported anti-migratory activity of the natural products. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Topological ring currents in the "empty" ring of benzo-annelated perylenes.

Science.gov (United States)

Dickens, Timothy K; Mallion, Roger B

2011-01-27

Cyclic conjugation in benzo-annelated perylenes is examined by means of the topological π-electron ring currents calculated for each of their constituent rings, in a study that is an exact analogy of a recent investigation by Gutman et al. based on energy-effect values for the corresponding rings in each of these structures. "Classical" approaches, such as Kekulé structures, Clar "sextet" formulas, and circuits of conjugation, predict that the central ring in perylene is "empty" and thus contributes negligibly to cyclic conjugation. However, conclusions from the present calculations of topological ring currents agree remarkably with those arising from the earlier study involving energy-effect values in that, contrary to what would be predicted from the classical approaches, rings annelated in an angular fashion relative to the central ring of these perylene structures materially increase the extent of that ring's involvement in cyclic conjugation. It is suggested that such close quantitative agreement between the predictions of these two superficially very different indices (energy effect and topological ring current) might be due to the fact that, ultimately, both depend, albeit in ostensibly quite different ways, only on an adjacency matrix that contains information about the carbon-carbon connectivity of the conjugated system in question.

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.

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

KAUST Repository

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

2014-01-01

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

On rings generating supernilpotent and special atoms | France ...

African Journals Online (AJOL)

We study prime rings which generate supernilpotent (respectively special) atoms, that is, atoms of the lattice of all supernilpotent (respectively special) radicals. A prime ring A is called a **-ring if the smallest special class containing A is closed under semiprime homomorphic images of A. A semiprime ring A whose every ...

A Short Synthetic Route to the Calystegine Alkaloids

DEFF Research Database (Denmark)

Skaanderup, Philip Robert; Madsen, Robert

2003-01-01

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

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

Science.gov (United States)

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

2015-02-02

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

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

Czech Academy of Sciences Publication Activity Database

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

2017-01-01

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

[Liesegang's rings resembling helminthiasis].

Science.gov (United States)

Zámecník, M; Riedl, I

1996-12-01

So called Liesegang's rings are lamellar corpuscles which develop after periodical precipitation of oversaturated solutions in gel medium. They can occur in cysts, closed cavities, inflammatory exudates and necroses. They resemble parasitic eggs, larvae or adult forms. A case of 28-year-old woman is presented with many Liesegang's rings in a stuff from dilated renal calyx. Their preliminary evaluation considered helminths, especially Dioctophyma renale.

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

KAUST Repository

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

2014-01-01

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

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

KAUST Repository

Eid, Ahmed A.

2014-04-01

turn over number (TON = 43) has been obtained following hydrogen treatment of tungsten alkylidyne supported on [N,O] SBA151100, in comparison with TON of zero in the obtained with [N,N] SBA15 and classical SiO2 silica support. Therefore, the cooperation between silylamine and silanol in close vicinity are required to improve the efficiency of the catalyst in the metathesis of propane.

Confinement and stability of crystalline beams in storage rings

International Nuclear Information System (INIS)

Haffmans, A.F.

1995-01-01

We present a fully analytical approach to the study of the confinement and stability of open-quote open-quote Crystalline Beams close-quote close-quote in storage rings, in terms of such fundamental accelerator concepts as tune shift and stopband. We consider a open-quote open-quote Crystalline Beam close-quote close-quote consisting of substrings, arranged symmetrically around the reference trajectory, and we examine the motion of a slightly perturbed test particle on one of them. Our approach quite naturally leads to the conclusion, that (a) storage rings need to be operated below the transition energy, and (b) the open-quote open-quote Crystalline Beam close-quote close-quote has the same periodicity as the storage ring. Each open-quote open-quote Crystalline Beam close-quote close-quote has an upper and lower limit of the spacing between the ions. The upper limit is determined by condition (b), and the lower limit is set by the stability of the test particle motion around the equilibrium. copyright 1995 American Institute of Physics

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

KAUST Repository

Callens, Emmanuel

2015-08-24

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

The Dynamical History of Chariklo and Its Rings

Energy Technology Data Exchange (ETDEWEB)

Wood, Jeremy [Hazard Community and Technical College, Community College Drive, Hazard, KY 41701 (United States); Horner, Jonti; Marsden, Stephen C. [Computational Engineering and Science Research Centre, University of Southern Queensland, West Street, Toowoomba, QLD 4350 (Australia); Hinse, Tobias C., E-mail: jeremy.wood@kctcs.edu [Korea Astronomy and Space Science Institute, 776 Daedukdae-ro, Yuseong-gu, Daejeon 305-348 (Korea, Republic of)

2017-06-01

Chariklo is the only small solar system body confirmed to have rings. Given the instability of its orbit, the presence of rings is surprising, and their origin remains poorly understood. In this work, we study the dynamical history of the Chariklo system by integrating almost 36,000 Chariklo clones backward in time for 1 Gyr under the influence of the Sun and the four giant planets. By recording all close encounters between the clones and planets, we investigate the likelihood that Chariklo’s rings could have survived since its capture to the Centaur population. Our results reveal that Chariklo’s orbit occupies a region of stable chaos, resulting in its orbit being marginally more stable than those of the other Centaurs. Despite this, we find that it was most likely captured to the Centaur population within the last 20 Myr, and that its orbital evolution has been continually punctuated by regular close encounters with the giant planets. The great majority (>99%) of those encounters within 1 Hill radius of the planet have only a small effect on the rings. We conclude that close encounters with giant planets have not had a significant effect on the ring structure. Encounters within the Roche limit of the giant planets are rare, making ring creation through tidal disruption unlikely.

Stereoselective total syntheses of three Lycopodium alkaloids, (-)-magellanine, (+)-magellaninone, and (+)-paniculatine, based on two Pauson-Khand reactions.

Science.gov (United States)

Kozaka, Takashi; Miyakoshi, Naoki; Mukai, Chisato

2007-12-21

The total syntheses of (-)-magellanine, (+)-magellaninone, and (+)-paniculatine were completed from diethyl l-tartrate via the common intermediate in a stereoselective manner. The crucial steps in these syntheses involved two intramolecular Pauson-Khand reactions of enynes: the first Pauson-Khand reaction constructed the bicyclo[4.3.0] carbon framework, the corresponding A and B rings of these alkaloids in a highly stereoselective manner, whereas the second Pauson-Khand reaction stereoselectively produced the bicyclo[3.3.0]skeleton, which could be converted into the C and D rings of the target natural products.

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

Science.gov (United States)

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

2004-12-14

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

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

KAUST Repository

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

2014-01-01

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

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.

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.

Liposomal Drug Delivery of Anticancer Agents

DEFF Research Database (Denmark)

Pedersen, Palle Jacob

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

Base-catalyzed tandem Michael/dehydro-Diels-Alder reaction of α,α-dicyanoolefins with electron-deficient 1,3-conjugated enynes: a facile entry to angularly fused polycycles.

Science.gov (United States)

Zhang, Mingrui; Zhang, Junliang

2014-01-07

Angularly fused carbocyclic frameworks and their heteroatom-substituted analogues exist in many natural products that display a broad and interesting range of biological activities. Preparation of polycyclic products by cycloaddition reactions have been the long-standing hot topic in the synthetic community. Dehydro-Diels-Alder (DDA) reactions are one class of dehydropericyclic reactions that are derived conceptually by systematic removal of hydrogen atom pairs. A base-promoted tandem Michael addition and DDA reaction of α,α-dicyanoolefins with electron-deficient 1,3-conjugated enynes was realized in which a DDA reaction takes place between the arylalkynes and electron-deficient tetrasubstituted olefin. The control experiments support the stepwise anionic reaction pathway rather than the concerted reaction pathway. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Ophiocerins from Non-Carbohydrate Sources

International Nuclear Information System (INIS)

Hong, Hui Jeong; Lee, Dong Min; Kang, Han Young

2010-01-01

Direct and unified synthetic routes to ophiocerin A, B, C, and D have been successfully developed. These syntheses are based on ring-closing metathesis and non-carbohydrate starting materials and are simpler and more efficient than the previous syntheses, as demonstrated in the case of ophiocerin B (2) (eleven steps from methyl α-D-glucopyranoside vs. four steps from 4-penten-2-ol) and ophiocerin A (1) (twelve steps from methyl α-D-glucopyranoside vs. three steps from 4-penten-2-ol). These routes will be useful for the practical synthesis of related natural products. Ophiocerins are comprised of four compounds isolated from the aqueous fungi Ophioceras venezuelense, each bearing a tetrahydropyran ring with an interesting array of substituents (Figure 1). Since substituted tetrahydropyran rings are found in many biologically important natural products, ophiocerins have attracted the attention of synthetic chemists

Divergent Synthesis of Diastereomeric Sphingosines from a Chiral Aziridine

Energy Technology Data Exchange (ETDEWEB)

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

2016-07-15

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

Mechanistic insights on the cycloisomerization of polyunsaturated precursors catalyzed by platinum and gold complexes.

Science.gov (United States)

Soriano, Elena; Marco-Contelles, José

2009-08-18

picture. The intramolecular nucleophilic attack of the double bond on the activated alkyne takes place by an endo-dig or exo-dig pathway to afford a cyclopropyl-metallocarbenoid. Through divergent routes, the cyclopropyl intermediate formed by exo-cyclopropanation could yield the metathesis adduct or bicyclic compounds. The endo-cyclization may be followed by a [1,2]-migration of the propargyl moiety to the internal acetylenic position to afford bicyclic [n.1.0] derivatives. This reaction mechanism is applicable for functional groups ranging from H to carboxylate propargyl substituents (Rautenstrauch reaction). In intramolecular reactions in which a shorter enyne bears a propargyl ester or in intermolecular reactions of an ester with an alkene, the ester preferentially attacks the activated alkyne because of enthalpic (ring strain) and entropic effects. Our calculations can predict the correct stereochemical outcome, which may aid the rational design of further stereoselective syntheses. The alkynes activated by electrophilic species can also react with other nucleophiles, such as aromatic rings. The calculations account for the high endo-selectivity observed and suggest that this transformation takes place through a Friedel-Crafts-type alkenylation mechanism, where the endo-dig cyclization promoted by PtCl(2) may involve a cyclopropylmetallacarbene as intermediate before the formation of the expected Wheland-type intermediate. These comparisons of the computational approach with experiment demonstrate the value of theory in the development of a solid mechanistic understanding of these reaction processes.

Minimizing guard ring dead space in silicon detectors with an n-type guard ring at the edge of the detector

International Nuclear Information System (INIS)

Palviainen, Tanja; Tuuva, Tuure; Leinonen, Kari

2007-01-01

Detectors with n-type silicon with an n + -type guard ring were investigated. In the present work, a new p + /n/n + detector structure with an n + guard ring is described. The guard ring is placed at the edge of the detector. The detector depletion region extends also sideways, allowing for signal collection very close to the n-guard ring. In this kind of detector structure, the dead space of the detector is minimized to be only below the guard ring. This is proved by simulations done using Silvaco/ATLAS software

Minimizing guard ring dead space in silicon detectors with an n-type guard ring at the edge of the detector

Energy Technology Data Exchange (ETDEWEB)

Palviainen, Tanja [Lappeenranta University of Technology, P.O. Box 20, FIN-53851 Lappeenranta (Finland)]. E-mail: tanja.palviainen@lut.fi; Tuuva, Tuure [Lappeenranta University of Technology, P.O. Box 20, FIN-53851 Lappeenranta (Finland); Leinonen, Kari [Lappeenranta University of Technology, P.O. Box 20, FIN-53851 Lappeenranta (Finland)

2007-04-01

Detectors with n-type silicon with an n{sup +}-type guard ring were investigated. In the present work, a new p{sup +}/n/n{sup +} detector structure with an n{sup +} guard ring is described. The guard ring is placed at the edge of the detector. The detector depletion region extends also sideways, allowing for signal collection very close to the n-guard ring. In this kind of detector structure, the dead space of the detector is minimized to be only below the guard ring. This is proved by simulations done using Silvaco/ATLAS software.

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

KAUST Repository

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

2016-01-01

The search for a low-cost process for the valorization of linear alpha-olefins combining high productivity and high selectivity is a longstanding goal for chemists. Herein, we report a soluble ruthenium olefin metathesis catalyst that performs the conversion of linear alpha-olefins to longer internal linear olefins with high selectivity (>99%) under neat conditions at low loadings (50 ppm) and without the need of expensive additives. This robust catalytic process allowed us to efficiently and selectively re-equilibrate the naphtha fraction (C-5-C-8) of a Fischer-Tropsch feed derived from non petroleum resources to a higher-value product range (C-9-C-14), useful as detergent and plasticizer precursors.

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

KAUST Repository

Rouen, Mathieu

2016-10-14

The search for a low-cost process for the valorization of linear alpha-olefins combining high productivity and high selectivity is a longstanding goal for chemists. Herein, we report a soluble ruthenium olefin metathesis catalyst that performs the conversion of linear alpha-olefins to longer internal linear olefins with high selectivity (>99%) under neat conditions at low loadings (50 ppm) and without the need of expensive additives. This robust catalytic process allowed us to efficiently and selectively re-equilibrate the naphtha fraction (C-5-C-8) of a Fischer-Tropsch feed derived from non petroleum resources to a higher-value product range (C-9-C-14), useful as detergent and plasticizer precursors.

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

KAUST Repository

Borguet, Yannick

2015-01-01

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

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

KAUST Repository

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

2017-01-01

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

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

KAUST Repository

Maity, Niladri

2018-02-15

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

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

KAUST Repository

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

2018-01-01

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

Chemical Sensors Based on Optical Ring Resonators

Science.gov (United States)

Homer, Margie; Manfreda, Allison; Mansour, Kamjou; Lin, Ying; Ksendzov, Alexander

2005-01-01

Chemical sensors based on optical ring resonators are undergoing development. A ring resonator according to this concept is a closed-circuit dielectric optical waveguide. The outermost layer of this waveguide, analogous to the optical cladding layer on an optical fiber, is a made of a polymer that (1) has an index of refraction lower than that of the waveguide core and (2) absorbs chemicals from the surrounding air. The index of refraction of the polymer changes with the concentration of absorbed chemical( s). The resonator is designed to operate with relatively strong evanescent-wave coupling between the outer polymer layer and the electromagnetic field propagating along the waveguide core. By virtue of this coupling, the chemically induced change in index of refraction of the polymer causes a measurable shift in the resonance peaks of the ring. In a prototype that has been used to demonstrate the feasibility of this sensor concept, the ring resonator is a dielectric optical waveguide laid out along a closed path resembling a racetrack (see Figure 1). The prototype was fabricated on a silicon substrate by use of standard techniques of thermal oxidation, chemical vapor deposition, photolithography, etching, and spin coating. The prototype resonator waveguide features an inner cladding of SiO2, a core of SixNy, and a chemical-sensing outer cladding of ethyl cellulose. In addition to the ring Chemical sensors based on optical ring resonators are undergoing development. A ring resonator according to this concept is a closed-circuit dielectric optical waveguide. The outermost layer of this waveguide, analogous to the optical cladding layer on an optical fiber, is a made of a polymer that (1) has an index of refraction lower than that of the waveguide core and (2) absorbs chemicals from the surrounding air. The index of refraction of the polymer changes with the concentration of absorbed chemical( s). The resonator is designed to operate with relatively strong

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

Science.gov (United States)

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

2017-10-20

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

Open-ring enhancement sign in diagnosing demyelinating pseudotumor

International Nuclear Information System (INIS)

Fang Liting; Wang Zhiping; Wang Linyou

2010-01-01

Objective: To describe open-ring enhancement sign on MRI of demyelinating pseudotumor. Methods: Contrast-enhanced MRI of histologically confirmed demyelinating pseudotumors (14 patients) and astrocytomas (21) was reviewed. Results: Of the 14 cases of demyelinating pseudotumor, open-ring enhancement pattern was observed in 6; closed ring enhancement in 2; nodular enhancement in 3; patchy enhancement in 1; slight enhancement in 1; and no enhancement in 1. Of the 21 cases of astrocytoma, there was complete ring or lace-like enhancement in 13, no contrast enhancement in 6, patchy enhancement in 2, and none with open-ring enhancement pattern. Conclusion: Open-ring enhancement is a valuable sign in differential diagnosis between demyelinating pseudotumor and astrocytoma. (authors)

Nicholas reactions in the construction of cyclohepta[de]naphthalenes and cyclohepta[de]naphthalenones. The total synthesis of microstegiol.

Science.gov (United States)

Taj, Rafiq A; Green, James R

2010-12-03

The application of the Nicholas reaction chemistry of 2,7-dioxygenated naphthalenes in the synthesis of cyclohepta[de]napthalenes and in the synthesis of (±)-microstegiol (1) is presented. The substitution profile of Nicholas monosubstitution (predominantly C-1) and disubstitution reactions (predominantly 1,6-) on 2,7-dioxygenated napthalenes is reported. Application of a 1,8-dicondensation product and selected C-1 monocondensation products to the construction of cyclohepta[de]naphthalenes by way of ring closing metathesis and intramolecular Friedel-Crafts reactions, respectively, is described. Deprotection of the C-7 oxygen function to the corresponding naphthol allows tautomerization to cyclohepta[de]naphthalene-1-ones upon seven-membered-ring closure in most cases, and replacement of the C-2 oxygen function in the naphthalene by a methyl group ultimately allows the synthesis of (±)-microstegiol.

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

Directory of Open Access Journals (Sweden)

Bassie B. Marvey

2009-01-01

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

Rh(I-catalyzed intramolecular [2 + 2 + 1] cycloaddition of allenenes: Construction of bicyclo[4.3.0]nonenones with an angular methyl group and tricyclo[6.4.0.01,5]dodecenone

Directory of Open Access Journals (Sweden)

Chisato Mukai

2011-04-01

Full Text Available The [RhCl(COdppp]2-catalyzed intramolecular carbonylative [2 + 2 + 1] cycloaddition of allenenes was developed to prepare bicyclo[4.3.0]nonenones possessing a methyl group at the ring junction, which is difficult to achieve by the Pauson–Khand reaction of the corresponding enynes. This method also provided a new procedure for the construction of the tricyclo[6.4.0.01,5]dodecenone framework in a satisfactory yield.

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

KAUST Repository

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

2018-01-01

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

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

International Nuclear Information System (INIS)

Frankovsky, Rainer

2013-01-01

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

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

Science.gov (United States)

Meng, Xiangtao; Edgar, Kevin J

2015-11-05

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

First- and second-generation total synthesis of ciguatoxin CTX3C.

Science.gov (United States)

Inoue, Masayuki; Miyazaki, Keisuke; Uehara, Hisatoshi; Maruyama, Megumi; Hirama, Masahiro

2004-08-17

More than 20,000 people suffer annually from ciguatera seafood poisoning in subtropical and tropical regions. The extremely low content of the causative neurotoxins, designated as ciguatoxins, in fish has hampered isolation, detailed biological studies, and preparation of anti-ciguatoxin antibodies for detecting these toxins. Furthermore, the large (3 nm in length) and complex molecular structure of ciguatoxins has impeded chemists from completing their total synthesis. In this article, the full details of studies leading to the total synthesis of ciguatoxin CTX3C are provided. The key elements of the first-generation approach include O,O-acetal formation from the right and left wing fragments, conversion from O,O-acetal to O,S-acetal, a radical reaction to cyclize the G ring, a ring-closing metathesis reaction to close the F ring, and final removal of the 2-naphtylmethyl protective groups. Subsequent studies provided a second-generation total synthesis, which is more concise and results in a higher yield. Second-generation synthesis was accomplished by using a direct method of constructing the key intermediate O,S-acetal from alpha-chlorosulfide and a secondary alcohol. These syntheses ensure a practical supply of ciguatoxin for biological applications.

Electrochemically Triggered Co-Conformational Switching in a [2]catenane Comprising a Non-Symmetric Calix[6]arene Wheel and a Two-Station Oriented Macrocycle

Directory of Open Access Journals (Sweden)

Valeria Zanichelli

2018-05-01

Full Text Available Catenanes with desymmetrized ring components can undergo co-conformational rearrangements upon external stimulation and can form the basis for the development of molecular rotary motors. We describe the design, synthesis and properties of a [2]catenane consisting of a macrocycle—the ‘track’ ring—endowed with two distinct recognition sites (a bipyridinium and an ammonium for a calix[6]arene—the ‘shuttle’ ring. By exploiting the ability of the calixarene to thread appropriate non-symmetric axles with directional selectivity, we assembled an oriented pseudorotaxane and converted it into the corresponding oriented catenane by intramolecular ring closing metathesis. Cyclic voltammetric experiments indicate that the calixarene wheel initially surrounds the bipyridinium site, moves away from it when it is reduced, and returns in the original position upon reoxidation. A comparison with appropriate model compounds shows that the presence of the ammonium station is necessary for the calixarene to leave the reduced bipyridinium site.

Flexible ring seal

International Nuclear Information System (INIS)

Abbes, Claude; Gournier, Andre; Rouaud, Christian; Villepoix, Raymond de.

1976-01-01

The invention concerns a flexible metal ring seal, able to ensure a perfect seal between two bearings due to the crushing and elastic deformation properties akin to similar properties in elastomers. Various designs of seal of this kind are already known, particularly a seal made of a core formed by a helical wire spring with close-wound turns and with high axial compression ratio, closed on itself and having the shape of an annulus. This wire ring is surrounded by at least one envelope having at rest the shape of a toroidal surface of which the generating circle does not close on itself. In a particular design mode, the seal in question can include, around the internal spring, two envelopes of which one in contact with the spring is composed of a low ductility elastic metal, such as mild steel or stainless steel and the other is, on the contrary, made of a malleable metal, such as copper or nickel. The first envelope evenly distributes the partial crushing of the spring, when the seal is tightened, on the second envelope which closely fits the two surfaces between which the seal operates. The stress-crushing curve characteristic of the seal comprises two separate parts, the first with a relatively sharp slope corresponds to the start of the seal compression phase, enabling at least some of these curves to reach the requisite seal threshold very quickly, then, beyond this, a second part, practically flat, where the stress is appreciably constant for a wide operating bracket [fr

Rings of Molecular Line Emission in the Disk Orbiting the Young, Close Binary V4046 Sgr

Science.gov (United States)

Dickson-Vandervelde, Dorothy; Kastner, Joel H.; Qi, C.; Forveille, Thierry; Hily-Blant, Pierre; Oberg, Karin; Wilner, David; Andrews, Sean; Gorti, Uma; Rapson, Valerie; Sacco, Germano; Principe, David

2018-01-01

We present analysis of a suite of subarcsecond ALMA Band 6 (1.1 - 1.4 mm) molecular line images of the circumbinary, protoplanetary disk orbiting V4046 Sgr. The ~20 Myr-old V4046 Sgr system, which lies a mere ~73 pc from Earth, consists of a close (separation ~10 Rsun) pair of roughly solar-mass stars that are orbited by a gas-rich crcumbinary disk extending to ~350 AU in radius. The ALMA images reveal that the molecules CO and HCN and their isotopologues display centrally peaked surface brightness morphologies, whereas the cyanide group molecules (HC3N, CH3CN), deuterated molecules (DCN, DCO+), hydrocarbons (as traced by C2H), and potential CO ice line tracers (N2H+, and H2CO) appear as a sequence of sharp and diffuse rings of increasing radii. The characteristic sizes of these molecular emission rings, which range from ~25 to >100 AU in radius, are evident in radial emission-line surface brightness profiles extracted from the deprojected disk images. We find that emission from 13CO emission transitions from optically thin to thick within ~50 AU, whereas C18O emission remains optically thin within this radius. We summarize the insight into the physical and chemical processes within this evolved protoplanetary disk that can be obtained from comparisons of the various emission-line morphologies with each other and with that of the continuum (large-grain) emission on size scales of tens of AU.This research is supported by NASA Exoplanets program grant NNX16AB43G to RIT

The Cryogenic Storage Ring CSR

OpenAIRE

von Hahn, Robert; Becker, Arno; Berg, Felix; Blaum, Klaus; Breitenfeldt, Christian; Fadil, Hisham; Fellenberger, Florian; Froese, Michael; George, Sebastian; Göck, Jürgen; Grieser, Manfred; Grussie, Florian; Guerin, Elisabeth A.; Heber, Oded; Herwig, Philipp

2016-01-01

An electrostatic cryogenic storage ring, CSR, for beams of anions and cations with up to 300 keV kinetic energy per unit charge has been designed, constructed, and put into operation. With a circumference of 35 m, the ion-beam vacuum chambers and all beam optics are in a cryostat and cooled by a closed-cycle liquid helium system. At temperatures as low as (5.5 ± 1) K inside the ring, storage time constants of several minutes up to almost an hour were observed for atomic and molecular, anion a...

Mechanical seal having a double-tier mating ring

Science.gov (United States)

Khonsari, Michael M.; Somanchi, Anoop K.

2005-09-13

An apparatus and method to enhance the overall performance of mechanical seals in one of the following ways: by reducing seal face wear, by reducing the contact surface temperature, or by increasing the life span of mechanical seals. The apparatus is a mechanical seal (e.g., single mechanical seals, double mechanical seals, tandem mechanical seals, bellows, pusher mechanical seals, and all types of rotating and reciprocating machines) comprising a rotating ring and a double-tier mating ring. In a preferred embodiment, the double-tier mating ring comprises a first and a second stationary ring that together form an agitation-inducing, guided flow channel to allow for the removal of heat generated at the seal face of the mating ring by channeling a coolant entering the mating ring to a position adjacent to and in close proximity with the interior surface area of the seal face of the mating ring.

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

KAUST Repository

Hamieh, Ali Imad Ali

2015-04-03

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

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

KAUST Repository

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

2015-01-01

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

Identification, synthesis and mass spectrometry of a macrolide from the African reed frog Hyperolius cinnamomeoventris

Directory of Open Access Journals (Sweden)

Markus Menke

2016-12-01

Full Text Available The contents of the gular glands of the male African reed frog Hyperolius cinnamomeoventris consist of a mixture of aliphatic macrolides and sesquiterpenes. While the known macrolide gephyromantolide A was readily identified, the structure of another major component was suggested to be a tetradecen-13-olide. The synthesis of the two candidate compounds (Z-5- and (Z-9-tetradecen-13-olide revealed the former to be the naturally occurring compound. The synthesis used ring-closing metathesis as key step. While the Hoveyda–Grubbs catalyst furnished a broad range of isomeric products, the (Z-selective Grubbs catalyst lead to pure (Z-products. Analysis by chiral GC revealed the natural frog compound to be (5Z,13S-5-tetradecen-13-olide (1. This compound is also present in the secretion of other hyperoliid frogs as well as in femoral glands of male mantellid frogs such as Spinomantis aglavei. The mass spectra of the synthesized macrolides as well as their rearranged isomers obtained during ring-closing metathesis showed that it is possible to assign the location of the double bond in an unsaturated macrolide on the basis of its EI mass spectrum. The occurrence of characteristic ions can be explained by the fragmentation pathway proposed in the article. In contrast, the localization of a double bond in many aliphatic open-chain compounds like alkenes, alcohols or acetates, important structural classes of pheromones, is usually not possible from an EI mass spectrum. In the article, we present the synthesis and for the first time elucidate the structure of macrolides from the frog family Hyperoliidae.

WR stars with ring nebulae

International Nuclear Information System (INIS)

Tutukov, A.

1982-01-01

It is shown that most of usually apparently single nitrogen WR stars with ring emission nebulae around them (WN + Neb) are a probable product of the evolution of a massive close binary with initial masses of components exceeding approximately 20 solar masses. (Auth.)

Vanishing of cohomology over Cohen–Macaulay rings

DEFF Research Database (Denmark)

Christensen, Lars Winther; Holm, Henrik Granau

2012-01-01

A 2003 counterexample to a conjecture of Auslander brought attention to a family of rings—colloquially called AC rings—that satisfy a natural condition on vanishing of cohomology. Several results attest to the remarkable homological properties of AC rings, but their definition is barely operational......, and it remains unknown if they form a class that is closed under typical constructions in ring theory. In this paper, we study transfer of the AC property along local homomorphisms of Cohen–Macaulay rings. In particular, we show that the AC property is preserved by standard procedures in local algebra. Our...

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

KAUST Repository

Rouen, Mathieu

2014-01-01

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

Laparoscopic appendicectomy using endo-ring applicator and fallope rings

International Nuclear Information System (INIS)

Ali, Iyoob V; Maliekkal, Joji I

2009-01-01

Wider adoption of laparoscopic appendicectomy (LA) is limited by problems in securing the appendiceal base as well as the cost and the duration compared with the open procedure. The objective of this study was to assess the feasibility and efficacy of a new method for securing the appendiceal base in LA, so as to make the entire procedure simpler and cheaper, and hence, more popular. Twenty-five patients who were candidates for appendicectomy (emergency as well as elective) and willing for the laparoscopic procedure were selected for this study. Ports used were 10 mm at the umbilicus, 5 mm at the lower right iliac fossa, and 10 mm at the left iliac fossa. Extremely friable, ruptured, or turgid organs of diameters larger than 8 mm were excluded from the study. The mesoappendix was divided close to the appendix by diathermy. Fallope rings were applied to the appendiceal base using a special ring applicator, and the appendix was divided and extracted through the lumen of the applicator. The procedure was successful in 23 (92%) cases, and the mean duration of the procedure was 20 minutes (15-32 minutes). There were no procedural complications seen during a median follow-up of two weeks. The equipment and rings were cheaper when compared with that of the standard methods of securing the base of the appendix. LA using fallope rings is a safe, simple, easy-to-learn, and economically viable method. (author)

Total Syntheses of Cyanthiwigins B, F, and G

KAUST Repository

Enquist, John A.

2011-07-18

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

Total Syntheses of Cyanthiwigins B, F, and G

KAUST Repository

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

2011-01-01

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

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

Science.gov (United States)

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

2006-08-31

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

Fano resonance and persistent current of a quantum ring

International Nuclear Information System (INIS)

Xiong Yongjian; Liang Xianting

2004-01-01

We investigate electron transport and persistent current of a quantum ring weakly attached to current leads. Assuming there is direct coupling (weakly or strongly) between two leads, electrons can transmit by the inter-lead coupling or tunneling through the quantum ring. The interference between the two paths yields asymmetric Fano line shape for conductance. In presence of interior magnetic flux, there is persistent current along the ring with narrow resonance peaks. The positions of the conductance resonances and the persistent current peaks correspond to the quasibound levels of the closed ring. This feature is helpful to determine the energy spectrum of the quantum ring. Our results show that the proposed setup provides a tunable Fano system

Ni(II

African Journals Online (AJOL)

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analytical chemistry, catalysis, electrochemistry, ring-opening metathesis ... Ethanol was dried over anhydrous copper(II) sulfate and distilled over metallic sodium. ... All bacteria were inoculated into Nutrient Broth (Difco) and incubated for 24 h ...

The Jovian rings as observed from Jupiter.

Science.gov (United States)

Malinnikova Bang, A.; Joergensen, J. L.; Joergensen, P. S.; Denver, T.; Connerney, J. E. P.; Bolton, S. J.; Levin, S.

2017-12-01

Juno entered a highly eliptic orbit around Jupiter on the 4. July 2016. Since then, it has completed 8 perijove passages. The Magnetometer experiment consists of two measurement platforms mounted 10m and 12m from the spacecraft spin axis, on one of three large solar panels. Each magnetometer platform is equipped with two star trackers to provide accurate attitude information to the vector magnetometers. The star trackers are pointed 13deg from the (anti) spin vector, and clocked 180deg to avoid simultaneous blinding effects from bright Jupiter only 6000km away, during perijove. This brings Juno well inside the innermost known satellite, Metis. The star trackers pointing close to, and above the Jovian horizon for most of each rotation of Juno, has an excellent view of the Jovian ring systems with a beta-angle close to 180deg. We report on the ring imaging performed during the first 8 orbits, discuss the structure, optical depth and moon sheparding of the inner rings as measured so far.

Saturn’s ring temperatures at equinox

Science.gov (United States)

Spilker, Linda J.; Ferrari, C.; Morishima, R.

2013-10-01

Modeling the thermal emission of Saturn's rings is challenging due to the numerous heating sources as well as the structural properties of the disk and of the particles that are closely related. At equinox, however, the main rings are externally heated by Saturn alone and the problem is somewhat simplified. We test the abilities of our current models to reproduce the temperatures observed with the Cassini CIRS instrument around equinox in August 2009. A simple semi-analytic model which includes mutual shadowing effects can mostly explain the radial profile of the equinox ring temperatures, except the model predicts lower temperatures than those observed for the A ring. The temperature variation at a given saturnocentric radius is primarily caused by observational geometry variations relative to Saturn. The observed temperature increases with decreasing Saturn-ring-observer angle. In addition, we found evidence that the leading hemispheres of particles are warmer than the trailing hemispheres at least for the C ring and probably for the A and B rings as well. This is explained if some fraction of particles has spin rates lower than the synchronous rotation rate as predicted by N-body simulations. The spin model for a monolayer ring (Ferrari, C., Leyrat, C., 2006, Astron. Astrophys. 447, 745-760) can fit the temperature variations with spacecraft longitude observed in the C ring with currently known thermal properties and a mixing of slow and fast rotators. The multilayer model (Morishima, R., Salo, H., Ohtsuki, K., 2009, Icarus 201, 634-654) can reproduce the temperatures of the B and C rings but gives A ring temperatures that are significantly lower than those observed as does the simple semi-analytic model. More advanced models which take into account self-gravity wakes may explain the A ring temperature behavior.

An N-body Integrator for Planetary Rings

Science.gov (United States)

Hahn, Joseph M.

2011-04-01

A planetary ring that is disturbed by a satellite's resonant perturbation can respond in an organized way. When the resonance lies in the ring's interior, the ring responds via an m-armed spiral wave, while a ring whose edge is confined by the resonance exhibits an m-lobed scalloping along the ring-edge. The amplitude of these disturbances are sensitive to ring surface density and viscosity, so modelling these phenomena can provide estimates of the ring's properties. However a brute force attempt to simulate a ring's full azimuthal extent with an N-body code will likely fail because of the large number of particles needed to resolve the ring's behavior. Another impediment is the gravitational stirring that occurs among the simulated particles, which can wash out the ring's organized response. However it is possible to adapt an N-body integrator so that it can simulate a ring's collective response to resonant perturbations. The code developed here uses a few thousand massless particles to trace streamlines within the ring. Particles are close in a radial sense to these streamlines, which allows streamlines to be treated as straight wires of constant linear density. Consequently, gravity due to these streamline is a simple function of the particle's radial distance to all streamlines. And because particles are responding to smooth gravitating streamlines, rather than discrete particles, this method eliminates the stirring that ordinarily occurs in brute force N-body calculations. Note also that ring surface density is now a simple function of streamline separations, so effects due to ring pressure and viscosity are easily accounted for, too. A poster will describe this N-body method in greater detail. Simulations of spiral density waves and scalloped ring-edges are executed in typically ten minutes on a desktop PC, and results for Saturn's A and B rings will be presented at conference time.

Mucin-producing signet ring cell adenoma of the thyroid

Directory of Open Access Journals (Sweden)

Gulwani Hanni

2008-10-01

Full Text Available Signet ring cell adenoma of the thyroid, though rare, is well documented. This change is chiefly due to intracellular accumulation of thyroglobulin that appears mucinous. Awareness of this entity is important as it may closely simulate a metastatic mucin-secreting signet ring cell carcinoma. Although the mucinous material in signet ring cells has been reported to stain positive with thyroglobulin, in some cases it may not be so. We herein describe a rare case of a 46-year-old man who was hypothyroid and the mass removed from the thyroid showed a mucin-producing signet ring cell adenoma of the thyroid.

Generation of Stoichiometric Ethylene and Isotopic Derivatives and Application in Transition Metal-Catalyzed Vinylation and Enyne Metathesis

DEFF Research Database (Denmark)

Min, Geanna; Bjerglund, Klaus Meier; Kramer, Søren

2013-01-01

Ethylene is one of the most important building blocks in industry for the production of polymers and commodity chemicals. 13C- and D-isotope-labeled ethylenes are also valuable reagents with applications ranging from polymer-structure determination, reaction-mechanism elucidation to the preparation...... of more complex isotopically labeled compounds. However, these isotopic derivatives are expensive, and are flammable gases, which are difficult to handle. We have developed a method for the controlled generation of ethylene and its isotopic variants including, for the first time, fully isotopically...... labeled ethylene, from simple alkene precursors by using Ru catalysis. Applying a two-chamber reactor allows both the synthesis of ethylene and its immediate consumption in a chemical transformation permitting reactions to be performed with only stoichiometric amounts of this two carbon olefin...

Some notes on the rings with sacred inscriptions from Pannonia

Directory of Open Access Journals (Sweden)

András Szabó

2015-02-01

Full Text Available More than a hundred rings bearing inscriptions are known from the territory of Roman Pannonia. Among these close to 30 artefacts can be regarded as rings displaying inscriptions of religious significance. Besides the Silvanus-rings, well-known to the archaeological research, some new groups of rings featuring sacred inscriptions can be distinguished according to the dedications. The aim of this paper is to analyse these objects and their religious backgrounds with the help of some archaeological, epigraphical and literary sources and to point out some of the questionable observations of the earlier research.

TRANSVERSE PHASE SPACE PAINTING FOR SNS ACCUMULATOR RING INJECTION.

Energy Technology Data Exchange (ETDEWEB)

BEEBE-WANG,J.; LEE,Y.Y.; RAPARIA,D.; WEI,J.

1999-03-29

The result of investigation and comparison of a series of transverse phase space painting schemes for the injection of SNS accumulator ring [1] is reported. In this computer simulation study, the focus is on the creation of closed orbit bumps that give desired distributions at the target. Space charge effects such as tune shift, emittance growth and beam losses are considered. The results of pseudo end-to-end simulations from the injection to the target through the accumulator ring and Ring to Target Beam Transfer (RTBT) system [2] are presented and discussed.

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

Directory of Open Access Journals (Sweden)

Hatice Mutlu

2010-12-01

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

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

DEFF Research Database (Denmark)

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

2012-01-01

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

Kleinian singularities and the ground ring of c=1 string theory

International Nuclear Information System (INIS)

Ghoshal, D.; Jatkar, D.P.; Mukhi, S.

1993-01-01

We investigate the nature of the ground ring of c=1 string theory at the special ADE points in the c=1 moduli space associated to discrete subgroups of SU(2). The chiral ground rings at these points are shown to define the ADE series of singular varieties introduced by Klein. The non-chiral ground rings relevant to closed-string theory are 3 real dimensional singular varieties obtained as U(1) quotients of the kleinian varieties. The unbroken symmetries of the theory at these points are the volume-preserving diffeomorphisms of these varieties. The theory of kleinian singularities has a close relation to that of complex hyperKaehler surfaces, or gravitational instantons. We speculate on the relevance of these instantons and of self-dual gravity in c=1 string theory. (orig.)

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

Science.gov (United States)

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

2012-04-01

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

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

Directory of Open Access Journals (Sweden)

Mohsine Driowya

2016-08-01

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

Efficient synthetic methods for the installation of boron-nitrogen bonds in conjugated organic molecules.

Science.gov (United States)

Morgan, Matthew M; Piers, Warren E

2016-04-14

Polycyclic aromatic hydrocarbons in which one or more CC units have been replaced by isoelectronic BN units have attracted interest as potentially improved organic materials in various devices. This promise has been hampered by a lack of access to gram quantities of these materials. However, the exploitation of keystone reactions such as ring closing metathesis, borylative cyclization of amino styrenes and electrophilic borylation has lead to strategies for access to workable amounts of material. These strategies can be augmented by judicious postfunctionalization reactions to diversify the library of materials available. This Frontier article highlights some of the recent successes and shows that the long promised applications of BN-doped PAHs are beginning to be explored in a meaningful way.

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

KAUST Repository

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

2013-01-01

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

Injection, compression and stability of intense ion-rings

International Nuclear Information System (INIS)

Sudan, R.N.

1975-01-01

Recent advances in pulsed high power ion beam technology make possible the creation of intense ion-rings with strong self-magnetic fields by single pulse injection. Such ion rings have several uses in controlled fusion e.g., to produce a min parallel B parallel magnetic geometry with a mirror ratio much higher than is possible with external conductors. For even stronger ion rings a min parallel B parallel with closed lines of force (ASTRON type) can be created. For this purpose, since the ion energies required are much higher than are available from high power sources, magnetic compression can be utilized to increase the ion energy. The success of this scheme depends critically on the stability of the ion ring. The low frequency perturbations of the ring-plasma system is examined by means of a generalization of the energy principle which established sufficient conditions for stability. The high-frequency micro-instabilities and their nonlinear consequences are discussed in terms of conventional techniques

Exact wave functions of two-electron quantum rings.

Science.gov (United States)

Loos, Pierre-François; Gill, Peter M W

2012-02-24

We demonstrate that the Schrödinger equation for two electrons on a ring, which is the usual paradigm to model quantum rings, is solvable in closed form for particular values of the radius. We show that both polynomial and irrational solutions can be found for any value of the angular momentum and that the singlet and triplet manifolds, which are degenerate, have distinct geometric phases. We also study the nodal structure associated with these two-electron states.

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.

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

International Nuclear Information System (INIS)

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

2004-01-01

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

On the evolution of vortex rings with swirl

International Nuclear Information System (INIS)

Naitoh, Takashi; Okura, Nobuyuki; Gotoh, Toshiyuki; Kato, Yusuke

2014-01-01

A laminar vortex ring with swirl, which has the meridional velocity component inside the vortex core, was experimentally generated by the brief fluid ejection from a rotating outlet. The evolution of the vortex ring was investigated with flow visualizations and particle image velocimetry measurements in order to find the influence of swirling flow in particular upon the transition to turbulence. Immediately after the formation of a vortex ring with swirl, a columnar strong vortex along the symmetric axis is observed in all cases of the present experiment. Then the characteristic fluid discharging from a vortex ring with swirl referred to as “peeling off” appears. The amount of discharging fluid due to the “peeling off” increases with the angular velocity of the rotating outlet. We conjectured that the mechanism generating the “peeling off” is related to the columnar strong vortex by close observations of the spatio-temporal development of the vorticity distribution and the cutting 3D images constructed from the successive cross sections of a vortex ring. While a laminar vortex ring without swirl may develop azimuthal waves around its circumference at some later time and the ring structure subsequently breaks, the swirling flow in a vortex ring core reduces the amplification rate of the azimuthal wavy deformation and preserved its ring structure. Then the traveling distance of a vortex ring can be extended using the swirl flow under certain conditions

On the evolution of vortex rings with swirl

Energy Technology Data Exchange (ETDEWEB)

Naitoh, Takashi, E-mail: naitoh.takashi@nitech.ac.jp [Department of Engineering Physics, Electronics and Mechanics, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan); Okura, Nobuyuki, E-mail: ohkura@meijo-u.ac.jp [Department of Vehicle and Mechanical Engineering, Meijo University, 1-501 Shiogamaguchi Tempaku-ku, Nagoya 468-8502 (Japan); Gotoh, Toshiyuki, E-mail: gotoh.toshiyuki@nitech.ac.jp [Department of Scientific and Engineering Simulation, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan); Kato, Yusuke [Controller Business Unit Engineering Division 1, Engineering Department 3, Denso Wave Incorporated, 1 Yoshiike Kusagi Agui-cho, Chita-gun Aichi 470-2297 (Japan)

2014-06-15

A laminar vortex ring with swirl, which has the meridional velocity component inside the vortex core, was experimentally generated by the brief fluid ejection from a rotating outlet. The evolution of the vortex ring was investigated with flow visualizations and particle image velocimetry measurements in order to find the influence of swirling flow in particular upon the transition to turbulence. Immediately after the formation of a vortex ring with swirl, a columnar strong vortex along the symmetric axis is observed in all cases of the present experiment. Then the characteristic fluid discharging from a vortex ring with swirl referred to as “peeling off” appears. The amount of discharging fluid due to the “peeling off” increases with the angular velocity of the rotating outlet. We conjectured that the mechanism generating the “peeling off” is related to the columnar strong vortex by close observations of the spatio-temporal development of the vorticity distribution and the cutting 3D images constructed from the successive cross sections of a vortex ring. While a laminar vortex ring without swirl may develop azimuthal waves around its circumference at some later time and the ring structure subsequently breaks, the swirling flow in a vortex ring core reduces the amplification rate of the azimuthal wavy deformation and preserved its ring structure. Then the traveling distance of a vortex ring can be extended using the swirl flow under certain conditions.

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-04-03

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

Evidence of Accretion in Saturn's F Ring (Invited)

Science.gov (United States)

Agnor, C. B.; Buerle, K.; Murray, C. D.; Evans, M. W.; Cooper, N. J.; Williams, G. W.

2010-12-01

Lying slightly outside the classical Roche radius and being strongly perturbed by the adjacent moons Prometheus and Pandora, Saturn's F ring represents a unique astrophysical laboratory for examining the processes of mass accretion and moonlet formation. Recent images from the Cassini spacecraft reveal optically thick clumps, capable of casting shadows, and associated structures in regions of the F ring following close passage by Prometheus. Here we examine the accretion environment of the F ring and Prometheus' role in moonlet formation and evolution. Using the observed structures adjacent to these clumps and dynamical arguments we estimate the masses of these clumps and find them comparable to that of ~10-20-km contiguous moonlets. Further, we show that Prometheus' perturbations on the F ring create regions of enhanced density and low relative velocity that may accelerate the accretion of clumps and moonlets.

Correction of vertical dispersion and betatron coupling for the CLIC damping ring

CERN Document Server

Korostelev, M S

2006-01-01

The sensitivity of the CLIC damping ring to various kinds of alignment errors has been studied. Without any correction, fairly small vertical misalignments of the quadrupoles and, in particular, the sextupoles, introduce unacceptable distortions of the closed orbit as well as intolerable spurious vertical dispersion and coupling due to the strong focusing optics of the damping ring. A sophisticated beam-based correction scheme has been developed to bring the design target emittances and the dynamic aperture back to the ideal value. The correction using dipolar correctors and several skew quadrupole correctors allows a minimization of the closed-orbit distortion, the cross-talk between vertical and horizontal closed orbits, the residual vertical dispersion and the betatron coupling.

The small displacement elastic solution to the ball-on-ring testing method

DEFF Research Database (Denmark)

Frandsen, Henrik Lund

2012-01-01

The ball-on-ring experiment is used for testing of the biaxial strength of ceramics. In this work the solution for the stress distribution and displacements of the disc specimen in the ball-on-ring experiment are determined on closed form. The solution comprises the displacement field and its...

Three families of mitered Borromean ring sculptures

NARCIS (Netherlands)

Verhoeff, T.; Verhoeff, K.; Delp, K.; Kaplan, C.S.; McKenna, D.; Sarhangi, R.

2015-01-01

Artists have drawn inspiration from many mathematical structures, such as regular tilings, lattices, symmetry groups, regular polyhedra, knots, and links. A particularly well-known link goes by the name Borromean rings. It consists of three closed loops (“rings”) that cannot be taken apart without

Graphene rings in magnetic fields: Aharonov–Bohm effect and valley splitting

International Nuclear Information System (INIS)

Wurm, J; Wimmer, M; Richter, K; Baranger, H U

2010-01-01

We study the conductance of mesoscopic graphene rings in the presence of a perpendicular magnetic field by means of numerical calculations based on a tight-binding model. First, we consider the magnetoconductance of such rings and observe the Aharonov–Bohm effect. We investigate different regimes of the magnetic flux up to the quantum Hall regime, where the Aharonov–Bohm oscillations are suppressed. Results for both clean (ballistic) and disordered (diffusive) rings are presented. Second, we study rings with smooth mass boundary that are weakly coupled to leads. We show that the valley degeneracy of the eigenstates in closed graphene rings can be lifted by a small magnetic flux, and that this lifting can be observed in the transport properties of the system

Contradiction between the results of observations of resistance and critical current quantum oscillations in asymmetric superconducting rings

International Nuclear Information System (INIS)

Gurtovoi, V. L.; Dubonos, S. V.; Karpii, S. V.; Nikulov, A. V.; Tulin, V. A.

2007-01-01

Magnetic field dependences of critical current, resistance, and rectified voltage of asymmetric (half circles of different widths) and symmetrical (half circles of equal widths) aluminum rings close to the super-conducting transition were measured. All these dependences are periodic magnetic field functions with periods corresponding to the flux quantum in the ring. The periodic dependences of critical current measured in opposite directions were found to be close to each other for symmetrical rings and shifted with respect to each other by half the flux quantum in asymmetric rings with ratios between half circle widths of from 1.25 to 2. This shift of the dependences by a quarter of the flux quantum as the ring becomes asymmetric makes critical current anisotropic, which explains the effect of alternating current rectification observed for asymmetric rings. Shifts of the extrema of the periodic dependences of critical current by a quarter of the flux quantum directly contradict the results obtained by measuring asymmetric ring resistance oscillations, whose extrema are, as for symmetrical rings, observed at magnetic fluxes equal to an integer and a half of flux quanta

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

Science.gov (United States)

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

2017-06-01

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

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

KAUST Repository

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

2015-01-01

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

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

KAUST Repository

Chen, Yin

2015-01-21

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

Catalysts and methods for ring opening metathesis polymerization

Energy Technology Data Exchange (ETDEWEB)

Schrock, Richard Royce; Autenrieth, Benjamin

2018-04-03

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

Rotating circular strings, and infinite non-uniqueness of black rings

International Nuclear Information System (INIS)

Emparan, Roberto

2004-01-01

We present new self-gravitating solutions in five dimensions that describe circular strings, i.e., rings, electrically coupled to a two-form potential (as e.g., fundamental strings do), or to a dual magnetic one-form. The rings are prevented from collapsing by rotation, and they create a field analogous to a dipole, with no net charge measured at infinity. They can have a regular horizon, and we show that this implies the existence of an infinite number of black rings, labeled by a continuous parameter, with the same mass and angular momentum as neutral black rings and black holes. We also discuss the solution for a rotating loop of fundamental string. We show how more general rings arise from intersections of branes with a regular horizon (even at extremality), closely related to the configurations that yield the four-dimensional black hole with four charges. We reproduce the Bekenstein-Hawking entropy of a large extremal ring through a microscopic calculation. Finally, we discuss some qualitative ideas for a microscopic understanding of neutral and dipole black rings. (author)

Hubble again views Saturn's Rings Edge-on

Science.gov (United States)

1995-01-01

Saturn's magnificent ring system is seen tilted edge-on -- for the second time this year -- in this NASA Hubble Space Telescope picture taken on August 10, 1995, when the planet was 895 million miles (1,440 million kilometers) away. Hubble snapped the image as Earth sped back across Saturn's ring plane to the sunlit side of the rings. Last May 22, Earth dipped below the ring plane, giving observers a brief look at the backlit side of the rings. Ring-plane crossing events occur approximately every 15 years. Earthbound observers won't have as good a view until the year 2038. Several of Saturn's icy moons are visible as tiny starlike objects in or near the ring plane. They are from left to right, Enceladus, Tethys, Dione and Mimas. 'The Hubble data shows numerous faint satellites close to the bright rings, but it will take a couple of months to precisely identify them,' according to Steve Larson (University of Arizona). During the May ring plane crossing, Hubble detected two, and possibly four, new moons orbiting Saturn. These new observations also provide a better view of the faint E ring, 'to help determine the size of particles and whether they will pose a collision hazard to the Cassini spacecraft,' said Larson. The picture was taken with Hubble's Wide Field Planetary Camera 2 in wide field mode. This image is a composite view, where a long exposure of the faint rings has been combined with a shorter exposure of Saturn's disk to bring out more detail. When viewed edge-on, the rings are so dim they almost disappear because they are very thin -- probably less than a mile thick.The Wide Field/Planetary Camera 2 was developed by the Jet Propulsion Laboratory and managed by the Goddard Spaced Flight Center for NASA's Office of Space Science.This image and other images and data received from the Hubble Space Telescope are posted on the World Wide Web on the Space Telescope Science Institute home page at URL http://oposite.stsci.edu/pubinfo/

FORMATION OF CENTAURS’ RINGS THROUGH THEIR PARTIAL TIDAL DISRUPTION DURING PLANETARY ENCOUNTERS

Energy Technology Data Exchange (ETDEWEB)

Hyodo, Ryuki; Charnoz, Sébastien [Institut de Physique du Globe, F-75005 Paris, France (France); Genda, Hidenori [Earth-Life Science Institute, Tokyo Institute of Technology, Tokyo 152-8550 (Japan); Ohtsuki, Keiji [Department of Planetology, Kobe University, Kobe 657-8501 (Japan)

2016-09-01

Centaurs are minor planets orbiting between Jupiter and Neptune that have or had crossing orbits with one or more giant planets. Recent observations and reinterpretation of previous observations have revealed the existence of ring systems around 10199 Chariklo and 2060 Chiron. However, the origin of the ring systems around such a minor planet is still an open question. Here, we propose that the tidal disruption of a differentiated object that experiences a close encounter with a giant planet could naturally form diverse ring–satellite systems around the Centaurs. During the close encounter, the icy mantle of the passing object is preferentially ripped off by the planet's tidal force and the debris is distributed mostly within the Roche limit of the largest remnant body. Assuming the existence of a 20−50 wt% silicate core below the icy mantle, a disk of particles is formed when the objects pass within 0.4–0.8 of the planet's Roche limit with the relative velocity at infinity 3−6 km s{sup −1} and 8 hr initial spin period of the body. The resultant ring mass is 0.1%–10% of the central object's mass. Such particle disks are expected to spread radially, and materials spreading beyond the Roche limit would accrete into satellites. Our numerical results suggest that ring formation would be a natural outcome of such extreme close encounters, and Centaurs can naturally have such ring systems because they cross the orbits of the giant planets.

FORMATION OF CENTAURS’ RINGS THROUGH THEIR PARTIAL TIDAL DISRUPTION DURING PLANETARY ENCOUNTERS

International Nuclear Information System (INIS)

Hyodo, Ryuki; Charnoz, Sébastien; Genda, Hidenori; Ohtsuki, Keiji

2016-01-01

Centaurs are minor planets orbiting between Jupiter and Neptune that have or had crossing orbits with one or more giant planets. Recent observations and reinterpretation of previous observations have revealed the existence of ring systems around 10199 Chariklo and 2060 Chiron. However, the origin of the ring systems around such a minor planet is still an open question. Here, we propose that the tidal disruption of a differentiated object that experiences a close encounter with a giant planet could naturally form diverse ring–satellite systems around the Centaurs. During the close encounter, the icy mantle of the passing object is preferentially ripped off by the planet's tidal force and the debris is distributed mostly within the Roche limit of the largest remnant body. Assuming the existence of a 20−50 wt% silicate core below the icy mantle, a disk of particles is formed when the objects pass within 0.4–0.8 of the planet's Roche limit with the relative velocity at infinity 3−6 km s"−"1 and 8 hr initial spin period of the body. The resultant ring mass is 0.1%–10% of the central object's mass. Such particle disks are expected to spread radially, and materials spreading beyond the Roche limit would accrete into satellites. Our numerical results suggest that ring formation would be a natural outcome of such extreme close encounters, and Centaurs can naturally have such ring systems because they cross the orbits of the giant planets.

Measuring the electron-ion ring parameters by bremsstrahlung

International Nuclear Information System (INIS)

Inkin, V.D.; Mozelev, A.A.; Sarantsev, V.P.

1982-01-01

A system is described for measuring the number of electrons and ions in the electron-ion rings of a collective heavy ion accelerator. The system operation is based on detecting gamma quanta of bremsstrahlung following the ring electron interaction with the nuclei of neutral atoms and ions at different stages of filling the ring with ions. The radiation detector is a scintillation block - a photomultiplier operating for counting with NaI(Tl) crystal sized 30x30 mm and ensuring the detection efficiency close to unity. The system apparatus is made in the CAMAC standard and rems on-line with the TRA/i miniature computer. The block-diagrams of the system and algorithm of data processing are presented. A conclusion is drawn that the results of measuring the ring parameters with the use of the diagnostics system described are in good agreement within the range of measuring errors with those obtained by means of the diagnostics system employing synchrotron radiation and induction sensors

Design studies for the electron storage ring EUTERPE

Energy Technology Data Exchange (ETDEWEB)

Boling, Xi

1995-05-18

The 400 MeV electron storage ring EUTERPE is under construction at Eindhoven University of Technology. The ring is to be used as an experimental tool for accelerator physics studies and synchroton radiation applications. The main task of the current research work is the electron optical design of the ring. Lattice design is a basis for machine design as a whole. Design aspects regarding the basic lattice, based on single particle dynamics, include determination of the equilibrium beam size and bunch length, design of achromatic bending sections, selection of tune values, correction of chromaticity, and minimization of the natural emittance in the ring. The basic lattice designed for the EUTERPE ring has a high flexibility so that different electron optical modes can be realized easily. In low energy storage rings with a high beam current, collective effects can cause a significant change in the bunch length, the transverse emittance and the beam lifetime. In order to ensure a good optical performance for the ring, the choice of suitable parameters concerning the vacuum and RF system are essential as far as collective effects are concerned. An estimation of the collective effects in the ring is given. The injector for EUTERPE is a 75 MeV racetrack microtron which is injected from a 10 MeV linac. In order to get sufficient beam current in the ring, a special procedure of continuous injection with an adjustable locally shifted closed orbit has been presented. Details of the injection procedure and numerical simulations are given. (orig./HSI).

Design studies for the electron storage ring EUTERPE

International Nuclear Information System (INIS)

Xi Boling.

1995-01-01

The 400 MeV electron storage ring EUTERPE is under construction at Eindhoven University of Technology. The ring is to be used as an experimental tool for accelerator physics studies and synchroton radiation applications. The main task of the current research work is the electron optical design of the ring. Lattice design is a basis for machine design as a whole. Design aspects regarding the basic lattice, based on single particle dynamics, include determination of the equilibrium beam size and bunch length, design of achromatic bending sections, selection of tune values, correction of chromaticity, and minimization of the natural emittance in the ring. The basic lattice designed for the EUTERPE ring has a high flexibility so that different electron optical modes can be realized easily. In low energy storage rings with a high beam current, collective effects can cause a significant change in the bunch length, the transverse emittance and the beam lifetime. In order to ensure a good optical performance for the ring, the choice of suitable parameters concerning the vacuum and RF system are essential as far as collective effects are concerned. An estimation of the collective effects in the ring is given. The injector for EUTERPE is a 75 MeV racetrack microtron which is injected from a 10 MeV linac. In order to get sufficient beam current in the ring, a special procedure of continuous injection with an adjustable locally shifted closed orbit has been presented. Details of the injection procedure and numerical simulations are given. (orig./HSI)

Periodic seasonal variation of magnets level of the STB ring

International Nuclear Information System (INIS)

Takahashi, Shigenobu

2003-01-01

The Stretcher-Booster (STB) ring, a 1.2 GeV electron synchrotron, was completed in December, 1997 at the Laboratory of Nuclear Sciences (LNS), Tohoku University. The total weight more than 400 tons were placed near the STB ring, such as concrete blocks for radiation shielding and a spectrometer magnet for nuclear physics experiments after the completion of the STB ring. Re-surveying of magnets alignment was started after 2000. Very recently a new building of an experimental hall was constructed close to the building of the STB ring for use of high energy γ-ray from the electron beam. The building will give rise the changes of magnet levels due to its seasonal distortion. The measurements of the magnet level after construction are continued as well as an expected change of the closed orbit distortion (COD) in the STB ring. The serious influence of the variation of the magnet level may be a change of the beam orbit of extracted beam in the stretcher operation. Difference of the orbit distortion reaches more than 5 mm. Correlation between the COD and the seasonal change of the magnet position is not clear at the moment. However, the machine operation and the beam diagnostics are getting better recently. Continuous surveying of the magnet level will be a useful data for a feed forward correction of the beam orbit. Future subjects and prospects are discussed on surveying. (Y. Tanaka)

Ring Theory

CERN Document Server

Jara, Pascual; Torrecillas, Blas

1988-01-01

The papers in this proceedings volume are selected research papers in different areas of ring theory, including graded rings, differential operator rings, K-theory of noetherian rings, torsion theory, regular rings, cohomology of algebras, local cohomology of noncommutative rings. The book will be important for mathematicians active in research in ring theory.

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

KAUST Repository

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

2015-01-01

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

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

KAUST Repository

Żukowska, Karolina

2015-08-20

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

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

KAUST Repository

Mazoyer, Etienne

2013-05-01

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

Synthesis of (+)-dumetorine and congeners by using flow chemistry technologies.

Science.gov (United States)

Riva, Elena; Rencurosi, Anna; Gagliardi, Stefania; Passarella, Daniele; Martinelli, Marisa

2011-05-23

An efficient total synthesis of the natural alkaloid (+)-dumetorine by using flow technology is described. The process entailed five separate steps starting from the enantiopure (S)-2-(piperidin-2-yl)ethanol 4 with 29% overall yield. Most of the reactions were carried out by exploiting solvent superheating and by using packed columns of immobilized reagents or scavengers to minimize handling. New protocols for performing classical reactions under continuous flow are disclosed: the ring-closing metathesis reaction with a novel polyethylene glycol-supported Hoveyda catalyst and the unprecedented flow deprotection/Eschweiler-Clarke methylation sequence. The new protocols developed for the synthesis of (+)-dumetorine were applied to the synthesis of its simplified natural congeners (-)-sedamine and (+)-sedridine. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

KAUST Repository

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

2010-01-01

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

Functional roles of the pepper RING finger protein gene, CaRING1, in abscisic acid signaling and dehydration tolerance.

Science.gov (United States)

Lim, Chae Woo; Hwang, Byung Kook; Lee, Sung Chul

2015-09-01

Plants are constantly exposed to a variety of biotic and abiotic stresses, which include pathogens and conditions of high salinity, low temperature, and drought. Abscisic acid (ABA) is a major plant hormone involved in signal transduction pathways that mediate the defense response of plants to abiotic stress. Previously, we isolated Ring finger protein gene (CaRING1) from pepper (Capsicum annuum), which is associated with resistance to bacterial pathogens, accompanied by hypersensitive cell death. Here, we report a new function of the CaRING1 gene product in the ABA-mediated defense responses of plants to dehydration stress. The expression of the CaRING1 gene was induced in pepper leaves treated with ABA or exposed to dehydration or NaCl. Virus-induced gene silencing of CaRING1 in pepper plants exhibited low degree of ABA-induced stomatal closure and high levels of transpirational water loss in dehydrated leaves. These led to be more vulnerable to dehydration stress in CaRING1-silenced pepper than in the control pepper, accompanied by reduction of ABA-regulated gene expression and low accumulation of ABA and H2O2. In contrast, CaRING1-overexpressing transgenic plants showed enhanced sensitivity to ABA during the seedling growth and establishment. These plants were also more tolerant to dehydration stress than the wild-type plants because of high ABA accumulation, enhanced stomatal closure and increased expression of stress-responsive genes. Together, these results suggest that the CaRING1 acts as positive factor for dehydration tolerance in Arabidopsis by modulating ABA biosynthesis and ABA-mediated stomatal closing and gene expression.

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

Directory of Open Access Journals (Sweden)

Albert Poater

2016-01-01

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

Report of the eRHIC Ring-Ring Working Group

Energy Technology Data Exchange (ETDEWEB)

Aschenauer, E. C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Berg, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Blaskiewicz, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Brennan, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Fedotov, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Fischer, W. [Brookhaven National Lab. (BNL), Upton, NY (United States); Litvinenko, V. [Brookhaven National Lab. (BNL), Upton, NY (United States); Montag, C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Palmer, R. [Brookhaven National Lab. (BNL), Upton, NY (United States); Parker, B. [Brookhaven National Lab. (BNL), Upton, NY (United States); Peggs, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Ptitsyn, V. [Brookhaven National Lab. (BNL), Upton, NY (United States); Ranjbar, V. [Brookhaven National Lab. (BNL), Upton, NY (United States); Tepikian, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Trbojevic, D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Willeke, F. [Brookhaven National Lab. (BNL), Upton, NY (United States)

2015-10-13

This report evaluates the ring-ring option for eRHIC as a lower risk alternative to the linac-ring option. The reduced risk goes along with a reduced initial luminosity performance. However, a luminosity upgrade path is kept open. This upgrade path consists of two branches, with the ultimate upgrade being either a ring-ring or a linac-ring scheme. The linac-ring upgrade could be almost identical to the proposed linac-ring scheme, which is based on an ERL in the RHIC tunnel. This linac-ring version has been studied in great detail over the past ten years, and its significant risks are known. On the other hand, no detailed work on an ultimate performance ring-ring scenario has been performed yet, other than the development of a consistent parameter set. Pursuing the ring-ring upgrade path introduces high risks and requires significant design work that is beyond the scope of this report.

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

KAUST Repository

Saggio, Guillaume

2010-10-04

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

Survey and alignment of photon factory storage ring at KEK

International Nuclear Information System (INIS)

Araki, A.; Honjo, I.; Katoh, M.; Kamiya, Y.; Kihara, M.

1987-01-01

The heights of the magnets for both the ring and the beam transport line (BT-line) have been periodically measured at the Photon Factory. The accumulated data showed that the ring was considerably declined due to the construction of the large experimental hall and the tunnel of the TRISTAN project, and that the BT-line also sank several centimeters at some locations. These displacements of the magnets produce a significantly large closed orbit distortion and the vertical dispersion

Resting state networks' corticotopy: the dual intertwined rings architecture.

Directory of Open Access Journals (Sweden)

Salma Mesmoudi

Full Text Available How does the brain integrate multiple sources of information to support normal sensorimotor and cognitive functions? To investigate this question we present an overall brain architecture (called "the dual intertwined rings architecture" that relates the functional specialization of cortical networks to their spatial distribution over the cerebral cortex (or "corticotopy". Recent results suggest that the resting state networks (RSNs are organized into two large families: 1 a sensorimotor family that includes visual, somatic, and auditory areas and 2 a large association family that comprises parietal, temporal, and frontal regions and also includes the default mode network. We used two large databases of resting state fMRI data, from which we extracted 32 robust RSNs. We estimated: (1 the RSN functional roles by using a projection of the results on task based networks (TBNs as referenced in large databases of fMRI activation studies; and (2 relationship of the RSNs with the Brodmann Areas. In both classifications, the 32 RSNs are organized into a remarkable architecture of two intertwined rings per hemisphere and so four rings linked by homotopic connections. The first ring forms a continuous ensemble and includes visual, somatic, and auditory cortices, with interspersed bimodal cortices (auditory-visual, visual-somatic and auditory-somatic, abbreviated as VSA ring. The second ring integrates distant parietal, temporal and frontal regions (PTF ring through a network of association fiber tracts which closes the ring anatomically and ensures a functional continuity within the ring. The PTF ring relates association cortices specialized in attention, language and working memory, to the networks involved in motivation and biological regulation and rhythms. This "dual intertwined architecture" suggests a dual integrative process: the VSA ring performs fast real-time multimodal integration of sensorimotor information whereas the PTF ring performs multi

Resting State Networks' Corticotopy: The Dual Intertwined Rings Architecture

Science.gov (United States)

Mesmoudi, Salma; Perlbarg, Vincent; Rudrauf, David; Messe, Arnaud; Pinsard, Basile; Hasboun, Dominique; Cioli, Claudia; Marrelec, Guillaume; Toro, Roberto; Benali, Habib; Burnod, Yves

2013-01-01

How does the brain integrate multiple sources of information to support normal sensorimotor and cognitive functions? To investigate this question we present an overall brain architecture (called “the dual intertwined rings architecture”) that relates the functional specialization of cortical networks to their spatial distribution over the cerebral cortex (or “corticotopy”). Recent results suggest that the resting state networks (RSNs) are organized into two large families: 1) a sensorimotor family that includes visual, somatic, and auditory areas and 2) a large association family that comprises parietal, temporal, and frontal regions and also includes the default mode network. We used two large databases of resting state fMRI data, from which we extracted 32 robust RSNs. We estimated: (1) the RSN functional roles by using a projection of the results on task based networks (TBNs) as referenced in large databases of fMRI activation studies; and (2) relationship of the RSNs with the Brodmann Areas. In both classifications, the 32 RSNs are organized into a remarkable architecture of two intertwined rings per hemisphere and so four rings linked by homotopic connections. The first ring forms a continuous ensemble and includes visual, somatic, and auditory cortices, with interspersed bimodal cortices (auditory-visual, visual-somatic and auditory-somatic, abbreviated as VSA ring). The second ring integrates distant parietal, temporal and frontal regions (PTF ring) through a network of association fiber tracts which closes the ring anatomically and ensures a functional continuity within the ring. The PTF ring relates association cortices specialized in attention, language and working memory, to the networks involved in motivation and biological regulation and rhythms. This “dual intertwined architecture” suggests a dual integrative process: the VSA ring performs fast real-time multimodal integration of sensorimotor information whereas the PTF ring performs multi

Energetic ion injection and formation of the storm-time symmetric ring current

Directory of Open Access Journals (Sweden)

L. Xie

2006-12-01

Full Text Available An extensive study of ring current injection and intensification of the storm-time ring current is conducted with three-dimensional (3-D test particle trajectory calculations (TPTCs. The TPTCs reveal more accurately the process of ring current injection, with the main results being the following: (1 an intense convection electric field can effectively energize and inject plasma sheet particles into the ring current region within 1–3 h. (2 Injected ions often follow chaotic trajectories in non-adiabatic regions, which may have implications in storm and ring current physics. (3 The shielding electric field, which arises as a consequence of enhanced convection and co-exists with the injection and convection electric field, may cause the original open trajectories of injected ions with higher energy to change into closed ones, thus playing a role in the formation of the symmetric ring current.

An unusually strong Einstein ring in the radio source PKS1830-211

International Nuclear Information System (INIS)

Jauncey, D.L.

1991-01-01

RADIO observations of the strong, flat-spectrum radio source PKS1830-211 revealed a double structure, with a separation of 1 arcsec, suggesting that it might be a gravitationally lensed object. We have now obtained high-resolution radio images of PKS1830-211 from several interferometric radiotelescope networks, which show an unusual elliptical ring-like structure connecting the two brighter components. The presence of the ring, and the similarity of the two brighter spots, argue strongly that this is indeed a gravitationally lensed system, specifically an Einstein ring in which lens and lensed object are closely aligned. Although the source is close to the galactic plane, it seems that both the lens and background (lensed) object are extragalactic. This object is one hundred times brighter than either of the two previously discovered radio Einstein rings, and is among the six brightest flat-spectrum sources in the sky. Its brightness makes it a peculiar object: it must involve either a chance alignment of a lensing object with an unusually bright background source, or an alignment with a less bright object but amplified to an unusual degree. (author)

Plug the socket of the main closing valve in a nuclear power plant

International Nuclear Information System (INIS)

Neupauer, J.; Bednar, B.

1988-01-01

The plug is designed for closing the main closing valve socket during a refuelling shutdown of a nuclear power plant. The plug is fixed in the using jaws forced against the socket ring part. The socket is sealed by expanding a ring between two cone trays. A valve provided in the plug allows draining the pipe. The plug is inserted in the socket using a jib suspended on a rail. Following sealing both sockets the inner surfaces of the closing valve can be decontaminated. Following decontamination, a water-proof cover is slid over the plug protecting the plug moving mechanism from damage. (J.B.). 1 fig

Ring distributions leading to species formation: a global topographic analysis of geographic barriers associated with ring species.

Science.gov (United States)

Monahan, William B; Pereira, Ricardo J; Wake, David B

2012-03-12

In the mid 20th century, Ernst Mayr and Theodosius Dobzhansky championed the significance of circular overlaps or ring species as the perfect demonstration of speciation, yet in the over 50 years since, only a handful of such taxa are known. We developed a topographic model to evaluate whether the geographic barriers that favor processes leading to ring species are common or rare, and to predict where other candidate ring barriers might be found. Of the 952,147 geographic barriers identified on the planet, only about 1% are topographically similar to barriers associated with known ring taxa, with most of the likely candidates occurring in under-studied parts of the world (for example, marine environments, tropical latitudes). Predicted barriers separate into two distinct categories: (i) single cohesive barriers (barriers - formed by groups of barriers (each 184,000 to 1.7 million km2) in close geographic proximity (totaling 1.9 to 2.3 million km2) - associated with taxa that differentiate at larger spatial scales (birds: Phylloscopus trochiloides and Larus (sp. argentatus and fuscus)). When evaluated globally, we find a large number of cohesive barriers that are topographically similar to those associated with known ring taxa. Yet, compared to cohesive barriers, an order of magnitude fewer composite barriers are similar to those that favor ring divergence in species with higher dispersal. While these findings confirm that the topographic conditions that favor evolutionary processes leading to ring speciation are, in fact, rare, they also suggest that many understudied natural systems could provide valuable demonstrations of continuous divergence towards the formation of new species. Distinct advantages of the model are that it (i) requires no a priori information on the relative importance of features that define barriers, (ii) can be replicated using any kind of continuously distributed environmental variable, and (iii) generates spatially explicit hypotheses of

A Feeding Strategy in Inner L-Shape Ring Hot Rolling Process

Directory of Open Access Journals (Sweden)

Wen Meng

2017-01-01

Full Text Available In order to make the inner L-shape ring polling process with a closed die structure (ILRRCDS on the top and bottom of the driven roll stable, at first, this paper established the mathematical model for ILRRCDS. Then, the plastic penetration and biting-in conditions for ILRRCDS were deduced based on plain ring rolling theory. Moreover, a feeding strategy that can realize a constant growth of the ring’s outer radius was proposed and the reasonable value ranges of the feed rate of the mandrel were determined. The numerical simulation model for ILRRCDS is established based on ABAQUS software. Finally, the equivalent plastic strain (PEEQ and temperature distributions of rolled ring were obtained. The results indicated that the proposed feeding strategy can realize a stable ILRRCDS. At the end of ILRRCDS, the PEEQ at the inner radius surface of the ring is maximum, the PEEQ at the outer radius surface of the ring takes the second place, and the PEEQ at the middle part of ring is minimum. With the increase of rolling time, the higher temperature zone of the rolled ring gradually moves from the center part of the ring to the “inner corner zone” of the ring.

ASSOCIATIVE RINGS SOLVED AS LIE RINGS

Directory of Open Access Journals (Sweden)

M. B. Smirnov

2011-01-01

Full Text Available The paper has proved that an associative ring which is solvable of a n- class as a Lie ring has a nilpotent ideal of the nilpotent class not more than 3×10n–2  and a corresponding quotient ring satisfies an identity [[x1, x2, [x3, x4

Zinc mediated domino elimination-alkylation of methyl 5-iodopentofuranosides

DEFF Research Database (Denmark)

Hyldtoft, Lene; Poulsen, Carina Storm; Madsen, Robert

1999-01-01

5-Iodopentofuranosides are converted with zinc and allyl/propargyl bromide into dienes/enynes which are further used in carbohydrate annulation reactions.......5-Iodopentofuranosides are converted with zinc and allyl/propargyl bromide into dienes/enynes which are further used in carbohydrate annulation reactions....

Novel Reactivity Of The Cationic Complex

International Nuclear Information System (INIS)

Wang, J.; Dash, A.K.; Eisen, AM.; Berthet, J.C.; Ephritikhine, M.

2002-01-01

The catalytic chemistry of electrophilic d 0 /f organometallic complexes is nowadays under intense investigation, reaching a high level of sophistication. General aspects concerning these complexes are concentrated for most studies to the functionalization of unsaturated organic molecules. To cite an instance, the actinide-promoted oligomerization of terminal alkynes is of essential present concern since it may introduce to a diversity of organic enynes and oligoacetylene products that are valuable synthons for the synthesis of natural products. Enynes are the simplest oligomerization products of alkynes. We have demonstrated that organoactinides complexes of the type [Cp* 2 AnMe 2 AnMe 2 ] (Cp* = C 5 Me 5 ; An = U, Th) are active catalysts for the linear oligomerization of terminal alkynes and the extent of oligomerization was found to be strongly dependent on the electronic and steric properties of the alkyne substituents. Bulky alkynes were reacted with high regioselectivity toward dimer and/or trimers whereas for non-bulky alkynes, these compounds were transformed into oligomers with a total deficiency of regioselectivity. The addition of primary amines to the catalytic cycle, for An = Th, granted the chemoselective formation of dimers, chemoselectively, whereas for An = U, this control was not succeeded. In distinction to the neutral organoactinide complexes, homogeneous cationic d 0 /f n actinide complexes have been used as in the homogeneous polymerization of olefins as extremely active catalysts. Hence, the catalytic alkyne oligomerization is a opportune route to explore insertions and σ-bond metathesis reactivity of complexes. We have recently shown that the reaction of terminal alkynes (RC≡CH), promoted by [(Et 2 N) 3 U][BPh 4 ], in toluene, produces efficiently mostly the gem dimers (for R = Me, i Pr and n Bu) as the major products, whereas for bulky alkynes (R = t MS or t Bu) small amounts of the cis dimer was concomitantly obtained. A plausible

Mapping Ring Particle Cooling across Saturn's Rings with Cassini CIRS

Science.gov (United States)

Brooks, Shawn M.; Spilker, L. J.; Edgington, S. G.; Pilorz, S. H.; Deau, E.

2010-10-01

Previous studies have shown that the rings' thermal inertia, a measure of their response to changes in the thermal environment, varies from ring to ring. Thermal inertia can provide insight into the physical structure of Saturn's ring particles and their regoliths. Low thermal inertia and quick temperature responses are suggestive of ring particles that have more porous or fluffy regoliths or that are riddled with cracks. Solid, coherent particles can be expected to have higher thermal inertias (Ferrari et al. 2005). Cassini's Composite Infrared Spectrometer has recorded millions of spectra of Saturn's rings since its arrival at Saturn in 2004 (personal communication, M. Segura). CIRS records far infrared radiation between 10 and 600 cm-1 (16.7 and 1000 µm) at focal plane 1 (FP1), which has a field of view of 3.9 mrad. Thermal emission from Saturn's rings peaks in this wavelength range. FP1 spectra can be used to infer ring temperatures. By tracking how ring temperatures vary, we can determine the thermal inertia of the rings. In this work we focus on CIRS observations of the shadowed portion of Saturn's rings. The thermal budget of the rings is dominated by the solar radiation absorbed by its constituent particles. When ring particles enter Saturn's shadow this source of energy is abruptly cut off. As a result, ring particles cool as they traverse Saturn's shadow. From these shadow observations we can create cooling curves at specific locations across the rings. We will show that the rings' cooling curves and thus their thermal inertia vary not only from ring to ring, but by location within the individual rings. This research was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under contract with NASA. Copyright 2010 California Institute of Technology. Government sponsorship acknowledged.

Saturn's F Ring Core: Calm in the Midst of Chaos

Science.gov (United States)

Cuzzi, J. N.; Whizin, A. D.; Hogan, R. C.; Dobrovolskis, A. R.; Dones, L.; Showalter. M. R.; Colwell, J. E.; Scargle, J. D.

2013-01-01

The long-term stability of the narrow F Ring core has been hard to understand. Instead of acting as "shepherds", Prometheus and Pandora together stir the vast preponderance of the region into a chaotic state, consistent with the orbits of newly discovered objects like S/2004S6. We show how a comb of very narrow radial locations of high stability in semimajor axis is embedded within this otherwise chaotic region. The stability of these semimajor axes relies fundamentally on the unusual combination of rapid apse precession and long synodic period which characterizes the region. This situation allows stable "antiresonances" to fall on or very close to traditional Lindblad resonances which, under more common circumstances, are destabilizing. We present numerical integrations of tens of thousands of test particles over tens of thousands of Prometheus orbits that map out the effect. The stable antiresonance zones are most stable in a subset of the region where Prometheus first-order resonances are least cluttered by Pandora resonances. This region of optimum stability is paradoxically closer to Prometheus than a location more representative of "torque balance", helping explain a longstanding paradox. One stable zone corresponds closely to the currently observed semimajor axis of the F Ring core. While the model helps explain the stability of the narrow F Ring core, it does not explain why the F Ring material all shares a common apse longitude; we speculate that collisional damping at the preferred semimajor axis (not included in the current simulations) may provide that final step. Essentially, we find that the F Ring core is not confined by a combination of Prometheus and Pandora, but a combination of Prometheus and precession.

Multiple Coulomb ordered strings of ions in a storage ring

International Nuclear Information System (INIS)

Hasse, Rainer W.

2002-01-01

We explain that the anomalous frequency shifts of very close masses measured in the high precision mass measurement experiments in the ESR storage ring result from the locking of Coulomb interacting strings of ions. Here two concentric strings which run horizontally close to each other for many revolutions are captured into a single string if their thermal clouds overlap. They give up their identity and lock into an average frequency

Spin frustration effects in an odd-member antiferromagnetic ring and the magnetic Mobius strip

International Nuclear Information System (INIS)

Cador, Olivier; Gatteschi, Dante; Sessoli, Roberta; Barra, Anne-Laure; Timco, Grigore A.; Winpenny, Richard E.P.

2005-01-01

The magnetic properties of the first odd-member antiferromagnetic ring comprising eight chromium(III) ions, S=32 spins, and one nickel(II) ion, S=1 spin, are investigated. The ring possesses an even number of unpaired electrons and a S=0 ground state but, due to competing AF interactions, the first excited spin states are close in energy. The spin frustrated ring is visualized by a Mobius strip. The 'knot' of the strip represents the region of the ring where the AF interactions are more frustrated. In the particular case of this bimetallic ring electron paramagnetic resonance (EPR) has unambiguously shown that the frustration is delocalized on the chromium chain, while the antiparallel alignment is more rigid at the nickel site

Spin frustration effects in an odd-member antiferromagnetic ring and the magnetic Mobius strip

Energy Technology Data Exchange (ETDEWEB)

Cador, Olivier [Laboratory of Molecular Magnetism, Department of Chemistry and UdR INSTM, Universita degli Studi di Firenze, Via Lastruccia n. 3, 50019 Sesto Fiorentino (Italy); Gatteschi, Dante [Laboratory of Molecular Magnetism, Department of Chemistry and UdR INSTM, Universita degli Studi di Firenze, Via Lastruccia n. 3, 50019 Sesto Fiorentino (Italy); Sessoli, Roberta [Laboratory of Molecular Magnetism, Department of Chemistry and UdR INSTM, Universita degli Studi di Firenze, Via Lastruccia n. 3, 50019 Sesto Fiorentino (Italy)]. E-mail: roberta.sessoli@unifi.it; Barra, Anne-Laure [Laboratoire des Champs Magnetiques Intenses-CNRS, F-38042 Grenoble Cede 9 (France); Timco, Grigore A. [Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom); Winpenny, Richard E.P. [Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom)

2005-04-15

The magnetic properties of the first odd-member antiferromagnetic ring comprising eight chromium(III) ions, S=32 spins, and one nickel(II) ion, S=1 spin, are investigated. The ring possesses an even number of unpaired electrons and a S=0 ground state but, due to competing AF interactions, the first excited spin states are close in energy. The spin frustrated ring is visualized by a Mobius strip. The 'knot' of the strip represents the region of the ring where the AF interactions are more frustrated. In the particular case of this bimetallic ring electron paramagnetic resonance (EPR) has unambiguously shown that the frustration is delocalized on the chromium chain, while the antiparallel alignment is more rigid at the nickel site.

ACCELERATORS: Beam based alignment of the SSRF storage ring

Science.gov (United States)

Zhang, Man-Zhou; Li, Hao-Hu; Jiang, Bo-Cheng; Liu, Gui-Min; Li, De-Ming

2009-04-01

There are 140 beam position monitors (BPMs) in the Shanghai Synchrotron Radiation Facility (SSRF) storage ring used for measuring the closed orbit. As the BPM pickup electrodes are assembled directly on the vacuum chamber, it is important to calibrate the electrical center offset of the BPM to an adjacent quadrupole magnetic center. A beam based alignment (BBA) method which varies individual quadrupole magnet strength and observes its effects on the orbit is used to measure the BPM offsets in both the horizontal and vertical planes. It is a completely automated technique with various data processing methods. There are several parameters such as the strength change of the correctors and the quadrupoles which should be chosen carefully in real measurement. After several rounds of BBA measurement and closed orbit correction, these offsets are set to an accuracy better than 10 μm. In this paper we present the method of beam based calibration of BPMs, the experimental results of the SSRF storage ring, and the error analysis.

Conceptual design of a moving-ring reactor

International Nuclear Information System (INIS)

Smith, A.C. Jr.; Ashworth, C.P.; Abreu, K.E.

1983-01-01

A design of a prototype Moving-Ring Reactor has been completed. The fusion fuel is confined in current-carrying rings of magnetically field-reversed plasma (''compact toroids''). The plasma rings, formed by a coaxial plasma gun, undergo adiabatic magnetic compression to ignition temperature while they are being injected into the reactor's burner section. The cylindrical burner chamber is divided into three ''burn stations''. Separator coils and a slight axial guide-field gradient are used to shuttle the ignited toroids rapidly from one burn station to the next, pausing for one third of the total burn time at each station. D-T- 3 He ice pellets refuel the rings at a rate which maintains constant radiated power. The first wall and tritium breeding blanket designs make credible use of helium cooling, SiC and Li 2 O to minimize structural radioactivity. ''Hands-on'' maintenance is possible on all reactor components outside the blanket. The first wall and blanket are designed to shut the reactor down passively in the event of a loss-of-coolant or loss-of-flow accident. Helium removes heat from the first wall, blanket and shield, and is used in a closed-cycle gas turbine to produce electricity. Energy residing in the plasma ring at the end of the burn is recovered via magnetic expansion. Electrostatic direct conversion is not used in this design. The reactor produces a constant net power of 99 MW(e). (author)

Ring distributions leading to species formation: a global topographic analysis of geographic barriers associated with ring species

Directory of Open Access Journals (Sweden)

Monahan William B

2012-03-01

Full Text Available Abstract Background In the mid 20th century, Ernst Mayr and Theodosius Dobzhansky championed the significance of circular overlaps or ring species as the perfect demonstration of speciation, yet in the over 50 years since, only a handful of such taxa are known. We developed a topographic model to evaluate whether the geographic barriers that favor processes leading to ring species are common or rare, and to predict where other candidate ring barriers might be found. Results Of the 952,147 geographic barriers identified on the planet, only about 1% are topographically similar to barriers associated with known ring taxa, with most of the likely candidates occurring in under-studied parts of the world (for example, marine environments, tropical latitudes. Predicted barriers separate into two distinct categories: (i single cohesive barriers (2, associated with taxa that differentiate at smaller spatial scales (salamander: Ensatina eschscholtzii; tree: Acacia karroo; and (ii composite barriers - formed by groups of barriers (each 184,000 to 1.7 million km2 in close geographic proximity (totaling 1.9 to 2.3 million km2 - associated with taxa that differentiate at larger spatial scales (birds: Phylloscopus trochiloides and Larus (sp. argentatus and fuscus. When evaluated globally, we find a large number of cohesive barriers that are topographically similar to those associated with known ring taxa. Yet, compared to cohesive barriers, an order of magnitude fewer composite barriers are similar to those that favor ring divergence in species with higher dispersal. Conclusions While these findings confirm that the topographic conditions that favor evolutionary processes leading to ring speciation are, in fact, rare, they also suggest that many understudied natural systems could provide valuable demonstrations of continuous divergence towards the formation of new species. Distinct advantages of the model are that it (i requires no a priori information on the

New developments in ultrasonic inspection of retaining rings on generators in operation

International Nuclear Information System (INIS)

Koch-Mathian, A.

1990-01-01

The ultrasonic inspection of retaining rings of operating generators has been operational since 1986. The aim of this presentation is to outline the experience acquired on many retaining rings on different types of generators. In-situ inspections have made it possible to detect more exactly the different shape echoes for the various elements located beneath the retaining ring such as rotor teeth, damping and epoxy insulation. Various methods of identifying these parts are currently being developed. Investigation on corroded retaining rings has made it possible to demonstrate the close correlation between the transverse beam detection and the presence of actual cracks identified by micrograph. The specific facies of these cracks precludes the use of classic dimensioning techniques, but a method based on longitudinal wave detection has already given encouraging results

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

Indian Academy of Sciences (India)

Unknown

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

A Stereoselective [3+1] Ring Expansion for the Synthesis of Highly Substituted Methylene Azetidines.

Science.gov (United States)

Schmid, Steven C; Guzei, Ilia A; Schomaker, Jennifer M

2017-09-25

The reaction of rhodium-bound carbenes with strained bicyclic methylene aziridines results in a formal [3+1] ring expansion to yield highly substituted methylene azetidines with excellent regio- and stereoselectivity. The reaction appears to proceed through an ylide-type mechanism, where the unique strain and structure of the methylene aziridine promotes a ring-opening/ring-closing cascade that efficiently transfers chirality from substrate to product. The resultant products can be elaborated into new azetidine scaffolds containing vicinal tertiary-quaternary and even quaternary-quaternary stereocenters. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Plasma confinement in a magnetic field of the internal ring current

International Nuclear Information System (INIS)

Shafranov, Vitaly; Popovich, Paul; Samitov, Marat

2000-01-01

Plasma confinement in compact region surrounding an internal ring current is considered. As the limiting case of large aspect ratio system the cylindrical plasma is considered initially. Analysis of the cylindrical tubular plasma equilibrium and stability against the most dangerous flute (m=0) and kink (m=1) modes revealed the possibility of the MHD stable plasma confined by magnetic field of the internal rod current, with rather peaked plasma pressure and maximal local beta β(γ)=0.4. In case of the toroidal internal ring system an additional external magnetic field creates the boundary separatrix witch limits the plasma volume. The dependence of the plasma pressure profiles, marginally stable with respect to the flute modes, from the shape of the external plasma boundary (separatrix) in such kind closed toroidal systems is investigated. The internal ring system with circular poloidal magnetic mirror, where the ring supports could be placed, is proposed. (author)

Black rings

International Nuclear Information System (INIS)

Emparan, Roberto; Reall, Harvey S

2006-01-01

A black ring is a five-dimensional black hole with an event horizon of topology S 1 x S 2 . We provide an introduction to the description of black rings in general relativity and string theory. Novel aspects of the presentation include a new approach to constructing black ring coordinates and a critical review of black ring microscopics. (topical review)

Efficient Homodifunctional Bimolecular Ring-Closure Method for Cyclic Polymers by Combining RAFT and Self-Accelerating Click Reaction.

Science.gov (United States)

Qu, Lin; Sun, Peng; Wu, Ying; Zhang, Ke; Liu, Zhengping

2017-08-01

An efficient metal-free homodifunctional bimolecular ring-closure method is developed for the formation of cyclic polymers by combining reversible addition-fragmentation chain transfer (RAFT) polymerization and self-accelerating click reaction. In this approach, α,ω-homodifunctional linear polymers with azide terminals are prepared by RAFT polymerization and postmodification of polymer chain end groups. By virtue of sym-dibenzo-1,5-cyclooctadiene-3,7-diyne (DBA) as small linkers, well-defined cyclic polymers are then prepared using the self-accelerating double strain-promoted azide-alkyne click (DSPAAC) reaction to ring-close the azide end-functionalized homodifunctional linear polymer precursors. Due to the self-accelerating property of DSPAAC ring-closing reaction, this novel method eliminates the requirement of equimolar amounts of telechelic polymers and small linkers in traditional bimolecular ring-closure methods. It facilitates this method to efficiently and conveniently produce varied pure cyclic polymers by employing an excess molar amount of DBA small linkers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The cryogenic storage ring CSR

Science.gov (United States)

von Hahn, R.; Becker, A.; Berg, F.; Blaum, K.; Breitenfeldt, C.; Fadil, H.; Fellenberger, F.; Froese, M.; George, S.; Göck, J.; Grieser, M.; Grussie, F.; Guerin, E. A.; Heber, O.; Herwig, P.; Karthein, J.; Krantz, C.; Kreckel, H.; Lange, M.; Laux, F.; Lohmann, S.; Menk, S.; Meyer, C.; Mishra, P. M.; Novotný, O.; O'Connor, A. P.; Orlov, D. A.; Rappaport, M. L.; Repnow, R.; Saurabh, S.; Schippers, S.; Schröter, C. D.; Schwalm, D.; Schweikhard, L.; Sieber, T.; Shornikov, A.; Spruck, K.; Sunil Kumar, S.; Ullrich, J.; Urbain, X.; Vogel, S.; Wilhelm, P.; Wolf, A.; Zajfman, D.

2016-06-01

An electrostatic cryogenic storage ring, CSR, for beams of anions and cations with up to 300 keV kinetic energy per unit charge has been designed, constructed, and put into operation. With a circumference of 35 m, the ion-beam vacuum chambers and all beam optics are in a cryostat and cooled by a closed-cycle liquid helium system. At temperatures as low as (5.5 ± 1) K inside the ring, storage time constants of several minutes up to almost an hour were observed for atomic and molecular, anion and cation beams at an energy of 60 keV. The ion-beam intensity, energy-dependent closed-orbit shifts (dispersion), and the focusing properties of the machine were studied by a system of capacitive pickups. The Schottky-noise spectrum of the stored ions revealed a broadening of the momentum distribution on a time scale of 1000 s. Photodetachment of stored anions was used in the beam lifetime measurements. The detachment rate by anion collisions with residual-gas molecules was found to be extremely low. A residual-gas density below 140 cm-3 is derived, equivalent to a room-temperature pressure below 10-14 mbar. Fast atomic, molecular, and cluster ion beams stored for long periods of time in a cryogenic environment will allow experiments on collision- and radiation-induced fragmentation processes of ions in known internal quantum states with merged and crossed photon and particle beams.

The cryogenic storage ring CSR.

Science.gov (United States)

von Hahn, R; Becker, A; Berg, F; Blaum, K; Breitenfeldt, C; Fadil, H; Fellenberger, F; Froese, M; George, S; Göck, J; Grieser, M; Grussie, F; Guerin, E A; Heber, O; Herwig, P; Karthein, J; Krantz, C; Kreckel, H; Lange, M; Laux, F; Lohmann, S; Menk, S; Meyer, C; Mishra, P M; Novotný, O; O'Connor, A P; Orlov, D A; Rappaport, M L; Repnow, R; Saurabh, S; Schippers, S; Schröter, C D; Schwalm, D; Schweikhard, L; Sieber, T; Shornikov, A; Spruck, K; Sunil Kumar, S; Ullrich, J; Urbain, X; Vogel, S; Wilhelm, P; Wolf, A; Zajfman, D

2016-06-01

An electrostatic cryogenic storage ring, CSR, for beams of anions and cations with up to 300 keV kinetic energy per unit charge has been designed, constructed, and put into operation. With a circumference of 35 m, the ion-beam vacuum chambers and all beam optics are in a cryostat and cooled by a closed-cycle liquid helium system. At temperatures as low as (5.5 ± 1) K inside the ring, storage time constants of several minutes up to almost an hour were observed for atomic and molecular, anion and cation beams at an energy of 60 keV. The ion-beam intensity, energy-dependent closed-orbit shifts (dispersion), and the focusing properties of the machine were studied by a system of capacitive pickups. The Schottky-noise spectrum of the stored ions revealed a broadening of the momentum distribution on a time scale of 1000 s. Photodetachment of stored anions was used in the beam lifetime measurements. The detachment rate by anion collisions with residual-gas molecules was found to be extremely low. A residual-gas density below 140 cm(-3) is derived, equivalent to a room-temperature pressure below 10(-14) mbar. Fast atomic, molecular, and cluster ion beams stored for long periods of time in a cryogenic environment will allow experiments on collision- and radiation-induced fragmentation processes of ions in known internal quantum states with merged and crossed photon and particle beams.

The cryogenic storage ring CSR

Energy Technology Data Exchange (ETDEWEB)

Hahn, R. von; Becker, A.; Berg, F.; Blaum, K.; Fadil, H.; Fellenberger, F.; Froese, M.; George, S.; Göck, J.; Grieser, M.; Grussie, F.; Guerin, E. A.; Herwig, P.; Karthein, J.; Krantz, C.; Kreckel, H.; Lange, M.; Laux, F.; Lohmann, S.; Menk, S. [Max-Planck-Institut für Kernphysik, 69117 Heidelberg (Germany); and others

2016-06-15

An electrostatic cryogenic storage ring, CSR, for beams of anions and cations with up to 300 keV kinetic energy per unit charge has been designed, constructed, and put into operation. With a circumference of 35 m, the ion-beam vacuum chambers and all beam optics are in a cryostat and cooled by a closed-cycle liquid helium system. At temperatures as low as (5.5 ± 1) K inside the ring, storage time constants of several minutes up to almost an hour were observed for atomic and molecular, anion and cation beams at an energy of 60 keV. The ion-beam intensity, energy-dependent closed-orbit shifts (dispersion), and the focusing properties of the machine were studied by a system of capacitive pickups. The Schottky-noise spectrum of the stored ions revealed a broadening of the momentum distribution on a time scale of 1000 s. Photodetachment of stored anions was used in the beam lifetime measurements. The detachment rate by anion collisions with residual-gas molecules was found to be extremely low. A residual-gas density below 140 cm{sup −3} is derived, equivalent to a room-temperature pressure below 10{sup −14} mbar. Fast atomic, molecular, and cluster ion beams stored for long periods of time in a cryogenic environment will allow experiments on collision- and radiation-induced fragmentation processes of ions in known internal quantum states with merged and crossed photon and particle beams.

Variations in Ring Particle Cooling across Saturn's Rings with Cassini CIRS

Science.gov (United States)

Brooks, S. M.; Spilker, L. J.; Pilorz, S.; Edgington, S. G.; Déau, E.; Altobelli, N.

2010-12-01

Cassini's Composite Infrared Spectrometer has recorded over two million of spectra of Saturn's rings in the far infrared since arriving at Saturn in 2004. CIRS records far infrared radiation between 10 and 600 cm-1 ( 16.7 and 1000 μ {m} ) at focal plane 1 (FP1), which has a field of view of 3.9 mrad. Thermal emission from Saturn’s rings peaks in this wavelength range. Ring temperatures can be inferred from FP1 data. By tracking how ring temperatures vary, we can determine the thermal inertia of the rings. Previous studies have shown that the rings' thermal inertia, a measure of their response to changes in the thermal environment, varies from ring to ring. Thermal inertia can provide insight into the physical structure of Saturn's ring particles and their regoliths. Low thermal inertia and rapidly changing temperatures are suggestive of ring particles that have more porous or fluffy regoliths or that are riddled with cracks. Solid particles can be expected to have higher thermal inertias. Ferrari et al. (2005) fit thermal inertia values of 5218 {Jm)-2 {K}-1 {s}-1/2 to their B ring data and 6412 {Jm)-2 {K}-1 {s}-1/2 to their C ring data. In this work we focus on CIRS observations of the shadowed portion of Saturn's rings. The rings’ thermal budget is dominated by its absorption of solar radiation. As a result, ring particles abruptly cool as they traverse Saturn's shadow. From these shadow observations we can create cooling curves at specific locations across the rings. We will show that the rings' cooling curves and thus their thermal inertia vary not only from ring to ring, but by location within the individual rings. This research was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under contract with NASA. Copyright 2010 California Institute of Technology. Government sponsorship acknowledged.

Space charge and magnet error simulations for the SNS accumulator ring

International Nuclear Information System (INIS)

Beebe-Wang, J.; Fedotov, A.V.; Wei, J.; Machida, S.

2000-01-01

The effects of space charge forces and magnet errors in the beam of the Spallation Neutron Source (SNS) accumulator ring are investigated. In this paper, the focus is on the emittance growth and halo/tail formation in the beam due to space charge with and without magnet errors. The beam properties of different particle distributions resulting from various injection painting schemes are investigated. Different working points in the design of SNS accumulator ring lattice are compared. The simulations in close-to-resonance condition in the presence of space charge and magnet errors are presented. (author)

Primitivity and weak distributivity in near rings and matrix near rings

International Nuclear Information System (INIS)

Abbasi, S.J.

1993-08-01

This paper shows the structure of matrix near ring constructed over a weakly distributive and primative near ring. It is proved that a weakly distributive primitive near ring is a ring and the matrix near rings constructed over it is also a bag. (author). 14 refs

Analytical solutions for the invariant spin field for model storage rings

International Nuclear Information System (INIS)

Mane, S.R.

2002-01-01

We present nonperturbative analytical expressions for the invariant spin field for several storage ring models. In particular, we solve the important models of a ring with one Snake and a single resonance driving term, and a ring with two Snakes and a single resonance driving term. We also treat several other models, all of which contain Siberian Snakes. Our solutions contain some novel features, e.g. in some cases the polarization does not point along the direction of the closed-orbit spin quantization axis. We also include vertical resonance driving terms, and consider the contributions of sextupoles and higher order multipoles to the resonance driving terms, and argue that these can play a significant role in some circumstances. We offer some brief remarks on the so-called Snake resonances. We relate our results to observations of higher-order depolarizing spin resonances for polarized proton beams in a real ring, and offer some suggestions as to how our ideas might be verified

Alstom Francis Turbine Ring Gates: from Retrofitting to Commissioning

Science.gov (United States)

A, Nguyen P.; G, Labrecque; M-O, Thibault; M, Bergeron; A, Steinhilber; D, Havard

2014-03-01

The Ring Gate synchronisation system developed by Alstom is new and patented. It uses hydraulic cylinders connected in pairs by a serial connection. The new hydraulic synchronisation system, when compared to the previous mechanical synchronisation system, has several advantages. It is a compact design; it reduces the number of mechanical components as well as maintenance costs. The new system maintains the Ring Gates robustness. The new approach is an evolution from mechanical to hydraulic synchronization assisted by electronic control. The new synchronization system eliminates several mechanical components that used to add wear and friction and which are usually difficult to adjust during maintenance. Tension chains and sprockets and associated controls are eliminated. Through the position sensors, the redundancy of the ring gate synchronization system makes it predictable and reliable. The electronic control compensates for any variation in operation, for example a leak in the hydraulic system. An emergency closing is possible without the electronic control system due to the stiffness of hydraulic serial connection in the hydraulic cylinder pairs. The Ring Gate can work safely against uneven loads and frictions. The development will be reviewed and its application discussed through commissioning results.

Alstom Francis Turbine Ring Gates: from Retrofitting to Commissioning

International Nuclear Information System (INIS)

Nguyen P A; Labrecque G; Thibault M-O; Bergeron M; Steinhilber A; Havard D

2014-01-01

The Ring Gate synchronisation system developed by Alstom is new and patented. It uses hydraulic cylinders connected in pairs by a serial connection. The new hydraulic synchronisation system, when compared to the previous mechanical synchronisation system, has several advantages. It is a compact design; it reduces the number of mechanical components as well as maintenance costs. The new system maintains the Ring Gates robustness. The new approach is an evolution from mechanical to hydraulic synchronization assisted by electronic control. The new synchronization system eliminates several mechanical components that used to add wear and friction and which are usually difficult to adjust during maintenance. Tension chains and sprockets and associated controls are eliminated. Through the position sensors, the redundancy of the ring gate synchronization system makes it predictable and reliable. The electronic control compensates for any variation in operation, for example a leak in the hydraulic system. An emergency closing is possible without the electronic control system due to the stiffness of hydraulic serial connection in the hydraulic cylinder pairs. The Ring Gate can work safely against uneven loads and frictions. The development will be reviewed and its application discussed through commissioning results

Relationship between carbon-14 concentrations in tree-ring cellulose and atmospheric CO2

International Nuclear Information System (INIS)

Yamada, Yoshimune; Yasuike, Kaeko; Komura, Kazuhisa

2008-01-01

Concentrations of organically-bound 14 C in the tree-ring cellulose of a Japanese Cedar (Cryptomeria japonica) grown in a rural region of Kanazawa, Ishikawa prefecture, Japan (36.5degN, 136.7degE), were measured for the ring-years from 1989 to 1998 to study relationship between 14 C concentrations in tree-ring cellulose and atmospheric CO 2 in a narrow region. An interesting result in comparing our data of tree-ring cellulose with those of atmospheric CO 2 is that the 14 C concentration in tree-ring cellulose was close to the corresponding average from mid-June to early September of 14 C concentrations in atmospheric CO 2 . Furthermore, the 14 C concentrations in tree-ring cellulose were found to be merely influenced by the drastic decrease of 14 C concentrations in atmospheric CO 2 in winter, which might be caused by air pollution from the Asian continent and additional local fossil fuel contribution. These results suggest that the 14 C concentration in tree-ring cellulose for a given growing year reflects the 14 C concentrations of atmospheric CO 2 during the warm summer months. (author)

Design Research on Three-Phase PWM Rectifier Based on Double Closed Loop Control Technology

Directory of Open Access Journals (Sweden)

Guang Ya LIU

2014-02-01

Full Text Available Based on the high frequency of three-phase voltage source PWM rectifier, this paper established a mathematical model of three phase current inner ring and outer ring voltage, and put forward the setting method of three phase double closed loop control. Finally, it was verified through simulation. The experimental results show that Three-phase output of DC voltage is stable with the operation of regulating systems, the current flowing into the grid tends to be sinusoidal and power factor is close to 1, which greatly reduce the interference of harmonics on the grid, thus improve grid operation.

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

KAUST Repository

Dey, Raju

2016-08-19

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

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

KAUST Repository

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

2016-01-01

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

Interaction of ring dark solitons with ring impurities in Bose-Einstein condensates

International Nuclear Information System (INIS)

Xue Jukui

2005-01-01

The interaction of ring dark solitons/vortexes with the ring-shaped repulsive and attractive impurities in two-dimensional Bose-Einstein condensates is investigated numerically. Very rich interaction phenomena are obtained, i.e., not only the interaction between the ring soliton and the impurity, but also the interaction between vortexes and the impurity. The interaction characters, i.e., snaking of ring soliton, quasitrapping or reflection of ring soliton and vortexes by the impurity, strongly depend on initial ring soliton velocity, impurity strength, initial position of ring soliton and impurity. The numerical results also reveal that ring dark solitons/vortexes can be trapped and dragged by an adiabatically moving attractive ring impurity

Fundamental Design Principles of Linear Collider Damping Rings, with an Application to CLIC

CERN Document Server

Potier, J P

2000-01-01

Damping Rings for Linear Colliders have to produce very small normalised emittances at a high repetition rate. A previous paper presented analytical expressions for the equilibrium emittance of an arc cell as a function of the deflection angle per dipole. In addition, an expression for the lattice parameters providing the minimum emittance, and a strategy to stay close to this, were proposed. This analytical approach is extended to the detailed design of Damping Rings, taking into account the straight sections and the damping wigglers. Complete rings, including wiggler and injection insections, were modelled with the MAD [1] program, and their performance was found to be in good agreement with the analytical calculation. With such an approach it is shown that a Damping Ring corresponding to the Compact Linear Collider (CLIC) parameters at 0.5 and 1 TeV centre-of-mass energy, and tunable for two different sets of emittance and injection repetition rate, can be designed using the same ring layout.

Design of low energy ring(s)

CERN Document Server

Lachaize, Antoine

During the last two years, several upgrades of the initial baseline scenario were studied with the aim of increasing the average intensity of ion beams in the accelerator chain of the Beta Beam complex. This is the reason why the Rapid Cycling Synchrotron (RCS) specifications were reconsidered many times [1], [2], [3].General considerations on the optical design were presented at the Beta Beam Task Meetings held at CERN and at Saclay in 2005 [4]. More detailed beam optics studies were performed during the next months. Lattices, RF system parameters, multi-turn injection scheme, fast extraction, closed orbit correction and chromaticity correction systems were proposed for different versions of the RCS [5], [6], [7].Finally, the RCS specifications have stabilized in November 2006 after the fourth Beta Beam Task Meeting when it was decided to fix the maximum magnetic rigidity of ion beams to 14.47 T.m (3.5 GeV equivalent proton energy) and to adopt a ring physical radius of 40 m in order to facilitate injectio...

Characterization of the International Linear Collider damping ring optics

Science.gov (United States)

Shanks, J.; Rubin, D. L.; Sagan, D.

2014-10-01

A method is presented for characterizing the emittance dilution and dynamic aperture for an arbitrary closed lattice that includes guide field magnet errors, multipole errors and misalignments. This method, developed and tested at the Cornell Electron Storage Ring Test Accelerator (CesrTA), has been applied to the damping ring lattice for the International Linear Collider (ILC). The effectiveness of beam based emittance tuning is limited by beam position monitor (BPM) measurement errors, number of corrector magnets and their placement, and correction algorithm. The specifications for damping ring magnet alignment, multipole errors, number of BPMs, and precision in BPM measurements are shown to be consistent with the required emittances and dynamic aperture. The methodology is then used to determine the minimum number of position monitors that is required to achieve the emittance targets, and how that minimum depends on the location of the BPMs. Similarly, the maximum tolerable multipole errors are evaluated. Finally, the robustness of each BPM configuration with respect to random failures is explored.

Development and status of superconducting SR-ring

International Nuclear Information System (INIS)

Toyota, Eijiro; Tomimasu, Takio.

1991-01-01

Recently, attention has been paid to synchrotron radiation as a powerful tool for material science research, and for the most advanced research, stronger beam is sought for, therefore, large scale synchrotron radiation source facilities are going to be constructed. In contrast with the move toward large scale like this, effort is exerted to reduce the size by using superconductivity and to utilize for industries. Especially Japan precedes most in this field, and has already succeeded in the beam generation. This move to reduce size and pursue economic efficiency is noteworthy as that of supplementing the trend to large scale on the other hand, and its outline is explained. Synchrotron radiation means the strong beam emitted in tangential direction when the electrons or positrons moving at the velocity close to the velocity of light are bent in a magnetic field. The device which stably generates synchrotron radiation is an electron storage ring. The features of synchrotron radiation are explained. The history of synchrotron radiation research, the trend of development of superconducting synchrotron radiation ring, the actual examples of superconducting SR rings and their problems are described. (K.I.)

Storage Rings

International Nuclear Information System (INIS)

Fischer, W.

2010-01-01

Storage rings are circular machines that store particle beams at a constant energy. Beams are stored in rings without acceleration for a number of reasons (Tab. 1). Storage rings are used in high-energy, nuclear, atomic, and molecular physics, as well as for experiments in chemistry, material and life sciences. Parameters for storage rings such as particle species, energy, beam intensity, beam size, and store time vary widely depending on the application. The beam must be injected into a storage ring but may not be extracted (Fig. 1). Accelerator rings such as synchrotrons are used as storage rings before and after acceleration. Particles stored in rings include electrons and positrons; muons; protons and anti-protons; neutrons; light and heavy, positive and negative, atomic ions of various charge states; molecular and cluster ions, and neutral polar molecules. Spin polarized beams of electrons, positrons, and protons were stored. The kinetic energy of the stored particles ranges from 10 -6 eV to 3.5 x 10 12 eV (LHC, 7 x 10 12 eV planned), the number of stored particles from one (ESR) to 1015 (ISR). To store beam in rings requires bending (dipoles) and transverse focusing (quadrupoles). Higher order multipoles are used to correct chromatic aberrations, to suppress instabilities, and to compensate for nonlinear field errors of dipoles and quadrupoles. Magnetic multipole functions can be combined in magnets. Beams are stored bunched with radio frequency systems, and unbunched. The magnetic lattice and radio frequency system are designed to ensure the stability of transverse and longitudinal motion. New technologies allow for better storage rings. With strong focusing the beam pipe dimensions became much smaller than previously possible. For a given circumference superconducting magnets make higher energies possible, and superconducting radio frequency systems allow for efficient replenishment of synchrotron radiation losses of large current electron or positron beams

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

KAUST Repository

Pump, Eva

2015-11-09

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

Discrete breathers for a discrete nonlinear Schrödinger ring coupled to a central site.

Science.gov (United States)

Jason, Peter; Johansson, Magnus

2016-01-01

We examine the existence and properties of certain discrete breathers for a discrete nonlinear Schrödinger model where all but one site are placed in a ring and coupled to the additional central site. The discrete breathers we focus on are stationary solutions mainly localized on one or a few of the ring sites and possibly also the central site. By numerical methods, we trace out and study the continuous families the discrete breathers belong to. Our main result is the discovery of a split bifurcation at a critical value of the coupling between neighboring ring sites. Below this critical value, families form closed loops in a certain parameter space, implying that discrete breathers with and without central-site occupation belong to the same family. Above the split bifurcation the families split up into several separate ones, which bifurcate with solutions with constant ring amplitudes. For symmetry reasons, the families have different properties below the split bifurcation for even and odd numbers of sites. It is also determined under which conditions the discrete breathers are linearly stable. The dynamics of some simpler initial conditions that approximate the discrete breathers are also studied and the parameter regimes where the dynamics remain localized close to the initially excited ring site are related to the linear stability of the exact discrete breathers.

Opening a spiropyran ring by way of an exciplex intermediate.

Science.gov (United States)

Benniston, Andrew C; Harriman, Anthony; Howell, Sarah L; Li, Peiyi; Lydon, Donocadh P

2007-02-02

A molecular dyad has been synthesized in which the main chromophore is a 1,4-diethynylated benzene residue terminated with pyrene moieties, this latter unit acting as a single chromophore. A spiropyran group has been condensed to the central phenylene ring so as to position a weak electron donor close to the pyrene unit. Illumination of the pyrene-based chromophore leads to formation of a fluorescent exciplex in polar solvents but pyrene-like fluorescence is observed in nonpolar solvents. The exciplex has a lifetime of a few nanoseconds and undergoes intersystem crossing to the pyrene-like triplet state with low efficiency. Attaching a 4-nitrobenzene group to the open end of the spiropyran unit creates a new route for decay of the exciplex whereby the triplet state of the spiropyran is formed. Nonradiative decay of this latter species results in ring opening to form the corresponding merocyanine species. Rate constants for the various steps have been obtained from time-resolved fluorescence spectroscopy carried out over a modest temperature range. Under visible light illumination, the merocyanine form reverts to the original spiropyran geometry so that the cycle is closed. Energy transfer from the pyrene chromophore to the merocyanine unit leads to an increased rate of ring closure and serves to push the steady-state composition in favor of the spiropyran form.

Synthesis of naturally occurring iminosugars from D-fructose by the use of a zinc-mediated fragmentation reaction

DEFF Research Database (Denmark)

Lauritsen, Anne; Madsen, Robert

2006-01-01

A short synthesis of 1,4-dideoxy-1,4-imino-D-arabinitol (DAB) and a formal synthesis of australine are described. In both cases, D-fructose is employed as the starting material and converted into a protected methyl 6-deoxy-6-iodo-furanoside. Zinc-mediated fragmentation produces an unsaturated...... ketone which serves as a key building block for both syntheses. Ozonolysis, reductive amination with benzylamine and deprotection affordfs 1,4-dideoxy-1,4-imino-D-arabinitol in only 7 steps and 11% overall yield from D-fructose. Alternatively, reductive amination with homoallylamine, ring......-closing metathesis and protecting group manipulations give rise to an intermediate which can be converted into australine in 3 steps. The intermediate is prepared by two different strategies both of which use a total of 9 steps. The first strategy utilizes benzyl ethers for protection of fructose while the second...

Rings in drugs.

Science.gov (United States)

Taylor, Richard D; MacCoss, Malcolm; Lawson, Alastair D G

2014-07-24

We have analyzed the rings, ring systems, and frameworks in drugs listed in the FDA Orange Book to understand the frequency, timelines, molecular property space, and the application of these rings in different therapeutic areas and target classes. This analysis shows that there are only 351 ring systems and 1197 frameworks in drugs that came onto the market before 2013. Furthermore, on average six new ring systems enter drug space each year and approximately 28% of new drugs contain a new ring system. Moreover, it is very unusual for a drug to contain more than one new ring system and the majority of the most frequently used ring systems (83%) were first used in drugs developed prior to 1983. These observations give insight into the chemical novelty of drugs and potentially efficient ways to assess compound libraries and develop compounds from hit identification to lead optimization and beyond.

A Saturn Ring Observer Mission Using Multi-Mission Radioisotope Power Systems

International Nuclear Information System (INIS)

Abelson, Robert D.; Spilker, Thomas R.; Shirley, James H.

2006-01-01

Saturn remains one of the most fascinating planets within the solar system. To better understand the complex ring structure of this planet, a conceptual Saturn Ring Observer (SRO) mission is presented that would spend one year in close proximity to Saturn's A and B rings, and perform detailed observations and measurements of the ring particles and electric and magnetic fields. The primary objective of the mission would be to understand ring dynamics, including the microphysics of individual particles and small scale (meters to a few kilometers) phenomena such as particle agglomeration behavior. This would be accomplished by multispectral imaging of the rings at multiple key locations within the A and B rings, and by ring-particle imaging at an unprecedented resolution of 0.5 cm/pixel. The SRO spacecraft would use a Venus-Earth-Earth-Jupiter Gravity Assist (VEEJGA) and be aerocaptured into Saturn orbit using an advanced aeroshell design to minimize propellant mass. Once in orbit, the SRO would stand off from the ring plane 1 to 1.4 km using chemical thrusters to provide short propulsive maneuvers four times per revolution, effectively causing the SRO vehicle to 'hop' above the ring plane. The conceptual SRO spacecraft would be enabled by the use of a new generation of multi-mission Radioisotope Power Systems (RPSs) currently being developed by NASA and DOE. These RPSs include the Multi-Mission Radioisotope Thermoelectric Generator (MMRTG) and Stirling Radioisotope Generator (SRG). The RPSs would generate all necessary electrical power (≥330 We at beginning of life) during the 10-year cruise and 1-year science mission (∼11 years total). The RPS heat would be used to maintain the vehicle's operating and survival temperatures, minimizing the need for electrical heaters. Such a mission could potentially launch in the 2015-2020 timeframe, with operations at Saturn commencing in approximately 2030

Dissociative recombination and excitation in ion storage rings

International Nuclear Information System (INIS)

Larsson, Mats

2000-01-01

The application of ion storage rings to the study of electron-molecular ion interaction has led to an experimental breakthrough. The development since the first experiments with molecular ions in storage rings about seven years ago, which in themselves represented a big leap forward, has been striking, and was impossible to envision at the outset. The development has been driven by advances in accelerator physics, detector technology, challenging applications in astrophysics and atmospheric physics, and by a close interplay with theory. Despite the remarkable progress, many important questions remain unanswered. For example, even for someone with a good knowledge of molecular physics it may come as a surprise that it is far from understood how the simplest polyatomic molecule H 3 + recombines with electrons, and it remains an experimental controversy at what rate it recombines

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

Science.gov (United States)

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

2008-01-01

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

Parametric instability of spinning elastic rings excited by fluctuating space-fixed stiffnesses

Science.gov (United States)

Liu, Chunguang; Cooley, Christopher G.; Parker, Robert G.

2017-07-01

This study investigates the vibration of rotating elastic rings that are dynamically excited by an arbitrary number of space-fixed discrete stiffnesses with periodically fluctuating stiffnesses. The rotating, elastic ring is modeled using thin-ring theory with radial and tangential deformations. Primary and combination instability regions are determined in closed-form using the method of multiple scales. The ratio of peak-to-peak fluctuation to average discrete stiffness is used as the perturbation parameter, so the resulting perturbation analysis is not limited to small mean values of discrete stiffnesses. The natural frequencies and vibration modes are determined by discretizing the governing equations using Galerkin's method. Results are demonstrated for compliant gear applications. The perturbation results are validated by direct numerical integration of the equations of motion and Floquet theory. The bandwidths of the instability regions correlate with the fractional strain energy stored in the discrete stiffnesses. For rings with multiple discrete stiffnesses, the phase differences between them can eliminate large amplitude response under certain conditions.

First turn beam correction for the Advanced Photon Source storage ring

International Nuclear Information System (INIS)

Qian, Y.; Crosbie, E.; Teng, L.

1991-01-01

A procedure was developed for precise realignment of the quadrupoles in a synchrotron radiation storage ring which can substantially ease the required precision of the initial survey. The procedure consists of first using the injected beam to obtain a closed orbit which is centered on the beam position monitors by the correction dipoles. The strengths of the correction dipoles then give the required fine-adjustment of the quadrupole positions. In this paper the authors discuss only the algorithm for obtaining the closed orbit

White Ring; White ring

Energy Technology Data Exchange (ETDEWEB)

Aoki, H.; Yuzawa, H. [Nikken Sekkei Ltd., Osaka (Japan)

1998-01-05

White Ring is a citizen`s gymnasium used for figure skating and short track speed skating games of 18th Winter Olympic Games in 1998. White Ring is composed of a main-arena and a sub-arena. For the main-arena with an area 41mtimes66m, an ice link can be made by disengaging the potable floor and by flowing brine in the bridged polystyrene pipes embedded in the concrete floor. Due to the fortunate groundwater in this site, well water is used for the outside air treatment energy in 63% during heating and in 35% during cooling. Ammonia is used as a cooling medium for refrigerating facility. For the heating of audience area in the large space, heat load from the outside is reduced by enhancing the heat insulation performance of the roof of arena. The audience seats are locally heated using heaters. For the White Ring, high quality environment is realized for games through various functions of the large-scale roof of the large space. Success of the big event was expected. 15 figs., 4 tabs.

Strings, vortex rings, and modes of instability

Directory of Open Access Journals (Sweden)

Steven S. Gubser

2015-03-01

Full Text Available We treat string propagation and interaction in the presence of a background Neveu–Schwarz three-form field strength, suitable for describing vortex rings in a superfluid or low-viscosity normal fluid. A circular vortex ring exhibits instabilities which have been recognized for many years, but whose precise boundaries we determine for the first time analytically in the small core limit. Two circular vortices colliding head-on exhibit stronger instabilities which cause splitting into many small vortices at late times. We provide an approximate analytic treatment of these instabilities and show that the most unstable wavelength is parametrically larger than a dynamically generated length scale which in many hydrodynamic systems is close to the cutoff. We also summarize how the string construction we discuss can be derived from the Gross–Pitaevskii Lagrangian, and also how it compares to the action for giant gravitons.

Token Ring Project

Directory of Open Access Journals (Sweden)

Adela Ionescu

2007-01-01

Full Text Available Ring topology is a simple configuration used to connect processes that communicate among themselves. A number of network standards such as token ring, token bus, and FDDI are based on the ring connectivity. This article will develop an implementation of a ring of processes that communicate among themselves via pipe links. The processes are nodes in the ring. Each process reads from its standard input and writes in its standard output. N-1 process redirects the its standard output to a standard input of the process through a pipe. When the ring-structure is designed, the project can be extended to simulate networks or to implement algorithms for mutual exclusion

Tracheal ceramic rings for tracheomalacia: a review after 17 years.

Science.gov (United States)

Göbel, Gyula; Karaiskaki, Niki; Gerlinger, Imre; Mann, Wolf J

2007-10-01

Despite different support techniques, the surgical management of tracheomalacia is still a challenging problem. Satisfactory results after internal stenting are above 80%, whereas, when performing external stenting using biocompatible ceramic rings, results are reported at over 90%. The purpose of this study was to examine the efficiency of surgical treatment in patients with segmentary tracheomalacia using external ceramic ring grafts. In this retrospective study, we collected data from 12 patients who underwent surgery during the last 17 years for symptomatic segmentary tracheomalacia by use of biocompatible aluminum-oxide ceramic rings. All except one patient had undergone previous tracheostomy, six had a history of long-term intubation, two had previous trauma, and two patients had previous cancer treatment including radiotherapy. One of the patients still had an existing tracheostoma, which was closed when a ceramic ring was implanted. Tracheal wall collapse with pseudoglottis formation or flattened anterior-posterior tracheal diameter was documented with fiberoscopy at rest, and both pre- and postoperative airway resistance measurements were performed in all 12 patients using a spirometer. After malacic segments were found to be expandable using rigid tracheoscopy while the patient was under general anesthesia, preparation of the trachea was performed using a midline vertical incision in the neck. Subsequently, the malacic trachea was expanded by placing and suturing proper-sized ceramic ring(s) around it. In all patients, surgical expansion of the malacic segment using ceramic rings was successfully carried out without major complications while inspiratory stridor was resolved. Airway resistance decreased significantly from an average of 0.62 to 0.385 kPascal. Although the results of applying internal tracheal stents are encouraging, complications such as stent migration, granulation tissue and fistula formation, and mucociliary transport arrest are possible

Analysis of oil consumption in cylinder of diesel engine for optimization of piston rings

Science.gov (United States)

Zhang, Junhong; Zhang, Guichang; He, Zhenpeng; Lin, Jiewei; Liu, Hai

2013-01-01

The performance and particulate emission of a diesel engine are affected by the consumption of lubricating oil. Most studies on oil consumption mechanism of the cylinder have been done by using the experimental method, however they are very costly. Therefore, it is very necessary to study oil consumption mechanism of the cylinder and obtain the accurate results by the calculation method. Firstly, four main modes of lubricating oil consumption in cylinder are analyzed and then the oil consumption rate under common working conditions are calculated for the four modes based on an engine. Then, the factors that affect the lubricating oil consumption such as working conditions, the second ring closed gap, the elastic force of the piston rings are also investigated for the four modes. The calculation results show that most of the lubricating oil is consumed by evaporation on the liner surface. Besides, there are three other findings: (1) The oil evaporation from the liner is determined by the working condition of an engine; (2) The increase of the ring closed gap reduces the oil blow through the top ring end gap but increases blow-by; (3) With the increase of the elastic force of the ring, both the left oil film thickness and the oil throw-off at the top ring decrease. The oil scraping of the piston top edge is consequently reduced while the friction loss between the rings and the liner increases. A neural network prediction model of the lubricating oil consumption in cylinder is established based on the BP neural network theory, and then the model is trained and validated. The main piston rings parameters which affect the oil consumption are optimized by using the BP neural network prediction model and the prediction accuracy of this BP neural network is within 8%, which is acceptable for normal engineering applications. The oil consumption is also measured experimentally. The relative errors of the calculated and experimental values are less than 10%, verifying the

Semi-algebraic function rings and reflectors of partially ordered rings

CERN Document Server

Schwartz, Niels

1999-01-01

The book lays algebraic foundations for real geometry through a systematic investigation of partially ordered rings of semi-algebraic functions. Real spectra serve as primary geometric objects, the maps between them are determined by rings of functions associated with the spectra. The many different possible choices for these rings of functions are studied via reflections of partially ordered rings. Readers should feel comfortable using basic algebraic and categorical concepts. As motivational background some familiarity with real geometry will be helpful. The book aims at researchers and graduate students with an interest in real algebra and geometry, ordered algebraic structures, topology and rings of continuous functions.

Size filtering effect in vertical stacks of In(Ga)As/GaAs self-assembled quantum rings

International Nuclear Information System (INIS)

Ouerghui, W.; Melliti, A.; Maaref, M.A.; Martinez-Pastor, J.; Gomis, J.; Granados, D.; Garcia, J.M.

2006-01-01

We present a systematic study of closely In(Ga)As/InAs quantum rings (QRs) grown by molecular beam epitaxy (MBE). Photoluminescence (PL) experiments show a strong filtering effect in the ring being stacked and simultaneous linewidth narrowing for the appropriate layer thickness (thinner thickness). If the spacer thickness is further reduced, a strong coupling between the nanostructures is produced and the signal shifts to low energy

Rotating ring-ring electrode theory and experiment

NARCIS (Netherlands)

Kuiken, H.K.; Bakkers, E.P.A.M.; Ligthart, H.; Kellyb, J.J.

2000-01-01

A model is presented for the rotating ring-ring electrode. Although the electrode is defined by four characteristic lengths, it is shown that the collection efficiency depends on only two dimensionless parameters. A simple relationship between these and the corresponding parameters for the rotating

Optimization of the geometrical stability in square ring laser gyroscopes

International Nuclear Information System (INIS)

Santagata, R; Beghi, A; Cuccato, D; Belfi, J; Beverini, N; Virgilio, A Di; Ortolan, A; Porzio, A; Solimeno, S

2015-01-01

Ultra-sensitive ring laser gyroscopes are regarded as potential detectors of the general relativistic frame-dragging effect due to the rotation of the Earth. Our project for this goal is called GINGER (gyroscopes in general relativity), and consists of a ground-based triaxial array of ring lasers aimed at measuring the rotation rate of the Earth with an accuracy of 10 −14 rad s −1 . Such an ambitious goal is now within reach, as large-area ring lasers are very close to the required sensitivity and stability. However, demanding constraints on the geometrical stability of the optical path of the laser inside the ring cavity are required. Thus, we have begun a detailed study of the geometry of an optical cavity in order to find a control strategy for its geometry that could meet the specifications of the GINGER project. As the cavity perimeter has a stationary point for the square configuration, we identify a set of transformations on the mirror positions that allows us to adjust the laser beam steering to the shape of a square. We show that the geometrical stability of a square cavity strongly increases by implementing a suitable system to measure the mirror distances, and that the geometry stabilization can be achieved by measuring the absolute lengths of the two diagonals and the perimeter of the ring. (paper)

Kayser-Fleischer Rings

Science.gov (United States)

... Support Contacts Lab Tracker/Copper Calculator Stories Programs & Research ... About Everything you need to know about Wilson Disease Kayser-Fleischer Rings Definition Kayser-Fleischer Ring: Clinical sign. Brownish-yellow ring visible around the corneo- ...

Planetary Rings

Science.gov (United States)

Nicholson, P. D.

2001-11-01

A revolution in the studies in planetary rings studies occurred in the period 1977--1981, with the serendipitous discovery of the narrow, dark rings of Uranus, the first Voyager images of the tenuous jovian ring system, and the many spectacular images returned during the twin Voyager flybys of Saturn. In subsequent years, ground-based stellar occultations, HST observations, and the Voyager flybys of Uranus (1986) and Neptune (1989), as well as a handful of Galileo images, provided much additional information. Along with the completely unsuspected wealth of detail these observations revealed came an unwelcome problem: are the rings ancient or are we privileged to live at a special time in history? The answer to this still-vexing question may lie in the complex gravitational interactions recent studies have revealed between the rings and their retinues of attendant satellites. Among the four known ring systems, we see elegant examples of Lindblad and corotation resonances (first invoked in the context of galactic disks), electromagnetic resonances, spiral density waves and bending waves, narrow ringlets which exhibit internal modes due to collective instabilities, sharp-edged gaps maintained via tidal torques from embedded moonlets, and tenuous dust belts created by meteoroid impact onto parent bodies. Perhaps most puzzling is Saturn's multi-stranded, clumpy F ring, which continues to defy a simple explanation 20 years after it was first glimpsed in grainy images taken by Pioneer 11. Voyager and HST images reveal a complex, probably chaotic, dynamical interaction between unseen parent bodies within this ring and its two shepherd satellites, Pandora and Prometheus. The work described here reflects contributions by Joe Burns, Jeff Cuzzi, Luke Dones, Dick French, Peter Goldreich, Colleen McGhee, Carolyn Porco, Mark Showalter, and Bruno Sicardy, as well as those of the author. This research has been supported by NASA's Planetary Geology and Geophysics program and the

Borgring: the discovery of a Viking Age ring fortress

DEFF Research Database (Denmark)

Goodchild, Helen; Holm, Nanna; Sindbæk, Søren Michael

2017-01-01

-type ring fortress. Borgring is the first such monument to be found in Denmark in over six decades, and provides an opportunity to investigate a type-site of Viking Age military organisation and conflict. The authors argue that Borgring complements a varied group of fortification structures in late Viking...... Age Denmark, part of a military network close to contemporaneous European ideas of military kingship and defence....

Beam-beam diagnostics from closed-orbit distortion

International Nuclear Information System (INIS)

Furman, M.; Chin, Y.H.; Eden, J.; Kozanecki, W.; Tennyson, J.; Ziemann, V.

1992-07-01

We study the applicability of beam-beam deflection techniques as a tuning tool for asymmetric B factories, focusing on PEP-II as an example. Assuming that the closed orbits of the two beams are separated vertically at the interaction point by a local orbit bump that is nominally closed, we calculate the residual beam orbit distortions due to the beam-beam interaction. Difference orbit measurements, performed at points conveniently distant from the interaction point (IP), provide distinct signatures that can be used to maintain the beams in collision and perform detailed optical diagnostics at the IP. A proposal to test this method experimentally at the TRISTAN ring is briefly discussed

Flow dynamics in distillation columns packed with Dixon rings as used in isotope separation

International Nuclear Information System (INIS)

Gilath, C.; Cohen, H.; Wolf, D.

1977-01-01

Packed distillation columns are common in isotope separation. The pressure drop serves as an indication for the hydrodynamic state of the column. Models were formulated for flow and pressure drop dynamics in packed distillation columns. These models were confirmed on columns packed with Dixon rings and operated with water for separation of oxygen isotopes. Liquid holdup displacement is very important in isotope separation practice. Experiments proved that distillation columns packed with Dixon rings exhibit a behaviour close to plug flow. (author)

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

Directory of Open Access Journals (Sweden)

Laia Arnedo

2017-03-01

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

Preparation for electron ring - plasma ring merging experiments in RECE-MERGE

International Nuclear Information System (INIS)

Taggart, D.; Sekiguchi, A.; Fleischmann, H.H.

1986-01-01

The formation of a mixed-CT using relativistic electron rings and gun-produced plasma rings by MERGE-ing them axially is simulated. This process is similar to the axial stacking of relativistic electron rings in RECE-Christa. The results of their first plasm production experiment are reported here. After study of the gun-produced plasma's properties is completed, the gun will be mounted at the downstream end of the vacuum tank and the source of relativistic electron rings will be at the upstream end. The two rings, formed at opposite ends of the tank, will be translated axially and merged

Exploiting Confinement Effects to Tune Selectivity in Cyclooctane Metathesis

KAUST Repository

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

2017-01-01

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

Gold Nanoparticles with Externally Controlled, Reversible Shifts of Local Surface Plasmon Resonance Bands

Science.gov (United States)

Yavuz, Mustafa S.; Jensen, Gary C.; Penaloza, David P.; Seery, Thomas A. P.; Pendergraph, Samuel A.; Rusling, James F.; Sotzing, Gregory A.

2010-01-01

We have achieved reversible tunability of local surface plasmon resonance in conjugated polymer functionalized gold nanoparticles. This property was facilitated by the preparation of 3,4-ethylenedioxythiophene (EDOT) containing polynorbornene brushes on gold nanoparticles via surface-initiated ring-opening metathesis polymerization. Reversible tuning of the surface plasmon band was achieved by electrochemically switching the EDOT polymer between its reduced and oxidized states. PMID:19839619

A general harmonic spin matching formalism for the suppression of depolarisation caused by closed orbit distortion in electron storage rings

International Nuclear Information System (INIS)

Barber, D.P.; Mais, H.; Ripken, G.; Rossmanith, R.

1985-03-01

We present a general formalism for correcting perturbations to the equilibrium sspin axis in electron storage rings due to the orbit errors so that depolarizing effects due to machine misalignments can be controlled. The method proposed is suitable for rings containing e.g. solenoids, skew quadrupoles and vertical bends and since it is based on a SLIM-like representation of the orbital and spin motion it can be conveniently realized as a straight forward extension to that program. (orig.)

Colliding and merging galaxies. II. S0 galaxies with polar rings

International Nuclear Information System (INIS)

Schweizer, F.; Whitmore, B.D.; Rubin, V.C.

1983-01-01

We first present a detailed optical study of A0136-0801, a 16 1/2 -mag ''spindle'' galaxy girdled by a ring of gas, dust, and young stars. The spindle is a normal S0 disk seen nearly edge-on, as shown by its photometric profile and fast rotation (v/sub rot//sigma/sub v/ = 2.2); a prolate structure seems to be ruled out. The surrounding ring runs over the poles of this S0 disk and serves as a probe of the vertical potential. The ring motions suggest that a massive halo extends far beyond the S0 disk (out to 3R 25 ) and that this halo is more nearly spherical than flat. We then list 22 related galaxies and derive that a few percent of all field S0's possess near-polar rings or disks. We suggest that these structures are due to a second event, most likely the transfer of mass from a companion galaxy during a close encounter and occasionally also the merger of a companion. Although accretion occurs presumably at random angles, polar rings are favored statistically because of their slow differential precession and consequent longevity. Alternate evolutionary schemes are also discussed. Finally, we suggest that M82 may be forming a polar ring from former M81 material, and predict that the ''tilted bulge'' of UGC 7576 is an S0 disk seen nearly edge-on

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

KAUST Repository

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

2013-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Doledec, G.

1999-10-05

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

Ring faults and ring dikes around the Orientale basin on the Moon.

Science.gov (United States)

Andrews-Hanna, Jeffrey C; Head, James W; Johnson, Brandon; Keane, James T; Kiefer, Walter S; McGovern, Patrick J; Neumann, Gregory A; Wieczorek, Mark A; Zuber, Maria T

2018-08-01

The Orientale basin is the youngest and best-preserved multiring impact basin on the Moon, having experienced only modest modification by subsequent impacts and volcanism. Orientale is often treated as the type example of a multiring basin, with three prominent rings outside of the inner depression: the Inner Rook Montes, the Outer Rook Montes, and the Cordillera. Here we use gravity data from NASA's Gravity Recovery and Interior Laboratory (GRAIL) mission to reveal the subsurface structure of Orientale and its ring system. Gradients of the gravity data reveal a continuous ring dike intruded into the Outer Rook along the plane of the fault associated with the ring scarp. The volume of this ring dike is ~18 times greater than the volume of all extrusive mare deposits associated with the basin. The gravity gradient signature of the Cordillera ring indicates an offset along the fault across a shallow density interface, interpreted to be the base of the low-density ejecta blanket. Both gravity gradients and crustal thickness models indicate that the edge of the central cavity is shifted inward relative to the equivalent Inner Rook ring at the surface. Models of the deep basin structure show inflections along the crust-mantle interface at both the Outer Rook and Cordillera rings, indicating that the basin ring faults extend from the surface to at least the base of the crust. Fault dips range from 13-22° for the Cordillera fault in the northeastern quadrant, to 90° for the Outer Rook in the northwestern quadrant. The fault dips for both outer rings are lowest in the northeast, possibly due to the effects of either the direction of projectile motion or regional gradients in pre-impact crustal thickness. Similar ring dikes and ring faults are observed around the majority of lunar basins.

Groups, rings, modules

CERN Document Server

Auslander, Maurice

2014-01-01

This classic monograph is geared toward advanced undergraduates and graduate students. The treatment presupposes some familiarity with sets, groups, rings, and vector spaces. The four-part approach begins with examinations of sets and maps, monoids and groups, categories, and rings. The second part explores unique factorization domains, general module theory, semisimple rings and modules, and Artinian rings. Part three's topics include localization and tensor products, principal ideal domains, and applications of fundamental theorem. The fourth and final part covers algebraic field extensions

Saturn's Rings Edge-on

Science.gov (United States)

1995-01-01

In one of nature's most dramatic examples of 'now-you see-them, now-you-don't', NASA's Hubble Space Telescope captured Saturn on May 22, 1995 as the planet's magnificent ring system turned edge-on. This ring-plane crossing occurs approximately every 15 years when the Earth passes through Saturn's ring plane.For comparison, the top picture was taken by Hubble on December 1, 1994 and shows the rings in a more familiar configuration for Earth observers.The bottom picture was taken shortly before the ring plane crossing. The rings do not disappear completely because the edge of the rings reflects sunlight. The dark band across the middle of Saturn is the shadow of the rings cast on the planet (the Sun is almost 3 degrees above the ring plane.) The bright stripe directly above the ring shadow is caused by sunlight reflected off the rings onto Saturn's atmosphere. Two of Saturn's icy moons are visible as tiny starlike objects in or near the ring plane. They are, from left to right, Tethys (slightly above the ring plane) and Dione.This observation will be used to determine the time of ring-plane crossing and the thickness of the main rings and to search for as yet undiscovered satellites. Knowledge of the exact time of ring-plane crossing will lead to an improved determination of the rate at which Saturn 'wobbles' about its axis (polar precession).Both pictures were taken with Hubble's Wide Field Planetary Camera 2. The top image was taken in visible light. Saturn's disk appears different in the bottom image because a narrowband filter (which only lets through light that is not absorbed by methane gas in Saturn's atmosphere) was used to reduce the bright glare of the planet. Though Saturn is approximately 900 million miles away, Hubble can see details as small as 450 miles across.The Wide Field/Planetary Camera 2 was developed by the Jet Propulsion Laboratory and managed by the Goddard Spaced Flight Center for NASA's Office of Space Science.This image and other images and

The Rotating Ring-Ring Electrode. Theory and Experiment

NARCIS (Netherlands)

Kuiken, H.K.; Bakkers, E.P.A.M.; Ligthart, H.; Kelly, J.J.

2000-01-01

A model is presented for the rotating ring-ring electrode. Although the electrode is defined by four characteristic lengths, it is shown that the collection efficiency depends on only two dimensionless parameters. A simple relationship between these and the corresponding parameters for the rotating

Impact of storage rings on elementary particle physics

International Nuclear Information System (INIS)

Trilling, G.H.

1979-03-01

It is well known that new experimental discoveries often closely follow the development of new technology. There is hardly a better example of this than the close coupling between new discoveries in the frontiers of elementary particle physics and the development of the art and science of making high-energy accelerators. It is almost twenty-five years since the construction of the Bevatron made possible the discovery of the antiproton; and, since that time, knowledge and understanding of particle physics has made enormous strides in step with new developments in both the accelerator and the detector arts. An attempt is made to document how intimately many of the recent advances have been tied to the success in the development of storage rings and colliding beams

The vacuum interlock system for the CELSIUS ring

International Nuclear Information System (INIS)

Gajewski, K.

1990-01-01

A vacuum interlock system has been designed and built for the CELSIUS storage ring. The ultrahigh-vacuum system of CELSIUS has a design pressure of 10 -11 mbar. This is achieved by using vacuum-fired stainless-steel chambers, baking the whole ring to 300degC and running some 50 sputter ion and titanium sublimation pumps. The turbopumps, combined with roughing pumps, are used during the pump-down and the bake-out. The pressure is monitored by Penning vacuum gauges. There is a number of programmable pressure thresholds set to trigger various events (like closing the sector valves, disabling the bake-out, etc.). The interlock system is based on the Mitsubishi programmable logic controller (PLC). An IBM PC is used as an operator's console. The operation and performance of the system is described. On the basis of present experience an upgrading of the system is suggested. (orig.)

Wear Analysis of Top Piston Ring to Reduce Top Ring Reversal Bore Wear

Directory of Open Access Journals (Sweden)

P. Ilanthirayan

2017-12-01

Full Text Available The piston rings are the most important part in engine which controls the lubricating oil consumption and blowby of the gases. The lubricating film of oil is provided to seal of gases towards crankcase and also to give smooth friction free translatory motion between rings and liner. Of the three rings present top ring is more crucial as it does the main work of restricting gases downwards the crankcase. Boundary lubrication is present at the Top dead centre (TDC and Bottom dead centre (BDC of the liner surface. In addition to this, top ring is exposed to high temperature gases which makes the oil present near the top ring to get evaporated and decreasing its viscosity, making metal-metal contact most of the time. Due to this at TDC, excess wear happens on the liner which is termed as Top ring reversal bore wear. The wear rate depends upon many parameters such as lubrication condition, viscosity index, contact type, normal forces acting on ring, geometry of ring face, surface roughness, material property. The present work explores the wear depth for different geometries of barrel ring using Finite Element model with the help of Archard wear law and the same is validated through experimentation. The study reveals that Asymmetric barrel rings have less contact pressure which in turn reduces the wear at Top dead centre.

Forming mechanism and avoiding measures of blue-ring on electronic beam welding sample after water corrosion

International Nuclear Information System (INIS)

Ren Defang; Luo Xiandian; Tong Shenxiu; Guo Xulin; Peng Haiqing

2001-01-01

After water corrosion in compliance with ASTM G2, the blue ring appears on the nuclear fuel rod samples of AFA 2G welded by using a Big Chamber Electron Beam Welder made in Russia. The characteristics, appearance, chemical composition, microstructure of b lue ring a nd some condition test are described. The mechanism of forming blue ring may be depicted as following: welding metal vapor and the splash produced by secondary and scatter electrons on metal clamp and gun body deposit in the area between HAZ and substrate because of the water cooling down effects on the clamp; these deposits, after water corrosion, appears as blue ring on the fuel rod surface. Avoiding measure is that the side of the clamp closing to weld seal is chamfered, while making the welding chamber cleaner

PREFACE: Special section on vortex rings Special section on vortex rings

Science.gov (United States)

Fukumoto, Yasuhide

2009-10-01

This special section of Fluid Dynamics Research includes five articles on vortex rings in both classical and quantum fluids. The leading scientists of the field describe the trends in and the state-of-the-art development of experiments, theories and numerical simulations of vortex rings. The year 2008 was the 150th anniversary of 'vortex motion' since Hermann von Helmholtz opened up this field. In 1858, Helmholtz published a paper in Crelle's Journal which put forward the concept of 'vorticity' and made the first analysis of vortex motion. Fluid mechanics before that was limited to irrotational motion. In the absence of vorticity, the motion of an incompressible homogeneous fluid is virtually equivalent to a rigid-body motion in the sense that the fluid motion is determined once the boundary configuration is specified. Helmholtz proved, among other things, that, without viscosity, a vortex line is frozen into the fluid. This Helmholtz's law immediately implies the preservation of knots and links of vortex lines and its implication is enormous. One of the major trends of fluid mechanics since the latter half of the 20th century is to clarify the topological meaning of Helmholtz's law and to exploit it to develop theoretical and numerical methods to find the solutions of the Euler equations and to develop experimental techniques to gain an insight into fluid motion. Vortex rings are prominent coherent structures in a variety of fluid motions from the microscopic scale, through human and mesoscale to astrophysical scales, and have attracted people's interest. The late professor Philip G Saffman (1981) emphasized the significance of studies on vortex rings. One particular motion exemplifies the whole range of problems of vortex motion and is also a commonly known phenomenon, namely the vortex ring or smoke ring. Vortex rings are easily produced by dropping drops of one liquid into another, or by puffing fluid out of a hole, or by exhaling smoke if one has the skill

6D “Garren” snake cooler and ring cooler for µ{sup ±} cooling of a muon collider

Energy Technology Data Exchange (ETDEWEB)

Ding, X., E-mail: xding@bnl.gov [UCLA, Los Angeles, CA 90095 (United States); Berg, J.S. [Brookhaven National Laboratory, Upton, NY 11973 (United States); Cline, D. [UCLA, Los Angeles, CA 90095 (United States); Garren, Al [Particle Beam Lasers, Inc., Northridge, CA 91324 (United States); Kirk, H.G. [Brookhaven National Laboratory, Upton, NY 11973 (United States)

2014-12-21

Six dimensional cooling of large emittance µ{sup +} and µ{sup −} beams is required in order to obtain the desired luminosity for a muon collider. In our previous study, we demonstrated that a 6D “Garren” ring cooler using both dipoles and solenoids in four 90{sup 0} achromatic arcs can give substantial cooling in all six phase space dimensions. In this paper, we describe the injection/extraction requirements of this four-sided ring. We also present the performance of an achromat-based 6D “Garren” snake cooler. The achromatic design permits the design to easily switch between a closed ring and a snaking geometry on injection or extraction from the ring.

Vortex rings

CERN Document Server

Akhmetov, D G

2009-01-01

This text on vortex rings covers their theoretical foundation, systematic investigations, and practical applications such as the extinction of fires at gushing oil wells. It pays special attention to the formation and motion of turbulent vortex rings.

Towards the Fourier limit on the super-ACO Storage Ring FEL

International Nuclear Information System (INIS)

Couprie, M.E.; De Ninno, G.; Moneron, G.; Nutarelli, D.; Hirsch, M.; Garzella, D.; Renault, E.; Roux, R.; Thomas, C.

2001-01-01

Systematic studies on the Free Electron Laser (FEL) line and micropulse have been performed on the Super-ACO storage ring FEL with a monochromator and a double-sweep streak camera under various conditions of operation (detuning, 'CW' and Q-switched mode). From these data, it appears that the FEL is usually operated very close to the Fourier limit

Towards the Fourier limit on the super-ACO Storage Ring FEL

CERN Document Server

Couprie, Marie Emmanuelle; Garzella, D; Hirsch, M; Moneron, G; Nutarelli, D; Renault, E; Roux, R; Thomas, C

2001-01-01

Systematic studies on the Free Electron Laser (FEL) line and micropulse have been performed on the Super-ACO storage ring FEL with a monochromator and a double-sweep streak camera under various conditions of operation (detuning, 'CW' and Q-switched mode). From these data, it appears that the FEL is usually operated very close to the Fourier limit.

Achievement of ultralow emittance coupling in the Australian Synchrotron storage ring

Directory of Open Access Journals (Sweden)

R. Dowd

2011-01-01

Full Text Available Investigations into producing an electron beam with ultralow vertical emittance have been conducted using the Australian Synchrotron 3 GeV storage ring. A method of tuning the emittance coupling (ϵ_{y}/ϵ_{x} has been developed using a machine model calibrated through the linear optics from closed orbits method. Direct measurements of the beam emittance have not been possible due to diagnostic limitations, however two independent indirect measurements both indicate a vertical emittance of 1.2–1.3 pm rad (ϵ_{y}/ϵ_{x}=0.01%. Other indirect measurements support the validity of these results. This result is the smallest vertical emittance currently achieved in a storage ring.

Multielemental analyses of tree rings by inductively coupled plasma mass spectrometry

International Nuclear Information System (INIS)

Hall, G.S.

1990-01-01

Inductively coupled plasma mass spectrometry (ICP-MS) was evaluated for major, minor, trace, and ultra-trace elemental analyses of individual tree rings. The samples were obtained from an old-growth Douglas fir growing near Mount St. Helens volcano, and from trees at various other North American sites. Eightly percent of elements from Li to U had detection limits in the solid (wood) below 8.0 ng g -1 . Two anomalous peaks occur in Mount St. Helens samples at A.D. 1478 and 1490 that closely correlate with past eruptions of the volcano. These results show that ICP-MS is a rapid and sensitive analytical method for multielemental analyses of individual tree rings. (author) 16 refs.; 2 figs.; 2 tabs

FUZZY RINGS AND ITS PROPERTIES

Directory of Open Access Journals (Sweden)

Karyati Karyati

2017-01-01

  One of algebraic structure that involves a binary operation is a group that is defined  an un empty set (classical with an associative binary operation, it has identity elements and each element has an inverse. In the structure of the group known as the term subgroup, normal subgroup, subgroup and factor group homomorphism and its properties. Classical algebraic structure is developed to algebraic structure fuzzy by the researchers as an example semi group fuzzy and fuzzy group after fuzzy sets is introduced by L. A. Zadeh at 1965. It is inspired of writing about semi group fuzzy and group of fuzzy, a research on the algebraic structure of the ring is held with reviewing ring fuzzy, ideal ring fuzzy, homomorphism ring fuzzy and quotient ring fuzzy with its properties. The results of this study are obtained fuzzy properties of the ring, ring ideal properties fuzzy, properties of fuzzy ring homomorphism and properties of fuzzy quotient ring by utilizing a subset of a subset level  and strong level  as well as image and pre-image homomorphism fuzzy ring.   Keywords: fuzzy ring, subset level, homomorphism fuzzy ring, fuzzy quotient ring

Experimental and histological studies on appearance mechanism of ring enhancement

International Nuclear Information System (INIS)

Takasugi, Shinsuke; Kageyama, Takefumi; Yamashita, Shigeru; Kusaka, Kazumasa; Ueda, Shin

1980-01-01

Intracerebral hematoma was experimentally induced in 26 adult dogs of mixed breed by injecting autologous venous blood into the internal capsule of dogs. CT images and histological findings of these dogs with intracerebral hematoma were compared with time, and causes of changes in contrast enhancement (CE) CT images and CE positive images were discussed pathologically. It was thought that CE-CT positive images of intracerebral hematoma did not show special phenomena which occurred variously according to causes of hematoma, but general phenomena observed in the process of recovery of general intracerebral hematoma. Ring enhancement appeared mostly about 9 days after hematoma formation. There was a close relationship between appearance of ring enhancement and new vascularization which appeared in the process of recovery of hematoma. It was also thought that blood-brain barrier (B.B.B.) such as normal cerebral capillary vessels did not exist because new vascularization had the fine structure similar to muscle type capillary vessels. Ring enhancement might be seen probably because of the accumulation of contrast medium in regions where new vascularization without B.B.B. appeared. (Tsunoda, M.)

Use of Tritium Accelerator Mass Spectrometry for Tree Ring Analysis

Science.gov (United States)

LOVE, ADAM H.; HUNT, JAMES R.; ROBERTS, MARK L.; SOUTHON, JOHN R.; CHIARAPPA - ZUCCA, MARINA L.; DINGLEY, KAREN H.

2010-01-01

Public concerns over the health effects associated with low-level and long-term exposure to tritium released from industrial point sources have generated the demand for better methods to evaluate historical tritium exposure levels for these communities. The cellulose of trees accurately reflects the tritium concentration in the source water and may contain the only historical record of tritium exposure. The tritium activity in the annual rings of a tree was measured using accelerator mass spectrometry to reconstruct historical annual averages of tritium exposure. Milligram-sized samples of the annual tree rings from a Tamarix located at the Nevada Test Site are used for validation of this methodology. The salt cedar was chosen since it had a single source of tritiated water that was well-characterized as it varied over time. The decay-corrected tritium activity of the water in which the salt cedar grew closely agrees with the organically bound tritium activity in its annual rings. This demonstrates that the milligram-sized samples used in tritium accelerator mass spectrometry are suited for reconstructing anthropogenic tritium levels in the environment. PMID:12144257

Ring and peg electrodes for minimally-Invasive and long-term sub-scalp EEG recordings.

Science.gov (United States)

Benovitski, Y B; Lai, A; McGowan, C C; Burns, O; Maxim, V; Nayagam, D A X; Millard, R; Rathbone, G D; le Chevoir, M A; Williams, R A; Grayden, D B; May, C N; Murphy, M; D'Souza, W J; Cook, M J; Williams, C E

2017-09-01

Minimally-invasive approaches are needed for long-term reliable Electroencephalography (EEG) recordings to assist with epilepsy diagnosis, investigation and more naturalistic monitoring. This study compared three methods for long-term implantation of sub-scalp EEG electrodes. Three types of electrodes (disk, ring, and peg) were fabricated from biocompatible materials and implanted under the scalp in five ambulatory ewes for 3months. Disk electrodes were inserted into sub-pericranial pockets. Ring electrodes were tunneled under the scalp. Peg electrodes were inserted into the skull, close to the dura. EEG was continuously monitored wirelessly. High resolution CT imaging, histopathology, and impedance measurements were used to assess the status of the electrodes at the end of the study. EEG amplitude was larger in the peg compared with the disk and ring electrodes (pEEG, mechanical stability, and lower chewing artifact. Whereas, ring electrode arrays tunneled under the scalp enable minimal surgical techniques to be used for implantation and removal. Copyright © 2017 Elsevier B.V. All rights reserved.

Vortex-ring-induced large bubble entrainment during drop impact

KAUST Repository

Thoraval, Marie-Jean

2016-03-29

For a limited set of impact conditions, a drop impacting onto a pool can entrap an air bubble as large as its own size. The subsequent rise and rupture of this large bubble plays an important role in aerosol formation and gas transport at the air-sea interface. The large bubble is formed when the impact crater closes up near the pool surface and is known to occur only for drops that are prolate at impact. Herein we use experiments and numerical simulations to show that a concentrated vortex ring, produced in the neck between the drop and the pool, controls the crater deformations and pinchoff. However, it is not the strongest vortex rings that are responsible for the large bubbles, as they interact too strongly with the pool surface and self-destruct. Rather, it is somewhat weaker vortices that can deform the deeper craters, which manage to pinch off the large bubbles. These observations also explain why the strongest and most penetrating vortex rings emerging from drop impacts are not produced by oblate drops but by more prolate drop shapes, as had been observed in previous experiments.

Natural occupation numbers in two-electron quantum rings.

Science.gov (United States)

Tognetti, Vincent; Loos, Pierre-François

2016-02-07

Natural orbitals (NOs) are central constituents for evaluating correlation energies through efficient approximations. Here, we report the closed-form expression of the NOs of two-electron quantum rings, which are prototypical finite-extension systems and new starting points for the development of exchange-correlation functionals in density functional theory. We also show that the natural occupation numbers for these two-electron paradigms are in general non-vanishing and follow the same power law decay as atomic and molecular two-electron systems.

Natural occupation numbers in two-electron quantum rings

Energy Technology Data Exchange (ETDEWEB)

Tognetti, Vincent, E-mail: vincent.tognetti@univ-rouen.fr [Normandy Univ., COBRA UMR 6014 & FR 3038, Université de Rouen, INSA Rouen, CNRS, 1 rue Tesniére, 76821 Mont Saint Aignan, Cedex (France); Loos, Pierre-François [Research School of Chemistry, Australian National University, Canberra ACT 2601 (Australia)

2016-02-07

Natural orbitals (NOs) are central constituents for evaluating correlation energies through efficient approximations. Here, we report the closed-form expression of the NOs of two-electron quantum rings, which are prototypical finite-extension systems and new starting points for the development of exchange-correlation functionals in density functional theory. We also show that the natural occupation numbers for these two-electron paradigms are in general non-vanishing and follow the same power law decay as atomic and molecular two-electron systems.

Magmatic development of the outer Vøring margin from seismic data

Science.gov (United States)

Breivik, Asbjørn; Faleide, Jan Inge; Mjelde, Rolf; Flueh, Ernst; Murai, Yoshio

2014-09-01

The Vøring Plateau off mid-Norway is a volcanic passive margin, located north of the East Jan Mayen Fracture Zone (EJMFZ). Large volumes of magmatic rocks were emplaced during Early Eocene margin formation. In 2003, an ocean bottom seismometer survey was acquired over the margin. One profile crosses from the Vøring Plateau to the Vøring Spur, a bathymetric high north of the EJMFZ. The P wave data were ray traced into a 2-D crustal velocity model. The velocity structure of the Vøring Spur indicates up to 15 km igneous crustal thickness. Magmatic processes can be estimated by comparing seismic velocity (VP) with igneous thickness (H). This and two other profiles show a positive H-VP correlation at the Vøring Plateau, consistent with elevated mantle temperature at breakup. However, during the first 2 Ma magma production was augmented by a secondary process, possibly small-scale convection. From ˜51.5 Ma excess melting may be caused by elevated mantle temperature alone. Seismic stratigraphy around the Vøring Spur shows that it was created by at least two uplift events, with the main episode close to the Miocene/Pliocene boundary. Low H-VP correlation of the spur is consistent with renewed igneous growth by constant, moderate-degree mantle melting, not related to the breakup magmatism. The admittance function between bathymetry and free-air gravity shows that the high is near local isostatic equilibrium, precluding that compressional flexure at the EJMFZ uplifted the high. We find a proposed Eocene triple junction model for the margin to be inconsistent with observations.

Capturing spiral radial growth of conifers using the superellipse to model tree-ring geometric shape.

Science.gov (United States)

Shi, Pei-Jian; Huang, Jian-Guo; Hui, Cang; Grissino-Mayer, Henri D; Tardif, Jacques C; Zhai, Li-Hong; Wang, Fu-Sheng; Li, Bai-Lian

2015-01-01

Tree-rings are often assumed to approximate a circular shape when estimating forest productivity and carbon dynamics. However, tree rings are rarely, if ever, circular, thereby possibly resulting in under- or over-estimation in forest productivity and carbon sequestration. Given the crucial role played by tree ring data in assessing forest productivity and carbon storage within a context of global change, it is particularly important that mathematical models adequately render cross-sectional area increment derived from tree rings. We modeled the geometric shape of tree rings using the superellipse equation and checked its validation based on the theoretical simulation and six actual cross sections collected from three conifers. We found that the superellipse better describes the geometric shape of tree rings than the circle commonly used. We showed that a spiral growth trend exists on the radial section over time, which might be closely related to spiral grain along the longitudinal axis. The superellipse generally had higher accuracy than the circle in predicting the basal area increment, resulting in an improved estimate for the basal area. The superellipse may allow better assessing forest productivity and carbon storage in terrestrial forest ecosystems.

Closed orbit distortion and the beam-beam interaction

Energy Technology Data Exchange (ETDEWEB)

Furman, M.; Chin, Y.H.; Eden, J. [Lawrence Berkeley Lab., CA (United States); Kozanecki, W. [CEA Centre d`Etudes Nucleaires de Saclay, 91 - Gif-sur-Yvette (France)]|[Stanford Linear Accelerator Center, Menlo Park, CA (United States); Tennyson, J.; Ziemann, V. [Stanford Linear Accelerator Center, Menlo Park, CA (United States)

1992-06-01

We study the applicability of beam-beam deflection techniques as a tuning tool for the SLAC/LBL/LLNL B factory, PEP-II. Assuming that the closed orbits of the two beams are separated vertically at the interaction point by a local orbit bump that is nominally closed, we calculate the residual beam orbit distortions due to the beam-beam interaction. Difference orbit measurements, performed at points conveniently distant from the IP, provide distinct coordinate- or frequency-space signatures that can be used to maintain the beams in collision and perform detailed optical diagnostics at the IP. A proposal to test this method experimentally at the TRISTAN ring is briefly discussed.

Closed orbit distortion and the beam-beam interaction

International Nuclear Information System (INIS)

Furman, M.; Chin, Y.H.; Eden, J.; Kozanecki, W.; Tennyson, J.; Ziemann, V.

1992-01-01

We study the applicability of beam-beam deflection techniques as a tuning tool for the SLAC/LBL/LLNL B factory, PEP-II. Assuming that the closed orbits of the two beams are separated vertically at the interaction point by a local orbit bump that is nominally closed, we calculate the residual beam orbit distortions due to the beam-beam interaction. Difference orbit measurements, performed at points conveniently distant from the IP, provide distinct coordinate- or frequency-space signatures that can be used to maintain the beams in collision and perform detailed optical diagnostics at the IP. A proposal to test this method experimentally at the TRISTAN ring is briefly discussed

A correlation for safety valve blowdown and ring settings

International Nuclear Information System (INIS)

Singh, A.; Shak, D.

1982-01-01

The blowdown of a spring loaded safety valve is defined as the difference between the pressure at which the valve opens and the pressure at which the valve fully closes under certain fluid flow conditions. Generally, the blowdown is expressed in terms of percentage of the opening pressure. An extensive series of tests carried out in the EPRI/PWR Utilities Valve Test Program has shown that the blowdown of safety valves can in general be strongly dependent upon the valve geometry and other parameters such as ring adjustments, spring stiffness, backpressure etc. In the present study, correlations have been developed using the EPRI safety valve test data to predict the expected blowdown as a function of adjustment ring settings for geometrically similar valves under steam discharge conditions. The correlation is validated against two different size Dresser valves

RINGED ACCRETION DISKS: EQUILIBRIUM CONFIGURATIONS

Energy Technology Data Exchange (ETDEWEB)

Pugliese, D.; Stuchlík, Z., E-mail: d.pugliese.physics@gmail.com, E-mail: zdenek.stuchlik@physics.cz [Institute of Physics and Research Centre of Theoretical Physics and Astrophysics, Faculty of Philosophy and Science, Silesian University in Opava, Bezručovo náměstí 13, CZ-74601 Opava (Czech Republic)

2015-12-15

We investigate a model of a ringed accretion disk, made up by several rings rotating around a supermassive Kerr black hole attractor. Each toroid of the ringed disk is governed by the general relativity hydrodynamic Boyer condition of equilibrium configurations of rotating perfect fluids. Properties of the tori can then be determined by an appropriately defined effective potential reflecting the background Kerr geometry and the centrifugal effects. The ringed disks could be created in various regimes during the evolution of matter configurations around supermassive black holes. Therefore, both corotating and counterrotating rings have to be considered as being a constituent of the ringed disk. We provide constraints on the model parameters for the existence and stability of various ringed configurations and discuss occurrence of accretion onto the Kerr black hole and possible launching of jets from the ringed disk. We demonstrate that various ringed disks can be characterized by a maximum number of rings. We present also a perturbation analysis based on evolution of the oscillating components of the ringed disk. The dynamics of the unstable phases of the ringed disk evolution seems to be promising in relation to high-energy phenomena demonstrated in active galactic nuclei.

Stirling engine piston ring

Science.gov (United States)

Howarth, Roy B.

1983-01-01

A piston ring design for a Stirling engine wherein the contact pressure between the piston and the cylinder is maintained at a uniform level, independent of engine conditions through a balancing of the pressure exerted upon the ring's surface and thereby allowing the contact pressure on the ring to be predetermined through the use of a preloaded expander ring.

Physics of quantum rings

International Nuclear Information System (INIS)

Fomin, Vladimir M.

2014-01-01

Presents the new class of materials of quantum rings. Provides an elemental basis for low-cost high-performance devices promising for electronics, optoelectronics, spintronics and quantum information processing. Explains the physical properties of quantum rings to cover a gap in scientific literature. Presents the application of most advanced nanoengineering and nanocharacterization techniques. This book deals with a new class of materials, quantum rings. Innovative recent advances in experimental and theoretical physics of quantum rings are based on the most advanced state-of-the-art fabrication and characterization techniques as well as theoretical methods. The experimental efforts allow to obtain a new class of semiconductor quantum rings formed by capping self-organized quantum dots grown by molecular beam epitaxy. Novel optical and magnetic properties of quantum rings are associated with non-trivial topologies at the nanoscale. An adequate characterization of quantum rings is possible on the basis of modern characterization methods of nanostructures, such as Scanning Tunneling Microscopy. A high level of complexity is demonstrated to be needed for a dedicated theoretical model to adequately represent the specific features of quantum rings. The findings presented in this book contribute to develop low-cost high-performance electronic, spintronic, optoelectronic and information processing devices based on quantum rings.

How does the blue-ringed octopus (Hapalochlaena lunulata) flash its blue rings?

Science.gov (United States)

Mäthger, Lydia M; Bell, George R R; Kuzirian, Alan M; Allen, Justine J; Hanlon, Roger T

2012-11-01

The blue-ringed octopus (Hapalochlaena lunulata), one of the world's most venomous animals, has long captivated and endangered a large audience: children playing at the beach, divers turning over rocks, and biologists researching neurotoxins. These small animals spend much of their time in hiding, showing effective camouflage patterns. When disturbed, the octopus will flash around 60 iridescent blue rings and, when strongly harassed, bite and deliver a neurotoxin that can kill a human. Here, we describe the flashing mechanism and optical properties of these rings. The rings contain physiologically inert multilayer reflectors, arranged to reflect blue-green light in a broad viewing direction. Dark pigmented chromatophores are found beneath and around each ring to enhance contrast. No chromatophores are above the ring; this is unusual for cephalopods, which typically use chromatophores to cover or spectrally modify iridescence. The fast flashes are achieved using muscles under direct neural control. The ring is hidden by contraction of muscles above the iridophores; relaxation of these muscles and contraction of muscles outside the ring expose the iridescence. This mechanism of producing iridescent signals has not previously been reported in cephalopods and we suggest that it is an exceptionally effective way to create a fast and conspicuous warning display.

α-Skew π-McCoy Rings

Directory of Open Access Journals (Sweden)

Areej M. Abduldaim

2013-01-01

Full Text Available As a generalization of α-skew McCoy rings, we introduce the concept of α-skew π-McCoy rings, and we study the relationships with another two new generalizations, α-skew π1-McCoy rings and α-skew π2-McCoy rings, observing the relations with α-skew McCoy rings, π-McCoy rings, α-skew Armendariz rings, π-regular rings, and other kinds of rings. Also, we investigate conditions such that α-skew π1-McCoy rings imply α-skew π-McCoy rings and α-skew π2-McCoy rings. We show that in the case where R is a nonreduced ring, if R is 2-primal, then R is an α-skew π-McCoy ring. And, let R be a weak (α,δ-compatible ring; if R is an α-skew π1-McCoy ring, then R is α-skew π2-McCoy.

Closing the gap

International Nuclear Information System (INIS)

Moxon, Suzanne

1999-01-01

The problem of fish going through turbines at hydroelectric power plants and the growing concern over the survival rate of salmon at the US Army Corps operated Bonneville lock and dam on the Columbia river in the Pacific Northwest is discussed. The protection of the fish, the assessment of the hazards facing fish passing through turbines, the development of a new turbine, and improved turbine efficiency that reduces cavitation, turbulence and shear flow are examined. The closing of the gap between the turbine blades, hub and discharge ring to increase efficiency and reduce the risk to fish, and the development of the minimum gap runner (MGR) are described, and the lower maximum permitted power output of MGR is noted. (UK)

VUV optical ring resonator for Duke storage ring free electron laser

Energy Technology Data Exchange (ETDEWEB)

Park, S.H.; Litvinenko, V.N.; Madey, J.M.J. [Duke Univ., Durham, NC (United States)] [and others

1995-12-31

The conceptual design of the multifaceted-mirror ring resonator for Duke storage ring VUV FEL is presented. The expected performance of the OK-4 FEL with ring resonator is described. We discuss in this paper our plans to study reflectivity of VUV mirrors and their resistivity to soft X-ray spontaneous radiation from OK-4 undulator.

Interaction Region Design for a Ring-Ring LHeC

CERN Document Server

Thompson, L N S; Bernard, N R; Fitterer, M; Holzer, B; Klein, M; Kostka, P

2011-01-01

tively low energy and moderately high intensity provides high luminosity TeV-scale e-p collisions at one of the LHC interaction points, running simultaneously with existing experiments. Two designs are studied; an electron ring situated in the LHC tunnel, and an electron linac. The focus of this paper is on the ring design. Designing an e-p machine presents interesting accelerator physics and design challenges, particularly when considering the interaction region. These include coupled optics, beam separation and unconventional mini-beta focusing schemes. Designs are constrained by an array of interdependent factors, including beam-beam interaction, detector dimensions and acceptance, luminosity and synchrotron radiation. Methods of addressing these complex issues are discussed. The current designs for the LHeC Ring-Ring interaction region and long straight section are presented and discussed, in the context of the project goals and design challenges encountered. Future developments and work are also discusse...

Closed orbit feedback with digital signal processing

International Nuclear Information System (INIS)

Chung, Y.; Kirchman, J.; Lenkszus, F.

1994-01-01

The closed orbit feedback experiment conducted on the SPEAR using the singular value decomposition (SVD) technique and digital signal processing (DSP) is presented. The beam response matrix, defined as beam motion at beam position monitor (BPM) locations per unit kick by corrector magnets, was measured and then analyzed using SVD. Ten BPMs, sixteen correctors, and the eight largest SVD eigenvalues were used for closed orbit correction. The maximum sampling frequency for the closed loop feedback was measured at 37 Hz. Using the proportional and integral (PI) control algorithm with the gains Kp = 3 and K I = 0.05 and the open-loop bandwidth corresponding to 1% of the sampling frequency, a correction bandwidth (-3 dB) of approximately 0.8 Hz was achieved. Time domain measurements showed that the response time of the closed loop feedback system for 1/e decay was approximately 0.25 second. This result implies ∼ 100 Hz correction bandwidth for the planned beam position feedback system for the Advanced Photon Source storage ring with the projected 4-kHz sampling frequency

On Roots of Polynomials and Algebraically Closed Fields

Directory of Open Access Journals (Sweden)

Schwarzweller Christoph

2017-10-01

Full Text Available In this article we further extend the algebraic theory of polynomial rings in Mizar [1, 2, 3]. We deal with roots and multiple roots of polynomials and show that both the real numbers and finite domains are not algebraically closed [5, 7]. We also prove the identity theorem for polynomials and that the number of multiple roots is bounded by the polynomial’s degree [4, 6].

Vertical dispersion produced by random closed orbit distortions and sextupoles

International Nuclear Information System (INIS)

Suzuki, Toshio.

1977-01-01

Vertical dispersion appears even in a machine designed with plane symmetry because of vertical closed orbit distortions, linear coupling and coupling due to sextupoles. This gives rise to several undesirable effects in an electron-positron storage ring such as PEP. Vertical dispersion at the interaction point will increase beam height and reduce luminosity. Vertical dispersion around the ring will modify vertical emittance and partition numbers for synchrotron radiation damping. It will also induce betatron-synchrotron resonance and affect chromaticity correction. Vertical dispersion due to random closed orbit distortions and sextupoles has been studied by Piwinski, and he has indicated that correction of chromaticity and chromatic change of β-function is important. However, he has assumed one error element and evaluated the dispersion at the position of the element. We generalize his argument to a more realistic case and derive more precise criteria for the correction of vertical dispersion. Horizontal dispersion due to perturbations is also studied. Vertical dispersion due to linear coupling is neglected in this note, since it has been studied by other authors. 7 refs

Record of the Solar Activity and of Other Geophysical Phenomenons in Tree Ring

Science.gov (United States)

Rigozo, Nivaor Rodolfo

1999-01-01

Tree ring studies are usually used to determine or verify climatic factors which prevail in a given place or region and may cause tree ring width variations. Few studies are dedicated to the geophysical phenomena which may underlie these tree ring width variations. In order to look for periodicities which may be associated to the solar activity and/or to other geophysical phenomena which may influence tree ring growth, a new interactive image analysis method to measure tree ring width was developed and is presented here. This method makes use of a computer and a high resolution flatbed scanner; a program was also developed in Interactive Data Language (IDL 5.0) to study ring digitized images and transform them into time series. The main advantage of this method is the tree ring image interactive analysis without needing complex and high cost instrumentation. Thirty-nine samples were collected: 12 from Concordia - S. C., 9 from Canela - R. S., 14 from Sao Francisco de Paula - R. S., one from Nova Petropolis - R. S., 2 from Sao Martinho da Serra - R. S. e one from Chile. Fit functions are applied to ring width time series to obtain the best long time range trend (growth rate of every tree) curves and are eliminated through a standardization process that gives the tree ring index time series from which is performed spectral analysis by maximum entropy method and iterative regression. The results obtained show periodicities close to 11 yr, 22 yr Hale solar cycles and 5.5 yr for all sampling locations 52 yr and Gleissberg cycles for Concordia - S. C. and Chile samples. El Nino events were also observed with periods around 4 e 7 yr.

Uniquely Strongly Clean Group Rings

Institute of Scientific and Technical Information of China (English)

WANG XIU-LAN

2012-01-01

A ring R is called clean if every element is the sum of an idempotent and a unit,and R is called uniquely strongly clean (USC for short) if every element is uniquely the sum of an idempotent and a unit that commute.In this article,some conditions on a ring R and a group G such that RG is clean are given.It is also shown that if G is a locally finite group,then the group ring RG is USC if and only if R is USC,and G is a 2-group.The left uniquely exchange group ring,as a middle ring of the uniquely clean ring and the USC ring,does not possess this property,and so does the uniquely exchange group ring.

Influence of ring growth rate on damage development in hot ring rolling

NARCIS (Netherlands)

Wang, C.; Geijselaers, H. J.M.; Omerspahic, E.; Recina, V.; van den Boogaard, A. H.

2015-01-01

As an incremental forming process of bulk metal, ring rolling provides a cost effective process route to manufacture seamless rings. In the production of hot rolled rings, defects such as porosity can sometimes be found in high alloyed steel, manufactured from ingots having macro-segregation. For

Ring rotational speed trend analysis by FEM approach in a Ring Rolling process

Science.gov (United States)

Allegri, G.; Giorleo, L.; Ceretti, E.

2018-05-01

Ring Rolling is an advanced local incremental forming technology to fabricate directly precise seamless ring-shape parts with various dimensions and materials. In this process two different deformations occur in order to reduce the width and the height of a preform hollow ring; as results a diameter expansion is obtained. In order to guarantee a uniform deformation, the preform is forced toward the Driver Roll whose aim is to transmit the rotation to the ring. The ring rotational speed selection is fundamental because the higher is the speed the higher will be the axial symmetry of the deformation process. However, it is important to underline that the rotational speed will affect not only the final ring geometry but also the loads and energy needed to produce it. Despite this importance in industrial environment, usually, a constant value for the Driver Roll angular velocity is set so to result in a decreasing trend law for the ring rotational speed. The main risk due to this approach is not fulfilling the axial symmetric constrain (due to the diameter expansion) and to generate a high localized ring section deformation. In order to improve the knowledge about this topic in the present paper three different ring rotational speed trends (constant, linearly increasing and linearly decreasing) were investigated by FEM approach. Results were compared in terms of geometrical and dimensional analysis, loads and energies required.

Mechanical improvement of metal reinforcement rings for a finite ring-shaped superconducting bulk

Science.gov (United States)

Huang, Chen-Guang; Zhou, You-He

2018-03-01

As a key technique, reinforcement of type-II superconducting bulks with metal rings can efficiently improve their mechanical properties to enhance the maximum trapped field. In this paper, we study the magnetostrictive and fracture behaviors of a finite superconducting ring bulk reinforced by three typical reinforcing structures composed of metal rings during the magnetizing process by means of the minimization of magnetic energy and the finite element method. After a field-dependent critical current density is adopted, the magnetostriction, pinning-induced stress, and crack tip stress intensity factor are calculated considering the demagnetization effects. The results show that the mechanical properties of the ring bulk are strongly dependent on the reinforcing structure and the material and geometrical parameters of the metal rings. Introducing the metal ring can significantly reduce the hoop stress, and the reduction effect by internal reinforcement is much improved relative to external reinforcement. By comparison, bilateral reinforcement seems to be the best candidate structure. Only when the metal rings have particular Young's modulus and radial thickness will they contribute to improve the mechanical properties the most. In addition, if an edge crack is pre-existing in the ring bulk, the presence of metal rings can effectively avoid crack propagation since it reduces the crack tip stress intensity factor by nearly one order of magnitude.

Ring correlations in random networks.

Science.gov (United States)

Sadjadi, Mahdi; Thorpe, M F

2016-12-01

We examine the correlations between rings in random network glasses in two dimensions as a function of their separation. Initially, we use the topological separation (measured by the number of intervening rings), but this leads to pseudo-long-range correlations due to a lack of topological charge neutrality in the shells surrounding a central ring. This effect is associated with the noncircular nature of the shells. It is, therefore, necessary to use the geometrical distance between ring centers. Hence we find a generalization of the Aboav-Weaire law out to larger distances, with the correlations between rings decaying away when two rings are more than about three rings apart.

Simulation of magnetization and levitation properties of arrays of ring-shaped type-II superconductors

Energy Technology Data Exchange (ETDEWEB)

Liu, Jun, E-mail: linxj8686@163.com; Huang, Chenguang; Yong, Huadong; Zhou, Youhe, E-mail: zhouyh@lzu.edu.cn

2017-03-15

Highlights: • A strong magnetic coupling appears if the gap between the superconducting rings is small. • The saturation magnetization of superconducting rings is related to the radial gap but independent of the vertical gap. • The array of rings in a non-uniform field experiences a levitation force, which increases with increasing height or thickness of the rings. - Abstract: This paper presents an analysis of the magnetic and mechanical properties of arrays of superconducting rings arranged in axial, radial, and matrix configurations under different magnetic fields. In terms of the Bean's critical state model and the minimum magnetic energy method, the dependences of the magnetization and levitation behaviors on the geometry, number, and gap of the superconducting rings are obtained. The results show that when the applied field is spatially uniform, the magnetic property of the superconducting array is associated with the gaps between the rings. For the case of small gaps, the entire array becomes not easy to be fully penetrated by the induced currents, and the magnetic field profiles of which are almost the same as ones in a single large ring. If the superconducting array is fully penetrated, its saturation magnetization value is affected by the radial interval and, however, is almost independent of the vertical separation. When the applied field produced by a cylindrical permanent magnet is nonuniform, the superconducting array will be subjected to a levitation force. The levitation force increases monotonically and finally reaches a saturation value with increasing height or thickness of the rings, and such saturation value is closely related to the inner radius of the array.

Alpha - Skew Pi - Armendariz Rings

Directory of Open Access Journals (Sweden)

Areej M Abduldaim

2018-03-01

Full Text Available In this article we introduce a new concept called Alpha-skew Pi-Armendariz rings (Alpha - S Pi - ARas a generalization of the notion of Alpha-skew Armendariz rings.Another important goal behind studying this class of rings is to employ it in order to design a modern algorithm of an identification scheme according to the evolution of using modern algebra in the applications of the field of cryptography.We investigate general properties of this concept and give examples for illustration. Furthermore, this paperstudy the relationship between this concept and some previous notions related to Alpha-skew Armendariz rings. It clearly presents that every weak Alpha-skew Armendariz ring is Alpha-skew Pi-Armendariz (Alpha-S Pi-AR. Also, thisarticle showsthat the concepts of Alpha-skew Armendariz rings and Alpha-skew Pi- Armendariz rings are equivalent in case R is 2-primal and semiprime ring.Moreover, this paper proves for a semicommutative Alpha-compatible ringR that if R[x;Alpha] is nil-Armendariz, thenR is an Alpha-S Pi-AR. In addition, if R is an Alpha - S Pi -AR, 2-primal and semiprime ring, then N(R[x;Alpha]=N(R[x;Alpha]. Finally, we look forwardthat Alpha-skew Pi-Armendariz rings (Alpha-S Pi-ARbe more effect (due to their properties in the field of cryptography than Pi-Armendariz rings, weak Armendariz rings and others.For these properties and characterizations of the introduced concept Alpha-S Pi-AR, we aspire to design a novel algorithm of an identification scheme.

Coupling correction using closed orbit measurements

International Nuclear Information System (INIS)

Safranek, J.; Krinsky, S.

1994-01-01

The authors describe a coupling correction scheme they have developed and used to successfully reduce the vertical emittance of the NSLS X-Ray ring by a factor of 6 to below 2 A. This gives a vertical to horizontal emittance ratio of less than 0.2%. They find the strengths of 17 skew quadrupoles to simultaneously minimize the vertical dispersion and the coupling. As a measure of coupling they utilize the shift in vertical closed orbit resulting from a change in strength of a horizontal steering magnet. Experimental measurements confirm the reduced emittance

Feasibility of beam crystallization in a cooler storage ring

Directory of Open Access Journals (Sweden)

Yosuke Yuri

2005-11-01

Full Text Available It has been known theoretically that a charged-particle beam circulating in a storage ring exhibits an “ordered” configuration at the space-charge limit. Such an ultimate state of matter is called a crystalline beam whose emittance is ideally equal to zero except for quantum noise. This paper discusses how close one can come to various ordered states by employing currently available accelerator technologies. The dynamic nature of ultracold beams and conditions required for crystallization are briefly reviewed. Molecular dynamics simulations are performed to study the feasibility of this unique phenomenon, considering practical situations in general cooling experiments. It is pointed out that several essential obstacles must be overcome to reach a three-dimensional crystalline state in a storage ring. Doppler laser cooling of ion beams is also numerically simulated to explore the possibility of beam crystallization in an existing machine.

Plasma-ring, fast-opening switch

International Nuclear Information System (INIS)

Hartman, C.W.; Eddleman, J.; Hammer, J.H.

1986-01-01

The authors discuss a fast-opening switch concept based on magnetically confined plasma rings, PROS (for Plasma Ring Opening Switch). In PROS, the plasma ring, confined by Bθ /sub and B/poloidal /sub fields of a compact torus, provide a low mass, localized conduction path between coaxial electrodes. To operate the switch, driver current is passed across the electrodes through the ring, storing inductive energy in external inductance and between the electrodes on the driver side of the ring. The ring is accelerated away from the driver by the field of the driver current and passes over a load gap transferring the current to the load. The authors distinguish two configurations in PROS, straight PROS where the electrodes are coaxial cylinders, and cone PROS with conical electrodes. In straight PROS ring acceleration takes place during the inductive store period as in foil switches, but with the localized ring providing the current path. Increased performance is predicted for the cone PROS (see figure) which employs compression of the ring in the cone during the inductive store period. Here, the B/θ /sub field of the driver forces the ring towards the apex of the cone but the force is in near balance with the opposing component of the radial equilibrium force of the ring along the cone. As a result, the ring undergoes a slow, quasistatic compression limited only by resistive decay of the ring field. Slow compression allows inductive storage with low-power drivers (homopoloar, magneto cumulative generators, high C-low V capacitor banks, etc.). Near the apex of the cone, near peak compression, the ring is allowed to enter a straight coaxial section where, because of low-mass, it rapidly accelerates to high velocity and crosses the load gap

A study of channeling patterns from strained Si1-xGex/Si bilayers close to (011) axes

NARCIS (Netherlands)

Breese, MBH; Smulders, PJM

This paper characterises the angular intensity distribution of MeV protons transmitted through strained Si1-xGex/Si bilayers close to the axis. The ring-like intensity distribution produced by the front layer axis when it is aligned close to the beam direction is projected either towards or away

Fusion Rings for Quantum Groups

DEFF Research Database (Denmark)

Andersen, Henning Haahr; Stroppel, Catharina

2014-01-01

We study the fusion rings of tilting modules for a quantum group at a root of unity modulo the tensor ideal of negligible tilting modules. We identify them in type A with the combinatorial rings from Korff, C., Stroppel, C.: The sl(ˆn)k-WZNW fusion ring: a combinato-rial construction...... and a realisation as quotient of quantum cohomology. Adv. Math. 225(1), 200–268, (2010) and give a similar description of the sp2n-fusion ring in terms of non-commutative symmetric functions. Moreover we give a presentation of all fusion rings in classical types as quotients of polynomial rings. Finally we also...... compute the fusion rings for type G2....

The LSU Electron Storage Ring, the first commercially-built storage ring

International Nuclear Information System (INIS)

Sah, R.

1990-01-01

The Brobeck Division of Maxwell Laboratories, Inc., is building the first industrially-produced storage ring. It will be located at Louisiana State University (LSU) at the Center for Advanced Microstructures and Devices (CAMD) in Baton Rouge. The purpose of this electron storage ring is to provide intense beams of x-rays to advance the state-of-the-art in lithography and to permit research in a broad area. This facility consists of a 1.2 GeV, 400 mA electron storage ring with a 200 MeV linac injector. The magnet lattice is a Chasman-Green design (double-bend achromat), and the ring circumference is 55.2 meters. There are four 3.0 meter, dispersion-free straight sections, one for injection, one for the 500 MHz RF cavity, and two for possible future insertion devices. The storge ring construction project is in the detailed-design stage, and many systems are in the initial stages of fabrication. 4 figs., 1 tab

Fusion rings and fusion ideals

DEFF Research Database (Denmark)

Andersen, Troels Bak

by the so-called fusion ideals. The fusion rings of Wess-Zumino-Witten models have been widely studied and are well understood in terms of precise combinatorial descriptions and explicit generating sets of the fusion ideals. They also appear in another, more general, setting via tilting modules for quantum......This dissertation investigates fusion rings, which are Grothendieck groups of rigid, monoidal, semisimple, abelian categories. Special interest is in rational fusion rings, i.e., fusion rings which admit a finite basis, for as commutative rings they may be presented as quotients of polynomial rings...

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

KAUST Repository

Holcombe, Thomas W.

2009-10-14

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

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

KAUST Repository

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

2009-01-01

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

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

Institute of Scientific and Technical Information of China (English)

YUE Xuyi; QIU Xiaolong; QING Fengling

2009-01-01

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

Evaluation of ring impedance of the Photon Factory storage ring

International Nuclear Information System (INIS)

Kiuchi, T.; Izawa, M.; Tokumoto, S.; Hori, Y.; Sakanaka, S.; Kobayashi, M.; Kobayakawa, H.

1992-05-01

The loss parameters of the ducts in the Photon Factory (PF) storage ring were evaluated using the wire method and the code TBCI. Both the measurement and the calculation were done for a different bunch length (σ) ranging from 23 to 80 ps. The PF ring impedance was estimated to be |Z/n|=3.2 Ω using the broadband impedance model. The major contribution to the impedance comes from the bellows and the gate valve sections. Improvements of these components will lower the ring impedance by half. (author)

[right] - DUST RING AROUND STAR OFFERS NEW CLUES INTO PLANET FORMATION

Science.gov (United States)

2002-01-01

A NASA Hubble Space Telescope false-color near infrared image of a novel type of structure seen in space - a dust ring around a star. Superficially resembling Saturn's rings -- but on a vastly larger scale -- the 'hula-hoop' around the star called HR 4796A offers new clues into the possible presence of young planets. The near-infrared light reflecting off the dust ring is about 1,000 times fainter than the illuminating central star. Astronomers used a coronagraphic camera on Hubble's Near Infrared Camera and Multi-Object Spectrometer (NICMOS), specifically designed to enable observations of very faint and low surface brightness objects in the close proximity to bright stars. Even with the coronagraph, the glare from HR 4796A overwhelms the much-fainter ring at distances less than about 4 billion miles (inside the blacked-out circle, centered on the star). Hubble's crisp view was able to resolve the ring, seen at lower resolution at longer wavelengths, in ground-based thermal infrared images, as a disk with some degree of central clearing. The ring has an angular radius of 1.05 arc seconds, equivalent to the apparent size of a dime seen more than 4 miles away. Unlike the extensive disks of dust seen around other young stars, the HR 4796A dust ring, 6.5 billion miles from the star, is tightly confined within a relatively narrow zone less than 17 Astronomical Units wide. An Astronomical Unit is the distance from the Earth to the Sun). For comparison, the ring width is approximately equal to the distance separating the orbits of Mars and Uranus in our own Solar System. All dust rings, whether around stars or planets, can only stay intact by some mechanism confining the dust, likely the gravitational tug of unseen planets. The image was taken on March 15, 1998, centered at a near infrared wavelength of 1.1 microns. The false-color corresponds to the ring's brightness (yellow is bright, purple is faint). The ring, which is undoubtedly circular, appears elliptical since

Tree Rings: Timekeepers of the Past.

Science.gov (United States)

Phipps, R. L.; McGowan, J.

One of a series of general interest publications on science issues, this booklet describes the uses of tree rings in historical and biological recordkeeping. Separate sections cover the following topics: dating of tree rings, dating with tree rings, tree ring formation, tree ring identification, sample collections, tree ring cross dating, tree…

Signatures of topological phase transitions in mesoscopic superconducting rings

International Nuclear Information System (INIS)

Pientka, Falko; Romito, Alessandro; Duckheim, Mathias; Oppen, Felix von; Oreg, Yuval

2013-01-01

We investigate Josephson currents in mesoscopic rings with a weak link which are in or near a topological superconducting phase. As a paradigmatic example, we consider the Kitaev model of a spinless p-wave superconductor in one dimension, emphasizing how this model emerges from more realistic settings based on semiconductor nanowires. We show that the flux periodicity of the Josephson current provides signatures of the topological phase transition and the emergence of Majorana fermions (MF) situated on both sides of the weak link even when fermion parity is not a good quantum number. In large rings, the MF hybridize only across the weak link. In this case, the Josephson current is h/e periodic in the flux threading the loop when fermion parity is a good quantum number but reverts to the more conventional h/2e periodicity in the presence of fermion-parity changing relaxation processes. In mesoscopic rings, the MF also hybridize through their overlap in the interior of the superconducting ring. We find that in the topological superconducting phase, this gives rise to an h/e-periodic contribution even when fermion parity is not conserved and that this contribution exhibits a peak near the topological phase transition. This signature of the topological phase transition is robust to the effects of disorder. As a byproduct, we find that close to the topological phase transition, disorder drives the system deeper into the topological phase. This is in stark contrast to the known behavior far from the phase transition, where disorder tends to suppress the topological phase. (paper)

Some Aspects of Ring Theory

CERN Document Server

Herstein, IN

2011-01-01

S. Amitsur: Associative rings with identities.- I.N. Herstein: Topics in ring theory.- N. Jacobson: Representation theory of Jordan algebras.- I. Kaplansky: The theory of homological dimension.- D. Buchsbaum: Complexes in local ring theory.- P.H. Cohn: Two topics in ring theory.- A.W. Goldie: Non-commutative localisation.

Improving the Accuracy of Laplacian Estimation with Novel Variable Inter-Ring Distances Concentric Ring Electrodes

Directory of Open Access Journals (Sweden)

Oleksandr Makeyev

2016-06-01

Full Text Available Noninvasive concentric ring electrodes are a promising alternative to conventional disc electrodes. Currently, the superiority of tripolar concentric ring electrodes over disc electrodes, in particular, in accuracy of Laplacian estimation, has been demonstrated in a range of applications. In our recent work, we have shown that accuracy of Laplacian estimation can be improved with multipolar concentric ring electrodes using a general approach to estimation of the Laplacian for an (n + 1-polar electrode with n rings using the (4n + 1-point method for n ≥ 2. This paper takes the next step toward further improving the Laplacian estimate by proposing novel variable inter-ring distances concentric ring electrodes. Derived using a modified (4n + 1-point method, linearly increasing and decreasing inter-ring distances tripolar (n = 2 and quadripolar (n = 3 electrode configurations are compared to their constant inter-ring distances counterparts. Finite element method modeling and analytic results are consistent and suggest that increasing inter-ring distances electrode configurations may decrease the truncation error resulting in more accurate Laplacian estimates compared to respective constant inter-ring distances configurations. For currently used tripolar electrode configuration, the truncation error may be decreased more than two-fold, while for the quadripolar configuration more than a six-fold decrease is expected.

Improving the Accuracy of Laplacian Estimation with Novel Variable Inter-Ring Distances Concentric Ring Electrodes

Science.gov (United States)

Makeyev, Oleksandr; Besio, Walter G.

2016-01-01

Noninvasive concentric ring electrodes are a promising alternative to conventional disc electrodes. Currently, the superiority of tripolar concentric ring electrodes over disc electrodes, in particular, in accuracy of Laplacian estimation, has been demonstrated in a range of applications. In our recent work, we have shown that accuracy of Laplacian estimation can be improved with multipolar concentric ring electrodes using a general approach to estimation of the Laplacian for an (n + 1)-polar electrode with n rings using the (4n + 1)-point method for n ≥ 2. This paper takes the next step toward further improving the Laplacian estimate by proposing novel variable inter-ring distances concentric ring electrodes. Derived using a modified (4n + 1)-point method, linearly increasing and decreasing inter-ring distances tripolar (n = 2) and quadripolar (n = 3) electrode configurations are compared to their constant inter-ring distances counterparts. Finite element method modeling and analytic results are consistent and suggest that increasing inter-ring distances electrode configurations may decrease the truncation error resulting in more accurate Laplacian estimates compared to respective constant inter-ring distances configurations. For currently used tripolar electrode configuration, the truncation error may be decreased more than two-fold, while for the quadripolar configuration more than a six-fold decrease is expected. PMID:27294933

An Efficient Code-Based Threshold Ring Signature Scheme with a Leader-Participant Model

Directory of Open Access Journals (Sweden)

Guomin Zhou

2017-01-01

Full Text Available Digital signature schemes with additional properties have broad applications, such as in protecting the identity of signers allowing a signer to anonymously sign a message in a group of signers (also known as a ring. While these number-theoretic problems are still secure at the time of this research, the situation could change with advances in quantum computing. There is a pressing need to design PKC schemes that are secure against quantum attacks. In this paper, we propose a novel code-based threshold ring signature scheme with a leader-participant model. A leader is appointed, who chooses some shared parameters for other signers to participate in the signing process. This leader-participant model enhances the performance because every participant including the leader could execute the decoding algorithm (as a part of signing process upon receiving the shared parameters from the leader. The time complexity of our scheme is close to Courtois et al.’s (2001 scheme. The latter is often used as a basis to construct other types of code-based signature schemes. Moreover, as a threshold ring signature scheme, our scheme is as efficient as the normal code-based ring signature.

Radar imaging of Saturn's rings

Science.gov (United States)

Nicholson, Philip D.; French, Richard G.; Campbell, Donald B.; Margot, Jean-Luc; Nolan, Michael C.; Black, Gregory J.; Salo, Heikki J.

2005-09-01

We present delay-Doppler images of Saturn's rings based on radar observations made at Arecibo Observatory between 1999 and 2003, at a wavelength of 12.6 cm and at ring opening angles of 20.1°⩽|B|⩽26.7°. The average radar cross-section of the A ring is ˜77% relative to that of the B ring, while a stringent upper limit of 3% is placed on the cross-section of the C ring and 9% on that of the Cassini Division. These results are consistent with those obtained by Ostro et al. [1982, Icarus 49, 367-381] from radar observations at |B|=21.4°, but provide higher resolution maps of the rings' reflectivity profile. The average cross-section of the A and B rings, normalized by their projected unblocked area, is found to have decreased from 1.25±0.31 to 0.74±0.19 as the rings have opened up, while the circular polarization ratio has increased from 0.64±0.06 to 0.77±0.06. The steep decrease in cross-section is at variance with previous radar measurements [Ostro et al., 1980, Icarus 41, 381-388], and neither this nor the polarization variations are easily understood within the framework of either classical, many-particle-thick or monolayer ring models. One possible explanation involves vertical size segregation in the rings, whereby observations at larger elevation angles which see deeper into the rings preferentially see the larger particles concentrated near the rings' mid-plane. These larger particles may be less reflective and/or rougher and thus more depolarizing than the smaller ones. Images from all four years show a strong m=2 azimuthal asymmetry in the reflectivity of the A ring, with an amplitude of ±20% and minima at longitudes of 67±4° and 247±4° from the sub-Earth point. We attribute the asymmetry to the presence of gravitational wakes in the A ring as invoked by Colombo et al. [1976, Nature 264, 344-345] to explain the similar asymmetry long seen at optical wavelengths. A simple radiative transfer model suggests that the enhancement of the azimuthal

Study of improvement in 1st ring`s gas-seal; Top ring no gas seal seino kojo no kento

Energy Technology Data Exchange (ETDEWEB)

Ando, H; Tateishi, Y; Fujimura, K; Hitosugi, H [Nippon Piston Ring Co. Ltd., Tokyo (Japan)

1997-10-01

The authors studied the effect of an angle of 1st ring twist on the amount of blow-by concerning higher speed/higher output engines for motorcycles. As a result, the authors found the twist made the ring restrained in a ring groove of piston , and confirmed its suitable range for blow-by. By means of the developed optimization method, the authors have achieved significant reduction in blow-by at high engine speed. 1 ref., 9 figs., 2 tabs.

Asteroseismic effects in close binary stars

Science.gov (United States)

Springer, Ofer M.; Shaviv, Nir J.

2013-09-01

Turbulent processes in the convective envelopes of the Sun and stars have been shown to be a source of internal acoustic excitations. In single stars, acoustic waves having frequencies below a certain cut-off frequency propagate nearly adiabatically and are effectively trapped below the photosphere where they are internally reflected. This reflection essentially occurs where the local wavelength becomes comparable to the pressure scale height. In close binary stars, the sound speed is a constant on equipotentials, while the pressure scale height, which depends on the local effective gravity, varies on equipotentials and may be much greater near the inner Lagrangian point (L1). As a result, waves reaching the vicinity of L1 may propagate unimpeded into low-density regions, where they tend to dissipate quickly due to non-linear and radiative effects. We study the three-dimensional propagation and enhanced damping of such waves inside a set of close binary stellar models using a WKB approximation of the acoustic field. We find that these waves can have much higher damping rates in close binaries, compared to their non-binary counterparts. We also find that the relative distribution of acoustic energy density at the visible surface of close binaries develops a ring-like feature at specific acoustic frequencies and binary separations.

The role of substorms in the formation of the ring current

International Nuclear Information System (INIS)

Rostoker, G.

1996-01-01

It has long been recognized that the formation of the terrestrial ring current is accompanied by strong substorm expansive phase activity in the auroral oval. While large amplitude substorm activity seems to be a prerequisite for ring current formation to take place, it has long been puzzling as to why some large amplitude substorm activity in the auroral oval is not associated with significant ring current development. In this paper I shall outline the basis for the renovated boundary layer dynamics model of magnetospheric substorms showing how the onset of the substorm expansive phase can be associated with a sudden decrease in shielding space charge in the region of the near-Earth plasma sheet threaded by Region 2 field-aligned currents. I shall suggest that an episode of sufficiently large southward IMF lasting over a sufficiently lengthy period of time can lead to a sequence of substorm expansive phases, each one being initiated closer to the Earth than the previous one. Each expansive phase is attributed to a sudden decrease in radially localized cross-tail current (viz. a decrease in shielding space charge) and with each onset the inner edge of the plasma sheet moves inward. The inductive electric field associated with each crosstail current decrease is responsible for the acceleration of already energetic particles to energies of significance for ring current formation. Only when the inner edge of the crosstail current is sufficiently close to the Earth do the acceleration processes associated with substorm onset produce a long lived ring current. copyright 1996 American Institute of Physics

Viscosity of ring polymer melts

KAUST Repository

Pasquino, Rossana

2013-10-15

We have measured the linear rheology of critically purified ring polyisoprenes, polystyrenes, and polyethyleneoxides of different molar masses. The ratio of the zero-shear viscosities of linear polymer melts η0,linear to their ring counterparts η0,ring at isofrictional conditions is discussed as a function of the number of entanglements Z. In the unentangled regime η0,linear/η 0,ring is virtually constant, consistent with the earlier data, atomistic simulations, and the theoretical expectation η0,linear/ η0,ring = 2. In the entanglement regime, the Z-dependence of ring viscosity is much weaker than that of linear polymers, in qualitative agreement with predictions from scaling theory and simulations. The power-law extracted from the available experimental data in the rather limited range 1 < Z < 20, η0,linear/η0,ring ∼ Z 1.2±0.3, is weaker than the scaling prediction (η0,linear/η0,ring ∼ Z 1.6±0.3) and the simulations (η0,linear/ η0,ring ∼ Z2.0±0.3). Nevertheless, the present collection of state-of-the-art experimental data unambiguously demonstrates that rings exhibit a universal trend clearly departing from that of their linear counterparts, and hence it represents a major step toward resolving a 30-year-old problem. © 2013 American Chemical Society.

Viscosity of ring polymer melts

KAUST Repository

Pasquino, Rossana; Vasilakopoulos, Thodoris C.; Jeong, Youncheol; Lee, Hyojoon; Rogers, Simon A.; Sakellariou, Georgios; Allgaier, Jü rgen B.; Takano, Atsushi; Brá s, Ana Rita E; Chang, Taihyun; Gooß en, Sebastian; Pyckhout-Hintzen, Wim; Wischnewski, Andreas; Hadjichristidis, Nikolaos; Richter, Dieter R.; Rubinstein, Michael H.; Vlassopoulos, Dimitris

2013-01-01

We have measured the linear rheology of critically purified ring polyisoprenes, polystyrenes, and polyethyleneoxides of different molar masses. The ratio of the zero-shear viscosities of linear polymer melts η0,linear to their ring counterparts η0,ring at isofrictional conditions is discussed as a function of the number of entanglements Z. In the unentangled regime η0,linear/η 0,ring is virtually constant, consistent with the earlier data, atomistic simulations, and the theoretical expectation η0,linear/ η0,ring = 2. In the entanglement regime, the Z-dependence of ring viscosity is much weaker than that of linear polymers, in qualitative agreement with predictions from scaling theory and simulations. The power-law extracted from the available experimental data in the rather limited range 1 < Z < 20, η0,linear/η0,ring ∼ Z 1.2±0.3, is weaker than the scaling prediction (η0,linear/η0,ring ∼ Z 1.6±0.3) and the simulations (η0,linear/ η0,ring ∼ Z2.0±0.3). Nevertheless, the present collection of state-of-the-art experimental data unambiguously demonstrates that rings exhibit a universal trend clearly departing from that of their linear counterparts, and hence it represents a major step toward resolving a 30-year-old problem. © 2013 American Chemical Society.

New Way of Characterizing the State of the Ring Current

Science.gov (United States)

Wolf, R.; Bao, S.; Gkioulidou, M.; Yang, J.; Toffoletto, F.

2017-12-01

The flux tube entropy S is invariant in ideal MHD and is a good way to characterize the degree to which a closed flux tube is loaded with particle energy. Flux tube entropy generally increases with increasing geocentric distance. A flux tube that is injected from the plasma sheet into the ring current tends to be a bubble that has a lower S value than typical plasma sheet flux tubes, and it tends to penetrate to a position where the surroundings matches its S. From this point of view, a good way to characterize the state of the ring current is through the function dF/dS, which specifies how much magnetic flux is occupied by tubes with different degrees of loading. By displaying dF/dS curves before and during storm main phases simulated with the RCM-E code, we determine that, in the model, the injection of the stormtime ring current consists of replacing pre-storm low-S flux tubes with tubes from the plasma sheet that have a certain limited range of S, which is well below typical plasma-sheet values. We also display dF/dS curves for passes by the Van Allen Probes before and during storm main phases, and compare with the RCM-E-derived curves, to gain insight into the nature of the flux tubes that are injected to form the real storm-time ring current.

Læring og refleksion

DEFF Research Database (Denmark)

Wahlgren, B.; Rattleff, Pernille; Høyrup, S.

State of the art inden for forskning om læring på arbejdspladsen samt gennemgang af læringsteori og refleksionsbegrebet hos Dewey, Dreyfus, Schön, Argyris, Kolb, Jarvis, Mezirow og Brookfield. Afsluttes med diskussion af syntetiseret model for læring på arbejdspladsen.......State of the art inden for forskning om læring på arbejdspladsen samt gennemgang af læringsteori og refleksionsbegrebet hos Dewey, Dreyfus, Schön, Argyris, Kolb, Jarvis, Mezirow og Brookfield. Afsluttes med diskussion af syntetiseret model for læring på arbejdspladsen....

Birth Control Ring

Science.gov (United States)

... Health Food & Fitness Diseases & Conditions Infections Drugs & Alcohol School & Jobs Sports Expert Answers (Q&A) Staying Safe Videos for Educators Search English Español Birth Control Ring KidsHealth / For Teens / Birth Control Ring What's ...

From coffee ring to spherulites ring of poly(ethylene oxide) film from drying droplet

Science.gov (United States)

Hu, Yinchun; Zhang, Xuerong; Qiu, Maibo; Wei, Yan; Zhou, Qiong; Huang, Di

2018-03-01

We discuss how the "spherulites ring" morphology and "coffee ring" profile of PEO film formed by the drying droplet at glass substrate with different heating rate. Upon increasing the heating rate of substrate, it is found that deposited PEO film from drying droplet shows the unusually observed "coffee ring" profile and "spherulites ring" morphology. The main mechanism for this phenomenon is proposed to be an enhanced Marangoni convection which is induced by the increased solute concentration gradient and reduced viscous force above 70 °C. A simple formation mechanism of the unusually observed "coffee ring" profile and "spherulites ring" morphology is proposed. These findings can be exploited to trace the center of Marangoni convection, with potential applications in designing the spherulite patterns of crystalline polymer films in ink-jet printing and self-assembly fields.

Anterior Pituitary Aplasia in an Infant with Ring Chromosome 18p Deletion

Directory of Open Access Journals (Sweden)

Edward J. Bellfield

2016-01-01

Full Text Available We present the first reported case of an infant with 18p deletion syndrome with anterior pituitary aplasia secondary to a ring chromosome. Endocrine workup soon after birth was reassuring; however, repeat testing months later confirmed central hypopituitarism. While MRI reading initially indicated no midline defects, subsequent review of the images confirmed anterior pituitary aplasia with ectopic posterior pituitary. This case demonstrates how deletion of genetic material, even if resulting in a chromosomal ring, still results in a severe syndromic phenotype. Furthermore, it demonstrates the necessity of close follow-up in the first year of life for children with 18p deletion syndrome and emphasizes the need to verify radiology impressions if there is any doubt as to the radiologic findings.

Systematic Search for Rings around Kepler Planet Candidates: Constraints on Ring Size and Occurrence Rate

Science.gov (United States)

Aizawa, Masataka; Masuda, Kento; Kawahara, Hajime; Suto, Yasushi

2018-05-01

We perform a systematic search for rings around 168 Kepler planet candidates with sufficient signal-to-noise ratios that are selected from all of the short-cadence data. We fit ringed and ringless models to their light curves and compare the fitting results to search for the signatures of planetary rings. First, we identify 29 tentative systems, for which the ringed models exhibit statistically significant improvement over the ringless models. The light curves of those systems are individually examined, but we are not able to identify any candidate that indicates evidence for rings. In turn, we find several mechanisms of false positives that would produce ringlike signals, and the null detection enables us to place upper limits on the size of the rings. Furthermore, assuming the tidal alignment between axes of the planetary rings and orbits, we conclude that the occurrence rate of rings larger than twice the planetary radius is less than 15%. Even though the majority of our targets are short-period planets, our null detection provides statistical and quantitative constraints on largely uncertain theoretical models of the origin, formation, and evolution of planetary rings.

On the Covariance of Moore-Penrose Inverses in Rings with Involution

OpenAIRE

Mahzoon, Hesam

2014-01-01

We consider the so-called covariance set of Moore-Penrose inverses in rings with an involution. We deduce some new results concerning covariance set. We will show that if $a$ is a regular element in a ${C}^{\\ast }$ -algebra, then the covariance set of $a$ is closed in the set of invertible elements (with relative topology) of ${C}^{\\ast }$ -algebra and is a cone in the ${C}^{\\ast }$ -algebra.

Optimization of magnet sorting in a storage ring using genetic algorithms

International Nuclear Information System (INIS)

Chen Jia; Wang Lin; Li Weimin; Gao Weiwei

2013-01-01

In this paper, the genetic algorithms are applied to the optimization problem of magnet sorting in an electron storage ring, according to which the objectives are set so that the closed orbit distortion and beta beating can be minimized and the dynamic aperture maximized. The sorting of dipole, quadrupole and sextupole magnets is optimized while the optimization results show the power of the application of genetic algorithms in magnet sorting. (authors)

Simulation of a resonant-type ring magnet power supply with multiple resonant cells and energy storage chokes

International Nuclear Information System (INIS)

Kim, J.M.S.; Blackmore, E.W.; Reiniger, K.W.

1992-01-01

For the TRIUMF KAON Factory Booster Ring, a resonant-type magnet power supply has been proposed for the dipole magnet excitation. The Booster Ring magnet power supply system based on resonant circuits, coupled with distributed energy make-up networks, is a complex system, sensitive to many system parameters. When multiple resonant cells, each with its own energy make-up network, are connected in a ring, it is very difficult to derive closed-form solutions to determine the operating conditions of the power supply system. A meaningful way to understand and analyze such a complex system is to use a simulation tool. This paper presents the analysis of operating conditions of the resonant-type ring magnet power supply with multiple resonant cells, using the circuit simulation tool, SPICE. The focus of the study is on the effect of circuit parameter variations in energy storage chokes

Structure and dynamics of ringed galaxies

International Nuclear Information System (INIS)

Buta, R.J.

1984-01-01

In many spiral and SO galaxies, single or multiple ring structures are visible in the disk. These inner rings (r), outer rings (R), and nuclear rings (nr) were investigated by means of morphology, photometry, and spectroscopy in order to provide basic data on a long neglected phenomenon. The metric properties of each ring are investigated and found to correlate with the structure of the parent galaxy. When properly calibrated, inner rings in barred (SB) systems can be used as geometric extragalactic distance indicators to distances in excess of 100 Mpc. Other statistics are presented that confirm previous indications that the rings have preferred shapes, relative sizes, and orientations with respect to bars. A survey is made of the less homogeneous non-barred (SA) ringed systems, and the causes of the inhomogeneity are isolated. It is shown that rings can be identified in multiple-ring SA systems that are exactly analogous to those in barred spirals

Variability of the tree-rings structure of Gmelin’s larch at northern tree line (peninsula of Taymyr

Directory of Open Access Journals (Sweden)

V. V. Fakhrutdinova

2017-04-01

Full Text Available The study of tree-ring cell structure changes as the result of tree adaptation to varying environmental conditions becomes increasingly important to predict future vegetation shifts under projected climate changes. The estimate of intrapopulation annual variability of wood anatomy characteristics is particularly informative. It helps to divide the contribution of different ecological factors to total features dispersion. In this work, a comparative analysis of individual and climatic variability of tree ring structure characteristics of Gmelin’s larch Larix gmelinii (Rupr. growth within northernmost forest was carried out. The trees from forest-tundra boundary has greater radial growth intensity, forms the bigger conductive zone in rings with wider mean lumen area in comparison with trees from closed forest. This result can be explained by adaptive features and height ecological xylem plasticity of larch. The tree rings structure of larch from boundary with tundra is determined by largely current weather conditions. Is because these ones evince high adaptive plasticity on the level of xylem structure. The xylem reflects joint changes of climate factors and local ecological conditions. The trees from closed forest are characterized by larger individual variability. The local conditions in oldest forest (for example, bad hydrothermal soil conditions inhibit the radial growth and sensitivity to environmental factors. In this case, the trees on individual level are tended to save the normal functioning of water-transport system. The significant differences in ratio individual to climate variability of tree ring structure characteristics can be caused by the different in the level of ecological habitat heterogeneity or the different in the level genetic within-population heterogeneity.

Multiplicative Structure and Hecke Rings of Generator Matrices for Codes over Quotient Rings of Euclidean Domains

Directory of Open Access Journals (Sweden)

Hajime Matsui

2017-12-01

Full Text Available In this study, we consider codes over Euclidean domains modulo their ideals. In the first half of the study, we deal with arbitrary Euclidean domains. We show that the product of generator matrices of codes over the rings mod a and mod b produces generator matrices of all codes over the ring mod a b , i.e., this correspondence is onto. Moreover, we show that if a and b are coprime, then this correspondence is one-to-one, i.e., there exist unique codes over the rings mod a and mod b that produce any given code over the ring mod a b through the product of their generator matrices. In the second half of the study, we focus on the typical Euclidean domains such as the rational integer ring, one-variable polynomial rings, rings of Gaussian and Eisenstein integers, p-adic integer rings and rings of one-variable formal power series. We define the reduced generator matrices of codes over Euclidean domains modulo their ideals and show their uniqueness. Finally, we apply our theory of reduced generator matrices to the Hecke rings of matrices over these Euclidean domains.

Ring current and auroral electrojets in connection with interplanetary medium parameters during magnetic storm

Directory of Open Access Journals (Sweden)

Y. I. Feldstein

1994-06-01

Full Text Available The relationship between the auroral electrojet indices (AE and the ring current magnetic field (DR was investigated by observations obtained during the magnetic storm on 1-3 April 1973. During the storm main phase the DR development is accompanied by a shift of the auroral electrojets toward the equator. As a result, the standard AE indices calculated on the basis of data from auroral observatories was substantially lower than the real values (AE'. To determine AE' during the course of a storm main phase data from subauroral magnetic observatories should be used. It is shown that the intensity of the indices (AE' which take into account the shift of the electrojets is increased substantially relative to the standard indices during the storm main phase. AE' values are closely correlated with geoeffective solar wind parameters. A high correlation was obtained between AE' and the energy flux into the ring current during the storm main phase. Analysis of magnetic field variations during intervals with intense southward IMF components demonstrates a decrease of the saturation effect of auroral electrojet currents if subauroral stations magnetic field variations are taken into account. This applies both to case studies and statistical data. The dynamics of the electrojets in connection with the development of the ring current and of magnetospheric substorms can be described by the presence (absence of saturation for minimum (maximum AE index values during a 1-h interval. The ring current magnetic field asymmetry (ASY was calculated as the difference between the maximum and minimum field values along a parallel of latitude at low latitudes. The ASY value is closely correlated with geoeffective solar wind parameters and simultaneously is a more sensitive indicator of IMF Bz variations than the symmetric ring current. ASY increases (decreases faster during the main phase (the recovery phase than DR. The magnetic field decay at low latitudes in the

Binomial Rings: Axiomatisation, Transfer and Classification

OpenAIRE

Xantcha, Qimh Richey

2011-01-01

Hall's binomial rings, rings with binomial coefficients, are given an axiomatisation and proved identical to the numerical rings studied by Ekedahl. The Binomial Transfer Principle is established, enabling combinatorial proofs of algebraical identities. The finitely generated binomial rings are completely classified. An application to modules over binomial rings is given.

AN N-BODY INTEGRATOR FOR GRAVITATING PLANETARY RINGS, AND THE OUTER EDGE OF SATURN'S B RING

International Nuclear Information System (INIS)

Hahn, Joseph M.; Spitale, Joseph N.

2013-01-01

A new symplectic N-body integrator is introduced, one designed to calculate the global 360° evolution of a self-gravitating planetary ring that is in orbit about an oblate planet. This freely available code is called epi i nt, and it is distinct from other such codes in its use of streamlines to calculate the effects of ring self-gravity. The great advantage of this approach is that the perturbing forces arise from smooth wires of ring matter rather than discreet particles, so there is very little gravitational scattering and so only a modest number of particles are needed to simulate, say, the scalloped edge of a resonantly confined ring or the propagation of spiral density waves. The code is applied to the outer edge of Saturn's B ring, and a comparison of Cassini measurements of the ring's forced response to simulations of Mimas's resonant perturbations reveals that the B ring's surface density at its outer edge is σ 0 = 195 ± 60 g cm –2 , which, if the same everywhere across the ring, would mean that the B ring's mass is about 90% of Mimas's mass. Cassini observations show that the B ring-edge has several free normal modes, which are long-lived disturbances of the ring-edge that are not driven by any known satellite resonances. Although the mechanism that excites or sustains these normal modes is unknown, we can plant such a disturbance at a simulated ring's edge and find that these modes persist without any damping for more than ∼10 5 orbits or ∼100 yr despite the simulated ring's viscosity ν s = 100 cm 2 s –1 . These simulations also indicate that impulsive disturbances at a ring can excite long-lived normal modes, which suggests that an impact in the recent past by perhaps a cloud of cometary debris might have excited these disturbances, which are quite common to many of Saturn's sharp-edged rings

Galactic rings revisited - I. CVRHS classifications of 3962 ringed galaxies from the Galaxy Zoo 2 Database

Science.gov (United States)

Buta, Ronald J.

2017-11-01

Rings are important and characteristic features of disc-shaped galaxies. This paper is the first in a series that re-visits galactic rings with the goals of further understanding the nature of the features and for examining their role in the secular evolution of galaxy structure. The series begins with a new sample of 3962 galaxies drawn from the Galaxy Zoo 2 citizen science data base, selected because zoo volunteers recognized a ring-shaped pattern in the morphology as seen in Sloan Digital Sky Survey colour images. The galaxies are classified within the framework of the Comprehensive de Vaucouleurs revised Hubble-Sandage system. It is found that zoo volunteers cued on the same kinds of ring-like features that were recognized in the 1995 Catalogue of Southern Ringed Galaxies. This paper presents the full catalogue of morphological classifications, comparisons with other sources of classifications and some histograms designed mainly to highlight the content of the catalogue. The advantages of the sample are its large size and the generally good quality of the images; the main disadvantage is the low physical resolution that limits the detectability of linearly small rings such as nuclear rings. The catalogue includes mainly inner and outer disc rings and lenses. Cataclysmic (`encounter-driven') rings (such as ring and polar ring galaxies) are recognized in less than 1 per cent of the sample.

Quantum Fourier Transform Over Galois Rings

OpenAIRE

Zhang, Yong

2009-01-01

Galois rings are regarded as "building blocks" of a finite commutative ring with identity. There have been many papers on classical error correction codes over Galois rings published. As an important warm-up before exploring quantum algorithms and quantum error correction codes over Galois rings, we study the quantum Fourier transform (QFT) over Galois rings and prove it can be efficiently preformed on a quantum computer. The properties of the QFT over Galois rings lead to the quantum algorit...

Novel manifestations of the Aharonov-Bohm effect in quantum rings and Moebius rings

International Nuclear Information System (INIS)

Fomin, Vladimir M.

2013-01-01

- An overview is given on the recent experimental and theoretical advancements in studies of novel manifestations of the Aharonov-Bohm quantum-interference effect for excitons confined to self assembled quantum rings and other semiconductor nanostructures with ring-like states of charge carriers as well as for electrons in Moebius rings at the micro- and nanoscale. The exciton Aharonov-Bohm effect can be effectively controlled by an out-of-plane magnetic field, a vertical electric field, a spin disorder. A 'delocalization-to-localization' transition for the electron ground state occurs in a Moebius ring as it is made more inhomogeneous. (authors)

Ring closure in actin polymers

Energy Technology Data Exchange (ETDEWEB)

Sinha, Supurna, E-mail: supurna@rri.res.in [Raman Research Institute, Bangalore 560080 (India); Chattopadhyay, Sebanti [Doon University, Dehradun 248001 (India)

2017-03-18

We present an analysis for the ring closure probability of semiflexible polymers within the pure bend Worm Like Chain (WLC) model. The ring closure probability predicted from our analysis can be tested against fluorescent actin cyclization experiments. We also discuss the effect of ring closure on bend angle fluctuations in actin polymers. - Highlights: • Ring closure of biopolymers. • Worm like chain model. • Predictions for experiments.

On P-coherent endomorphism rings

Indian Academy of Sciences (India)

A ring is called right -coherent if every principal right ideal is finitely presented. Let M R be a right -module. We study the -coherence of the endomorphism ring of M R . It is shown that is a right -coherent ring if and only if every endomorphism of M R has a pseudokernel in add M R ; S is a left -coherent ring if and ...

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

KAUST Repository

Samantaray, Manoja

2014-01-22

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